Patent Application
20100255285
The present invention relates generally to nanostructures and in particular to TiO2-containing, macro-sized nanostructures, methods of making same, and applications of same.
Great efforts are currently devoted to the studies on one-dimensional (1D) nanostructures due to a wealth of unique physical and chemical properties associated with the 1D structural confinement in nanoscale [1]. Due to their high thermal stability and chemical inertness, inorganic nanofibers including nanowires and nanotubes can be assembled into a free standing membrane (FSM) for important applications at high temperatures and in harsh environments [2]. To make the FSM robust, the inorganic nanofibers should be ultra-long and “woven” properly. Such inorganic FSMs could then possess unique porosity, permeability, thermal stability, chemical inertness, robustness, and catalytic properties, all of which would largely differentiate the nanofiber FSMs from the monodispersed nanofibers and the bulk phases of the same/similar chemical formula.
The fabrication of inorganic nanostructured FSM was demonstrated in 1996 on the growth of an oriented mesoporous silica film at the mica-water interface under the help of surfactant molecules [3]. Later, a different solution route to making a mesoporous FSM of anatase nanocrystallites has been developed [4]. Thereafter, fabrications of functional FSMs using 1D inorganic nanostructures have been discussed more often in literature. Recently, nanofibers of microporous manganese oxides have been cast into a paper-like FSM with a precisely controlled layer-by-layer alignment for the nanofibers [5]. Sheets of entangled V2O5 nanofibers were made to have the high Young's modulus, large actuator-generated stress, and significant actuator stroke at low applied voltage [6]. In addition, carbon nanotubes (CNT) have been used for fabricating functional FSMs. The buckypaper containing coaxial carbon nanotubes with improved mechanical property, thermal conductivity, and structural stability has been first reported [7]. Lately, strong, transparent, and multifunctional sheets of orthogonally organized CNTs were made with the gravimetric strength better than that of sheets of high-strength steel [8].
However, the abovementioned inorganic nanofiber FSMs may not be stable during a prolonged heating in air above 550° C. [5]. CNTs, on the other hand, may be fast oxidized in such a harsh calcination. Thus, the development of a thermal stable and chemically inert TiO2-based nanofiber FSM would be of great interest for advancing the existing technologies in high temperature catalysis, sensing, sorption and separation. Furthermore, large scale fabrication of robust, thermal-stable, and multifunctional macroscopic three-dimensional (3D) structures directly from the ID nanomaterials has remained as a challenge.
Therefore, a heretofore unaddressed need exists in the art to address the aforementioned deficiencies and inadequacies.
In one aspect, the present invention relates to a method for synthesizing macro-sized nanostructures. In one embodiment, the method includes the steps of mixing an amount of TiO2 powders with a volume of an alkali or alkaline solution to form a mixture; and heating the mixture at a temperature higher than 160° C. for a period of time effective to allow TiO2-containing, macro-sized nanostructures to form, where the TiO2-containing, macro-sized nanostructures form in an environment that has no presence of a substrate that comprises Ti. The method further comprises the step of washing the TiO2-containing, macro-sized nanostructures with distilled water or a dilute acid. In one embodiment, the TiO2-containing, macro-sized nanostructures comprise substantially nanofibers with a typical diameter in the range of about 20 nm to 150 nm. The nanofibers are substantially in the TiO2-B phase or titanate phase.
In one embodiment, the mixture is contained in a container and sealed therein. The heating step comprises the step of placing the sealed container containing the mixture in an oven for heating, where the temperature for heating the mixture is in the range of about 180-300° C., and the period of time of heating is in the range of about 3-960 hours.
In one embodiment, the alkali solution comprises one of sodium hydroxide (NaOH), potassium hydroxide (KOH), lithium hydroxide (LiOH), rubidium hydroxide (RbOH), cesium hydroxide (CsOH), and any combination of them, while the alkaline solution comprises one of magnesium hydroxide [Mg(OH)2], or calcium hydroxide [Ca(OH)2], strontium hydroxide [Sr(OH)2], barium hydroxide [Ba(OH)2], and any combination of them.
In another aspect, the present invention relates to TiO2-containing, macro-sized nanostructures synthesized according to the above method.
In yet another aspect, the present invention relates to a synthetic nanostructure. In one embodiment, the synthetic nanostructure includes a reaction product of a chemical reaction according to the formula of:
2NaOH+3TiO2═Na2Ti3O7+H2O,
where the chemical reaction takes place at a temperature higher than 160° C. for a period of time effective to allow the reaction product to form, and where the chemical reaction takes place in an environment that has no presence of a substrate that comprises Ti. In one embodiment, the chemical reaction takes place in a sealed container. The effective temperature is in the range of about 180-300° C. The effective period of time is in the range of about 3-960 hours.
In one embodiment, a first reactant TiO2 is provided in the form of powders, and a second reactant that comprises an inorganic base is provided in the form of solution. In one embodiment, the second reactant comprises NaOH, and the reaction product comprises a compound of the formula Na2Ti3O7. The compound of the formula Na2Ti3O7, in one embodiment, is in the form of nanofiber with a typical diameter in the range of 20 nm to 150 nm.
