Patent Application
20160339160
The present embodiments generally relates to two-dimensional materials, such as graphene as well as graphene platelet-based polymers, and methods of use and production thereof.
Graphene represents a form of carbon in which the carbon atoms reside within a single atomically thin sheet or a few layered sheets (e.g., about 20 or less) of fused six-membered rings forming an extended planar lattice. In its various forms, graphene has garnered widespread interest for use in a number of applications, primarily due to its favorable combination of high electrical and thermal conductivity values, good in-plane mechanical strength, and unique optical and electronic properties. In many aspects, the properties of graphene parallel those of carbon nanotubes, since both nanomaterials are based upon an extended sp2-hybridized carbon framework. Other two-dimensional materials having a thickness of a few nanometers or less and an extended planar lattice are also of interest for various applications.
Two-dimensional graphene materials such as perforated graphene have been demonstrated as effective in filtration devices. However, the synthesis of these compositions may be costly or time consuming. Thus, there is a need for cheaper, more easily made compositions that can provide similar effects as graphene compositions, as well as new effects.
Some embodiments include a process comprising:
In some embodiments, the perforated two-dimensional material is graphene-based material. In some embodiments, graphene-based material is single-layer graphene. In some embodiments, the perforated two-dimensional material is graphene oxide. In some embodiments, the one or more occluding moieties are particles sized for at least partial introduction into an uncovered pore, but which cannot exit the uncovered pore. In some embodiments, the particles are deformable or swellable. In some embodiments, the particles are deformable and pressure or energy is applied to the particles after they are introduced into the at least one uncovered pore. In some embodiments, heat or light of a selected wavelength is applied to the particles after they are introduced into the at least one uncovered pore. In some embodiments, an electron or ion beam is applied to the particles after they are introduced into the at least one uncovered pore.
Some embodiments describe methods for at least partially occluding flow of liquid and/or chemical species and/or particles through apertures within sheets of graphene-based materials or other two-dimensional materials. Some embodiments also describe related methods for occluding pores in a composite membrane to generate membranes where flow through the pores is mediated through size-selected perforated graphene or other two-dimensional materials.
In one aspect, the methods involve reacting an occluding moiety with defects or apertures in sheets of graphene-based materials or other two dimensional materials or catalyzing a reaction in such defects or apertures to mitigate the defect or aperture, where mitigation includes closing or healing of the defect or aperture or decreasing the size of the defect or aperture. In healing the graphene-based material, perforations in the graphene-based material may or may not be healed. Fluorescently tagged moieties may be used to verify healing or failure of healing. In an embodiment, reacting or catalyzing a reaction is directed to defects or aperture having a certain size, geometry or functionality. The methods can involve flowing a chemical moiety through the perforations in a sheet of the two-dimensional material such that only the moiety passing through the sheet of the two-dimensional material is available to react or catalyze a reaction with the defect or aperture, i.e., with chemical moieties at the defect or aperture. By choosing the occlusion technique and the occluding moiety, larger apertures in a sheet of a two-dimensional material can become occluded, for example, in preference to smaller apertures, producing a sheet of two dimensional material with improved flow selectivity. In some cases it can be desirable to occlude substantially all the apertures in a sheet of a two-dimensional material, such that the treated sheet of two-dimensional material is substantially impervious to flow of fluids or chemical species there through. The sheets of a two-dimensional material having at least partially occluded apertures prepared according to the embodiments described herein can be used in separation techniques and systems, although they are also usable in other applications, such as selective barrier applications. In an embodiment, sheets of two-dimensional material having at least partially occluded apertures and particularly sheets where the majority (greater than about 50%) of the apertures or wherein substantially all of the apertures are occluded can be used as starting material for preparation of size-selective perforated graphene or other two-dimensional material, wherein perforations of a selected size range are introduced into the sheets in which apertures have been occluded.
In some embodiments, perforated graphene-based material having at least a portion of its apertures occluded with a chemical moiety is described herein.
In another aspect, some embodiments relate to methods of making composite membranes in which a sheet of graphene-based material or other two-dimensional material is disposed on a surface of a porous substrate wherein at least a portion of the pores of the substrate are covered by the sheet of two-dimensional material and in which pores in the substrate, that are not covered or are only partially covered, are occluded with one or more occluding moieties such that fluid or other chemical moieties cannot pass through the occluded pores. The size of the moiety provides a selectivity for which size of pores will be occluded. The methods herein in certain embodiments ensure that pores in the composite membrane that are covered by the two-dimensional material are not occluded which results in composite membranes with minimal reduction in membrane function. Composite membranes with occluded pores include those in which a portion of the uncovered substrate pores are occluded, those in which a majority (50% or more) of the uncovered substrate pores are occluded and those in which substantially all (95% or more) of the uncovered pores are occluded. The two-dimensional material covering the pores may be defect and aperture-free, or may be size-selective perforated. In an embodiment, the two-dimensional material of the composite membrane is perforated after treatment to occlude pores that are not covered by the two-dimensional material. Size-selective perforation after pore occlusion provides composite membranes useful for size-selective filtration. Composite membranes in which uncovered pores are occluded are useful, for example, as starting materials for preparation of size-selective filtration membranes.
Some embodiments also relate to composite membranes prepared by the methods herein wherein at least a portion of the uncovered pores of the substrate are occluded.
In an embodiment, the method of occluding uncovered pores includes introducing an occluding moiety into an uncovered pore. In an embodiment, the occluding moiety is one or more particles sized for at least partial entrance into the uncovered pore, but which do not pass through the pore. In an embodiment, the one or more particles are deformable after introduction into the pore by application of energy, for example, application of pressure, heat, light, particularly light of selected wavelength, or an ion or particle beam. In an embodiment, the one or more particles carry one or more chemical reactive groups which react or can be activated to react with compatible reactive groups in the pores, on the surface of the substrate or on other particles to facilitate anchoring of the one or more particles to occlude a pore.
In an embodiment, the occluding particles are swellable after entry into a pore. For example, the material from which the particle is made is selected such that it swells when contacted by material which is absorbed into the particle. In an embodiment, the particle is swellable on contact with a selected absorbable fluid. In an embodiment, the absorbable fluid is water or an aqueous solution. In an embodiment, the absorbable fluid is an organic solvent. In an embodiment, the absorbable fluid is a polar organic solvent. In an embodiment, the absorbable fluid is a non-polar organic solvent. In an embodiment, the occluding particles are hydrogel particles which swell on absorption of water. In an embodiment, the occluding particles are polymer particles which swell on adsorption of an organic solvent, such as cross linked organic thermoset polymers, for example.
In an embodiment, the one or more occluding particles are monodisperse with respect to particle size. In an embodiment, the one or more occluding particles have a selected range of particles sizes. In an embodiment, after initial occlusion of a pore by one or more particles of a given first size, additional secondary particles of a size less than that of the initial particles can optionally be introduced into a pore to further facilitate occlusion of the pore or to facilitate anchoring. In this embodiment, the first and secondary particles optionally carry reactive groups to facilitate reaction with compatible reactive groups on the surface of pores or on other particles. In this embodiment, after particle introduction, energy is optionally applied, for example, in the form of heat, light or ion beam irradiation to facilitate anchoring in the pores. The use of particles of different sizes can result in higher packing densities which can provide better occlusion of pores. Particle compositions can, for example, be employed for occlusion, which have bimodal or trimodal particle size distributions.
In an embodiment, the pore occluding moiety is one or more monomers or oligomers which are introduced into an uncovered pore and polymerized therein to form a polymer and occlude the pore. Polymerization may be activated by any known means that is not detrimental to the two-dimensional material or to the substrate, including for example, activation by heating to a selected temperature, irradiation with light of selected wavelength, and/or introduction of a polymerization catalyst, or other methods (see, for example, US patent application filed herewith, entitled SELECTIVE INTERFACIAL MITIGATION OF GRAPHENE DEFECTS, Atty Docket No. 111423-1097, incorporated herein in its entirety) In some embodiments, a polymerization catalyst may be activated by application of heat, light or other form of energy.
In an embodiment, the pores of the substrate can be shaped along their length to facilitate occlusion by one or more particles. For example, the pores may be tapered where the size of the opening into a pore (e.g., the pore diameter) is larger than the size of the exit from the pore. In an embodiment, the pores of the substrate can be shaped at one or both pore openings (entrance or exit openings) to facilitate occlusion by one or more particles. Substrate pores may be shaped to have a desired geometry, e.g., circular, oval, rectangular, slit, square mesh, or the like to facilitate occlusion by one or more particles. Pores may be provided with internal ridges or ledges to facilitate occlusion by one or more particles. The lip or ridge may be at the top of the pore. The size of the exit from the pore (e.g., the exit diameter) may be decreased with respect to the pore opening to facilitate occlusion by particles. Shaping of pores may be combined with use of deformable particles. Shaping of pores may be combined with the use of particles carrying one or more reactive groups and in this embodiment shaped pores or the entrance or exit of the pores can be provided with compatible reactive groups to facilitate anchoring in the shaped pores. Shaping of the pores may be combined with any particle occluding method described herein. Shaping of the pores may be combined with polymerization of monomer and/or oligomers in shaped pores to occlude the pores.
In another embodiment, pore occlusion is obtained without introduction of an occluding moiety. In this embodiment, uncovered pores are occluded by the deformation or swelling of the substrate material forming the pore. In this embodiment, uncovered pores are selectively contacted to induce deformation or swelling of the substrate forming the pore to occlude the pore. Contacting can, for example, be with energy such as heat, light or an ion beam. Contacting can, for example, be with an absorbable fluid, such as water, aqueous solution or organic solvent, such that the substrate material at the pore swells to occlude the pore. In a related embodiment, the pores are provided with a deformable or swellable coating distinct from the substrate material. In this embodiment, selective contacting of uncovered pores with energy in the form, for example, of heat, light or an ion beam deforms the pore coating to occlude the pore. In this embodiment, where the coating is swellable, selective contacting of an uncovered pore with an absorbable fluid results in swelling to occlude the pore. Swellable coatings can, for example, be formed from swellable hydrogels or swellable polymers.
In an embodiment, the particles or other substrate pore occluding moieties are themselves selectively permeable having permeability that is selected for a given application. Permeable materials could include hydrogels, polymers, proteins, zeolites, metal-organic framework materials, or thin film solution membranes. The particles could also be covered with a semipermeable layer. An example would be a silica particle covered with polyethylene glycol. In an embodiment, the occluding particles are made at least in part of hydroxycellulose which is semi-permeable.
In an embodiment, particles, other occluding moieties, monomers, oligomers and optional polymerization catalysts, are introduced selectively into substrate pores that are not covered by two-dimensional material (uncovered substrate pores) by a flow of fluid, including liquid or gas. The flow of fluid or gas carrying the occluding moieties will not enter covered substrate pores. In an embodiment, selective introduction employs application of a cross-flow of fluid along the membrane and application of pressure. The cross-flow carrying occluding moieties is applied along the surface of the composite membrane upon which the two-dimensional material is disposed. In an embodiment, a flow of particles is applied to the top surface of a composite membrane and particles enter uncovered pores. The introduction step is optionally followed by a step of application of energy, a curing step or other step to facilitate anchoring of particles. Thereafter a cleaning step may be applied to the top surface of the composite material to remove particles that have not entered uncovered pores. Cycles of a particle introduction step, optional anchoring steps and a cleaning step may be repeated to achieve a desired level of pore occlusion. The effectiveness of pore occlusion can be assessed by flow rate measurements through an occluded composite membrane. More specifically, flow rate of a selected moiety (fluid, chemical species or particle) of a given size can be used to assess the effectiveness of substrate pore occlusion. In an embodiment, two or more of such cycles are performed. In an embodiment, five or more of such cycles are performed. In an embodiment, 9 or more of such cycles are performed.
In an embodiment, a pore occlusion process includes introduction of occluding moieties, more specifically particles, into substrate pores that are not covered by two-dimensional material (uncovered substrate pores). In an embodiment, a pore occlusion process further includes a step of removing occluding moieties that are not within substrate pores from the composite membrane. Introduction and removal (cleaning) steps can be repeated until a desired level of occlusion is achieved. In an embodiment, as described herein, a step of application of energy or chemical reaction can be applied after introduction of occluding moieties into substrate pores to facilitate anchoring of the moieties in the substrate pore.
In an embodiment, the methods herein for occluding defects, apertures or uncovered substrate pores are combined with methods of detection of defects or apertures in the two-dimensional material, such that occlusion methods are selectively applied to those portions of a sheet of two-dimensional material or those portions of a composite membrane where occlusion is needed. Such detection methods can include localized application of a selected assay fluid, e.g., a detectible gas, such as SF6, to the two-dimensional material or to the composite membrane to detect the location (or approximate location) of defects, apertures or uncovered pores by passage of the assay fluid. Detection methods can also include localized resistance or capacitance measurement, where a change in resistance or capacitance is an indication of a defect or aperture. Detection methods can further include the localized detection of passage of analytes, particles, electrons or light, e.g., UV or visible light, through defects, apertures or through uncovered pores.
Some embodiments include a membrane comprising a cross-linked graphene platelet polymer comprising a plurality of cross-linked graphene platelets comprising a graphene portion and a cross-linking portion, the cross-linking portion contains a 4 to 10 atom link, and the cross-linked graphene platelet polymer being produced by reaction of an epoxide functionalized graphene platelet and a (meth)acrylate or (meth)acrylamide functionalized cross-linker. In some embodiments, the cross-linked graphene platelet polymer comprises cross-linked graphene platelets comprising a thiol moiety. In some embodiments, the cross-linked graphene platelet polymer further comprises a metal nanocluster. In some embodiments, the cross-linked graphene platelet polymer further comprises a quaternary alkyl-ammonium bromide. In some embodiments, the cross-linked graphene platelet polymer comprises cross-linked graphene platelets containing fluorocarbon functionalization. In some embodiments, each membrane is functionalized in a different manner. In some embodiments, a first filter comprises cross-linked graphene platelets comprising a thiol moiety. In some embodiments, a first filter comprises cross-linked graphene platelets comprising a quaternary alkyl-ammonium bromide. In some embodiments, a first filter comprises cross-linked graphene platelets comprising fluorocarbon.
Some embodiments a membrane comprising include a cross-linked graphene platelet polymer comprising a plurality of cross-linked graphene platelets, (a) comprising a graphene portion and a cross-linking portion, and the cross-linking portion contains a 4 to 10 atom link; or (b) comprising a plurality of graphene platelet portions and a plurality of cross-linking portions bound to the graphene platelet portions, wherein the cross-linking portions provide a spacing of about 1 nanometer between individual graphene platelet portions. In some embodiments, the cross-linked graphene platelet polymer comprises cross-linked graphene platelets comprising a thiol moiety. In some embodiments, the cross-linked graphene platelet polymer further comprises a metal nanocluster. In some embodiments, the cross-linked graphene platelet polymer further comprises a quaternary alkyl-ammonium bromide. In some embodiments, the cross-linked graphene platelet polymer comprises cross-linked graphene platelets containing fluorocarbon functionalization. Some embodiments include a filter module comprising at least two separate membranes of the above embodiments, wherein each membrane is functionalized in a different manner. In some embodiments, a first filter comprises cross-linked graphene platelets comprising a thiol moiety. In some embodiments, a first filter comprises cross-linked graphene platelets comprising a quaternary alkyl-ammonium bromide. In some embodiments, a first filter comprises cross-linked graphene platelets comprising fluorocarbon.
Other embodiments include a method of producing a filter or membrane composition comprising reacting one or more functionalized graphene platelets with one or more di-, tri- or tetra-functional crosslinking compounds. In some embodiments, the functionalized crosslinking compound is di-functionalized. In some embodiments, the crosslinking compound comprises one or more (meth)acrylate or (meth)acrylamide moieties. In some embodiments, the reacting step comprises applying e-beam or UV light to the one or more functionalized graphene platelets with one or more functionalized crosslinking compounds.
Other embodiments include a method of increasing purity of a liquid, comprising contacting a first portion of liquid having an impurity with a filter or membrane comprising a cross-linked graphene platelet polymer of any of the above embodiments to form a second portion of liquid, wherein the second portion of water contains a lower concentration of the impurity. In some embodiments, the liquid is an aqueous physiological liquid. In some embodiments, the liquid is water. In some embodiments, the impurity includes sodium and/or chloride ions. In some embodiments, the impurity includes an antibody. In some embodiments, the second portion of liquid is formed by passing the first portion of liquid through the filter comprising the cross-linked graphene platelet polymer. In some embodiments, the second portion of liquid contains 100-fold or less of the impurity as is found in the first portion of liquid.
Other embodiments include a method of producing a membrane composition comprising oxidizing a graphene platelet with an acid and an oxidizing agent at a temperature between 1 and 10 degrees Celsius to form a functionalized graphene platelet; and reacting one or more functionalized graphene platelets with one or more di-, tri- or tetra-functional crosslinking compounds.
Other embodiments include a method of producing a membrane precursor comprising oxidizing a graphene platelet with an acid and an oxidizing agent at a temperature between 1 and 10 degrees Celsius to form a functionalized graphene platelet; and reacting one or more functionalized graphene platelets to form a capped moiety that is not reactive under ambient conditions, but capable of converting to a reactive moiety upon, e.g., chemical, heat or UV treatment.
Other embodiments include a method of concentrating a composition of interest from a liquid or gas, comprising contacting a first portion of a liquid or gas having a material of interest with a filter comprising a cross-linked graphene platelet polymer of the above embodiments to form a second portion of liquid or gas, wherein the second portion of liquid or gas contains a lower concentration of the material of interest, and collecting the composition of interest that does not pass through the cross-linked graphene platelet polymer. In some embodiments, the liquid or gas is water. In some embodiments, the composition of interest is a rare-earth element.
