CN101668584A

CN101668584A - TiO 2Nanostructured, film and thin layer and preparation method thereof

Info

Publication number: CN101668584A
Application number: CN200780003042A
Authority: CN
Inventors: Z·瑞恩·田
Original assignee: University of Arkansas Technology Development Foundation
Current assignee: University of Arkansas Technology Development Foundation
Priority date: 2006-01-12
Filing date: 2007-01-12
Publication date: 2010-03-10
Also published as: CN101484977A; CN101484977B

Abstract

One aspect of the present invention relates to a kind of method of synthetic macro nanometer structure, and in one embodiment, this method comprises a large amount of TiO ₂Powder mixes with the alkali metal or the alkaline solution of certain volume, forming mixture, and being higher than heating described mixture a period of time under 160 ℃ the temperature, contains TiO with formation ₂The macro nanometer structure, wherein, the described TiO that contains ₂The macro nanometer structure in the environment that does not contain the matrix that comprises Ti, generate.These contain TiO ₂The macro nanometer structure can be used for forming free standing structure film and/or three-dimensional (3D) structure.

Description

TiO 2Nanostructured, film and thin layer and preparation method thereof

Technical field

The present invention relates to nanostructured, more particularly, relate to a kind of TiO of containing ₂Large scale (macro-sized) nanostructured, with and its production and application.

Background technology

Because in nano-scale (nanoscale), one dimension (1D) structural constraint (structuralconfinement) is relevant with its a large amount of unique physics and chemical property, thereby one-dimensional nano structure has been carried out a large amount of research [1].Because its high heat endurance and chemical inertness can be assembled to inorganic nano-fiber (comprising nano wire and nanotube) important application [2] of free standing structure film (FSM) to be used for high temperature and adverse circumstances.In order to make the FSM stalwartness, need especially long inorganic nano-fiber, and combination is tight between these inorganic nano-fibers.Then, the inorganic FSM that makes like this has unique porosity, permeability, heat endurance, chemical inertness, robustness and catalytic activity, and all these character that it has all are different from the nanofiber FSM of the body phase of going into property of single casting nanofiber and identical/similar chemical formula greatly.

The preparation that disclosed nanostructured FSM in 1996: under the assistance of surfactant molecule, at mica-water termination growth order mesoporous (oriented mesoporous) silicon fiml [3].After a while, disclose a kind of different solution, it can be used for preparing the mesoporous FSM[4 of anatase nano microcrystalline].In the literature more frequently discuss the functional FSM that adopt 1D inorganic nano structure thereafter.Recently, many micropores manganese oxide nanofiber is cast into paper shape FSM, and this nanofiber is adopted the accurately layering adjustment [5] of control.The thin slice that makes the V2O5 nanofiber twine under low applied voltage, have higher Young's modulus, bigger stress tension force (actuator generated stress) and brake stroke [6] significantly.In addition, CNT (CNT) is used to prepare functional FSM.At first report is the Bark paper (buckypaper) that comprises coaxial CNT, and this Bark paper has improved mechanical property, heat conductivity and structural stability [7].Recently, prepared firm, transparent and be the thin slice that multi-functional CNT quadrature constitutes, this thin slice has than the better gravimetric analysis intensity of high strength steel [8].

Yet, under 550 ℃ high temperature, in air during long-time heating, above-mentioned inorganic nano-fiber FSM and unstable [5].On the other hand, CNT oxidation fast easily in strong like this calcining.Therefore, based on TiO ₂Heat endurance and the chemically inert progress of nanofiber FSM be subjected to extensive concern, to advance high-temperature catalytic of the prior art, sensing, absorption and to separate.In addition, directly from a large amount of preparations of monodimension nanometer material preparation healthy and strong, heat-staple and multi-functional macroscopic three-dimensional structure remains a challenge.

Therefore, up to now, above-mentioned defective and deficiency still exist in the art, and need to solve.