In a further aspect, the present invention relates to a synthetic nanostructure. In one embodiment, the synthetic nanostructure includes a reaction product of several chemical reactions in sequence according to the formulae of:
2NaOH+3TiO2→Na2Ti3O7; (a)
Na2Ti3O7+2H+→2Na++H2Ti3O7; and (b)
H2Ti3O7→H2O+TiO2—B, (c)
where at least chemical reaction (a) takes place at a temperature higher than 160° C. for a period of time effective to allow the reaction product to form, and where at least chemical reaction (a) takes place in an environment that has no presence of a substrate that comprises Ti. In one embodiment, the effective temperature is in the range of about 180-300° C. The effective period of time is in the range of about 3-960 hours.
In one embodiment, a first reactant TiO2 is provided in the form of powders, a second reactant that comprises an inorganic base is provided in the form of solution. The second reactant in one embodiment comprises NaOH. In another embodiment, the second reactant comprises OH−. The reaction product comprises a compound of the formula Na2Ti3O7, where the compound of the formula Na2Ti3O7 is in the form of macro-sized nanofibers with a typical diameter in the range of 20 nm to 150 nm.
In one embodiment, at least chemical reaction (a) takes place in a sealed container. Chemical reaction (b) takes place substantially between 180° C. and 300° C. for a period of time effective to allow the compound of the formula H2Ti3O7 is in the form of macro-sized nanofibers to form. Chemical reaction (c) takes place in a calcination process, where the calcination process comprises one of a step of heating in a furnace at a temperature in the range of 300-600° C. in air and a step of burning in air.
The chemical reaction (c) causes the compound of the formula TiO2-B to form in the form of macro-sized nanofibers, where the compound of the formula TiO2-B is in the form of macro-sized nanofibers with a typical diameter in the range of 20 nm to 150 nm.
In yet a further aspect, the present invention relates to a method for synthesizing macro-sized nanostructures. In one embodiment, the method includes the step of heating a mixture of a solution and a reagent at a heating temperature for a period of time effective for the growth of reagent-based, macro-sized nanostructures, where the reagent-based, macro-sized nanostructures grow in an environment that has no presence of a substrate that is seeded with the reagent.
In one embodiment, the heating temperature is greater than 160° C. The period of time of heating is in the range of about 3-960 hours. The macro-sized nanostructures comprise nanofibers, nanotubes, nanowires, or any combinations of them.
In one embodiment, the mixture of the solution and the reagent is contained in a container and sealed therein. The reagent comprises TiO2 powders, and the solution comprises an alkali or alkaline solution.
In one aspect, the present invention relates to macro-sized nanostructures synthesized according to the method as disclosed above.
In another aspect, the present invention relates to a method for fabricating a free standing membrane. In one embodiment, the method includes the steps of providing a plurality of TiO2-containing, macro-sized nanostructures; casting the plurality of TiO2-containing, macro-sized nanostructures over a template film to form a free standing membrane over the template film; and drying the free standing membrane over the template film at a temperature for a period of time. In one embodiment, the free standing membrane is formed with multi-layers, and has a thickness in a range of about 10-1,000 micrometers. The free standing membrane is porous, permeable and zeolitic, chemically inert, biocompatible, and/or thermally stable.
The method further includes the step of removing the dried free standing membrane from the template film, where the removing step comprises the step of calcining the dried free standing membrane over the template film at a temperature in the range of 300-600° C. In one embodiment, the template film in one embodiment comprises one of an ashless filter paper and a polyethylene film.
In one embodiment, the providing step comprises the steps of mixing an amount of TiO2 powders with a volume of an alkali or alkaline solution to form a mixture; and heating the mixture at a temperature higher than 160° C. for a period of time effective to allow TiO2-containing, macro-sized nanostructures to form, where the TiO2-containing, macro-sized nanostructures form in an environment that has no presence of a substrate that comprises Ti. The TiO2-containing, macro-sized nanostructures comprise substantially TiO2-B nanofibers with a typical diameter in the range of 20 nm to 150 nm.
In one embodiment, the casting step comprises the steps of casting a first plurality of TiO2-containing, macro-sized nanostructures over the template film; drying the first plurality of TiO2-containing, macro-sized nanostructures cast over the template film at RT for a first period of time; subsequently casting at least one additional plurality of TiO2-containing, macro-sized nanostructures over the dried first plurality of TiO2-containing, macro-sized nanostructures cast over the template film; and drying the at least one additional plurality of TiO2-containing, macro-sized nanostructures cast over the dried first collection of TiO2-containing, macro-sized nanostructures cast over the template film at RT for a second period of time that is substantially different from or equal to the first period of time.
In one embodiment, the temperature of drying is substantially in the range of about 0-180° C. The period of time of drying is substantially in the range of about 0.5-30 hours.
In yet another aspect, the present invention relates to a free standing membrane fabricated according to the above method. The template film is substantially two-dimensional, and the free standing membrane as formed is substantially two-dimensional.
In a further aspect, the present invention relates to a free standing membrane. In one embodiment, the free standing membrane has a plurality of layers of TiO2-containing, macro-sized nanostructures. The TiO2-containing, macro-sized nanostructures are synthesized by mixing an amount of TiO2 powders with a volume of an alkali or alkaline solution to form a mixture; and heating the mixture at a temperature higher than 160° C. for a period of time effective to allow the TiO2-containing, macro-sized nanostructures to form, where the TiO2-containing, macro-sized nanostructures form in an environment that has no presence of a substrate that comprises Ti.
