Patent Application
20150209734
The present invention relates to a molecular filter and its method of preparation. Specifically, the present invention relates to a molecular filter comprising graphene- and graphene oxide-based compounds.
As the world's population and industry both grow, the need for fresh water increases at least proportionally to that growth. There is an increasing need for fresh water. Potential solutions to this problem are to desalinate sea water as well as purifying water that has been contaminated with pollutants unsuitable for human or animal consumption.
The most commonly used techniques for water filtration include distillation, processes that utilize selective osmosis, ionic processes, and crystallization. However, these processes consume large amounts of energy, resulting in a constant need for new and more economic methods.
Recently, nanomaterials have been used to develop filtering purification technologies.
D. Cohen-Tanugi and J. C. Grossman, “Water desalination across nanoporous graphene,” Nano Lett., 2012, 12 (7), pp. 3602-3608 show that at nanometer scale, pores in single-layered free-standing graphene can filter NaCl particles from aqueous solution from water. The authors show that the water permeability of the graphene filter is several orders of magnitude higher than conventional reverse osmosis membrane. This suggests that nanoporous graphene may serve a valuable role in water purification.
EP 2511002 discloses a graphene-containing separation membrane with enhanced separation efficiency of various materials with a high balance between permeability and selectivity. The publication also discloses use of the separation membrane in sea-water desalination equipment and in gas separation equipment. The graphene separation membrane according to this disclosure includes pores and the size of the pores and channels may be changed for example by changing the graphene growth rate.
U.S. 2012/0255899 discloses a separation membrane including graphene in use for gas separation. The separation membrane is also disclosed in connection with water desalination apparatus. The membrane of this disclosure is a multilayer graphene structure. The membrane includes channels or pores.
US2013/0098833 discloses a nanocomposite semi-permeable membrane for wastewater treatment, seawater desalination, and food and pharmaceutical processing. Among many other nanomaterials, the semi-permeable membrane may include graphite or graphene as well. The nanomaterials are present in a polymer matrix up to about 20 wt-% based on the weight of the polymer-matrix.
U.S. 2013/0256211 discloses a membrane configuration for a filtration or selective fluidic isolation. The configuration contains plane membranes that are constructed from perforated graphene materials. The apertures in the graphene membrane are made by selective oxidation or by laser-drilling.
U.S. Pat. No. 8,361,321 discloses a separation arrangement for isolation of chlorine, sodium and other ions from water. The arrangement comprises at least one perforated graphene sheet with apertures dimensioned to pass water molecules and not to pass the smallest relevant ions.
U.S. 2013/0100436 discloses a molecular filter including a rolled substrate. The rolled substrate may be graphene oxide-based sheets or bio-functionalized graphene.
U.S. 2011/0256376 discloses a laminate sheet including layered graphene oxide sheets and a polymer in spaces between each sheet.
US2012/0107593 discloses graphene oxide membrane materials of high surface area and high electrical conductivity. The membranes according to this disclosure may be of sizes of several thousand micrometers. The graphene oxide sheets of the disclosure are described in connection with a use in biomolecular sensors.
Accordingly there are various solutions for water filtration based on the microporous nature of graphene.
There is a continuous need in various industries for novel methods and materials for water filtration, water purification and water desalination.
The present invention provides novel nanomaterials for water filtration and purification.
It is an object of this invention to provide novel economic nanomaterials for water filtration and purification.
It is an object of this invention to provide an efficient molecular filter.
It is an object of this invention to provide a method to provide molecular filters.
It is another object of this invention to provide a molecular filter, comprising one or more sheets of graphene, one or more sheets of graphene oxide and optionally one or more layers of edge-functionalized graphene oxide. Preferably the graphene is few layered Mesograf® and the graphene oxide is Amphioxide™.
It is another object of this invention to provide a molecular filter, comprising one or more sheets of graphene, one or more sheets of graphene oxide and optionally one or more layers of edge-functionalized graphene oxide where the sheets are arranged in one or more stacks and each stack comprises at least few layered graphene and few layered graphene oxide.
It is yet another object of this invention to provide a molecular filter comprising one or more sheets of graphene, one or more sheets of graphene oxide and optionally one or more layers of edge-functionalized graphene oxide, wherein there are gaps between the one or more layers.
It is an object of this invention to provide a molecular filter comprising one or more sheets of graphene, one or more sheets of graphene oxide and optionally one or more layers of edge-functionalized graphene oxide, wherein the ration of graphene and graphene oxide is 1:1.