Additional embodiments include a method of producing a membrane precursor comprising oxidizing a graphene platelet with an acid and an oxidizing agent at a temperature between 1 and 10 degrees Celsius to form a functionalized graphene platelet; and reacting one or more functionalized graphene platelets to form a capped moiety that is not reactive under ambient conditions, but capable of converting to a reactive moiety upon, e.g., chemical, heat or UV treatment.
Some embodiments describe methods for introducing pores into the basal plane of a plurality of graphene sheets stacked upon one another. In embodiments, the methods involve exposing about 5-20 layers of stacked graphene sheets (i.e., multi-layer graphene) to a particle beam having an ion energy of about 1500 eV or greater (per ion) to produce damage tracks in the basal planes of the stacked graphene sheets. In further embodiments, the ion energy greater than about 1500 eV but less than about 10000 eV or greater than 1.5 keV and less than 100 keV. Some embodiments further describe perforation methods including the step of exposing a sheet of graphene-based material to an ion beam, the graphene-based material comprising multilayer graphene having from 5 to 20 layers of graphene.
In embodiments, the damage tracks extend through the multi-layer graphene. Thereafter, the damaged graphene sheets are exposed to a chemical etchant, such as an oxidant, that selectively attacks defects (e.g. triple carbon-carbon bonds) in the damage tracks to remove graphene-based carbon atoms within the damage tracks. The damage tracks are tunable in size based upon the ion and energy used. In an embodiment, the oxidant is selected from the group consisting of ozone, an aqueous solution of potassium permanganate, an aqueous solution of potassium permanganate and sulfuric acid, an aqueous solution of potassium permanganate and potassium hydroxide or a solution of hydrogen peroxide and sulfuric acid
In embodiments, the ion bombardment takes place while the graphene-based material is disposed on a substrate. In some embodiments, the bombardment and etching can take place while the graphene is disposed on a substrate. In embodiments, the substrate is a metal growth substrate or other substrate.
Multi-layer graphene sheets and graphene-based materials comprising multi-layer graphene having a plurality of pores penetrating through the stacked sheets are also described in some embodiments. Such perforated multi-layer graphene sheets will also be referred to herein as “perforated graphene” “perforated graphene-based materials” or “perforated two dimensional materials,” In some embodiments, the perforations can be about 50 nm in size or less, 20 nm in size or less, 10 nm in size or less, or less than about 5 nm in size, particularly in a size range from about 0.2 nm to about 50 nm, 0.2 nm to about 20 nm, 0.2 nm to about 10 nm or from about 0.2 nm to about 5 nm. In embodiments, about 5 to about 20 stacked graphene sheets are present in the multi-layer graphene. In an embodiment, after perforation of the sheet the structure of the graphene based material in unperforated regions of the sheet is similar to that of the starting unperforated graphene based material.
In some embodiments, perforated graphene and perforated graphene-based materials comprising multilayered graphene produced by the techniques described herein can be used in filtration applications. The size or size range of perforations is adapted to the intended application. Some of the pore size ranges describe herein are suitable for reverse osmosis filtration and molecular filtration applications.
Some embodiments describe membranes comprising a perforated two-dimensional material disposed upon a porous support structure for use in blood dialysis and blood filtration applications. Such two-dimensional materials are selectively perforated to provide for selective removal of one or more components from the blood. Two-dimensional materials include for example graphene-based materials.
Some embodiments describe hemodialysis membranes and systems in which perforated graphene-based material and other perforated two-dimensional materials are used as a replacement for polymer membranes in conventional hemodialysis systems. The perforated two-dimensional material, such as graphene-based material and graphene, can have a pore size of similar magnitude to those used in conventional membranes, while providing much greater permeability due the thinness of the graphene. In addition, the pores or perforations in the two-dimensional material, such as graphene-based material, can be selectively sized, functionalized, or otherwise manipulated to tailor the selectivity of the hemodialysis separation process. In some embodiments, perforated graphene-based material can have added selectivity (e.g. tailored, smaller pores than conventional membranes) while maintaining permeability.
Some embodiments also describe hemodialysis methods in which blood is exposed to a hemodialysis membrane formed from perforated two-dimensional material, such as graphene-based material, and at least one component is removed from the blood upon contacting the perforated graphene. In an embodiment, the at least on component removed is urea, measurement of the extent of removal of which can be used to assess the effectiveness of a given hemodialysis method to remove low molecular weight toxic species, e.g., low molecular weight toxic species which contribute to disease. In an embodiment, at least one undesirable component is removed, such as a low molecular weight toxic species or a lower molecular weight (e.g., less than about 35 kDa) protein which contributes to uremia or other disorder, without removal of albumin at levels detrimental to a given patient. In an embodiment, at least urea is removed without removal of detrimental levels of albumin.
The foregoing has outlined rather broadly the features of some embodiments in order that the detailed description that follows can be better understood. Additional features and advantages of some embodiments will be described hereinafter. These and other advantages and features will become more apparent from the following description.
A variety of two-dimensional materials useful according to inventive concepts disclosed herein are known in the art. In various embodiments, the two-dimensional material comprises graphene, carbon nanomembranes (CNM), molybdenum disulfide, or boron nitride (specifically the hexagonal crystalline form of boron nitride). In an embodiment, the two-dimensional material is a graphene-based material. In more particular embodiments, the two-dimensional material is graphene. Graphene according to some embodiments can include single-layer graphene, multi-layer graphene, or any combination thereof. Other nanomaterials having an extended two-dimensional molecular structure can also constitute the two-dimensional material in some embodiments. For example, molybdenum sulfide is a representative chalcogenide having a two-dimensional molecular structure, and other various chalcogenides can constitute the two-dimensional material in some embodiments. Choice of a suitable two-dimensional material for a particular application can be determined by a number of factors, including the chemical and physical environment into which the graphene or other two-dimensional material is to be terminally deployed.
In an embodiment, the two dimensional material useful in membranes herein is a sheet of graphene-based material. Graphene-based materials include, but are not limited to, single layer graphene, multilayer graphene or interconnected single or multilayer graphene domains and combinations thereof. In an embodiment, graphene-based materials also include materials which have been formed by stacking independent single sheet or multilayer graphene sheets. In embodiments, multilayer graphene includes 2 to 20 layers, 2 to 10 layers or 2 to 5 layers. In embodiments, graphene is the dominant material in a graphene-based material. For example, a graphene-based material comprises at least 30% graphene by weight, or at least 40% graphene, or at least 50% graphene, or at least 60% graphene, or at least 70% graphene, or at least 80% graphene, or at least 90% graphene, or at least 95% graphene. In embodiments, a graphene-based material comprises a range of graphene content selected from 30% to 95%, or from 40% to 80% from 50% to 70%, from 60% to 95% or from 75% to 100%. In embodiments, a graphene-based material comprises a range of up to 35% oxygen by atomic ratio.
As used herein, a “domain” refers to a region of a material where atoms are uniformly ordered into a crystal lattice. A domain is uniform within its boundaries, but different from a neighboring region. For example, a single crystalline material has a single domain of ordered atoms. In an embodiment, at least some of the graphene domains are nanocrystals, having a domain size from 1 to 100 nm or 10-100 nm. In an embodiment, at least some of the graphene domains have a domain size greater than 100 nm to 1 micron, or from 200 nm to 800 nm, or from 300 nm to 500 nm., and in some embodiments, at least some of the graphene domains are nanocrystals, having a domain size up to about 1 cm. “Grain boundaries” formed by crystallographic defects at edges of each domain differentiate between neighboring crystal lattices. In some embodiments, a first crystal lattice may be rotated relative to a second crystal lattice, by rotation about an axis perpendicular to the plane of a sheet, such that the two lattices differ in “crystal lattice orientation”.
In an embodiment, the sheet of graphene-based material comprises a sheet of single or multilayer graphene or a combination thereof. In an embodiment, the sheet of graphene-based material is a sheet of single or multilayer graphene or a combination thereof. In another embodiment, the sheet of graphene-based material is a sheet comprising a plurality of interconnected single or multilayer graphene domains. In an embodiment, the interconnected domains are covalently bonded together to form the sheet. When the domains in a sheet differ in crystal lattice orientation, the sheet is polycrystalline.
In embodiments, the thickness of the sheet of graphene-based material is from 0.34 to 10 nm, from 0.34 to 5 nm, or from 0.34 to 3 nm. In an embodiment, a sheet of graphene-based material comprises intrinsic defects. Intrinsic defects are those resulting from preparation of the graphene-based material in contrast to perforations which are selectively introduced into a sheet of graphene-based material or a sheet of graphene. Such intrinsic defects include, but are not limited to, lattice anomalies, pores, tears, cracks or wrinkles. Lattice anomalies can include, but are not limited to, carbon rings with other than 6 members (e.g. 5, 7 or 9 membered rings), vacancies, interstitial defects (including incorporation of non-carbon atoms in the lattice), and grain boundaries.
In an embodiment, a sheet of graphene-based material optionally further comprises non-graphenic carbon-based material located on the surface of the sheet of graphene-based material. In an embodiment, the non-graphenic carbon-based material does not possess long range order and may be classified as amorphous. In embodiments, the non-graphenic carbon-based material further comprises elements other than carbon and/or hydrocarbons. Non-carbon elements which may be incorporated in the non-graphenic carbon include, but are not limited to, hydrogen, oxygen, silicon, nitrogen, copper and iron. In embodiments, the non-graphenic carbon-based material comprises hydrocarbons. In embodiments, carbon is the dominant material in non-graphenic carbon-based material. For example, a non-graphenic carbon-based material comprises at least 30% carbon by weight, or at least 40% carbon, or at least 50% carbon, or at least 60% carbon, or at least 70% carbon, or at least 80% carbon, or at least 90% carbon, or at least 95% carbon. In embodiments, a non-graphenic carbon-based material comprises a range of carbon selected from 30% to 95%, or from 40% to 80%, or from 50% to 70%.
Two-dimensional materials in which pores are intentionally created are referred to herein as “perforated,” such as “perforated graphene-based materials,” “perforated two-dimensional materials,” or “perforated graphene.” Two-dimensional materials are, most generally, those which have atomically thin thickness from single-layer sub-nanometer thickness to a few nanometers and which generally have a high surface area. Two-dimensional materials include metal chalogenides (e.g., transition metal dichalogenides), transition metal oxides, hexagonal boron nitride, graphene, silicene and germanene (see: Xu et al. (2013) “Graphene-like Two-Dimensional Materials) Chemical Reviews 113:3766-3798).
Two-dimensional materials include graphene, a graphene-based material, a transition metal dichalcogenide, molybdenum sulfide, α-boron nitride, silicene, germanene, or a combination thereof. Other nanomaterials having an extended two-dimensional, planar molecular structure can also constitute the two-dimensional material in some embodiments. For example, molybdenum sulfide is a representative chalcogenide having a two-dimensional molecular structure, and other various chalcogenides can constitute the two-dimensional material in some embodiments. In another example, two-dimensional boron nitride can constitute the two-dimensional material in an embodiment of the inventive concepts disclosed herein. Choice of a suitable two-dimensional material for a particular application can be determined by a number of factors, including the chemical and physical environment into which the graphene, graphene-based or other two-dimensional material is to be deployed.
Some embodiments are directed, in part, to sheets of graphene-based material or other two-dimensional materials containing a plurality of perforations therein, where the perforations have a selected size and chemistry, as well as pore geometry. In embodiments, the perforated graphene, perforated graphene-based materials and other perforated two-dimensional materials contain a plurality of size-selected perforations ranging from about 3 to 15 angstroms in size. In a further embodiment, the perforation size ranges from 3 to 10 angstroms or from 3 to 6 angstroms in size. Some embodiments are further directed, in part, to perforated graphene, perforated graphene-based materials and other perforated two-dimensional materials containing a plurality of size-selected perforations ranging from about 3 to 15 angstroms in size and having a narrow size distribution, including but not limited to a 1-10% deviation in size or a 1-20% deviation in size. In an embodiment, the characteristic dimension of the perforations is from about 3 to 15 angstroms in size.
Some embodiments are also directed, in part, to perforated graphene, perforated graphene-based materials and other perforated two-dimensional materials containing a plurality of perforations ranging from about 5 to about 1000 angstroms in size. In further embodiments, the perforations range from 10 to 100 angstroms, 10 to 50 angstroms, 10 to 20 angstroms or 5 to 20 angstroms. In a further embodiment, the perforation size ranges from 100 nm up to 1000 nm or from 100 nm to 500 nm. Some embodiments are further directed, in part, to perforated graphene, perforated graphene-based materials and other perforated two-dimensional materials containing a plurality of perforations ranging from about 5 to 1000 angstrom in size and having a narrow size distribution, including but not limited to a 1-10% deviation in size or a 1-20% deviation in size. In an embodiment, the characteristic dimension of the perforations is from 5 to 1000 angstrom.
For circular perforations or apertures, the characteristic dimension is the diameter of the perforation or aperture. In embodiments relevant to non-circular pores, the characteristic dimension can be taken as the largest distance spanning the perforation or aperture, the smallest distance spanning the perforation or aperture, the average of the largest and smallest distance spanning the perforation or aperture, or an equivalent diameter based on the in-plane area of the perforation or aperture. As used herein, perforated graphene-based materials include materials in which non-carbon atoms have been incorporated at the edges of the pores.
Some embodiments describe methods directed to occluding apertures in a sheet of a graphene-based material or other two-dimensional material that are larger than a given threshold size, thereby reducing the plurality of apertures to a desired size and optionally with a specific chemistry. In embodiments, the reduced size of the aperture falls within the perforation and aperture size ranges given above. The threshold size can be chosen at will to meet the needs of a particular application. Perforations or apertures are sized as described herein to provide desired selective permeability of a species (atom, molecule, protein, virus, cell, etc.) for a given application. Selective permeability relates to the propensity of a porous material or a perforated two-dimensional material to allow passage (or transport) of one or more species more readily or faster than other species. Selective permeability allows separation of species which exhibit different passage or transport rates through perforations or apertures. In two-dimensional materials selective permeability correlates at least in part to the dimension or size (e.g., diameter) of perforations or apertures and the relative effective size of the species. Selective permeability of the perforations or apertures in two-dimensional materials such as graphene-based materials can also depend on functionalization of the perforation or aperture (if any) and the specific species that are to be separated. For electrically conductive two dimensional materials, selective permeability can be affected by application of a voltage bias to the membrane. Selective permeability of gases can also depend upon adsorption of a gas species on the filtration material, e.g., graphene. Adsorption at least in part can affect the local concentration of the gas species at the surface of the filtration material. Separation of two or more species in a mixture includes a change in the ratio(s) (weight or molar ratio) of the two or more species in the mixture after passage of the mixture through a perforated two-dimensional material.
The chemistry of the perforated apertures can be the same or different after being occluded according to the embodiments described herein. In various embodiments, occluding the apertures can involve occluding apertures within a particular size range such that no apertures remain within the size range, thereby conferred selectivity to the “healing” of the graphene-based material or other two-dimensional material. The embodiments of the healing processes described herein are applicable to both “through-holes” (i.e., pores in a single two-dimensional sheet) and “intralayer flow” (i.e., channels existing between stacked layers of individual single layer two-dimensional sheets or multiple layer sheets of 2D material. Channels can include laterally offset pores within multiple two-dimensional sheets. Through-holes can also exist in multiple two-dimensional sheets when the pores are not substantially laterally offset from one another in the various layers
The embodiments described herein allow specific chemistries to be readily applied in a homogenous manner to graphene-based materials and other two-dimensional materials to allow for tunable activity across many applications. While the chemistries described herein can be applied homogenously to an entire surface of the sheet of graphene or other two-dimensional material, they generally provide specific activation of particular perforations or apertures of a given size using a carefully sized moiety that allows for aperture modification to take place. The described techniques can be advantageous in allowing the homogenous application of chemistry to the graphene-based material or other two-dimensional material surface while only occluding perforations or apertures of a certain desired size. The homogenous application of the various chemistries described herein can facilitate scalable production and manufacturing ease. Perforation or aperture modification can confer a specific chemistry to the perforations or apertures (e.g., functional selectivity, hydrophobicity, and the like) and allow for at least partial occlusion of the perforations or apertures to take place in various embodiments. Such selective modification of the apertures can allow selective separations to take place using the graphene-based material, including size-based separations.
For example, perforations or apertures can be selectively modified by various known methods to contain hydrophobic moieties, hydrophilic moieties, ionic moieties, polar moieties, reactive chemical groups, for example, amine-reactive groups (chemical species that react with amines) carboxylate-reactive groups (chemical species that react with carboxylates), amines or carboxylates (among many others), polymers and various biological molecules, including for example, amino acids, peptide, polypeptides, enzymes or other proteins, carbohydrates and various nucleic acids.
Furthermore, the techniques described herein can be configured to at least partially occlude large apertures within the sheet of graphene-based material or other two-dimensional material in preference to smaller apertures, thereby allowing the smaller apertures to remain open and allow flow to be maintained therethrough. This type of selective flow can allow molecular sieving to take place using the graphene-based material or other two-dimensional material, rather than the solution-diffusion model provided by current polymeric solutions. In some aspects, apertures or defects are blocked to provide flow reduction or blockage within a range of 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, 95% or more. In further aspects, however, all the apertures and/or defects in a graphene-based material or other two-dimensional material can be occluded in order to substantially block passage or flow, herein 99% or more through the two-dimensional material or block passage or flow through the two-dimensional material entirely. In an embodiment, a graphene-based material or other two-dimensional material that is occluded in order to substantially or entirely block passage or flow through the material can be used as a starting material for forming a size-selected perforated two-dimensional material. Size-selected perforations can be introduced into the substantially or entirely blocked two-dimensional material employing art known methods for generating perforations of a selected size and, if any, a selected functionalization.