In one embodiment, the TiO2-containing, macro-sized nanostructures comprise substantially TiO2-containing nanofibers with a typical diameter in the range of 20 nm to 150 nm and a TiO2-B structure, where the TiO2-containing nanofibers in each layer are at least partially intertwined, thereby forming a plurality of voids therein.
The free standing membrane has a thickness in a range of from tens to hundreds of micrometers. The free standing membrane is porous, permeable and zeolitic, chemically inert, biocompatible, and/or thermally stable.
In yet a further aspect, the present invention relates to a method for fabricating a 3D structure directly from nanostructures. In one embodiment, the method includes the steps of providing a plurality of TiO2-containing, macro-sized nanostructures; casting the plurality of TiO2-containing, macro-sized nanostructures over a template for forming a 3D structure over the template, where the template has a configuration corresponding to the 3D structure to be formed; and drying the 3D structure over the template at a temperature for a period of time. The TiO2-containing, macro-sized nanostructures comprise nanofibers, nanotubes, nanowires, or any combinations of them.
The method further includes the step of removing the dried 3D structure from the template, where the removing step comprises the step of calcining the dried 3D structure over the template at a temperature in the range of 300-600° C. In one embodiment, the template is formed at least partially with one of an ashless filter paper and a polyethylene film.
The casting step in one embodiment comprises the steps of casting a first plurality of TiO2-containing, macro-sized nanostructures over the template; drying the first plurality of TiO2-containing, macro-sized nanostructures cast over the template at RT for a first period of time; subsequently casting at least one additional plurality of TiO2-containing, macro-sized nanostructures over the dried first plurality of TiO2-containing, macro-sized nanostructures cast over the template; and drying the at least one additional collection of TiO2-containing, macro-sized nanostructures cast over the dried first plurality of TiO2-containing, macro-sized nanostructures cast over the template at RT for a second period of time that is substantially different from or equal to the first period of time.
In one embodiment, the temperature of drying is substantially in the range of about 0-180° C. The period of time of drying is substantially in the range of about 0.5-30 hours.
In one embodiment, at least a portion of the 3D structure has a thickness in a range of from tens to hundreds of micrometers. At least a portion of the 3D structure is porous, permeable and zeolitic. In one embodiment, the 3D structure is chemically inert, biocompatible, and/or thermally stable.
In one aspect, the present invention relates to a 3D structure fabricated according to the method as disclosed above. At least a portion of the 3D structure is formed with multi-layers.
In another aspect, the present invention relates to a 3D structure. In one embodiment, the 3D structure includes a plurality of layers of TiO2-containing, macro-sized nanostructures. The TiO2-containing, macro-sized nanostructures are synthesized by the steps of mixing an amount of TiO2 powders with a volume of an alkali or alkaline solution to form a mixture; and heating the mixture at a temperature higher than 160° C. for a period of time effective to allow TiO2-containing, macro-sized nanostructures to form, where the TiO2-containing, macro-sized nanostructures form in an environment that has no presence of a substrate that comprises Ti. The TiO2-containing, macro-sized nanostructures comprise substantially TiO2-containing nanofibers with a typical diameter in the range of 20 nm to 150 nm and a TiO2-B structure, where the TiO2-containing nanofibers in each layer are at least partially intertwined, thereby forming 3D voids therein.
In one embodiment, at least portion of the 3D structure has a thickness in a range of from tens to hundreds of micrometers. At least portion of the 3D structure is porous, permeable and zeolitic. The 3D structure is chemically inert and/or thermally stable.
These and other aspects of the present invention will become apparent from the following description of the preferred embodiment taken in conjunction with the following drawings, although variations and modifications therein may be affected without departing from the spirit and scope of the novel concepts of the disclosure.
The accompanying drawings illustrate one or more embodiments of the invention and, together with the written description, serve to explain the principles of the invention. Wherever possible, the same reference numbers are used throughout the drawings to refer to the same or like elements of an embodiment, and wherein:
The present invention is more particularly described in the following examples that are intended as illustrative only since numerous modifications and variations therein will be apparent to those skilled in the art. Various embodiments of the invention are now described in detail. Referring to the drawings of
The terms used in this specification generally have their ordinary meanings in the art, within the context of the invention, and in the specific context where each term is used.
Certain terms that are used to describe the invention are discussed below, or elsewhere in the specification, to provide additional guidance to the practitioner in describing the apparatus and methods of the invention and how to make and use them. For convenience, certain terms may be highlighted, for example using italics and/or quotation marks. The use of highlighting has no influence on the scope and meaning of a term; the scope and meaning of a term is the same, in the same context, whether or not it is highlighted. It will be appreciated that the same thing can be said in more than one way. Consequently, alternative language and synonyms may be used for any one or more of the terms discussed herein, nor is any special significance to be placed upon whether or not a term is elaborated or discussed herein. Synonyms for certain terms are provided. A recital of one or more synonyms does not exclude the use of other synonyms. The use of examples anywhere in this specification, including examples of any terms discussed herein, is illustrative only, and in no way limits the scope and meaning of the invention or of any exemplified term. Likewise, the invention is not limited to various embodiments given in this specification. Furthermore, subtitles may be used to help a reader of the specification to read through the specification, which the usage of subtitles, however, has no influence on the scope of the invention.