Summary of the invention

In one aspect, the present invention relates to a kind of method of synthetic macro nanometer structure.In one embodiment, this method comprises a large amount of TiO ₂Powder mixes with the alkali metal or the alkaline solution of certain volume, forming mixture, and being higher than heating described mixture a period of time under 160 ℃ the temperature, contains TiO with formation ₂The macro nanometer structure.At this, the described TiO that contains ₂The macro nanometer structure in the environment that does not contain the matrix that comprises Ti, generate.This method further comprises employing distilled water or the described TiO of containing of diluted acid flushing ₂The step of macro nanometer structure.In one embodiment, this contains TiO ₂The macro nanometer structure generally comprise to have and be approximately the nanofiber of 20nm to the representative diameter of 150nm.This nanofiber generally is TiO ₂-B phase or metatitanic acid salt face.

In one embodiment, described mixture is placed in the container and with described seal of vessel.This heating steps comprises the described airtight container that comprises mixture is put in the baking oven and heats that at this, the temperature that heats this mixture is positioned at 180-300 ℃ scope, and is positioned at about 3-960 hour scope heat time heating time.

In one embodiment, the mixture that this alkali metal soln comprises following a kind of material or makes up arbitrarily in them: NaOH (NaOH), potassium hydroxide (KOH), lithium hydroxide (LiOH), rubidium hydroxide (RbOH), cesium hydroxide (CsOH), and described alkaline solution comprises following a kind of material or the mixture of any combination in them: magnesium hydroxide [Mg (OH) ₂], calcium hydroxide [Ca (OH) ₂], strontium hydroxide [Sr (OH) ₂] and barium hydroxide [Ba (OH) ₂].

On the other hand, the present invention relates to the macro nanometer structure synthetic according to said method.

Aspect another, the present invention relates to a kind of synthesis of nano structure.In one embodiment, this synthesis of nano structure comprises the chemical reaction product according to following reaction equation:

2NaOH+3TiO ₂＝Na ₂Ti ₃O ₇+H ₂O，

Wherein, this chemical reaction reacts a period of time being higher than under 160 ℃ the temperature, so that product forms, and at this, chemical reaction carries out in the environment that does not contain the matrix that comprises Ti.In one embodiment, this chemical reaction carries out in closed container.The effecting reaction temperature range is between about 180-300 ℃.The effective reaction time scope is between about 3-960 hour.

In one embodiment, provide the described first reactant TiO with form of powder ₂, and described second reactant comprises inorganic group, and provide with the form of solution.In one embodiment, second reactant comprises NaOH, and product comprises that chemical formula is Na ₂Ti ₃O ₇Compound.In one embodiment, described chemical formula is Na ₂Ti ₃O ₇Compound be form with nanofiber, its representative diameter scope is that 20nm is to 150nm.

On the other hand, the present invention relates to a kind of synthesis of nano structure.In one embodiment, this synthesis of nano structure comprises the chemical reaction product according to following reaction equation, and described reaction is carried out according to following order:

(a)2NaOH+3TiO ₂→Na ₂Ti ₃O ₇；

(b) Na ₂Ti ₃O ₇+ 2H ⁺→ 2Na ⁺+ H ₂Ti ₃O ₇With

(c)H ₂Ti ₃O ₇→H ₂O+TiO ₂-B，

Wherein, chemical reaction (a) is being higher than reaction a period of time under 160 ℃ the temperature so that product forms at least, and this at least chemical reaction (a) in the environment that does not contain the matrix that comprises Ti, carry out.In one embodiment, the effecting reaction temperature range is between about 180-300 ℃.The effective reaction time scope is between about 3-960 hour.

In one embodiment, provide the described first reactant TiO with form of powder ₂, and described second reactant comprises inorganic group, and provide with the form of solution.In one embodiment, second reactant comprises NaOH.In another embodiment, described second reactant comprises OH ^-Product comprises that chemical formula is Na ₂Ti ₃O ₇Compound, wherein said chemical formula is Na ₂Ti ₃O ₇Compound be form with nanofiber, its representative diameter scope is that 20nm is to 150nm.