Although the description herein is primarily directed to graphene-based materials, it is to be recognized that other two-dimensional materials or near two-dimensional materials can be treated in a like manner. The at least partially occluded graphene-based materials prepared according to the techniques described herein can be used for occluding fluid flow, particularly liquid or gas flow for separations, including filtration membranes and filtration systems. In addition, they can be used in optical or electronic applications.
In some embodiments, the graphene-based material can be transferred from its growth substrate to a porous substrate in the course of, before or after practicing the embodiments described herein.
By way of example, a sheet of a graphene-based material or sheet of another two-dimensional material can have a plurality of perforations therein, and a direction of fluid flow therethrough can establish an “upstream” side (alternative the top surface) and a “downstream” side (alternatively the bottom surface) of the sheet. The downstream side of the sheet of the graphene-based material or sheet of another two-dimensional material can be next to or in contact with a substrate, such as a porous substrate. In some embodiments, the substrate can provide support to the sheet of the graphene-based material while practicing the various techniques described herein. The perforations in the sheet of a graphene-based material or sheet of another two-dimensional material can be intentionally placed therein, or they can occur natively during its synthesis. According to some embodiments, the perforations can have a distribution of sizes, which can be known or unknown. By placing an occluding moiety within a flow contacting the graphene-based material or other two-dimensional material, apertures having a desired size profile can become occluded according to the embodiments described herein.
In some embodiments described herein, a fluid containing a sized moiety can be flowed through the sheet of graphene-based material or other two-dimensional material. The sized moiety can lodge in some of the apertures in the sheet and induce occlusion of at least the portion of the apertures in the sheet in which the sized moiety lodges. In other embodiments, a sized moiety can occlude fluid flow on the sheet of graphene-based material or other two-dimensional material from the upstream side of the graphene. Various embodiments of these various flow configurations are described below.
Occluding at least a portion of the apertures in the foregoing manner can result in reducing the size and number of apertures, possibly modifying a flow path and making the graphene-based material or other two-dimensional material suitable for use in an intended application. For example, the graphene-based material or sheet of another two-dimensional material can be processed in the foregoing manner to produce a cutoff pore size in a molecular filter. Depending on the nature of the moiety in the flow path, the moiety can be covalently or non-covalently attached to the graphene-based material, or mechanically connected to the graphene-based material.
In some embodiments, the “downstream” side of the sheet of graphene-based material can be “primed” or functionalized with oxygen via plasma oxidation or the like, such that the graphene-based material can be reactive with a moiety passing through the apertures. In some embodiments, the moiety in the flow path can bind to functional groups introduced to the graphene-based material, such that the moiety binds to the graphene-based material and the apertures become at least partially occluded. Suitable binding motifs can include, but are not limited to, addition chemistry, crosslinking, covalent bonding, condensation reactions, esterification, polymerization. In various embodiments, the occluding moiety can be sized to reflect a particular cutoff regime, such that it only passes through apertures having a certain threshold size or shape. For example, in various embodiments, the occluding moieties can be a substantially flat molecule or spherical in shape. POSS® silicones (polyhedral oligomeric silsesquioxanes), for example, represent one particular type of occluding moiety that can be made at a very specific size and functionalized to tether to oxygenated functionalization on the apertures. Other examples, of useful occluding moieties include fullerenes, dendrites, dextran, micelles or other lipid aggregates, and micro-gel particles. Some or all of these techniques may be applied to other two-dimensional materials as well.
In various embodiments, the graphene-based material can be perforated and functionalized with oxygen, such as treating the graphene-based material with oxygen or a dilute oxygen plasma, thereby functionalizing the graphene-based material with oxygen moieties. In some embodiments, the graphene based material can be functionalized in this manner while on a copper substrate, or any other metallic/growth, or polymeric substrate as it would be understood by one of skill in the art. Subsequently, the oxygen functionalities can be reacted via a chemistry that converts the oxygenated functionalities into a leaving group (such as a halide group, particularly a fluoro group, or sulfonic acid analogs, such as tosylates, triflates, mesylates, and the like). This chemistry results in sites on the substrate that are vulnerable to nucleophilic attack and can be used for additional chemistry, as detailed above, or allowing the graphene based material to bind to the substrate. In some embodiments, the graphene-based material can functionalized with oxygen so as to provide graphene oxide platelet membranes.
In other embodiments, the downstream side of the graphene-based material or other two-dimensional material can be primed with an occluding substance and a moiety that catalyzes the reaction of the occluding substance with the graphene or other two-dimensional material can pass through the apertures. Thus, in this case, the moiety does not become bonded to the graphene or other two-dimensional material itself.
In the foregoing embodiments, also depicted in
In still further embodiments, carbonaceous or non-carbonaceous materials can be flowed over the graphene based material or other two-dimensional material and become tethered to the open apertures. Suitable materials can include, for example, graphene nanoplatelets (GNPs), fullerenes of various sizes, hexagonal boron nitride, or carbon nanotubes. In more particular embodiments, tethering of the carbonaceous or non-carbonaceous material can be accomplished by utilizing a light or gentle ion beam, a high temperature annealing step, exposing to light to generate a photo-active reaction. The high temperature annealing step could comprise isocyanate crosslink chemistry. In some embodiments, flow through the two-dimensional material can become completely blocked. In some embodiments, smaller apertures can remain open.
In still other embodiments, functionalization or activation of multiple, potentially different layered sheets of graphene-based materials or other two-dimensional material (e.g. complementary chemistries) can be leveraged to allow for flow not only through channels, but also via intralayer flow. Healing or partial occlusion can result from further modification of apertures. That is, layered sheets of two-dimensional material can be differentially functionalized according to the embodiments described herein.
Some embodiments are directed, in part, to composite membranes formed from a porous substrate having a plurality of pores with a sheet of two-dimensional material disposed on the surface of the porous substrate and defining a top surface of the composite membrane. A portion of the pores of the substrate are covered by the two-dimensional material and a portion of the pores of the substrate are not covered by the two-dimensional material due, for example, to defects formed during synthesis of the two-dimensional material, formed during handling of the two-dimensional material, or formed when the two-dimensional material is disposed on the porous substrate. Defects or apertures in the two-dimensional material can result in undesired passage of species through the composite membrane. It is desired for use in filtration applications, that substantially all of the substrate pores are covered by the two-dimensional material so that passage through the membrane is primarily controlled by passage through the two-dimensional material. In a specific embodiment, substantially all pores of the substrate are covered by a two-dimensional material that contains perforations of a desired size range for selective passage through the membrane. In a specific embodiment, perforations in the two-dimensional material have a selected chemistry at the perforation as discussed above. The perforation in the two-dimensional material can have selected size or selected size range and discussed above. In a specific embodiment, the two-dimensional material is a graphene-based material. In a specific embodiment, the two-dimensional material is a graphene-based material which comprises single-layer graphene or multi-layer graphene.
Some embodiments provide methods for occluding uncovered substrate pores in the composite membrane as described above. In an embodiment, the method includes introducing one or more occluding moieties at least partially into at least one uncovered pore to occlude the at least one uncovered pore. In specific embodiments, 50% or more of the uncovered substrate pores are occluded. In more specific embodiments, 60% or more, 75% or more, 80% or more, 90% or more, 95% or more or 99% or more of the uncovered substrate pores are occluded. In specific embodiments, occlusion of uncovered pores reduced flow through the composite membrane (compared to the non-occlude membrane) by 50% or more. In specific embodiments, occlusion of uncovered pores reduced flow through the composite membrane (compared to the non-occluded membrane) by 60% or more, 75% or more, 80% or more, 90% or more, 95% or more or 99% or more.
The extent of occlusion of uncovered pores can be assessed by various methods. Detection of uncovered pores can, for example, be assessed using a selected assay fluid, e.g., a detectible gas, such as SF6, to detect the location (or approximate location) of uncovered pores by passage of the assay fluid. Uncovered pores may be detected by use of the passage of detectible chemical species, particles, electrons, UV or visible light through the pores. The presence of uncovered pores can also be detected by various imaging methods. The presence and or location (or approximate location) of pores can be assessed using various imaging methods (including scanning electron microscopy, scanning probe microscopy, scanning tunneling microscopy, atomic force microscopy, transmission electron microscopy, x-ray spectroscopy, etc.); detecting analyte, particles or ions passing through pores (using mass spectrometry, secondary mass spectrometry, Raman spectroscopy, residual gas analysis, detecting Auger electrons, detecting nanoparticles using a microbalance, detecting charged species with a Faraday cup, detecting secondary electrons, detecting movement of analyte through defects, employing an analyte detector, identifying a composition, mass, average radius, charge or size of an analyte; detecting electromagnetic radiation passing through defects; detecting electromagnetic radiation given off by analyte; and detecting electromagnetic radiation or particles back scattered from the membrane.
Uncovered substrate pores include those pores that are only partially covered, but through which non-selective passage can occur.
The porous substrate of the composite membrane can be any porous material compatible with a disposed two-dimensional material and particularly with a graphene-based material. The porous substrate is selected to be compatible with the application for which the composite membrane is intended. For example, compatible with the gases, liquids or other components which are to be in contact with the composite membrane. The porous substrate provides mechanical support for the two-dimensional material and must maintain this support during use. The porous support should substantially retain pores that are covered with two-dimensional material. In specific embodiments, the porous material is made of a polymer, metal glass or a ceramic
The pores in the substrate can have uniform pore diameter along the length of the pore, or they can have a diameter that varies along this length. Pores or pore openings (entrance or exit) can be shaped, as discussed below, to facilitate retention of occluding moieties in uncovered pores. Pores may be tapered, ridged or provided with one or more ledges to facilitate retention of occluding moieties in uncovered pores. In a specific embodiment, the pore entrance and/or the pore exit is narrowed compared to the rest of the pore to facilitate retention of occluding moieties. Pores in the substrate are preferably of uniform size and uniform density (e.g., uniformly spaced along the substrate). Pores may be independent or may be interconnected with other pores (tortuous or patterned). In embodiments, pores sizes (e.g. diameters) can range from 10 nm to 10 microns or more preferably from 50 nm to 500 nm. For methods and composite membranes herein a top surface of the membrane is defined as the surface upon which the two-dimensional material is disposed. One surface contains pore entrance openings and the second surface contains pore exit openings. Introduction of occluding moieties is through pore entry openings so that introduction of such moieties is selectively into pores that are not covered by two-dimension materials. Pore entrance and exits are defined by flow direction through pores.
Occluding moieties most generally include any material that can be selectively introduced into uncovered pores and retained therein to occlude the pore. A step of chemical reaction, application of energy in the form of heat, electromagnetic radiation (e.g., UV, visible or microwave irradiation), or contact with an absorbable material can be applied to deform, swell, polymerize, cross-link or otherwise facilitate retention of occluding materials in a pore. In an embodiment, the occluding materials are one or more particles sized for entrance at least in part into an uncovered pore. Particle size and pore shape may be selected to facilitate retention in the uncovered pores. Particles may be deformable, for example, by application of pressure, heat, microwave radiation or light of a selected wavelength (e.g. UV light), or by ion bombardment. Deformable particles introduced into pores are retained in pores after deformation. Particles may be swellable, where the size of a particle increases on contact with an absorbable material which induces swelling. The absorbable material can, for example, be a fluid including liquids or gases, water or an aqueous solution or a miscible mixture of water and an organic solvent, a polar organic solvent or a non-polar organic solvent. The swellable particle and the absorbable fluid are selected to achieve a desired level of swelling to achieve retention in the pore.
Occluding particles can be made of any suitable material. In specific embodiments, particles selected from metal particles, silica particles, particles of metal oxide, or polymer particles. In specific embodiments, particles are made of melamine, polystyrene or polymethyl methacrylate (PMMA). In a specific embodiment, the particles are made of latex (polystyrene). In specific embodiments, the substrate pore occluding particles are themselves permeable to provide a selective permeance through the occluded pores. In specific embodiments, the substrate pore occluding particles are permeable to fluid flow and provide for separation of components in the fluid. Permeable materials could include hydrogels, polymers, proteins, zeolites, metal-organic framework materials, or thin film solution membranes.
Particle size is generally selected based on the pores sizes present in the substrate so that the particle can enter the pore and be retained in the pore. Particles may be monodisperse if the pore entrance openings are uniform in size. A mixture of particles of different sizes can be employed when pore openings are non-uniform in size. A mixture of particles of different sizes (having a selected particle size distribution or being polydisperse in size) can be used, if pores with different (or unknown sizes) are present in the substrate. In an embodiment, the occluding particle is selected to have particle size that is approximately the same size as a pore entrance opening. The occluding particle may be slightly larger for tapered pores and slightly smaller for non-tapered pores such that the pores have a larger cross-section on the side of the substrate exposed to upstream flow. In an embodiment, particles are sized for at least partial introduction into an uncovered pore, but wherein the particle cannot exit the uncovered pore. Exit from the pore can be inhibited or prevented by using shaped pores in which the pores are narrowed at some point along its length. Particles useful in the methods herein will in an embodiment range in size from 10 nm to 10 microns.
In an embodiment, employing deformable or swellable particles, the respective particles are deformed or swollen after introduction to an uncovered pore.
In an embodiment occlusion may be facilitated through controlled fouling, where a fluid is flowed to the composite membrane surface, and material from the fluid is bonded to composite membrane pores that are defective. The fouling may be controlled such that it blocks non-selective pores.
In an embodiment occlusion may be facilitated through healing with particles in air. Particles are aerosolized and/or suspended in air and then forced through the membrane, such as by having convective flow of the air through the membrane. The convective flow of the air could be facilitated by applying a pressure differential across the membrane. The particles could be those described herein, with the methods described herein for fixing the particles to the membrane.
In an embodiment, occluding particles carry one or more chemical reactive groups for reaction with compatible reactive groups in the at least one uncovered pore, on the surface of the substrate at the uncovered pore or on other particles to facilitate anchoring of at least one particle in at least one uncovered pore. The particles can carry any one or more of a reactive chemical species, for example, the reactive species may be an amine, a carboxylate acid, an activated ester, a thiol, an aldehyde or a hydroxyl group. Particles useful in the inventive concepts disclosed herein which carry reactive groups can be prepared by known methods or may be obtained from commercial sources. Reactive groups on the particles can react with compatible reactive groups on the surface of the substrate at an uncovered pore, within the pore or at pore openings to facilitate retention in the pore. In an embodiment, particles may react with other particles in the pore to facilitate retention in the pore. One of ordinary skill in the art can employ a variety of chemically reactive groups to facilitate reaction with a pore to facilitate retention and anchoring in the pore. It will be appreciated that chemical reaction between particles, between particles and the pore surface, edges, openings or exits can be activated or induced by introduction of a reactive species, reagent or catalyst into a pore containing at least one occluding particle. It will also be appreciated that a chemical reaction between particles, between particles and the pore surface, edges, openings or exits can be activated or induced, for example, by heating, microwave irradiation, irradiation with light of selective wavelength (e.g., UV radiation) or by application of an ion beam, or by any method known in the art that is compatible with the materials employed.
In an embodiment, the occluding moieties are selected from one or more monomers, oligomers, uncured polymers or uncross-linked polymers. These occluding moieties are introduced selectively into uncovered pores and wherein the monomers, oligomers or polymers are polymerized, cured or cross-linked after they are introduced into the at least one uncovered pore. Polymerization can be effected for example by introduction of a polymerization catalyst, heating, microwave irradiation, or irradiation with light of a selected wavelength or by any method known in the art that is compatible with the materials employed. Curing of an uncured polymer or cross-linking of a polymer can be effected by any art-known method, for example by introduction of a curing or cross-linking reagent or application of heating, microwave irradiation, or irradiation with light of a selected wavelength or by any method known in the art that is compatible with the materials employed.
In an embodiment, the occlusion method further comprising a second step of introducing secondary particles into the at least one uncovered pore having a first particle therein occluding the uncovered pore, where the secondary particles are sized to be smaller than the first particle. In this embodiment, the initial particle and the secondary particles may be deformable or swellable as described above and may be deformed or swollen after introduction of the secondary particles. The initial particle and the secondary particles may carry one or more reactive groups as described above for chemical reaction of particles in the pores to facilitate retention in the pore.
In an embodiment, the composite membrane further comprises a coating layer on the top surface of the porous substrate between that surface and the sheet of two-dimensional material. Chemical reaction of a particle or other occluding moiety with reactive species on this coating at the entrance of the uncovered pore can facilitate anchoring and retention in the pore.
Occluding moieties are introduced to the top surface of the composite membrane where the occluding moieties can enter uncovered substrate pores. Introduction can be by any appropriate method and preferably is by application of a flow of fluid containing a selected concentration of occluding moieties. In a specific embodiment, the fluid is an aqueous solution carrying a selected concentration of occluding moieties. The concentration of occluding moieties in the flow introduced can be readily optimized empirically to optimize the effectiveness or efficiency of occlusion. Effectiveness or efficiency of occlusion can be assessed by measurement of the flow rate through the composite membrane, by accumulation rate of permeate or by an assessment of the selectivity of flow. A decreasing flow rate or a leveling off of permeate accumulation indicates successful occlusion. In an embodiment, the flow of occluding moieties includes a surfactant to decrease or minimize clumping or aggregation of occluding moieties and to facilitate entry of occluding moieties into uncovered pores. The inclusion of an appropriate surfactant is particularly beneficial for the introduction of occluding particles. In a specific embodiment, the surfactant is a non-ionic surfactant, such as (polyethylene glycol sorbitan monooleate). One of ordinary skill in the art can readily select a surfactant appropriate for the methods herein.
In a preferred embodiment, introduction of occluding moieties to the top surface of the composite membrane is by application of a cross-flow to the surface. The velocity of the cross-flow can be varied according to desired results. According to an embodiment, the pressure and flow may be varied as desired. In an embodiment, the shear velocity of the flow may be controlled. In an embodiment, the pressure across the composite membrane may be stopped while shear flowing. In an embodiment, the pressure on both sides of the membrane may be equalized. In an embodiment, the pressure may be controlled in cycles to alternately provide flow forward and then backward. The pressure on one or both sides of the membrane may be pulsed. Further, peristaltic pump rate and dimensions of the channel through the composite membrane may be controlled according to embodiments.