As used herein, “about” or “approximately” shall generally mean within 20 percent, preferably within 10 percent, and more preferably within 5 percent of a given value or range. Numerical quantities given herein are approximate, meaning that the term “about” or “approximately” can be inferred if not expressly stated.
As used herein, the term “photocatalysis” refers to a process of the acceleration of a photoreaction in the presence of a photocatalyst. When a photocatalyst TiO2 captures ultraviolet light (UV) either from sunlight or fluorescent light, it forms activated oxygen from water or oxygen in the air. This process is similar to photosynthesis, in which chlorophyll captures sunlight to turn water and carbon dioxide into oxygen and glucose. The formed activated oxygen is strong enough to oxidize and decompose organic materials, pollutants or smelling gas, and kill bacteria.
Making large-scale, multifunctional, paper-like FSMs and the FSM-based 3D macroscopic devices purely from long inorganic functional nanowires is challenging in many nanomaterial systems. The present invention, among other things, discloses methods of synthesis of macro-sized nanostructures and direct fabrications of FSMs and FSM-based 3D devices using the macro-sized nanostructures, and also potential applications in photocatalysis, writing-erasing-rewriting information, microfiltration, controlled drug release, and the likes.
The description will be made as to the embodiments of the present invention in conjunction with the accompanying drawings of
According to the present invention, in one embodiment, TiO2-containing, macro-sized nanostructures are synthesized by mixing an amount of TiO2 powders with a volume of an alkali or alkaline solution to form a mixture that is contained in a containers and sealed therein, placing the sealed container containing the mixture in an oven for heating, and then heating the mixture therein at a temperature higher than 160° C. for a period of time effective to allow TiO2-containing, macro-sized nanostructures to form. In one embodiment, the temperature for heating the mixture is in the range of about 180-300° C., and the period of time of heating is in the range of about 3-960 hours. The formed TiO2-containing, macro-sized nanostructures is then washed with distilled water or a dilute acid.
The alkali solution can be one of NaOH, p KOH, LiOH, RbOH, CsOH, and any combinations of them. The alkaline solution can be one of Mg(OH)2, Ca(OH)2, Sr(OH)2, Ba(OH)2, and any combinations of them.
According the present invention, the TiO2-containing, macro-sized nanostructures are formed in an environment that has no presence of a substrate that comprises Ti, such that the TiO2-containing, macro-sized nanostructures comprise substantially nanofibers with a typical diameter in the range of about 20 nm to 150 nm and a typical length in the range of about hundreds of micrometers to few millimeters, as shown in
Conventionally, TiO2-containing nanostructures are produced by treating the TiO2 powders in a concentrated solution of NaOH at a temperature about 150° C. [10] or lower temperatures. The nanostructures were formed on a substrate that is seeded with TiO2 powders. The resultant nanostructures comprise substantially nanotubes that are typically about several to tens of micrometers in length.
The synthetic process of the TiO2-containing, macro-sized nanostructures according to the present invention, however, requires the heating temperature be greater than 160° C. for a period of time effective to allow TiO2-containing, macro-sized nanostructures to form, and therefore results in macro-sized nanofibers about hundreds of micrometers to few millimeters in length, where the macro-sized nanofibers grow in an environment that has no presence of a substrate that is seeded with TiO2 powders. For example, in one embodiment, the macro-sized nanofibers were synthesized by first adding about 0.3 g of the TiO2 powders (Degussa P25) into about 40 mL of 10 M alkali or alkaline solution in a 150 mL Teflon-lined autoclave container. The container was then sealed and heated in an oven for about 1-7 days at a temperature substantially above 160° C. for the growth of macro-sized nanofibers in length. Other containers can also be used to practice the current invention. After the reaction (growth), the synthesized nanofibers were washed with distilled water. The synthesized nanofibers were white and pulp-like and could be used to form FSMs and/or 3D structures including cups and tubes.
In another aspect, the present invention relates to TiO2-containing, macro-sized nanostructures synthesized according to the above method.
In yet another aspect, the present invention relates to a synthetic nanostructure. The synthetic nanostructure includes a reaction product of a chemical reaction according to the formula of
2NaOH+3TiO2═Na2Ti3O7+H2O,
where the chemical reaction takes place at a temperature higher than 160° C. for a period of time effective to allow the reaction product to form, and furthermore, the chemical reaction takes place in an environment that has no presence of a substrate that comprises Ti. In one embodiment, the chemical reaction takes place in a sealed container. The effective temperature is in the range of about 180-300° C. The effective period of time is in the range of about 3-960 hours.
A first reactant TiO2 is provided in the form of powders, and a second reactant that comprises an inorganic base is provided in the form of solution. In one embodiment, the second reactant comprises NaOH and the reaction product comprises a compound of the formula Na2Ti3O7. The compound of the formula Na2Ti3O7 is in the form of nanofiber with a typical diameter in the range of 20 nm to 150 nm.
The synthesized nanofibers can be used to form 2D FSMs and/or 3D structures including cups and tubes.