It is an object of this invention to provide a molecular filter comprising one or more sheets of graphene, one or more sheets of graphene oxide and one or more layers of edge-functionalized graphene oxide, wherein the ration of graphene: graphene oxide:edge functionalized graphene oxide is 2:2:1
It is yet another object of this invention to provide a molecular filter comprising one or more sheets of graphene, one or more sheets of graphene oxide and optionally one or more sheets of edge-functionalized graphene oxide, wherein the filter is covered with fluorinated polymer or the ends of the layers are covered with fluorinated polymer.
It is yet another object of this invention to provide a method to purify and filter water, said method comprising the steps of: a) providing sheets of few layered graphene, few layered graphene oxide and edge-functionalized graphene oxide; b) arranging the sheets in layers, where each layer comprises at least one sheet of graphene, graphene oxide or functionalized graphene oxide; c) allowing water to be drawn into the sheet layer based on hydrophilic and hydrophobic characteristics of the layers; and d) allowing the water molecules to travel through the layers based on the hydrophilic and hydrophobic characteristics of the layers.
Graphene is one of the crystalline forms of carbon. In graphene, carbon atoms are arranged in a regular hexagonal pattern. Graphene can also be described as a one-atom thick layer of the layered mineral graphite.
Graphene has been synthesized by many methods, including: mechanical exfoliation (“Scotch tape” method), chemical vapor deposition, epitaxial growth, and solution based approaches. Fabrication of large-area graphene is a known challenge because currently, the average size of graphene sheets is 0.5-1 μm2.
International patent application publication WO2013/089642 for National University of Singapore discloses a process for forming expanded hexagonal layered minerals and derivatives from raw graphite ore using electrochemical charging. This process includes immersing at least a portion of graphite rock in a slurry comprised of a mixture of expanded graphite, a metal salt, and an organic solvent. This process also includes electrochemically charging the graphite rock by incorporating the graphite rock into at least one electrode and performing electrolysis through the slurry. This is done by via the electrode that is incorporated into the graphite. This electrolysis introduces the organic solvent as well as ions from the metal salt (via the slurry) into the interlayer spacings of the graphite rock to form 1st stage charged graphite that exfoliates from the graphite rock. This process further includes expanding the 1st stage charged graphite by applying an expanding force to increase the spacing between the atomic layers. This process optionally includes the slurry being comprised of the following: 25-65 wt % or 15-20 wt % graphite rock; 0.1-10 wt % or 0.1-5 wt % graphite flake; and an electrolyte, comprising 100-200 g/L or 80-160 g/L of LiClO4 (5-10 wt %) in propylene carbonate having 40-80 wt % or 70-80 wt %. Mesograf® is large area few layered graphene sheets manufactured by the method disclosed in WO2013/089642.
These few layered graphene sheets, made in one step process from graphite ore, have an average area of 300-500 μm2. Mesograf® is the preferable few graphene used in this invention and it is obtainable from Graphite Zero Pte. Ltd., Singapore. Mesograf® has extraordinary characters that make it superior to other graphene materials. A Raman spectrum of Mesograf® has almost no D-band as opposed to graphene made by Hummer's method. Raman spectroscopy is commonly used to characterize graphene. The band is typically very weak in graphite, but more pronounced in graphene made via Hummer's method (combining sulfuric acid, sodium nitrate, and potassium permanganate to oxidize graphene).
Functionalized graphene oxide is preferably made directly from Amphioxide™.
Amphioxide™ is graphene that is at least 20% oxidized and obtained by oxidizing few layered graphene (Mesograf®). Amphioxide™ retains the layer structure of Mesograf®. Graphene oxide, including Amphioxide™ are highly hydrophilic. Amphioxide™ obtainable from Grafoid, Inc., located in Ottawa, Canada, is the preferred graphene oxide of this disclosure. Graphene oxide sheets of the present invention are preferably Amphioxide™ sheets and they have a lateral size of about 100 micrometers. The sheet may have lateral size as large as 200 micrometers.
Graphene is a highly conductive material and it is considered to be a hydrophobic, meaning that it repels water. The few layered graphene (e.g. Mesograf®) is also a highly conductive material, and has hydrophobic properties.
Graphene oxide is a compound of carbon, oxygen and hydrogen in variable rations. Traditionally graphene oxide is obtained by treating graphite with a strong oxidizing agent. Maximally oxidized graphene is yellow solid with carbon: oxygen ratio between 2.1 and 2.0.