In an embodiment, the pore occlusion method further comprising a step of cleaning the top surface after introduction of occluding moieties into uncovered pores to remove occluding moieties that have not entered uncovered pores. This cleaning step can comprise flow of an appropriate fluid (gas or liquid) to or across the top surface of the membrane. In a specific embodiment, a flow of water or an aqueous solution is applied to or across the top surface of the membrane. In a specific embodiment, the aqueous solution contains a surfactant (as discussed above) to decrease clumping or aggregation of particles on the top surface.
In an embodiment, the introduction and cleaning steps as well any intervening steps to facilitate retention of particles in uncovered pores (e.g., deformation, chemical reaction, swelling or application of energy) are repeated until additional occlusion of pores ends or until a selected level of uncovered pore occlusion is achieved. As discussed above, various methods for accessing the extent or efficiency of pore occlusion can be employed.
In an embodiment, cycles of introduction and cleaning can be repeated until at least 80% of the uncovered pores are occluded. In an embodiment, cycles of introduction and cleaning can be repeated until at least 95% of the uncovered pores are occluded. In an embodiment, cycles of introduction and cleaning can be repeated until at least 99% of the uncovered pores are occluded.
In preferred embodiments, the two-dimensional material is a graphene-based material. In preferred embodiments, the two-dimensional materials is a sheet of graphene containing single layer graphene, few layer graphene (having 2-20 layers) or multilayer graphene.
In an embodiment, the pore occlusion method can be practiced without introducing an occluding moiety into uncovered pores. In this embodiment, a composite membrane as discussed above is provided wherein a sheet of two-dimensional material covers at least a portion of the pores of the substrate; but wherein at least one pore of the substrate is not covered by the two-dimensional material. In this embodiment, the substrate material forming the pores comprises a swellable material. The substrate itself may be made of a swellable material or more preferably the substrate material surrounding the pores is formed of a swellable material. For example, a coating of swellable material can be applied to the inside surfaces of the substrate pores. Selective introduction of an absorbable material into the uncovered pores results in local swelling of the swellable material surrounding the uncovered pore and occlusion of the uncovered pore. In an embodiment, the uncovered pores are selectively contacted with an absorbable fluid.
Some embodiments further provide a composite membrane comprising a porous substrate having a plurality of pores and a sheet of two-dimensional material disposed on a surface of the porous substrate and defining a top surface of the membrane, wherein the sheet of two-dimensional material covers at least a portion of the pores of the substrate, wherein at least one pore of the substrate is not covered by the two-dimensional material and wherein at least one uncovered pore of the substrate is occluded with an occluding moiety. In an embodiment, the composite membrane has at least one uncovered pore occluded with one or more particles or occluded with a polymer, cured polymer or cross-linked polymer formed in the at least one uncovered pore.
In embodiments illustrated in
Some embodiments provided herein are cross-linked graphene platelet polymers, compositions thereof, filtration devices comprising the cross-linked graphene platelet polymers and/or compositions thereof and methods for using and making the same.
Some of the polymers described herein comprise a graphene portion or moiety and a crosslinking portion or moiety.
The graphene portion or moiety may be a graphene platelet that may be chemically bound directly or indirectly to one or more crosslinking portions or moieties. Crosslinking may be by covalent or other bonding mechanism such as ionic, van der Waals, etc.
The graphene portion in some embodiments comprises a reacted graphene platelet.
The graphene platelet may have a very thin but wide aspect ratio. The graphene platelet may comprise several sheets of graphene, for example 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 sheets of graphene. It is understood that the various sheets are not necessarily the same width, e.g., one or more of the sheets may be a partial sheet that covers only a portion of the sheet in which it is associated with or in contact. For example, a partial sheet may cover about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 98%, 99% of the portion of the sheet in which it is associated with or in contact.
The particle diameter of the graphene platelet may range from sub-micron (for example, about 10 nm, 50 nm, 100 nm, 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, or 1000 nm) up to about 100 microns (for example up to about 1 micron, 2 microns, 3 microns, 4 microns, 5 microns, 6 microns, 7 microns, 8 microns, 9 microns, 10 microns, 20 microns, 30 microns, 40 microns, 50 microns, 60 microns, 70 microns, 80 microns, 90 microns, 100 microns). Various ranges between the disclosed particle diameters may be utilized. It is understood that the graphene platelets will not necessarily be perfect circular particles. Thus, the particle diameter may be measured from the widest points of the graphene platelet.
The size of the graphene platelets may also be expressed as an average size or a plurality of graphene platelets. For example, in some embodiments, the average size of a plurality of graphene platelets used may be about 10 nm, 50 nm, 100 nm, 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, or 1000 nm, about 100 microns (for example up to about 1 micron, 2 microns, 3 microns, 4 microns, 5 microns, 6 microns, 7 microns, 8 microns, 9 microns, 10 microns, 20 microns, 30 microns, 40 microns, 50 microns, 60 microns, 70 microns, 80 microns, 90 microns, 100 microns. The coefficient of variation for the average size may be greater than zero to about 25%. For example, the coefficient of variation may be about 0.01, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20.
The graphene platelets in some of the embodiments may be functionalized. This functionalization may result in a direct or indirect chemical bond to the one or more crosslinking portions or moieties, or it may provide additional functionality to the resulting cross-linked graphene platelet polymer.
In some embodiments, the graphene platelet comprises one or more reactive moieties capable of reacting with a crosslinking molecule. In some embodiments, the graphene platelet is functionalized as disclosed in Hunt, A., et al. Adv. Funct. Mater., 22(18), pp. 3950-3957, 2012. The one or more reactive moieties, for example, may be capable of reacting with a (meth)acrylate or (meth)acrylamide moiety, or may be capable of reacting, e.g., with a hydroxyl moiety, a carbonyl moiety, an epoxy moiety, an ether linkage, and phosphide, phosphate, sulfide and/or a sulfate. In some embodiments, the one or more reactive moieties of the graphene platelet can be an epoxy functional group or amine, and graphene/carbon nitride via reaction in a nitrogen plasma. In some embodiments, the one or more reactive moieties is a “capped” moiety that is capable of converting to a reactive moiety upon, e.g., chemical, heat or UV treatment. In various embodiments the graphene has a variable C/O ratio that maximizes the mechanical strength, and the variation is C/O ratio of 2/1, 5/1, 10/1, 20/1, 30/1, 40/1, 50/1, 60/1 70/1, 80/1 90/1, and 100/1. The speciation of the graphene would be either hydroxyl or epoxy, when reactions with amines or cyanates, can form one pot epoxy or urethane networks. In some embodiments, the one or more reactive moieties are a “capped” moiety that is capable of converting to a reactive moiety upon, e.g., chemical, heat or UV treatment. In some embodiments, the graphene platelet may comprise 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 reactive moieties. In some embodiments, a plurality of graphene platelets used in the polymer may have an average of about 2, 3, 4, 5, 6, 7, 8, 9 or 10 reactive moieties. The coefficient of variation for this average may be greater than zero to about 25%. For example, the coefficient of variation may be about 0.01, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20.
In some embodiments, the graphene platelet comprises one or more functional moieties. These moieties are different from the reactive moieties in that they do not react with the crosslinking molecule, but rather they ultimately impart some functionalization to the resulting cross-linked graphene platelet polymer. Some embodiments utilize functional moieties including thiol moieties, fluorocarbon functionalized areas of the graphene platelet and/or phosphorus, silane and siloxane functional groups.
The crosslinking portions or moieties in some embodiments may be a crosslinking portion that is chemically bound directly or indirectly to two or more graphene portions or moieties. The cross-linked graphene may form ordered layers wherein the crosslinking moiety controls the spacing between ordered layers.
In some embodiments, the crosslinking portion comprises a reacted di-, tri- or tetra-functional crosslinking compound. The functional group may be a (meth)acrylate or (meth)acrylamide moiety, or may be capable of reacting with a hydroxyl or epoxy moiety. In some embodiments, the di-, tri- or tetra-functional crosslinking compound contains the same functional groups. In other embodiments, the functional groups on the di-, tri- or tetra-functional crosslinking compound are different. The crosslinking compound also includes a spacer portion between the functional groups. The spacer group remains in the crosslinking portions or moieties after the functional groups have reacted. For example, the spacer group may comprise 1 to 10 atoms in a linear chain, for example, carbon, oxygen or sulfur atoms, phosphide, phosphate or inorganic moieties as well, silicon and transition metals. The length of the spacer groups will determine the class of the filtered species. The spacer group between adjacent or laterally stacked graphene platelets of 1 to 6 carbons, with a carbon-carbon single bond of 1.54 Å, allows for selectivity of ionic filtration, for species up to 1 nm in diameter. Longer spacers, or branching can enable selectivity for viruses and other pathogens. For example, the spacer may be longer, but still provide spacing between graphene platelets that allows for selective size exclusion of certain viruses and other pathogens of a particular size. The spacing may be determined based on the desired viruses and other pathogen that should be excluded. In some embodiments, the spacer group is a C1-C10 linear chain, or a C3-C20 branched chain. One or more of the carbons may be replaced by an oxygen and/or sulfur atom. The C1-C10 linear chain or C3-C20 branched chain may comprise methylene groups, which may be optionally substituted with one or more halogen of hydroxyl group thiol groups, phosphate, or phosphide.
The crosslinking portions or moieties of some embodiments provide a spacing between two or more graphene portions or moieties. In some embodiments, the cross-linking portion or moiety provides a 4 to 10 atom link between two or more graphene portions or moieties. In other embodiments, the cross-linking portion provides a 4 to 10 atom link between two or more graphene portions or moieties provide a spacing between individual graphene platelet moieties of about 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, or 3.5 nm. The spacing between individual graphene platelet moieties may be determined by molecular modeling of the reacted cross-linking portion, or by microscopic methods, electroacoustic spectroscopy to measure particle and spacing size in aqueous media as well as the zeta potential of the surfaces. Also, x-ray diffraction may be employed to measure inter-plate gallery spacing in lamellar structures. Methods to control the spacing between vertically stacked graphene platelets can employ flexible, e.g., polyphenylene oxide repeat units or rigid carbon spacers with, e.g., polyphenylene or polynorbornene rods to provide a consistent spacer between graphene plates.
In other embodiments, the crosslinking portions or moieties of some embodiments can include spacer moieties. For example, the crosslinking portion may include moieties to attach to the graphene platelets (e.g., covalently, ionically, etc.) and the spacer moiety. Spacer substances can include polymers, fibers, hydrogels, molecules, nanostructures, nanoparticles and allotropes that are responsive to an environmental stimulus. In some embodiments, the spacer substance is a smart polymer, such as a hygroscopic polymer; a thin polymer that expands when hydrated; or an amorphous polymer, such as a porous amorphous polymer. In some embodiments, the spacer substance comprises electrospun fibers that can be swelled upon exposure to a solvent. In some embodiments the spacer substance comprises materials with a high thermal expansion coefficient, which expand or contract in response to a temperature stimulus. In some embodiments, the spacer substance is deliquescent. In some embodiments, the spacers are substantially inert. In some embodiments, the spacers are not inert (i.e., they can be reactive).
Exemplary spacer substances also include structural proteins, collagen, keratin, aromatic amino acids, and polyethylene glycol. Such spacer substances can be responsive to changes in tonicity of the environment surrounding the spacer substance, pi-bonding availability, and/or other environmental stimuli.
In some embodiments, the spacer substance is a piezoelectric, electrostrictive, or ferroelectric magnetic particle. In some embodiments, the magnetic particle comprises a molecular crystal with a dipole associated with the unit cell. In some embodiments, the magnetic particles can be oriented based on an external magnetic field. Exemplary magnetic particles include lithium niobate, nanocrystals of 4-dimethylamino-N-methyl-4-stilbazolium tosylate (DAST)), crystalline polytetrafluoroethylene (PTFE), electrospun PTFE, and combinations thereof.
In some embodiments, the spacer substance heats up faster or slower than its surroundings. Without being bound by theory, it is believed that such embodiments will allow the rate of passage of permeants, or a subset of permeants, across the membrane to be increased and/or decreased.
In some embodiments, spacer substances respond to electrochemical stimuli. For instance, a spacer substance can be an electrochemical material (e.g., lithium ferrophosphate), where a change in oxidation state of the spacer substance (e.g., from 2- to 3-) alters permeability of the membrane. In some embodiments, changing the oxidation state of the spacer substances alters the interaction between the spacer substance and potential permeants. In some embodiments, the change in oxidation state results from a redox-type reaction. In some embodiments, the change in oxidation state results from a voltage applied to the membrane.
In some embodiments, the spacer substance comprises contamination structures formed by utilizing a focused ion beam, e.g., to modify heavy levels of contamination on graphene-based material into more rigid structures. For instance, in some embodiments, mobilization and migration of contamination on the surface of the graphene-based material occurs—coupled in some embodiments with some slight beam induced deposition—followed by modification and induced bonding where the beam is applied. In some embodiments, combining contamination structures allows the geometry, thickness, rigidity, and composition of the spacer substance to be tuned to respond to an environmental stimulus (e.g., pressure).
Exemplary spacer substance includes particle substances such as metal nanoparticles (e.g., silver nanoparticles), oxide nanoparticles, octadecyltrichlorosilane nanoparticles, carbon nanotubes, and fullerenes. In some embodiments, the spacer substance includes nanorods, nano-dots (including decorated nano-dots), nanowires, nanostrands, and lacey carbon materials.
In some embodiments, the spacer moiety is responsive to an environmental stimulus, for example, the spacer substance may expand and/or contracts in response to the environmental stimulus. The spacer substance may reversibly expand and/or reversibly contract in response to the environmental stimulus. For instance, conformational changes between trans and cis forms of a spacer substance can alter the effective diameter of the spacer substance (by way of example, a spacer substance could be a polymer with an embedded diazo dye, where exposure to the appropriately colored light alters the volume of the dye based on cis-/trans-conformational changes). In some embodiments, the spacer substance undergoes a physical and/or chemical transformation that is pH-modulated or optically modulated. In some embodiments, the environmental stimulus degrades the spacer substance to alter the effective diameter of the spacer substance.
In some embodiments, the environmental stimulus induces a conformational change in the spacer substance that alters the effective length of the spacer substance. Environmental stimuli may include, for example, changes in temperature, pressure, pH, ionic concentration, solute concentration, tonicity, light, voltage, electric fields, magnetic fields, pi-bonding availability, and combinations thereof.
The polymers described herein may include additional monomeric components, biocompatible silicone, hexamethyl trisiloxane (D3), epoxy, both cyclohexyl epoxies, amenable to UV curing, and epichlorohydrin, amenable to substitution on the carbonyl functionality of graphene. The epichlorohydrin may be curable via thermal methods, and provides a durable, cross-linked graphene polymer. Some polymeric cross-linkers initiators may be curing agents, such as diamines. Other monomers and chain spacers may be included, such as aromatic and alkyl di-carboxylic acids curing via the hydroxyl functionality on the graphene platelets to create polyester cured graphene.
The cross-linked graphene platelet polymers described herein have a sufficient crosslink density to prevent large gaps of uncured section of graphene, which may allow, e.g., salt, to pass unimpeded through greater than about 1 nm holes (or spaces between platelets). In some embodiments, the cross-linked graphene platelet polymers have a crosslink density of 0-0.33 (for example, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.20, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.30, 0.31, 0.32, or 0.33, and measured by differential scanning calorimetry. In some other embodiments, the cross-linked graphene platelet polymer compositions contain less than about 5%, 4%, 3%, 2%, 1%, 0.5%, 0.1% holes (or spaces between platelets) greater than about 1 nm. In some other embodiments, the cross-linked graphene platelet polymer composition is substantially free of holes (or spaces between platelets) greater than about 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9 or 2 nm. In some embodiments, cross-linked graphene platelet polymer composition comprises holes (or spaces between platelets) between 0.5 and 2.0 nm. The other embodiments, the space between platelets changes in response to an environmental stimulus as described herein. The space between platelets may be between 0.5 and 2.0 nm after or before the change in response to an environmental stimulus as described herein.
In other embodiments, the cross-linked graphene platelet polymer composition has a crosslink density sufficient to reduce the sodium content in a 3.5% saline solution by at least 50, 60, 70, 80, 90 or 100 fold when passed through the cross-linked graphene platelet polymer composition having a thickness of about 100 nm. Other embodiments include, e.g., about 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, or 250 nm, or values in between.
As mentioned above, some embodiments of the graphene platelet comprise one or more functional moieties. In addition, the cross-linked graphene platelet polymer compositions may be further functionalized to remove or reduce one or more deleterious contaminant from a liquid or gas passing through the cross-linked graphene platelet polymer composition. For example, the holes (or spaces between platelets) within the cross-linked graphene platelet polymer composition may be patterned with silver nanoclusters that, e.g., deactivate the bacteria. In other embodiments, the cross-linked graphene platelet polymer composition may be further treated with quaternary alkyl-ammonium bromide compounds that, e.g., have been shown to coordinate with the phospholipid shell of viruses. In other embodiments, the cross-linked graphene platelet polymer composition may include ionically or chemisorbed ammonium compounds that are not covalently bound to the cross-linked graphene platelet polymer.
The cross-linked graphene platelet polymer may be formed into membranes that remove or reduce one or more deleterious contaminant from a liquid or gas passing through the cross-linked graphene platelet polymer composition. In some embodiments the liquid is water. In some embodiments, the cross-linked graphene platelet polymer compositions may be mounted on a support structure.