For example, a two-dimensional (2D) FSM can be formed by the following steps: at first, a plurality of TiO2-containing, macro-sized nanostructures are provided. Then the plurality of TiO2-containing, macro-sized nanostructures is cast over a template film to form a free standing membrane over the template film. Next, the free standing membrane cast over the template film is dried at a temperature for a period of time. The temperature of drying is substantially in the range of about 0-180° C. The period of time of drying is substantially in the range of about 0.5-30 hours. Finally, the dried free standing membrane is removed from the template film by calcining the dried free standing membrane over the template film at a temperature in the range of 300-600° C. for the template film of an ashless filter paper, or by hand for the template film of a polyethylene film. The template film is substantially 2D.
The casting step has the steps of casting a first plurality of TiO2-containing, macro-sized nanostructures over the template film; drying the first plurality of TiO2-containing, macro-sized nanostructures cast over the template film at RT for a first period of time; subsequently casting at least one additional plurality of TiO2-containing, macro-sized nanostructures over the dried first plurality of TiO2-containing, macro-sized nanostructures cast over the template film; and drying the at least one additional plurality of TiO2-containing, macro-sized nanostructures cast over the dried first collection of TiO2-containing, macro-sized nanostructures cast over the template film at RT for a second period of time that is substantially different from or equal to the first period of time.
Accordingly, the 2D FSM is formed with multi-layers and has a thickness in a range of from tens to hundreds of micrometers. The thickness of the 2D FSM is determined by the amount of TiO2-containing, macro-sized nanostructures cast over the template film. The TiO2-containing nanofibers in each layer are at least partially intertwined, thereby forming voids therein. The 2D FSM is porous, permeable and zeolitic, chemically inert, biocompatible, and/or thermally stable, as shown below.
The above disclosed procedures can also be utility to fabricate a 3D structure directly from nanostructures. In this case, a template having a 3D configuration corresponding to the 3D structure to be formed is utilized, instead of a 2D film. Accordingly, the 3D structure has a wall portion formed with multi-layers. The TiO2-containing nanofibers in each layer are at least partially intertwined, thereby forming voids therein. The wall portion of the 3D structure has a thickness in a range of from tens to hundreds of micrometers. At least a portion of the 3D structure is porous, permeable and zeolitic. The 3D structure is chemically inert, biocompatible, and/or thermally stable.
Referring to
In one aspect, the present invention relates to a synthetic nanostructure. In one embodiment, the synthetic nanostructure includes a reaction product of several chemical reactions in sequence according to the formulae of:
2NaOH+3TiO2→Na2Ti3O7; (a)
Na2Ti3O7+2H+→2Na++H2Ti3O7; and (b)
H2Ti3O7→H2O+TiO2—B, (c)
where at least chemical reaction (a) takes place at a temperature higher than 160° C. for a period of time effective to allow the reaction product to form, and furthermore, the at least chemical reaction (a) takes place in an environment that has no presence of a substrate that comprises Ti. In one embodiment, the effective temperature is in the range of about 180-300° C. The effective period of time is in the range of about 3-960 hours.
In one embodiment, a first reactant TiO2 is provided in the form of powders, and a second reactant that comprises an inorganic base is provided in the form of solution. The second reactant in one embodiment comprises NaOH. In another embodiment, the second reactant comprises OH−. The reaction product comprises a compound of the formula Na2Ti3O7. The compound of the formula Na2Ti3O7 is in the form of macro-sized nanofibers with a typical diameter in the range of 20 nm to 150 nm.
In one embodiment, at least chemical reaction (a) takes place in a sealed container. Chemical reaction (b) takes place substantially between 180° C. and 300° C. for a period of time effective to allow the compound of the formula H2Ti3O7 to form in the form of macro-sized nanofibers. Chemical reaction (c) takes place in a calcination process, where the calcination process can be a step of heating in a furnace at a temperature in the range of 300-600° C. in air and a step of burning in air.
The chemical reaction (c) causes the compound of the formula TiO2-B to form in the form of macro-sized nanofibers, where the compound of the formula TiO2-B as formed in the form of macro-sized nanofibers is with a typical diameter in the range of 20 nm to 150 nm.
In addition, the present invention can find many applications in a wide spectrum of fields, such as:
These and other aspects of the present invention are more specifically described below.
Without intent to limit the scope of the invention, exemplary methods and their related results according to the embodiments of the present invention are given below. Note that titles or subtitles may be used in the examples for convenience of a reader, which in no way should limit the scope of the invention. Moreover, certain theories are proposed and disclosed herein; however, in no way they, whether they are right or wrong, should limit the scope of the invention so long as the invention is practiced according to the invention without regard for any particular theory or scheme of action.
Synthesizing TiO2-containing, Macro-sized Nanofibers/Nanowires and Fabricating FSMs and 3D Devices: According to the present invention, a synthetic route for the hydrothermal synthesis of TiO2-containing, macro-sized nanofibers/nanowires at an effective temperature above 160° C. for an effective time period is disclosed.