Mesograf® Xide is edge-functionalized graphene, and is synthesized using Amphioxide™ as the starting material. Typically this is done by attaching, carbonyl (═CO) and hydroxyl (—OH) groups are attached to both sides and all edges of the few layered graphene oxide. However, in Mesograf® Xide these groups are only located at the edges of the individual layers of the few layered graphene oxide (Amphioxide™). This feature makes the edges of the Mesograf® Xide sheets to be hydrophilic while the surfaces of the sheets are hydrophobic.
Here, a combination material of graphene, graphene oxide and edge-functionalized graphene is disclosed for water filtration. The preferred materials for the filter are Mesograf® as few layered graphene, Amphioxide™ as the graphene and Mesograf® Xide as the edge-functionalized graphene. The combination material disclosed here is an efficient molecular filter. This should be contrasted with all of the previously disclosed graphene filters which incorporate pores imposed on graphene sheets. In the present invention the filtration is based on the movement of the water molecules in between the graphene oxide sheets, as well as the gaps between the stacks, comprising the three materials in varying order. The hydrophobic nature of graphene combined with the amphiphilic and hydrophilic action of graphene oxide and edge-functionalized graphene creates a way to actively draw the water into the structure and to direct the movement of the water molecules within the structure depending the arrangement of the structure's components.
The direction of the movement of water within the filter structure can be defined by providing different ratios and assemblies of the three differently hydrophobic or hydrophilic components or the structure.
An advantage of the water filter and the method in this disclosure as compared to previously known methods or devices is that the different hydrophobic and hydrophilic characteristics of the components the water filter move the water molecules to preferred directions. It should be noted that the movement of the water molecules within the structure is not based on gravity moving the water down through the layers but the water may be directed to move against gravity, it may be directed to move horizontally, downward or in any combinations.
As stated above, this filtering effect is not due to water moving through pores imposed in the sheets. Rather, the filtering effect is due to more complicated movement of the water between the various layers and through the gaps between sheets. Finally, the filter of this invention attracts the water molecules inside it, to specific areas where the filter is comprised of a highly hydrophilic material. Therefore there is no need for outside forces to sift the water through the filter; the hydrophilic materials in filter pull the water in and direct it through the filter due to the assembly of hydrophobic/hydrophilic materials throughout the structure.
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A skilled artisan understands that there are no limitations to the assembly of the layers and/or stacks. The direction of the movement of water molecule can be freely manipulated by changing the order and ratios of the three different types of sheets.
The layers are so arranged, that the distance between the layers and the stacks is such that the water molecule may enter the space but any contaminating particles or compounds would not get through.
The proportions of the three materials of this invention may be varied depending on the purpose the filter is made. According to one preferred embodiment the ratio of Mesograf® to Amphioxide™ is 1:1. According to another preferred embodiment the ratio of Mesograf® and Amphioxide™ is 1:2. According to one preferred embodiment the ratio of Mesograf® Xide to Mesograf® is 1:2. According to another embodiment the ratio may be 1:4. According to one preferred embodiment the ratio of Mesograf®:Amphioxide™:Mesograf® Xide is 2:2:1. According to one preferred embodiment the ratio is 4:4:1. The skilled artisan understands that the ratios may be changed to any ratio of the three components.
According to one preferred embodiment the Mesograf®: Amphioxide™: Mesograf® Xide-filter may be packed in a fluorinated polymer unit. One suitable example of such a fluorinated polymer is polytetrafluoroethylene, but other fluorinated polymers may as well be used. In particular, this polymer coating would be preferable at the ends of the filter. The purpose of this filter is to trap particles that may be detached from the filter layers. This is why these coating are particularly useful when attached to the ends of the present invention. It seems that during the two to five first passes of the water the filter materials may deteriorate to some degree, similarly as happens with activated carbon filters. In order to trap the graphene particles and prevent them from leaking into the environment, the filter may be packed into a polytetrafluoroethylene coating, the ends of the filter layers may be coated with polytetrafluoroethylene, or polytetrafluoroethylene may be even layered inside the filter. The graphene particles that might deteriorate from the filter layers are about 100 μm large, while polytetrafluoroethylene only allows particles smaller than 5 μm to pass through, which would allow the water pass through but would catch the graphene particles detached from the filter.
Although this invention has been described with a certain degree of particularity, it is to be understood that the present disclosure has been made only by way of illustration and that numerous changes in the details of construction and arrangement of parts may be resorted to without departing from the spirit and the scope of the invention.
This application claims priority from U.S. Provisional Patent Application No.: 61/933,038, filed on Jan. 29 2014, the contents of which are hereby incorporated by reference.
| Number | Date | Country | |
|---|---|---|---|
| 61933038 | Jan 2014 | US |