In other embodiments, the cross-linked graphene platelet polymer may be formed into membranes that isolate or concentrate one or more desired components from a liquid or gas passing through the cross-linked graphene platelet polymer composition. For example, rare earth ions may be isolated or concentrated from, e.g., seawater by reducing water content where certain components of the seawater (e.g., water) are capable of passing through the cross-linked graphene platelet polymer composition, but the desired compounds, such as rare earth ions, are incapable of passing through the cross-linked graphene platelet polymer composition.
The membranes in some embodiments may include more than one cross-linked graphene platelet polymer composition layers. For example, the different layers may be incorporated into a membrane module, wherein the various layers each has a particular functionality. For example, the filter module comprising at least two separate filters or membranes each comprising a cross-linked graphene platelet polymer composition layer, wherein each filter or membrane is functionalized in a different manner, e.g., wherein the cross-linking moieties generate a spacing of about 1 nanometer between individual graphene platelet moieties, wherein the cross-linking portion contains a 4 to 10 atom link, wherein the cross-linked graphene platelets comprise a thiol moiety, wherein the cross-linked graphene platelets further comprise a metal nanocluster, wherein the cross-linked graphene platelets further comprise a quaternary alkyl-ammonium bromide, or wherein the graphene platelet moieties contains fluorocarbon functionalization.
In some embodiments, different layers of the composite membrane module are all incorporated into a modular container, where different modules are incorporated as required to remove/remediate various contaminants as required by the end-user.
In other embodiments, the composite membrane may be used as a separation/barrier layer or for immunoisolation of a second material that is meant to be isolated from an immune response when placed in a biological system (e.g., an animal such as a mammal). For example, it may be used to separate one environment from another within a biological system. The spacing between individual graphene platelet moieties may be such that certain biological components are excluded from passing through the composite membrane.
In other embodiments, the composite membrane may be used in transdermal applications, wherein the spacing between individual graphene platelet moieties may be such that certain biological components are excluded from passing through the composite membrane.
The filters and membranes of some embodiments have broad application, including in water filtration, immune-isolation (i.e., protecting substances from an immune reaction), timed drug release (e.g., sustained or delayed release), hemodialysis, and hemofiltration. Some embodiments described herein comprise a method of water filtration, water desalination, water purification, immune-isolation, timed drug release, hemodialysis, or hemofiltration, where the method comprises exposing a membrane to an environmental stimulus, and wherein the membrane comprises a cross-linked graphene platelet polymer described herein.
Some embodiments include a method of increasing the purity of a liquid or gas, comprising contacting a first portion of a liquid or gas having an impurity with a filter or membrane comprising the cross-linked graphene platelet polymer compositions to form a second portion of a liquid or gas, wherein the second portion of a liquid or gas contains a lower concentration of the impurity. In some embodiments, the liquid or gas is liquid water. In other embodiments, the liquid or gas is a liquid in a physiological environment, e.g., in an animal, such as a mammal or human. In some embodiments, the impurity is a salt that may be ionized (e.g., NaCl salt or sodium and chloride ions) or a heavy metal or bacteria (or microorganisms, such as viruses) or a hydrocarbon or a larger biological compounds such as antibodies (whereas the filter or membrane can allow passage of biological compounds such as insulin, proteins and/or other biological material (e.g., RNA, DNA, and/or nucleic acids)). In some embodiments, the second portion of liquid or gas (e.g., water) is formed by passing the first portion of liquid or gas (e.g., water) through the cross-linked graphene platelet polymer compositions or filters or membranes of some embodiments. In some embodiments, the second portion of liquid or gas (e.g., water) contains 100-fold or less of the impurity as is found in the first portion of liquid or gas (e.g., water).
Some embodiments include a method of concentrating a material of interest from a liquid or gas, comprising contacting a first portion of a liquid or gas having a composition of interest with a filter or membrane comprising the cross-linked graphene platelet polymer compositions to form a second portion of liquid or gas, wherein the second portion of liquid or gas contains a lower concentration of the composition of interest, and collecting the composition of interest that does not pass through the filter or membrane. Some embodiments include a method of concentrating a composition of interest from water by reducing the water content of a solution of that composition. In some embodiments, the composition of interest may be a rare-earth element.
In some embodiments, the cross-linked graphene platelet polymer compositions and the filter or membrane may be used as a pre-filtration device. For example, some embodiments include a method of increasing the purity of water, comprising contacting a first portion of water having an impurity with a filter or membrane comprising the cross-linked graphene platelet polymer compositions to form a second portion of water, wherein the second portion of water contains a lower concentration of the impurity, followed by contacting the second portion of water with a perforated graphene filter or membrane. Some exemplary perforated graphene filters and membranes are described in the art.
Other embodiments include membranes wherein the spacing between individual graphene platelet moieties is such that is allows certain compounds to pass freely, but retards the passage of other, larger compounds. In some embodiments include membranes wherein the spacing and functionalization between individual graphene platelet moieties is such that is allows certain compounds to pass freely, but retards the passage of other compounds that interact with the graphene platelet moieties or a functional compound contained in the cross-linked graphene platelet polymer. In exemplary embodiments, a membrane that allows passage of water but excludes salt ions (e.g. Na+and Cl−) can be tuned to allow passage of both water and salt ions. In other exemplary embodiments, the membrane can be tuned to allow passage of biological compounds such as insulin, proteins and/or other biological material (e.g., RNA, DNA, and/or nucleic acids), but to exclude passage of other larger biological compounds such as antibodies. In some embodiments, the membrane can be tuned to be permeable to oxygen and nutrients, but to exclude passage of cells (such as immune cells), viruses, bacteria, antibodies, and/or complements of the immune system. In some embodiments, the membrane can be tuned from one that allows passage of antibodies to one that inhibits passage of antibodies.
Other embodiments include methods of encasing a material and selectively allowing matter of a certain size to contact the encased material. The linked graphene platelet polymer compositions and filters or membranes may be used as encapsulating materials within a biological system, wherein the spacing between individual graphene platelet moieties is such that is allows certain compounds to pass freely, but retards the passage of compounds, such as antibodies from traversing the graphene platelet polymer composition. In exemplary embodiments, a membrane that allows passage of water but excludes salt ions (e.g. Na+and Cl−) can be tuned to allow passage of both water and salt ions. In other exemplary embodiments, the membrane can be tuned to allow passage of biological compounds such as insulin, proteins and/or other biological material (e.g., RNA, DNA, and/or nucleic acids), but to exclude passage of other larger biological compounds such as antibodies. In some embodiments, the membrane can be tuned to be permeable to oxygen and nutrients, but to exclude passage of cells (such as immune cells), viruses, bacteria, antibodies, and/or complements of the immune system. In some embodiments, the membrane can be tuned from one that allows passage of antibodies to one that inhibits passage of antibodies.
The cross-linked graphene platelet polymers may be formed by reacting one or more functionalized graphene platelets with one or more functionalized crosslinking compounds of some embodiments. In some embodiments, the functionalized graphene platelets and the functionalized crosslinking compounds are reacted by heat or radiation (e.g., UV) or e-beam.
Some embodiments are directed, in part, to various processes for producing a plurality of holes in graphene, graphene-based materials and other two-dimensional materials. In an embodiment, the first layer comprises a sheet of graphene-based material. Graphene-based materials include, but are not limited to, single layer graphene, multilayer graphene or interconnected single or multilayer graphene domains and combinations thereof. In an embodiment, graphene-based materials also include materials which have been formed by stacking single or multilayer graphene sheets. In embodiments, multilayer graphene includes 2 to 20 layers, 2 to 10 layers or 2 to 5 layers. In embodiments, graphene is the dominant material in a graphene-based material. For example, a graphene-based material comprises at least 30% graphene, or at least 40% graphene, or at least 50% graphene, or at least 60% graphene, or at least 70% graphene, or at least 80% graphene, or at least 90% graphene, or at least 95% graphene. In embodiments, a graphene-based material comprises a range of graphene selected from 30% to 95%, or from 40% to 80% from 50% to 70%, from 60% to 95% or from 75% to 100%.
As used herein, a “domain” refers to a region of a material where atoms are uniformly ordered into a crystal lattice. A domain is uniform within its boundaries, but different from a neighboring region. For example, a single crystalline material has a single domain of ordered atoms. In an embodiment, at least some of the graphene domains are nanocrystals, having domain size from 1 to 100 nm or 10-100 nm. In an embodiment, at least some of the graphene domains have a domain size greater than 100 nm to 1 micron, or from 200 nm to 800 nm, or from 300 nm to 500 nm. “Grain boundaries” formed by crystallographic defects at edges of each domain differentiate between neighboring crystal lattices. In some embodiments, a first crystal lattice may be rotated relative to a second crystal lattice, by rotation about an axis perpendicular to the plane of a sheet, such that the two lattices differ in “crystal lattice orientation”.
In an embodiment, the sheet of graphene-based material comprises a sheet of single or multilayer graphene or a combination thereof. In an embodiment, the sheet of graphene-based material is a sheet of single or multilayer graphene or a combination thereof. In another embodiment, the sheet of graphene-based material is a sheet comprising a plurality of interconnected single or multilayer graphene domains. In an embodiment, the interconnected domains are covalently bonded together to form the sheet. When the domains in a sheet differ in crystal lattice orientation, the sheet is polycrystalline.
In embodiments, the thickness of the sheet of graphene-based material is from 0.34 to 10 nm, from 0.34 to 5 nm, or from 0.34 to 3 nm. In an embodiment, a sheet of graphene-based material comprises intrinsic defects. Intrinsic defects are those resulting from preparation of the graphene-based material in contrast to perforations which are selectively introduced into a sheet of graphene-based material or a sheet of graphene. Such intrinsic defects include, but are not limited to, lattice anomalies, pores, tears, cracks or wrinkles. Lattice anomalies can include, but are not limited to, carbon rings with other than 6 members (e.g. 5, 7 or 9 membered rings), vacancies, interstitial defects (including incorporation of non-carbon atoms in the lattice), and grain boundaries.
In an embodiment, the layer comprising the sheet of graphene-based material further comprises non-graphenic carbon-based material located on the surface of the sheet of graphene-based material. In an embodiment, the non-graphenic carbon-based material does not possess long range order and may be classified as amorphous. In embodiments, the non-graphenic carbon-based material further comprises elements other than carbon and/or hydrocarbons. Non-carbon elements which may be incorporated in the non-graphenic carbon include, but are not limited to, hydrogen, oxygen, silicon, copper and iron. In embodiments, the non-graphenic carbon-based material comprises hydrocarbons. In embodiments, carbon is the dominant material in non-graphenic carbon-based material. For example, a non-graphenic carbon-based material comprises at least 30% carbon, or at least 40% carbon, or at least 50% carbon, or at least 60% carbon, or at least 70% carbon, or at least 80% carbon, or at least 90% carbon, or at least 95% carbon. In embodiments, a non-graphenic carbon-based material comprises a range of carbon selected from 30% to 95%, or from 40% to 80%, or from 50% to 70%.
Such nanomaterials in which pores are intentionally created will be referred to herein as “perforated graphene”, “perforated graphene-based materials” or “perforated two-dimensional materials.” Some embodiments are also directed, in part, to perforated graphene, perforated graphene-based materials and other perforated two-dimensional materials containing a plurality of holes ranging from about 0.3 nm to about 10 nm in size. Some embodiments are further directed, in part, to perforated graphene, perforated graphene-based materials and other perforated two-dimensional materials containing a plurality of holes ranging from about 0.3 nm to about 10 nm in size and having a narrow size distribution, including but not limited to a 1-10% deviation in size or a 1-20% deviation in size. In an embodiment, the characteristic dimension of the holes is from 0.5 nm to 10 nm. For circular holes, the characteristic dimension is the diameter of the hole. In embodiments relevant to non-circular pores, the characteristic dimension can be taken as the largest distance spanning the hole, the smallest distance spanning the hole, the average of the largest and smallest distance spanning the hole, or an equivalent diameter based on the in-plane area of the pore. As used herein, perforated graphene-based materials include materials in which non-carbon atoms have been incorporated at the edges of the pores
As discussed above, conventional processes for perforating graphene and other two-dimensional materials with a plurality of holes can be limited in terms of the obtained hole density, hole size and size distribution. Perforated nanomaterials having small holes with an effective size of about 10 nm or less can be particularly difficult to produce with a sufficient hole density and size distribution to support many intended applications. Filtration applications, for example, can be significantly impacted by an inability to produce holes of a selective size and hole density, as selectivity and throughput flux can be severely impacted. Moreover, presently available techniques for perforating graphene and other two-dimensional materials are not believed to be scalable to large dimensional areas (e.g., one to tens of square centimeters or more) in order to support commercial production efforts.
Current methods for perforating graphene and other two-dimensional materials include both chemical and physical processes. Chemical processes generally involve both hole nucleation and hole growth stages. However, hole nucleation and hole growth are usually difficult to separate from one another, thereby leading to a broad distribution of hole sizes. Physical processes generally involve a brute force knockout of atoms from the planar structure of the two-dimensional material. However, physical processes are rather energy inefficient, especially when considering their scaleup for commercial production efforts. Moreover, high energy ions can actually interact rather poorly with graphene and other two-dimensional materials, leading to a poor yield of atoms ejected during the knockout process.
In an embodiment, energetic ion perforation processes for graphene, graphene-based materials and other two-dimensional materials can be significantly enhanced by conducting the perforation process with at least one layer of a second material in continuous contact with the graphene or other two-dimensional material during its exposure to a broad field or flood ion source. A broad field or flood ion source can provide an ion flux which is significantly reduced compared to a focused ion beam. In an embodiment, the ion flux is from 0.1 nA/mm2 to 100 nA/mm2. By utilizing a broad ion field in conjunction with at least one layer in continuous contact with the graphene or other two-dimensional material, significantly improved perforation can be obtained in the form of small hole sizes, narrow size distributions, and high hole densities. In an embodiment, the hole density is characterized by the spacing between the holes. In an embodiment where the average pore size is from 0.5 nm to 2.5 nm, the average spacing between the pores is from 0.5 nm to 5 nm. The processes of the some embodiments are readily distinguished from focused ion beam processes, which have higher ion fluxes and/or ion energies. The broad ion field processes of some embodiments are considerably more scalable in terms of areal coverage for commercial processing. Depending on their location, the layer(s) in continuous contact with the graphene or other two-dimensional material can impact the perforation process in several different ways, as discussed hereinafter.
In embodiments, the energetic ion perforation processes described herein utilize the knockout approach of physical perforation processes while also facilitating a discrete hole growth stage, like chemical processes. Unlike conventional chemical and physical perforation processes, however, the perforation processes of some embodiments advantageously separate the hole nucleation and growth stages from one another while still allowing nucleation and growth to occur in a highly concerted fashion. In embodiments, the one or more layers in continuous contact with the graphene or other two-dimensional material allow highly concerted nucleation and growth to occur. Specifically, the one or more layers allow hole nucleation to be followed in short order by hole growth as a result of a single incident ion impact with the graphene or other two-dimensional material In conventional processes, hole nucleation and growth are not concerted. Because the hole nucleation and growth are separated but concerted stages in the processes of some embodiments, a narrow hole size distribution can be obtained. Moreover, the processes of some embodiments are advantageously suited to produce holes that are about 10 nm in size or under, which can be desirable for a number of applications, including filtration. Further, the hole size and/or hole density can be adjusted to suit the needs of a particular application. In an embodiment, a higher fluence or exposure time increases the number of holes (until the holes begin to overlap). Higher ion energies can either increase or decrease the hole size depending on the details of the interaction. The hole density can be modulated by adjusting the exposure time of the graphene or other two-dimensional material to the ion source.
Thus, the processes of some embodiments are capable of providing all three of the key needs for perforated graphene, graphene-based materials and other two-dimensional materials (small hole size, narrow size distribution, and high hole density). Moreover, because they make use of a broad ion field for affecting perforation, the processes of some embodiments are advantageously scalable to large dimensional areas and can support commercial processing efforts.
As indicated above, the broad ion field used to affect perforation in embodiments of the processes of some embodiments provides ions with an ion energy ranging between about 0.75 keV and about 10 keV. In an embodiment the ion energy ranges from 1 keV to 10 keV. In an additional embodiment the ion energy ranges from 1 keV to 5 keV. In a further embodiment the ion energy ranges from 2 keV to 10 keV. In an additional embodiment the ion energy ranges from 5 keV to 10 keV. Some ions having energies within this range may interact poorly with graphene and other two-dimensional materials, producing only point defects in the planar structure in the form of 1-2 knocked out atoms per incident ion (single-vacancies and di-vacancies). In an embodiment, the holes produced by the processes of some embodiments produce holes larger in size than such a point defect. The processes of some embodiments, specifically the layer(s) in continuous contact with the graphene or other two-dimensional material, can produce holes larger in size than would be predicted on the basis of the ion energy alone. Without wishing to be bound by any particular belief, contact of the frontside or backside layer with the two-dimensional material during ion irradiation is believed to advantageously promote expansion of the defects into holes of meaningful size through converting the high energy incident ions into a thermal bombardment of the graphene or other two-dimensional material. Layers in different locations with respect to the ion source can facilitate this effect in several ways through bond energy mismatch, as discussed further herein below.
Although certain embodiments are described herein with graphene as the two-dimensional material, it is to be recognized that other two-dimensional materials can be used similarly in alternative embodiments unless otherwise specified herein. Thus, considerable flexibility can be realized by practicing some embodiments in order to produce a particular perforated two-dimensional material having a desired set of properties.
In various embodiments, processes described herein can include exposing a two-dimensional material in continuous contact with at least one layer to an ion source, and interacting a plurality of ions and/or neutralized ions from the ion source with the two-dimensional material and with the at least one layer. In embodiments, the ions and/or neutralized ions introduce a plurality of defects in the two-dimensional material and an interaction of the ions and/or neutralized ions with the at least one layer promotes expansion of the defects into a plurality of holes defined in the two-dimensional material. The at least one layer is in continuous contact with the two-dimensional material while the two-dimensional material is being exposed to the ion source.