In this exemplary embodiment, about 0.30 g of TiO2 powder (Degussa P25) was introduced into about 40 mL of 10 M alkali solution in a 150 mL Teflon-lined autoclave container. The container was then sealed and placed in an oven for heating. After the hydrothermal reaction in the oven a temperature above 160° C. for about 7 days, a white pulp-like product of the TiO2-containing, macro-sized nanofibers was collected, washed with distilled water or a dilute acid. The washed white pulp-like product of the TiO2-containing, macro-sized nanofibers was cast on a macroscopic template made of either an ashless filter-paper (Whatman) or polyethylene film, and then dried at RT. This casting-drying process was repeated for several times at RT, and followed thereafter by a heating at about 0-180° C. in an oven for about 0.5-30 hours. Accordingly, a 2D FSM paper or a 3D cup was formed with the TiO2-containing, macro-sized nanofibers on the macroscopic template. Then the macroscopic template was removed from the 2D FSM paper or the 3D cup. In this example, the macroscopic template includes a plastic plate or a cup.
Referring to
A systematic study on varying the fabrication parameters has suggested that the FSM paper's flexibility could be controlled by optimizing (a) the ratio of water to the nanowires in the pulp and (b) the time for drying the nanowire pulp. The preparation of such robust FSM has enabled one to directly cast the long nanowires, under the help of the 3D templates or molds, into macroscopic 3D devices such as tube, bowl, and cup, as shown in
As shown in
The successful casting of the FSMs or 3D membrane devices would depend on the morphology and spatial organization of the nanofibers. The long nanofibers can self-organize into the robust FSM and 3D membrane devices while nanoparticles or short nanofibers cannot. Further, the controlled assemblies of the nanofibers can determine the robustness of the 3D membrane device.
Surface morphologies and lateral structures of the TiO2-containing, macro-sized nanofibers, the free standing membrane and 3D devices of the nanofibers according to embodiments of the present invention were characterized by means of a transmission electron microscope (TEM), a scanning electron microscope (SEM), and a field emission scanning electron microscope (FESEM), energy-dispersive X-ray analyses (EDX), and X-ray diffraction (XRD), respectively. The SEM and EDX work was done on a Philips ESEM XL30 microscope. The XRD data were collected on a Philips X′Pert X-ray diffractometer. The TEM study was carried out on a JEOL X-100 microscope and JEOL 2010 FEG STEM/TEM.
The SEM, FESEM and TEM images of the wall portion of a nanofiber cup according to one embodiment of the present invention were shown in
A high resolution FESEM photographic image of the cup wall portion shown in
c was a TEM image of the nanofibers in the cup wall portion shown in
XRD patterns of the nanofibers confirm that the 1D nanowire samples resemble the titanate in lattice structure [13]. The XRD data have suggested that thus-formed nanowires should be the titanate phase, which is characterized by the following lattice parameters: [2θ=9.8° (001), 11.2° (200), 24.4° (110), and 29.7° (003), (JCPDS card No.: 47-0561)]. The titanate structure's basic building unit is a TiO6-octahedron [22]. The edge-shared (TiO6) octahedra would form a negatively charged layered structure. The countercations (e.g., Na+) sit in between the adjacent layers, thus resulting in variable interlayer distances depending on the size and the hydration degree of the cation, which would explain the flexibility of the long nanofibers [23].
The thermal stability of the nanofiber FSM was investigated by heating the membranes at temperatures above 500° C. in air for three hours.
As shown in
a shows a high resolution FESEM image of a nanofiber FSM having the intertwined nanofibers.
Briefly, the present invention, among other unique things, discloses methods of synthesizing TiO2-containing, macro-sized nanofibers and fabricating thermal-stable, robust, and multifunctional FSM-based 2D paper and 3D devices (e.g., tube, bowl, cup and so on) in nearly any macroscopic size and shape. Making long 1D nanostructures and then organizing them properly is critical in casting robust 2D FSMs directly out of the 1D nanomaterials. The inorganic 1D nanostructure is white, thermal stable, chemically inert, biocompatible, and capable of forming flexible mm-long nanofibers with the typical diameter less than 100 nm. Such inorganic nanofibers can form conformal membranes on macroscopic templates or molds of nearly any size for casting macroscopic vessels and tools by design. The nanofibers have attracted wide attentions due to their unique potentials in a wide range of applications including chemical sensing, photocatalysis, photovoltaics, varistors, gas sensors, and solar cells [9]. The nanofiber FSM and cup vessels are easily scaled up, and ideal for mass productions due to the use of the inexpensive raw TiO2 material. Due to the known thermal stability and chemical inertness, such inorganic nanofiber FSM catalysts can be recyclable and reusable over a wide temperature range. The cast inorganic nanofiber FSMs, vessels, and tools may find uses in hydrogen storage [18] and generation [19], environmental cleaning [20], sensing [21], catalytically splitting water and cracking oil, making protection mask and armor, fabricating flame-retardant fabric, filtering bacteria, photoassisted rewriting, controlled drug releases, and regenerating tissues, and the likes.
An immediate application of the TiO2-containing, macro-sized nanofibers is to provide a writing-erasing-rewriting function for information storage under the help of the UV irradiation. TiO2 is commonly utilized as an inexpensive and nontoxic photocatalyst. After being excited by UV light, the TiO2 can catalyze dye degradation [25].