In various embodiments, the two-dimensional material comprises graphene, molybdenum sulfide, or boron nitride. In more particular embodiments, the two-dimensional material can be graphene. Graphene according to some embodiments can include single-layer graphene, multi-layer graphene, or any combination thereof. Other nanomaterials having an extended two-dimensional molecular structure can also constitute the two-dimensional material in the some embodiments. For example, molybdenum sulfide is a representative chalcogenide having a two-dimensional molecular structure, and other various chalcogenides can constitute the two-dimensional material in some embodiments. Choice of a suitable two-dimensional material for a particular application can be determined by a number of factors, including the chemical and physical environment into which the graphene or other two-dimensional material is to be terminally deployed.
In various embodiments, the holes produced in the graphene or other two-dimensional material can range from about 0.3 nm to about 10 nm in size. In a more specific embodiment, the holes can range from about 0.5 nm to about 2.5 nm in size. In an additional embodiment, the hole size is from 0.3 to 0.5 nm. In a further embodiment, the hole size is from 0.5 to 10 nm. In an additional embodiment, the hole size is from 5 nm to 20 nm. In a further embodiment, the hole size is from 0.7 nm to 1.2 nm. In an additional embodiment, the hole size is from 10 nm to 50 nm. In embodiments where larger hole sizes are preferred, the hole size is from 50 nm to 100 nm, from 50 nm to 150 nm, or from 100 nm to 200 nm. Holes within these size ranges can be particularly desirable for filtration applications. The 0.5 nm to 2.5 nm size range can be particularly effective for use in reverse osmosis filtration applications.
Contact times for the graphene or other two-dimensional material with the ion source can range between about 0.1 seconds and about 120 second in order to produce an ion fluence sufficient to produce these hole densities. Longer contact times can be used if desired in order to modulate the number of holes obtained in the planar structure.
The ion source inducing perforation of the graphene or other two-dimensional material in some embodiments is considered to provide a broad ion field, also commonly referred to as an ion flood source. In an embodiment, the ion flood source does not include focusing lenses. In embodiments, the ion source is operated at less than atmospheric pressure, such as at 10−3 to 10−5 torr or 10−4 to 10−6 torr. In an embodiment, the environment also contains background amounts (e.g. on the order of 10−5 torr) of oxygen (O2), nitrogen (N2) or carbon dioxide (CO2). As indicated above, in an embodiment the ion source provides an ion dose ranging from 1×1010 ions/cm2 to 1×1017 ions/cm2 and having an ion energy ranging from 0.75 keV to 10 keV. In more particular embodiments, the ion energy can range from 1 keV to 10 keV or from 5 keV to 10 keV. In some embodiments, the ion dose can range between about 1×1011 ions/cm2 and about 1×1015 ions/cm2, between about 1×1012 ions/cm2 and about 1×1014 ions/cm2, or from 1×1013 ions/cm2 to 1×1019 ions/cm2. In an embodiment, the ion dose ranges from 1×1010 ions/cm2 to 1×1017 ions/cm2. In an additional embodiment the ion does ranges from 1×1011 ions/cm2 to 1×1015 ions/cm2. In a further embodiment, the ion dose ranges from 1×1013 ions/cm2 to 1×1019 ions/cm2. In an embodiment, the flux or beam current density is from 10 nA/nm2 to 100 nA/nm2. In embodiments, the ion beam may be perpendicular to the surface of the layers of the multilayered material (incidence angle of 0 degrees) or the incidence angle may be from 0 to 45 degrees, 0 to 20 degrees, 0 to 15 degrees or 0 to 10 degrees.
The ion source can provide any of a variety of ions suitable for inducing perforations in graphene, graphene-based materials and other two-dimensional materials. In an embodiment, the ion is singly charged. In another embodiment, the ion is multiply charged. In an embodiment, the ion is a noble gas ion (ion of an element from Group 18 of the periodic table). In an embodiment, the ion is other than a helium ion. In an embodiment the ion is an organic ion or organometallic ion. In an embodiment, the organic or organometallic ion has an aromatic component. In an embodiment, the molecular mass of the organic ion or organometallic ion is from 75 to 200 or 90 to 200. In illustrative embodiments, ions that can be supplied from the ion source to induce perforation of graphene or another two-dimensional material can include Xe+ ions, Ne+ ions, Ar+ ions, tropyllium ions (C7H7+) and ferrocenium ions [(C5H5)2Fe+]. In embodiments, when the ions are Xe+ ions, Ne+ ions, Ar+ ions, the dose is 1×1011 ions/cm2 to 1×1015 ions/cm2. In embodiments, when the ion comprises a plurality of elements (such as tropyllium and ferrocenium), the fluence is 1×1011 ions/cm2 to 1×1015 ions/cm2. In an embodiment, helium ions are provided with a dose from 1×1013 ions/cm2 to 1×1019 ions/cm2. The chosen ion and its energy can determine, at least in part, the size of the holes obtained in the graphene or other two dimensional material. In particular embodiments, the chosen ion and its energy can be chosen to eject fragments from the at least one layer toward the graphene or other two-dimensional material.
In an embodiment, the temperature of the multilayer composite is controlled during ion bombardment. In embodiment, the temperature is controlled from −130° C. to 200° C. or from −130° C. to 100° C. In an embodiment, the temperature may be selected to allow condensation of a gas on the frontside of the two-dimensional material. In an embodiment, where a metal backside layer is present, the temperature may be controlled from 50° C. to 80° C. The one or more layers in continuous contact with the graphene or other two-dimensional material can be a frontside layer or a backside layer, or both can be present. The term “frontside” refers to the condition of being on the same side of the two-dimensional material as the ion source. The term “backside” refers to the condition of being on the side of the two-dimensional material opposite the ion source. Depending on its location, the at least one layer can be natively or exogenously present on the graphene or other two-dimensional material, or the at least one layer can be intentionally deposited after formation of the graphene or other two dimensional material. For example, a metal growth substrate can constitute a backside layer in various embodiments.
Generally, the at least one layer has a bond energy that is weaker than that of graphene or the two-dimensional material, which is characterized by strong bonds. That is, when the at least one layer is interacted with the ion source, bonds are broken in the at least one layer in preference to the graphene or other two-dimensional material due to a bond energy mismatch. In some embodiments, the at least one layer can be a deposited layer such as deposited silicon, a deposited polymer, or any combination thereof. If the graphene or other two-dimensional material remains on its metal growth substrate, a deposited layer can constitute a frontside layer. However, if the graphene or other two-dimensional material has been removed from its metal growth substrate, a deposited layer can constitute either a frontside layer or a backside layer. Deposited polymers that can include any polymer material that suitably adheres to the graphene-based material or other two-dimensional material such as silicone polymers, for example. In an embodiment, the deposited polymer does not completely delaminate from the graphene-based material during ion bombardment. Other suitable polymer layers can be envisioned by one having ordinary skill in the art.
In some embodiments, a frontside layer deposited on the graphene or other two-dimensional material can have a thickness ranging between about 1 nm and about 10 nm. Thicker frontside layers can also be present, if desired. Although the frontside layer can be deposited exogenously during synthesis of the graphene or other two-dimensional material, the frontside layer can also be deposited in a separate operation in other embodiments. For example, the frontside layer can be deposited by sputtering, spraying, spin coating, atomic layer deposition, molecular beam epitaxy or like techniques in some embodiments.
Various layers will now be further described according to their location and function.
In some embodiments, the at least one layer can be at least a frontside layer disposed on the same side of the two-dimensional material as the ion source. Illustrative frontside layers can include those described above. When a frontside layer is present, ions from the ion source interact with the frontside layer before interacting with the graphene or other two-dimensional material. As discussed hereinafter, this type of interaction can still promote the creation and expansion of holes in the planar structure of the graphene or other two-dimensional material by ejecting layer fragments from the frontside layer and impacting the layer fragments with the graphene or other two-dimensional material to form holes therein. Since the frontside layer is relatively thin, it has a low stopping power and allows the ions and/or neutralized ions to penetrate through the frontside layer to further interact with the graphene.
In an embodiment, ion bombardment of the frontside layer generates a plume of more, but lower energy particles, impinging on the graphene or other two dimensional material. In more specific embodiments, processes of some embodiments can include ejecting toward the two-dimensional material a plurality of layer fragments from the frontside layer upon interaction of ions and/or neutralized ions therewith, and impacting the layer fragments with the two-dimensional material in an area of the two-dimensional material surrounding the defects created upon interacting the ions and/or neutralized ions with the two-dimensional material and promoting expansion of the defects into holes. Layer fragments can include atoms, ions, molecules or molecular fragments displaced from the frontside layer upon interaction of a high energy ion with the frontside layer. A frontside layer can be present in combination with a backside layer or a frontside layer can be present alone. Functions of the backside layer are discussed further below.
Without being bound by theory or mechanism, it is believed that hole definition or generation in the presence of a frontside layer can take place due to several synergistic effects. First, the graphene or other two-dimensional material can have an enhanced degree of chemical reactivity in the vicinity of the defects initially created by the high energy ions and/or neutralized ions. Second, the layer fragments from the frontside layer can turn a single impact event at the frontside layer into a plurality of impact events at the graphene or other two-dimensional material. Third, the layer fragments have a lower energy than do the incident high energy ions, thereby increasing the likelihood of successfully interacting with the graphene or other two-dimensional material in order to define a hole. Finally, because the frontside layer and the graphene or other two-dimensional material are in continuous contact with one another, the geometric spread of the layer fragments during their transit to the graphene or other two-dimensional material is minimal, thereby limiting the hole size. Thus, the combination of enhanced chemical reactivity in the vicinity of the defects and the more efficient interaction of the layer fragments with the graphene or other two-dimensional material can result in the definition of a hole.
As shown in
In some embodiments, the at least one layer in continuous contact with the graphene or other two dimensional material can be a backside layer disposed on a side of the graphene or other two-dimensional material opposite the ion source. In an embodiment, the backside layer is a metal growth substrate upon which the graphene or other two-dimensional material is grown, or the backside layer can be a secondary substrate to which the graphene or other two-dimensional material has been transferred following growth. In an embodiment, the secondary substrate is polymeric, including porous polymeric membranes. In either case, the backside layer can have a thickness that is significantly greater than that of the graphene or other two-dimensional material. Accordingly, the backside layer can have a much higher stopping power for the energetic ions and/or neutralized ions than does the graphene or other two-dimensional material. Upon stopping the energetic ions, the backside layer can disperse an impact energy of the ions and/or neutralized ions with the backside layer into an area of the graphene or other two-dimensional material surrounding the defects created upon interacting the ions with the two-dimensional material and promoting the expansion of the defects into holes. In more specific embodiments, a backside layer promotes expansion of defects in a two-dimensional material into holes in a manner somewhat similar to that described above for a frontside layer, in which fragments are directed towards the two-dimensional material. The backside layer may also promote formation of defects in the two-dimensional material. For example, even when an ion or neutralized ion does not form a hole when passing through the two-dimensional material, impact of the ions and/or neutralized ions with the backside layer may cause a small region in the backside layer to rapidly heat and expand, opening a hole in the graphene or other two-dimensional material.
Illustrative metal growth substrates upon which graphene, graphene-based materials and other two-dimensional materials can be grown and which can serve as the backside layer in some embodiments include various metal surfaces containing a transition metal. In the case of graphene, for example, copper or nickel can be particularly effective for promoting epitaxial graphene growth. In some embodiments, the metal growth substrate can be formed substantially entirely of a metal, such as a metal foil or a metal sheet. In other embodiments, the metal growth substrate can include a metal surface on a different subsurface material. For example, a ceramic substrate having a metal surface can be used as the metal growth substrate and backside layer in some embodiments.
Accordingly, in some embodiments, processes of some embodiments can include ejecting toward the two-dimensional material, such as graphene, a plurality of layer fragments from the backside layer upon interaction of the ions and/or neutralized ions therewith, and impacting the layer fragments with the two-dimensional material in an area of the two-dimensional material surrounding the defects and promoting expansion of the defects into holes. That is, the backside layer can promote energy transfer to the graphene or other two-dimensional material in the form of layer fragments having thermal velocities in order to promote the creation of holes in the graphene or other two-dimensional material.
In some embodiments, both a frontside layer and a backside layer can be in continuous contact with the graphene or other two-dimensional material as it is interacted with the ions and/or neutralized ions from the ion source. The layer fragments generated from both the frontside layer and the backside layer can work in concert with one another to expand the generated defects in the graphene or other two-dimensional material into a plurality of holes. For example, in some embodiments, layer fragments generated from a suitable frontside layer and metal atoms or metal ions generated from a backside metal growth substrate can impact graphene from both sides of its planar structure to promote the creation of holes therein. This can be particularly effective for perforating multi-layer two-dimensional materials, such as multi-layer graphene, for example by holding the particles in a local region.
Accordingly, in embodiments where both a frontside layer and a backside layer are present, processes of some embodiments can include ejecting toward the graphene or other two-dimensional material a plurality of layer fragments from the frontside layer upon interaction of the ions and/or neutralized ions therewith, ejecting toward the graphene or other two-dimensional material a plurality of layer fragments from the backside layer upon interaction of the ions and/or neutralized ions therewith, and impacting the layer fragments from both layers with the graphene or other two-dimensional material in an area surrounding the defects created upon interacting the ions and/or neutralized ions with the graphene or other two-dimensional material and promoting the expansion of the defects into holes.
In particular embodiments, processes of some embodiments can include exposing graphene on a metal growth substrate to an ion source, interacting a plurality of ions from the ion source with the graphene and with the metal growth substrate to introduce a plurality of defects in the graphene and an interaction of the ions and/or neutralized ions with the metal growth substrate ejecting toward the graphene a plurality of layer fragments including metal ions or metal atoms from the metal growth substrate, and expanding the defects in the graphene with the layer fragments to define a plurality of holes in the graphene. In an embodiment, the ion source provides to the graphene an ion dose ranging between about 1×1011 ions/cm2 and about 1×1017 ions/cm2 and having an ion energy ranging between about 0.75 keV and about 10 keV. The metal growth substrate is disposed on a side of the graphene opposite the ion source and constitutes a backside layer.
In some embodiments, the graphene can be coated with a frontside layer opposite the metal growth substrate that is disposed on the same side of the graphene as the ion source (see
In other particular embodiments, processes of some embodiments can include exposing graphene to an ion source, the graphene having thereon a frontside layer disposed on the same side of the graphene as the ion source, interacting a plurality of ions and/or neutralized ions from the ion source with the graphene and with the frontside layer to introduce a plurality of defects in the graphene and an interaction of the ions and/or neutralized ions with the frontside layer ejecting toward the graphene a plurality of layer fragments, and expanding the defects in the graphene with the layer fragments to define a plurality of holes in the graphene. In an embodiment, the ion source provides to the graphene an ion dose ranging between about 1×1011 ions/cm2 and about 1×1017 ions/cm2 and having an ion energy ranging between about 0.75 keV and about 10 keV.
In still other particular embodiments, processes of some embodiments can include exposing graphene to an ion source, the graphene being present on a backside layer located on a side of the graphene opposite the ion source, interacting a plurality of ions and/or neutralized ions from the ion source with the graphene and with the backside layer to introduce a plurality of defects in the graphene and an interaction of the ions and/or neutralized ions with the backside layer dispersing an impact energy of the ions and/or neutralized ions with the backside layer into an area of the graphene surrounding the defects created upon interacting the ions with the graphene an promoting expansion of the defects into holes. In an embodiment, the ion source provides to the graphene an ion dose ranging between about 1×1010 ions/cm2 and about 1×1017 ions/cm2 and having an ion energy ranging between about 0.75 keV and about 10 keV.
In more specific particular embodiments, processes of some embodiments can include exposing graphene to an ion source, the graphene being present on a backside layer located on a side of the graphene opposite the ion source, interacting a plurality of ions and/or neutralized ions from the ion source with the graphene and with the backside layer to introduce a plurality of defects in the graphene and an interaction of the ions and/or neutralized ions with the backside layer ejecting toward the graphene a plurality of layer fragments, and expanding the defects in the graphene with the layer fragments to define a plurality of holes in the graphene. In an embodiment, the ion source provides to the graphene an ion dose ranging between about 1×1010 ions/cm2 and about 1×1017 ions/cm2 and having an ion energy ranging between about 0.75 keV and about 10 keV.
The perforated graphene, graphene-based materials and other two-dimensional materials described herein can be used in a variety of applications including filtration, electronics, barrier layers and films, gas barriers, and the like. Illustrative filtration applications in which the perforated graphene, graphene-based materials and other perforated two-dimensional materials can be used include, for example, reverse osmosis, molecular filtration, ultrafiltration and nanofiltration processes. When used in various filtration processes, the perforated graphene or other perforated two-dimensional material can be perforated and then transferred to a porous secondary substrate, where the perforated graphene or other perforated two-dimensional filtration serves as the active filtration membrane.
Some embodiments are directed to membranes comprising a perforated two-dimensional material disposed upon a porous support structure for use in blood dialysis and blood filtration applications. Such two-dimensional materials are selectively perforated to provide for selective removal of one or more components from the blood. In specific embodiments, such two-dimensional materials are selectively perforated to provide for selective removal of one or more selected undesirable components from blood while retaining one or more selected desirable components in the blood.
Some embodiments are directed, in part, to hemodialysis membranes and hemodialysis systems containing selectively perforated graphene or another selectively perforated two-dimensional material. Some embodiments are also directed, in part, to methods for performing a hemodialysis treatment using a hemodialysis system containing such perforated graphene or another such perforated two-dimensional material. Methods herein include hemodialysis cross flow configurations. Methods herein include single-pass methods in which used dialysate is not recirculated and multi-pass systems in which used dialysate is mixed with fresh dialysate and reused.