In this example, four characters, “UARK”, of water-based ink (1.0×10−2 mol/L crystal violet) were written on a FSM paper 610 made of the TiO2-containing, macro-sized nanofibers according to the present invention. The FSM paper 610 with the written information of “UARK” was exposed to the UV light in air. After 15 minutes of exposition to the UV light, all the four characters “UARK” were disappeared, as shown in
Yearly, about 9.5 million hectares are deforested globally, and 35% of commercial wood is used for paper production [26]. Therefore, use of such rewritable, erasable, and heat-resistant inorganic nanofiber or nanowire paper might help save the disappearing forests.
Another application of the TiO2-containing, macro-sized nanofibers is in photocatalysis. The catalytic activity of the TiO2-B phase has been demonstrated to be better than that of other TiO2 phases [27]. Due to its macroporous nature, such robust nanowire-based membrane catalysts should have unique potentials for photocatalytic decompositions of organic pollutants [15] such as nerve agent simulants (NAS) [15], for example, (C2H5O)2P(O)(H2CSC6H5) (Aldrich).
In this exemplary embodiment, about 10 mg of the FSM made of the TiO2-containing, macro-sized nanofibers according to the present invention was soaked in about 10 mL of 1 mol/L Mg(NO3)2 solution at RT for about 12 hours. The soaked FSM was dried at RT, and then heated at a temperature above 100° C. for about 3 hours in air. The heated FSM is then placed in a solution containing a number of organic pollutants. In the example, the organic pollutants comprise NAS. A UV lamp Entella (model B100 AP/R) was positioned about 5 mm above the solution with the FSM for VU irradiation the solution. The concentrations (Ct) of the NAS were measured on a UV-visible spectrometer, for example, HP 8453 (Hewlett-Packard, Co.).
After a 15 minute UV irradiation on the solution having the nanowire FSM at RT, the NAS concentration (Ct) was reduced by 67.8%, (1−Ct/C0), from the initially NAS concentration (C0) (about 50 mL, and 4.5×10−7 mol/L originally). The decomposition rate (1−Ct/C0) of the NAS concentration in the case is indicated by bar 712 of
The spectroscopic measurements of the NAS concentrations were performed on the HP 8453 UV-visible spectrometer. Without the catalyst of the FSM, the NAS concentration decrease after the same UV irradiation was lower than the detection limit. Another blank test, using this FSM without the UV irradiation, caused the NAS concentration, as indicated by bar 718 of
In the TEM/SEM/XRD studies, no MgO nanoparticles could be seen on the nanofiber catalyst. The EDX study, however, shows that about 0.85 wt % of the Mg element exists in this catalyst. Both results have implied that the Mg species would likely be in a form of highly dispersed cluster(s), which encourages one to do the HRTEM work to identify the shape/size and then the role of the Mg-containing particles in this photocatalysis.
Parallel tests using the P25 and anatase TiO2 powder (325 mesh, Alfa Aesar) of the same weight resulted in the reduction of the NAS concentration by 35.0% and 8.0%, as indicated by bars 714 and 716 of
As disclosed in EXAMPLE 3, TiO2 is superb in photocatalytically decomposing organic pollutants including the nerve agent simulants (NAS) [15]. This is different from the catalyses on activated carbons [16] that have the dark color. Additionally, the TiO2 photocatalytic activity can be greatly enhanced by the presence of Mg(II) [17]. In this exemplary study, the photocatalytic properties of the nanofiber FSM were studied at the RT in the aqueous solutions of the NAS that was the diethyl phenylthiomethylphosphonate (DPTMP, C11H17O3PS) (Alfa Aesar).
Prior to the catalysis, the nanofiber FSM was firstly pretreated through a soaking in the solution of about 1 mol/L Mg(NO3)2 for about 12 hours at RT, then dried at RT and heated in air at a temperature above 100° C. for about 3 hours. The NAS solution was prepared by dissolving about 45 μmol of the DPTMP into about 100 mL water containing about 10 mg of the pretreated FSM. After a 15-min UV radiation from a lamp (Mineralight UVGL-58, λ=254 nm) that was positioned about 5 mm above the solution, the NAS concentration (Ct) in the solution was reduced by 98% (1−Ct/C0), as indicated by bar 722 of
This 98% catalytic conversion may be further improved by the optimizations of the reaction temperature, the time and the intensity of the UV radiation, and the structure and morphology as well as loading of the Mg-species. This 98% conversion is among the highest in the fast photocatalytic decomposition of the NAS in water at RT, indicating an unusual potential of the nanofiber FSM catalysts for making, for instance, new masks in civil defense applications. In comparison with the common practice in heterogeneous catalyses, uses of the nanofiber FSM catalysts can minimize the downstream recovery of the powdery catalysts and at the same time eliminate the use of the catalytic supports and binders. In addition, a more efficient use of the surface of each catalytic nanofiber, a negligible weight loss of the catalyst, and reuses of the catalyst through the high-temperature calcination could all be expected. A further detailed development on controlling the structure, size, and dispersion of the Mg-species on the nanofibers, together with the optimization of the FSM porosity could lead to the development of new inorganic nanofiber membrane catalysts for a variety of important catalysis-related applications.