Some embodiments are directed, in part, to blood filtration membranes and blood filtration systems containing selectively perforated graphene or another selectively perforated two-dimensional material. Some embodiments are also directed, in part, to methods for performing a hemodialysis treatment using a hemodialysis system containing such perforated graphene or another such perforated two-dimensional material
Graphene has garnered widespread interest for use in a number of applications due to its favorable mechanical and electronic properties. Graphene represents an atomically thin layer of carbon (or few carbon layers) in which the carbon atoms reside as closely spaced atoms at regular lattice positions. The regular lattice positions can have a plurality of defects present therein, which can occur natively or be intentionally introduced to the graphene basal plane. Such defects will also be equivalently referred to herein as “apertures,” “perforations,” or “holes.” The term “perforated graphene” will be used herein to denote a graphene sheet with defects in its basal plane, regardless of whether the defects are natively present or intentionally produced. Aside from such apertures, graphene and other two-dimensional materials (e.g., graphene oxide and the like) can represent an impermeable layer to many substances. Therefore, if they are sized properly, the apertures in the impermeable layer can be useful in retaining entities that are larger than the effective pore size. In this regard, a number of techniques have been developed for introducing a plurality of perforations in graphene and other two-dimensional materials, where the perforations have a desired size, number and chemistry about the perimeter of the perforations. Chemical modification of the apertures can allow entities having particular chemical characteristics to be preferentially retained or rejected as well.
Two-dimensional materials are, most generally, those which are atomically thin, with thickness from single-layer sub-nanometer thickness to a few nanometers, and which generally have a high surface area. Two-dimensional materials include metal chalogenides (e.g., transition metal dichalogenides), transition metal oxides, hexagonal boron nitride, graphene, silicene and germanene (see: Xu et al. (2013) “Graphene-like Two-Dimensional Materials) Chemical Reviews 113:3766-3798). Graphene represents a form of carbon in which the carbon atoms reside within a single atomically thin sheet or a few layered sheets (e.g., about 20 or less) of fused six-membered rings forming an extended sp2-hybridized carbon planar lattice. In its various forms, graphene has garnered widespread interest for use in a number of applications, primarily due to its favorable combination of high electrical and thermal conductivity values, good in-plane mechanical strength, and unique optical and electronic properties. Other two-dimensional materials having a thickness of a few nanometers or less and an extended planar lattice are also of interest for various applications. In an embodiment, a two dimensional material has a thickness of 0.3 to 1.2 nm. In other embodiments, a two dimensional material has a thickness of 0.3 to 3 nm.
In various embodiments, the two-dimensional material comprises a sheet of a graphene-based material. In an embodiment, the sheet of graphene-based material is a sheet of single- or multi-layer graphene or a sheet comprising a plurality of interconnected single- or multi-layer graphene domains. In embodiments, the multilayer graphene domains have 2 to 5 layers or 2 to 10 layers. In an embodiment, the layer comprising the sheet of graphene-based material further comprises non-graphenic carbon-based material located on the surface of the sheet of graphene-based material. In an embodiment, the amount of non-graphenic carbon-based material is less than the amount of graphene. In embodiments, the amount of graphene in the graphene-based material is from 60% to 95% or from 75% to 100%.
The technique used for forming the graphene or graphene-based material in the embodiments described herein is not believed to be particularly limited. For example, in some embodiments CVD graphene or graphene-based material can be used. In various embodiments, the CVD graphene or graphene-based material can be liberated from its growth substrate (e.g., Cu) and transferred to a polymer backing. In some embodiments, the growth substrate may be corrugated before or after the graphene deposition process to produce a graphene or graphene-based material with high surface area. In some embodiments, a growth substrate may be formed as a cylinder to form a sleeve of graphene or graphene-based material, thereby reducing the number of seams that must be sealed to form the enclosure.
The present inventors recognized that many of the techniques used to introduce perforations into graphene-based material and other two-dimensional materials produce perforations having pore sizes similar to those present in conventional hemodialysis membranes. Thus, they can be used for separating impurities having comparable size to those separated using conventional hemodialysis membranes. However, since single-layer or even multi-layer graphene are much thinner than conventional hemodialysis membranes, a much greater transfer rate can be realized, as expressed with the following formula.
Hence, very thin graphene membranes allow for a much greater transport rate to be realized, which can be least 100 times faster than in conventional hemodialysis membranes. In an embodiment, the graphene membranes can be used as a drop-in replacement for conventional hemodialysis membranes.
In addition to the increased transport rate, the size selectivity can advantageously allow decreased collateral metabolite loss to occur during dialysis. Further, the smoothness of the graphene membrane can allow for a lower anticoagulant load to be used during a dialysis procedure, and a reduced incidence of clotting can be realized. Finally, as a result of the foregoing, hemodialysis systems with a decreased footprint size and lower power requirements can be realized. Decreased patient treatment times can ultimately result. Any of these factors can increase profitability of hemodialysis centers.
Likewise, the techniques for introducing perforations to the graphene or graphene-based material are also not believed to be particularly limited, other than being chosen to produce perforations within a desired size range. Perforations are sized as described herein to provide desired selective permeability of a species (atom, molecule, protein, virus, cell, etc.) for a given application. Selective permeability relates to the propensity of a porous material or a perforated two-dimensional material to allow passage (or transport) of one or more species more readily or faster than other species. Selective permeability allows separation of species which exhibit different passage or transport rates. In two-dimensional materials selective permeability correlates to the dimension or size (e.g., diameter) of apertures and the relative effective size of the species. Selective permeability of the perforations in two-dimensional materials, such as graphene-based materials, can also depend on functionalization of perforations (if any) and the specific species that are to be separated. Separation of two or more species in a mixture includes a change in the ratio(s) (weight or molar ratio) of the two or more species in the mixture after passage of the mixture through a perforated two-dimensional material.
Graphene-based materials include, but are not limited to, single layer graphene, multilayer graphene or interconnected single or multilayer graphene domains and combinations thereof. In an embodiment, graphene-based materials also include materials which have been formed by stacking single layer or multilayer graphene sheets. In embodiments, multilayer graphene includes 2 to 20 layers, 2 to 10 layers or 2 to 5 layers. In embodiments, graphene is the dominant material in a graphene-based material. For example, a graphene-based material comprises at least 30% graphene, or at least 40% graphene, or at least 50% graphene, or at least 60% graphene, or at least 70% graphene, or at least 80% graphene, or at least 90% graphene, or at least 95% graphene. In embodiments, a graphene-based material comprises a range of graphene selected from 30% to 95%, from 40% to 80%, from 50% to 70%, from 60% to 95% or from 75% to 100%.
As used herein, a “domain” refers to a region of a material where atoms are uniformly ordered into a crystal lattice. A domain is uniform within its boundaries, but different from a neighboring region. For example, a single crystalline material has a single domain of ordered atoms. In an embodiment, at least some of the graphene domains are nanocrystals, having domain size from 1 to 100 nm or 10 to 100 nm. In an embodiment, at least some of the graphene domains have a domain size greater than 100 nm to 1 micron, or from 200 nm to 800 nm, or from 300 nm to 500 nm. “Grain boundaries” formed by crystallographic defects at edges of each domain differentiate between neighboring crystal lattices. In some embodiments, a first crystal lattice may be rotated relative to a second crystal lattice, by rotation about an axis perpendicular to the plane of a sheet, such that the two lattices differ in “crystal lattice orientation”.
In an embodiment, the sheet of graphene-based material comprises a sheet of single layer or multilayer graphene or a combination thereof. In an embodiment, the sheet of graphene-based material is a sheet of single layer or multilayer graphene or a combination thereof. In another embodiment, the sheet of graphene-based material is a sheet comprising a plurality of interconnected single or multilayer graphene domains. In an embodiment, the interconnected domains are covalently bonded together to form the sheet. When the domains in a sheet differ in crystal lattice orientation, the sheet is polycrystalline.
In embodiments, the thickness of the sheet of graphene-based material is from 0.34 to 10 nm, from 0.34 to 5 nm, or from 0.34 to 3 nm. In an embodiment, a sheet of graphene-based material comprises intrinsic defects. Intrinsic defects are those resulting from preparation of the graphene-based material in contrast to perforations which are selectively introduced into a sheet of graphene-based material or a sheet of graphene. Such intrinsic defects include, but are not limited to, lattice anomalies, pores, tears, cracks or wrinkles. Lattice anomalies can include, but are not limited to, carbon rings with other than 6 members (e.g. 5, 7 or 9 membered rings), vacancies, interstitial defects (including incorporation of non-carbon atoms in the lattice), and grain boundaries.
In an embodiment, the layer comprising the sheet of graphene-based material further comprises non-graphenic carbon-based material located on the surface of the sheet of graphene-based material. In an embodiment, the non-graphenic carbon-based material does not possess long range order and may be classified as amorphous. In embodiments, the non-graphenic carbon-based material further comprises elements other than carbon and/or hydrocarbons. Non-carbon elements which may be incorporated in the non-graphenic carbon include, but are not limited to, hydrogen, oxygen, silicon, copper and iron. In embodiments, the non-graphenic carbon-based material comprises hydrocarbons. In embodiments, carbon is the dominant material in non-graphenic carbon-based material. For example, a non-graphenic carbon-based material comprises at least 30% carbon, or at least 40% carbon, or at least 50% carbon, or at least 60% carbon, or at least 70% carbon, or at least 80% carbon, or at least 90% carbon, or at least 95% carbon. In embodiments, a non-graphenic carbon-based material comprises a range of carbon selected from 30% to 95%, or from 40% to 80%, or from 50% to 70%.
Such nanomaterials in which pores are intentionally created will be referred to herein as “perforated graphene”, “perforated graphene-based materials” or “perforated two-dimensional materials.” Some embodiments are also directed, in part, to perforated graphene, perforated graphene-based materials and other perforated two-dimensional materials containing a plurality of holes of size (or size range) appropriate for a given enclosure application. The size distribution of holes may be narrow, e.g., limited to a 1-10% deviation in size or a 1-20% deviation in size. In an embodiment, the characteristic dimension of the holes is selected for the application. For circular holes, the characteristic dimension is the diameter of the hole. In embodiments relevant to non-circular pores, the characteristic dimension can be taken as the largest distance spanning the hole, the smallest distance spanning the hole, the average of the largest and smallest distance spanning the hole, or an equivalent diameter based on the in-plane area of the pore. As used herein, perforated graphene-based materials include materials in which non-carbon atoms have been incorporated at the edges of the pores.
In various embodiments, the two-dimensional material comprises graphene, molybdenum disulfide, or boron nitride. In more particular embodiments, the two-dimensional material can be graphene. Graphene according to some embodiments can include single-layer graphene, multi-layer graphene, or any combination thereof. Other nanomaterials having an extended two-dimensional molecular structure can also constitute the two-dimensional material in some embodiments. For example, molybdenum sulfide is a representative chalcogenide having a two-dimensional molecular structure, and other various chalcogenides can constitute the two-dimensional material in some embodiments. Choice of a suitable two-dimensional material for a particular application can be determined by a number of factors, including the chemical and physical environment into which the graphene or other two-dimensional material is to be terminally deployed. For application in some embodiments, materials employed in making an enclosure are preferably biocompatible or can be made biocompatible.
The process of forming holes in graphene and other two-dimensional materials will be referred to herein as “perforation,” and such nanomaterials will be referred to herein as being “perforated.” In a graphene sheet an interstitial aperture is formed by each six-carbon atom ring structure in the sheet and this interstitial aperture is less than one nanometer across. In particular, this interstitial aperture is believed to be about 0.3 nanometers across its longest dimension (the center to center distance between carbon atoms being about 0.28 nm and the aperture being somewhat smaller than this distance). Perforation of sheets comprising two-dimensional network structures typically refers to formation of holes larger than the interstitial apertures in the network structure.
Due to the atomic-level thinness of graphene and other two-dimensional materials, it can be possible to achieve high liquid throughput fluxes during separation or filtration processes, even with holes that are in the ranges of 1-200 nm, 1-100 nm, 1-50 nm, or 1-20 nm.
Chemical techniques can be used to create holes in graphene and other two-dimensional materials. Exposure of graphene or another two-dimensional material to ozone or atmospheric pressure plasma (e.g., an oxygen/argon or nitrogen/argon plasma) can effect perforation. Other techniques, such as ion bombardment, can also be used to remove matter from the planar structure of two-dimensional materials in order to create holes. All such methods can be applied for preparation of perforated two-dimensional materials for use herein dependent upon the hole sizes or range of hole sizes desired for a given application. The terms holes, pores, apertures and perforations are used interchangeably herein.
In various embodiments of some embodiments, the holes produced in the graphene-based material or other two-dimensional material can range from about 0.3 nm to about 50 nm in size. In a more specific embodiment, hole sizes can range from 1 nm to 50 nm. In a more specific embodiment, hole sizes can range from 1 nm to 10 nm. In a more specific embodiment, hole sizes can range from 5 nm to 10 nm. In a more specific embodiment, hole sizes can range from 1 nm to 5 nm. In a more specific embodiment, the holes can range from about 0.5 nm to about 2.5 nm in size. In an additional embodiment, the hole size is from 0.3 to 0.5 nm. In a further embodiment, the hole size is from 0.5 to 10 nm. In an additional embodiment, the hole size is from 5 nm to 20 nm. In a further embodiment, the hole size is from 0.7 nm to 1.2 nm. In an additional embodiment, the hole size is from 10 nm to 50 nm.
Methods for perforating two-dimensional materials, including graphene-based materials and graphene have been described in the art and include among others, irradiation with ions, bombardment with particles, etching processes and focus ion beam drilling. Methods which allowing formation of pores or perforations of a selected size (dimension) are preferred. Pores may have any useful shape and may be substantially round or may be elongated, e.g., slit-shaped. The terms size and dimension of a pore refer to the widest dimension of the pore which depend upon the shape of the pore. The widest dimension of a round pore is the diameter of the round pore. In preferred embodiments, pore dimensions in dialysis membranes and filters range from about 1 nm to about 30 nm, or from about 1 nm to about 20 nm, or from about 1 nm to about 10 nm or from 1 nm to about 7 nm. In more specific embodiments, pores dimensions in the membranes and filters herein range up to 7 nm.
In an embodiment, the membranes herein are useful in filtering applications where high sheer is applied to reduce fouling
In accordance with some embodiments, a perforated graphene membrane mounted on a suitable bio-compatible support structure can be configured, for example, in a two chamber cross-flow vessel in a similar manner to today's polymer hemodialysis membranes.
In general, contaminated blood entering via conduit 2956 moves across a first surface of the graphene membrane (2955), controlled transport channels in its surface (nominally 1 atom thick and defined by the pore sizes of the perforations) allow a high flow rate of contaminants to be removed very efficiently from the blood and transported across the membrane into the other side of the chamber (2952) where a suitable draw solution (such as a dialysate) entering via conduit 2958, solubilizes or entrains the contaminants and carries them away for disposal via conduit 2959. Cleaned blood exits the system via conduit 2957 and as shown in
In a related multi-pass configuration, used dialysate exiting via conduit 2959 can in whole or in part be transferred via conduit 2965 to be mixed with fresh dialysate for recirculation through the system. Recirculation of dialysate decreases the volume of dialysate needed. In an embodiment in a multi-pass configuration, the used dialysate, such as that exiting via conduit 2959 can be filtered using a membrane as described herein having selected pore size to remove/reduce the levels of undesired contaminant in the used dialysate.
It is known in the art of hemodialysis that it can be important to employ dialysate with minimum undesired components. Thus filtering devices employing membranes of some embodiments which comprises selectively perforated two-dimensional materials, such as graphene, can also be employed in the preparation of dialysate or be employed to pre-filter dialysate prior to introduction into a dialyzer.
Alternate fluidic arrangements that optimize the transformational transport across the graphene membrane can also be used. Another embodiment with a sequence of concatenated filter chambers can alleviate the need for a diffusively active draw solution.
Regardless of the utilized membrane configuration, as a direct result of the increased transport efficiency, the patient treatment time can be greatly reduced, the level of currently infused anti-coagulants (such as heparin) can be greatly reduced because of the graphene surface neutrality and smoothness (minimizing stirring and agitation that can trigger the clotting sequence), and the rate of auxiliary metabolite removal can be carefully controlled so as to minimize depletion of beneficial electrolytes with simultaneous removal of undesired contaminants. Use of the membranes of some embodiments has the potential to decrease complement activation which can lead to allergic reactions during treatment and may also lead to acute intradialytic pulmonary hypertension, chronic low-grade systemic inflammation and leukocyte dysfunction.
In some embodiments, the graphene or other two-dimensional material can be functionalized. Particularly, the perimeter of the apertures within the graphene can be functionalized. Suitable techniques for functionalizing graphene will be familiar to one having ordinary skill in the art. Moreover, given the benefit of the present embodiments and an understanding consistent with one having ordinary skill in the art, a skilled artisan will be able to choose a suitable functionality for producing a desired interaction with an entity in a fluid, such as a biological fluid. For example, the apertures in a graphene can be functionalized such that they interact preferentially with a protein or class of proteins in deference to other biological entities of similar size, thereby allowing separations based upon chemical characteristics to take place. In some embodiments, pores of a given two-dimensional material are functionalized with a chemical species that is positively charge at physiologic pH (e. g., carries one or more amine groups). In some embodiments, pores of a given two-dimensional material are functionalized with a chemical species that is positively negatively charged at physiologic pH (e. g., carries one or more carboxyl or sulfonate groups). In some embodiments, pores of a given two-dimensional material are functionalized with a chemical species that is hydrophobic and in other embodiments pores of a given two-dimensional material are functionalized with a chemical species that is hydrophilic.