The nanofiber FSMs and 3D devices according to the present invention can find applications in the filtration of particles. In this example, aqueous suspensions of polystyrene latex microspheres including Alfa Aesar microspheres with 0.75, 1, 2, and 2.5 μm in diameter were provided for investigating the permeability of the nanowire membrane [5]. Each aqueous suspension had a concentration of 0.0025% (wt). The microfiltration using a TiO2-containing nanofiber cup (filter) was conducted within about 5 minutes. It had been shown that no 2-μm microspheres were detected in about 1 mL of the filtered sample (aqueous suspension). Those of 0.75 μm and 1 μm microspheres, however, penetrated the wall of the filter in the parallel tests, suggesting a size-exclusion function of the 3D devices in filtrations of micrometer-sized particles.
Furthermore, the TiO2-containing nanofiber membrane can be used for filtrations of bacteria spores in civil defense, environmental cleaning, neuron growth media to repair injured spinal cord, treatments of Alzheimer's and Parkinson's diseases, inject-able bone repair, portable MEMS (Micro Electro Mechanical Sensor) biosensors and membrane chem-sensors.
The unique integration of the permeation and the photocatalysis of a nanofiber membrane cup 910 according to the present invention were demonstrated in this example, as shown in
Macroporous 3D devices, walled by the scaffolding nanowires/nanofibers, are useful in controlling drug release [29]. In the exemplary example, a section of the TiO2-containing nanofiber FSM (74.0 mg) was pre-soaked in about 100 mL solution of about 0.001 mol/L crystal violet for about 12 hours at RT, and then placed in about 10 mL of fresh water at RT. The controlled drug release was monitored by the HP 8453 UV-visible spectrometer. After every 24 hours of the drug release, the TiO2-containing nanofiber FSM was transferred into another 10 mL of fresh water.
Furthermore, the 3D scaffolds of the TiO2-containing nanofiber/nanowires, after being coated with growth hormone, is very useful in directing the growth of stem cells for potential applications in regenerative medicine [30, 31].
Ceramic titanate nanowire (NW) is environmentally benign, biocompatible, chemically inert, surface functionalization easy, inexpensive, and thermally stable. In this example, a new composite is formed and usable for making tires. The new composite comprises TiO2-containing, macro-sized nanowires/nanofiber that are blended with rubber polymer. In comparison with the carbon black-based rubber composite, the NW-rubber composite can be grey in color, and may provide the new tire with better interfacing with polymer backbone, higher mechanical strength and lighter in weight or better gas mileage, and easier in handling on wet roadway.
In the tire-making, the NW could be short or long, depending on the application need. The short NW is made at a temperature around 150-160° C. within a few hours. The long NW is made at a temperature above 160° C. and with a reaction time longer than 1 day.
The TiO2-containing, macro-sized nanofibers according to the present invention is also usable in making a multi-functional vest/coat for nanomedicine, battlefield, sports, space, firefighter, and the likes. A multi-functional vest/coat 1300 is made at least partially with the TiO2-containing, macro-sized nanofiber fabric. For example, as shown in
The foregoing description of the exemplary embodiments of the invention has been presented only for the purposes of illustration and description and is not intended to be exhaustive or to limit the invention to the precise forms disclosed. Many modifications and variations are possible in light of the above teaching.
The embodiments were chosen and described in order to explain the principles of the invention and their practical application so as to enable others skilled in the art to utilize the invention and various embodiments and with various modifications as are suited to the particular use contemplated. Alternative embodiments will become apparent to those skilled in the art to which the present invention pertains without departing from its spirit and scope. Accordingly, the scope of the present invention is defined by the appended claims rather than the foregoing description and the exemplary embodiments described therein.
[6]. Gu G., Schmid M., Chiu P.-W., Minett A, Fraysse J., Kim G.-T., Roth S., Kozlov M., Muñoz E., Baughman R. H. Nature Mat. 2003, 2, 316.
This application claims the benefit, pursuant to 35 U.S.C. §119(e), of U.S. provisional patent application Ser. Nos. 60/758,492, filed Jan. 12, 2006, entitled “TiO2 NANOFIBER MEMBRANES, METHODS OF MAKING SAME, AND APPLICATIONS OF SAME,” by Z. Ryan Tian and Wenjun Dong, and 60/785,649, filed Mar. 23, 2006, entitled “TiO2 NANOFIBERS, MEMBRANES, AND FILMS, METHODS OF MAKING SAME, AND APPLICATIONS OF SAME,” by Z. Ryan Tian and Wenjun Dong, which are incorporated herein by reference in their entireties. Some references, which may include patents, patent applications and various publications, are cited and discussed in the description of this invention. The citation and/or discussion of such references is provided merely to clarify the description of the present invention and is not an admission that any such reference is “prior art” to the invention described herein. All references cited and discussed in this specification are incorporated herein by reference in their entireties and to the same extent as if each reference was individually incorporated by reference. In terms of notation, hereinafter, “[n]” represents the nth reference cited in the reference list. For example, [10] represents the 10th reference cited in the reference list, namely, Tian, Z. R., Voigt, J, A., Liu, J., Mckenzie, B., Xu, H., J. Am. Chem. Soc., 2003, 125, 12384.
| Number | Date | Country | |
|---|---|---|---|
| 60758492 | Jan 2006 | US | |
| 60785649 | Mar 2006 | US |