In some embodiments, the graphene or other two-dimensional material can be functionalized with a chemical entity so that the functionalization interacts preferentially with a particular type of biological entity (e.g., by a chemical interaction). In some or other embodiments, the graphene or other two-dimensional material can be functionalized such that it interacts electrically with a biological entity (e.g., by a preferential electrostatic interaction). Selective interactions based upon biological recognition are also possible.
Membranes herein include a perforated two-dimensional material supported on a porous substrate. The porous material is preferably biocompatible and in some embodiments is preferably suitable for implantation in a human or animal body. The porous substrate can be a polymer, ceramic or metal. Suitable materials include among others, poly(methyl methacrylate) (PMMA), polyesters, polyamides, polyimides, polyethylene, polypropylene, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polycarbonate, polyetherether-ketone polymers, i.e., PEEK™ polymers (Trademark Victrex, USA, Inc.) and particularly polyaryletheretherketone, polyvinyl chloride (PVC), and mixtures, copolymers and block copolymers thereof. Additionally, non-polymeric substrates such as Si, SiN, anodized alumina, porous ceramics, or sintered metals can be employed. In specific embodiments, the substrate is a biocompatible polymer. In an embodiment, suitable polymers for forming a porous or permeable fibrous layer are biocompatible, bioinert and/or medical grade materials. In specific embodiments, the substrate is a track-etched polymer. In specific embodiments, the substrate is track-etched polycarbonate.
In an embodiment, the support can itself have a porous structure wherein the pores are larger than those of the two-dimensional material. In an embodiment, the support structure is entirely porous. In embodiments, the support structure is at least in part non-porous.
In embodiments herein the two-dimensional material is a graphene-based material. In embodiments of herein, the two-dimensional material is graphene.
In embodiments herein at least a portion of the holes in the two-dimensional materials of the membranes are functionalized.
In embodiments herein at least a portion of the two-dimensional material is conductive and a voltage can be applied to at least a portion of the conductive two-dimensional material. The voltage can be an AC or DC voltage. The voltage can be applied from a source external to the membrane. In an embodiment, a membrane herein further comprises connectors and leads for application of a voltage from an external source to the two-dimensional material. Application of an electrical charge to a conductive membrane herein can additionally facilitate selective or targeted removal of components from blood, dialysate, and/or water. Additionally, the conductive properties of graphene-based or other two-dimensional membranes can allow for electrification to take place from an external source. In exemplary embodiments, an AC or DC voltage can be applied to conductive two-dimensional materials of the enclosure. The conductivity properties of graphene-based materials and graphene can provide additional gating to charged molecules. Electrification can occur permanently or only for a portion of the time to affect gating. Directional gating of charged molecules can be directed not only through the pores (or restrict travel through pores), but also to the surface of the graphene to adsorb or bind
Membranes herein can also be employed in blood filtration applications. In such applications, blood is passed through one or more or preferably two or more membranes in sequence to selectively remove components from the blood by size. For a membrane of given pore dimension, components of sufficiently smaller dimension compared to the pores will pass through the pores of the membrane while components of sufficiently larger dimension compared to the pores will not. Thus, filtration of selected blood components can be accomplished by passage of the blood through one or more membranes with selected pore dimensions.
An exemplary filtration configuration is illustrated in
As discussed above, hemodialysis and hemofiltration are employed to remove toxic substances such as creatinine and urea from the blood typically to replace or supplement such function of the kidneys. The term “removed” is used herein to encompass a decrease in level of the component after dialysis or filtration. It is noted that the term removed includes decreasing the level of toxic species in the blood to non-toxic levels or to with the range of concentrations found in those whose individuals who have normal kidney function. During hemodialysis and hemofiltration, it is undesirable, as is known in the art, to remove or significantly lower the concentration of certain components below their normal concentration range in individuals with normal kidney function. One such component is serum albumin the removal of too much of which can be detrimental to an individual. It is generally known in the art which blood components should be removed and which should be retained to in general achieve component levels that are within the normal concentration level of the components in the blood. In some cases, hemodialysis and hemofiltration are performed continuously in an attempt to maintain levels of toxic species in the blood at concentrations the same as those in individuals with normal kidney function. In many cases however, hemodialysis and hemofiltration are performed intermittently (e.g., on a set schedule) to lower levels of toxic species in the blood to normal or below normal levels. During the time between treatments, the levels of toxic species can build up in the blood.
The membranes of some embodiments formed by introduction of pores of selective dimension into sheets or layers of two-dimensional material are particularly suited to targeted removal of components based on size. As illustrated in
Although some embodiments provided herein are primarily directed to hemodialysis membranes and blood filtration membranes formed from graphene materials it is to be recognized that graphene oxide (GO) and reduced graphene oxide (rGO) can also be used in alternative embodiments. It will be appreciated that filtration devices containing membranes and membranes herein may be prepared from combinations of two-dimensional materials. Other perforated two-dimensional materials can also be used as well. In addition to in vivo hemodialysis and hemofiltration techniques, ex vivo dialysis and filtration techniques are also contemplated as well.
Methods for treating a patient using the disclosed membranes are also contemplated herein. These treatment methods are performed using the disclosed membranes in a manner similar to that used with conventional hemodialysis or hemofiltration techniques. In brief, the methods involve contacting blood from a patient with a graphene-based hemodialysis or hemofiltration membrane (or membrane configuration, as illustrated in
The membranes herein can further be employed for peritoneal dialysis and in renal assist devices. Peritoneal dialysis is also employed to remove waste products from blood when normal kidney function is lost or impaired. Blood vessels in the abdominal lining (the peritoneum) replace the function of the kidneys when a dialysate is flowed into and out of the peritoneal space. Membranes herein can be employed for filtration of dialysate in peritoneal dialysis. Renal assist devices include wearable and implantable devices for hemodialysis and peritoneal dialysis. Membranes herein can be employed to implement such devices as dialysis membranes and/or filtration devices. Certain renal assist devices (e.g., bio-artificial kidneys) include biological cells for carrying out certain metabolic functions. For example, an implantable artificial kidney can include a bio-cartridge of renal tubule cells which, mimic the metabolic and water-balance function of the kidneys. Two-dimensional materials, particularly graphene-based materials can be employed as selectively permeable enclosures to retain such cells and to allow selective entry of components into the enclosure and selective exit of components from the enclosure. Such enclosures can for example be employed in artificial kidney which contain a bio-cartridge. Such enclosure are described for example in U.S. application Ser. No. 14/656,190.
Ex vivo dialysis techniques can be conducted similarly. Such dialysis techniques can be conducted upon a biological fluid, such as blood, or upon other dialyzable fluids in need of contaminant removal therefrom.
Although some embodiments have been described with reference to the disclosed embodiments, those skilled in the art will readily appreciate that these only illustrative of some embodiments. It should be understood that various modifications can be made without departing from the spirit of the disclosure. Some embodiments can be modified to incorporate any number of variations, alterations, substitutions or equivalent arrangements not heretofore described, but which are commensurate with the spirit and scope of the embodiments. Additionally, while various embodiments of the disclosure have been described, it is to be understood that aspects of the disclosure may include only some of the described embodiments. Accordingly, the disclosure is not to be seen as limited by the foregoing description.
Every formulation or combination of components described or exemplified can be used to practice the embodiments, unless otherwise stated. Specific names of compounds are intended to be exemplary, as it is known that one of ordinary skill in the art can name the same compounds differently. When a compound is described herein such that a particular isomer or enantiomer of the compound is not specified, for example, in a formula or in a chemical name, that description is intended to include each isomers and enantiomer of the compound described individual or in any combination. One of ordinary skill in the art will appreciate that methods, device elements, starting materials and synthetic methods other than those specifically exemplified can be employed in the practice of the embodiments without resort to undue experimentation. All art-known functional equivalents, of any such methods, device elements, starting materials and synthetic methods are intended to be included in this disclosure. Whenever a range is given in the specification, for example, a temperature range, a time range, or a composition range, all intermediate ranges and subranges, as well as all individual values included in the ranges given are intended to be included in the disclosure. When a Markush group or other grouping is used herein, all individual members of the group and all combinations and subcombinations possible of the group are intended to be individually included in the disclosure.
As used herein, “comprising” is synonymous with “including,” “containing,” or “characterized by,” and is inclusive or open-ended and does not exclude additional, unrecited elements or method steps. As used herein, “consisting of” excludes any element, step, or ingredient not specified in the claim element. As used herein, “consisting essentially of” does not exclude materials or steps that do not materially affect the basic and novel characteristics of the claim. Any recitation herein of the term “comprising”, particularly in a description of components of a composition or in a description of elements of a device, is understood to encompass those compositions and methods consisting essentially of and consisting of the recited components or elements. The embodiments illustratively described herein suitably may be practiced in the absence of any element or elements, limitation or limitations which is not specifically disclosed herein.
The terms and expressions which have been employed are used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the disclosure claimed. Thus, it should be understood that although the present disclosure has been specifically disclosed by preferred embodiments and optional features, modification and variation of the concepts herein disclosed may be resorted to by those skilled in the art, and that such modifications and variations are considered to be within the scope of this disclosure as defined by the appended claims.
In general the terms and phrases used herein have their art-recognized meaning, which can be found by reference to standard texts, journal references and contexts known to those skilled in the art. The preceding definitions are provided to clarify their specific use in the context of the disclosure.
All references throughout this application, for example patent documents including issued or granted patents or equivalents; patent application publications; and non-patent literature documents or other source material; are hereby incorporated by reference herein in their entireties, as though individually incorporated by reference, to the extent each reference is at least partially not inconsistent with the disclosure in this application (for example, a reference that is partially inconsistent is incorporated by reference except for the partially inconsistent portion of the reference).
All patents and publications mentioned in the specification are indicative of the levels of skill of those skilled in the art to which the disclosure pertains. References cited herein are incorporated by reference herein in their entirety to indicate the state of the art, in some cases as of their filing date, and it is intended that this information can be employed herein, if needed, to exclude (for example, to disclaim) specific embodiments that are in the prior art. For example, when a compound is claimed, it should be understood that compounds known in the prior art, including certain compounds disclosed in the references disclosed herein (particularly in referenced patent documents), are not intended to be included in the claim.
This application is a continuation-in-part of U.S. application Ser. No. 14/610,770, filed Jan. 30, 2015, which claims the benefit of U.S. Provisional Application No. 61/934,530, filed Jan. 31, 2014, each of which is incorporated by reference herein in its entirety. This application is also a continuation-in-part of U.S. application Ser. No. 14/843,944, filed Sep. 2, 2015 which claims the benefit of U.S. Provisional Application No. 62/044,877, filed on Sep. 2, 2014, each of which is incorporated by reference herein in its entirety. This application is also a continuation-in-part of U.S. application Ser. No. 15/099,295, filed on Apr. 14, 2016, entitled “Graphene Platelet-Based Polymers and Uses Thereof,” which is incorporated by reference herein in its entirety. This application is also a continuation-in-part of U.S. application Ser. No. 15/099,482, filed on Apr. 14, 2016, entitled “METHOD FOR MAKING TWO-DIMENSIONAL MATERIALS AND COMPOSITE MEMBRANES THEREOF HAVING SIZE-SELECTIVE PERFORATIONS,” which is incorporated by reference herein in its entirety. This application is related to and claims the benefit of U.S. application Ser. No. 14/856,109, filed Sep. 16, 2015, which is incorporated by reference herein in its entirety. This application is related to and claims the benefit of U.S. application Ser. No. 14/656,657, filed Mar. 12, 2015, claiming the benefit of U.S. Provisional Application No. 61/951,660, filed Mar. 12, 2014, which are incorporated by reference herein in their entirety. This application is related to and claims the benefit of U.S. application Ser. No. 14/754,531, filed Jun. 29, 2015, which is incorporated by reference herein in its entirety. This application is related to and claims the benefit of U.S. application Ser. No. 14/609,325, filed Jan. 29, 2015, claiming the benefit of U.S. Provisional Application No. 61/934,537, filed Jan. 31, 2014, which are incorporated by reference herein in their entirety. This application is related to and claims the benefit of U.S. application Ser. No. 14/656,190, filed Mar. 12, 2015, claiming the benefit of U.S. Provisional Application No. 61/951,926, filed Mar. 12, 2014, which are incorporated by reference herein in their entirety. This application is related to and claims the benefit of U.S. application Ser. No. 14/656,580, filed Mar. 12, 2015, which claims priority to U.S. Provisional Application 61/951,930, filed Mar. 12, 2014, which are incorporated herein by reference in their entirety. This application is related to and claims the benefit of U.S. application Ser. No. 13/480,569, filed May 25, 2012, which is incorporated herein by reference in its entirety. This application is related to and claims the benefit of U.S. application Ser. No. 14/856,471, filed Sep. 16, 2015, which is incorporated by reference herein in its entirety. This application is related to and claims the benefit of U.S. application Ser. No. 14/707,808, filed May 8, 2015, claiming the benefit of U.S. Provisional Application No. 61/990,561, filed May 8, 2014 and U.S. Provisional Application No. 61/990,204, filed May 8, 2014, which are incorporated by reference herein in their entirety. This application is related to and claims the benefit of PCT Application No. PCT/US15/28948 and PCT/US15/18114, filed on May 1, 2014, claiming the benefit of U.S. Provisional Application No. 61/987,410, filed May 1, 2014, which are incorporated by reference herein in their entirety. This application is related to and claims the benefit of U.S. application Ser. No. 14/819,273, filed Aug. 5, 2015, which was a CIP and claimed the benefit of U.S. application Ser. No. 14/610,770, which claimed the benefit of U.S. Provisional Application No. 61/934,530, filed Jan. 31, 2014, which are incorporated by reference herein in their entirety. This application is related to and claims the benefit of U.S. application Ser. No. 14/843,944, filed Sep. 2, 2015, claiming the benefit of U.S. Provisional Application No. 62/044,877 filed Sep. 2, 2014, which is incorporated by reference herein in its entirety. This application is related to and claims the benefit of U.S. Provisional Application No. 62/313,581, filed Mar. 25, 2016, which is incorporated by reference herein in its entirety. This application is related to and claims the benefit of U.S. application Ser. No. 15/099,304, filed Apr. 14, 2016, entitled “METHODS FOR IN VIVO AND IN VITRO USE OF GRAPHENE AND OTHER TWO-DIMENSIONAL MATERIALS,” which is incorporated by reference herein in its entirety. This application is related to and claims the benefit of U.S. application Ser. No. 15/099,410, filed Apr. 14, 2016, entitled “SELECTIVE INTERFACIAL MITIGATION OF GRAPHENE DEFECTS,” which is incorporated by reference herein in its entirety. This application is related to and claims the benefit of U.S. application Ser. No. 15/099,420, filed Apr. 14, 2016, entitled “TWO-DIMENSIONAL MEMBRANE STRUCTURES HAVING FLOW PASSAGES,” which is incorporated by reference herein in its entirety. This application is related to and claims the benefit of U.S. application Ser. No. 15/099,289, filed Apr. 14, 2016, entitled “MEMBRANES WITH TUNABLE SELECTIVITY,” which is incorporated by reference herein in its entirety. This application is related to and claims the benefit of U.S. application Ser. No. 15/099,276, filed Apr. 14, 2016, entitled “BIOLOGICALLY-RELEVANT SELECTIVE ENCLOSURES FOR PROMOTING GROWTH AND VASCULARIZATION,” claiming the benefit of U.S. Provisional Application No. 62/202,056, filed Aug. 6, 2015, which are incorporated by reference herein in their entirety. This application is related to and claims the benefit of U.S. application Ser. No. 15/099,447, filed Apr. 14, 2016, entitled “HEALING OF THIN GRAPHITIC MEMBRANES VIA CHARGED PARTICLE IRRADIATION,” which is incorporated by reference herein in its entirety. This application is related to and claims the benefit of U.S. application Ser. No. 15/099,482, filed Apr. 14, 2016, entitled “METHOD FOR MAKING TWO-DIMENSIONAL MATERIALS AND COMPOSITE MEMBRANES THEREOF HAVING SIZE-SELECTIVE PERFORATIONS,” which is incorporated by reference herein in its entirety. This application is related to and claims the benefit of U.S. application Ser. No. 15/099,269, filed Apr. 14, 2016, entitled “PERFORATABLE SHEETS OF GRAPHENE-BASED MATERIAL,” claiming the benefit of U.S. Provisional Application No. 62/201,539, filed Aug. 5, 2015, which are incorporated by reference herein in their entirety. This application is related to and claims the benefit of U.S. application Ser. No. 15/099,099, filed Apr. 14, 2016, entitled “NANOPARTICLE MODIFICATION AND PERFORATION OF GRAPHENE,” claiming the benefit of U.S. Provisional Application No. 62/201,527, filed Aug. 5, 2015, which are incorporated by reference herein in their entirety. This application is related to and claims the benefit of U.S. application Ser. No. 15/099,056, filed Apr. 14, 2016, entitled “METHODS FOR IN SITU MONITORING AND CONTROL OF GRAPHENE DEFECT FORMATION OR HEALING,” which is incorporated by reference herein in its entirety. This application is related to and claims the benefit of U.S. application Ser. No. 15/099,464, filed Apr. 14, 2016, entitled “METHOD FOR TREATING GRAPHENE SHEETS FOR LARGE-SCALE TRANSFER USING FREE-FLOAT METHOD,” which is incorporated by reference herein in its entirety. This application is related to and claims the benefit of U.S. application Ser. No. 15/099,239, filed Apr. 14, 2016, entitled “PERFORATED SHEETS OF GRAPHENE-BASED MATERIAL,” claiming the benefit of U.S. Provisional Application No. 62/201,527, filed Aug. 5, 2015, which are incorporated by reference herein in their entirety. This application is related to and claims the benefit of U.S. application Ser. No. 15/099,193, filed Apr. 14, 2016, entitled “IMPLANTABLE GRAPHENE MEMBRANES WITH LOW CYTOTOXICITY,” which is incorporated by reference herein in its entirety.
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