In one embodiment, chemical reaction (a) carries out in airtight container at least.A period of time generally takes place in chemical reaction (b) between 180-300 ℃, so that chemical formula is H ₂Ti ₃O ₇Compound generate with the form of macro nanometer fiber.Chemical reaction (c) carries out in calcination process, and at this, described calcination process comprises a step that heats in the air in 300-600 ℃ temperature range in smelting furnace, and a step of burning in air.

Chemical reaction (c) makes that chemical formula is TiO ₂The compound of-B becomes the form of macro nanometer fiber, and wherein, described chemical formula is TiO ₂The compound of-B is the form of macro nanometer fiber, and its representative diameter scope is that 20nm is to 150nm.

Aspect another, the present invention relates to a kind of method that is used for synthetic macro nanometer structure.In one embodiment, this method is included in certain heating-up temperature and heats a kind of reactant and a kind of solution a period of time to generate the macro nanometer structure based on described reactant, wherein, described macro nanometer structure based on reactant generates in such environment, in described environment, there is not the crystal seed of described reactant.

In one embodiment, described heating-up temperature is higher than 160 ℃.Heat time heating time, scope was between about 3-960 hour.Described macro nanometer structure comprises nanofiber, nanotube, nano wire or their any combination.

In one embodiment, described solution and reactant are placed in the container, and seal described container.This reactant can comprise TiO ₂Powder, and described solution comprises alkali metal or alkaline solution.

In one aspect, the present invention relates to the macro nanometer structure synthetic according to said method.

On the other hand, the present invention relates to be used to prepare the method for free standing structure film.In one embodiment, described method comprises the following steps: to provide a plurality of TiO of containing ₂The macro nanometer structure; With described a plurality of TiO that contain ₂The macro nanometer structure be cast on the template film (template film) to form the free standing structure film on this template film; Free standing structure film a period of time on the described template film of certain temperature drying.In one embodiment, described free standing structure film is made of multilayer film, and its thickness range is the 10-1000 micron.Described free standing structure film is a porous, permeable and the class zeolite, chemically inert, biological compatible and/or heat-staple.

Described method further comprises the step that removes dried free standing structure film from described template film, at this, describedly removes the step that step is included in the dried free standing structure film on the described template film of calcining in 300-600 ℃ the temperature range.In one embodiment, described template film comprises ashless filter paper and polyethylene film.

In one embodiment, the described step that provides comprises the following steps: a large amount of TiO ₂Powder mixes with the alkali metal or the alkaline solution of certain volume, to form mixture; And, contain TiO with formation being higher than heating described mixture a period of time under 160 ℃ the temperature ₂The macro nanometer structure, wherein, the described TiO that contains ₂The macro nanometer structure in the environment that does not contain the matrix that comprises Ti, generate.This contains TiO ₂The macro nanometer structure generally comprise to have and be approximately the TiO of 20nm to the representative diameter of 150nm ₂-B nanofiber.

In one embodiment, the described step that is cast into comprises the following steps: to contain TiO with more than first ₂The macro nanometer structure be cast on the template film; The individual TiO that contains of on the template film described more than first will be cast into ₂Macro nanometer structure dry first period in RT (room temperature); Then the macro nanometer structure with at least one additional amount is cast into the individual TiO that contains of dried described more than first on the template film ₂The macro nanometer structure on; And will be cast into the individual TiO that contains of dried described more than first on the described template film ₂The macro nanometer structure of additional amount dry second period in RT of macro nanometer structure, described second period and described a period of time are identical or different.

In one embodiment, described baking temperature is generally in 0-180 ℃ scope.Drying time is generally in about 0.5-30 hour scope.

Aspect another, the present invention relates to free standing structure film according to method for preparing.Described template film generally is a two-dimensional structure, and the described free standing structure film of as above preparation generally is a two-dimensional structure.

Aspect further, the present invention relates to a kind of free standing structure film.In one embodiment, this free standing structure film has a plurality of TiO of containing ₂The layer of macro nanometer structure.Can synthesize this like this and contain TiO ₂The macro nanometer structure: with a large amount of TiO ₂Powder mixes with the alkali metal or the alkaline solution of certain volume, to form mixture; And, contain TiO with formation being higher than heating described mixture a period of time under 160 ℃ the temperature ₂The macro nanometer structure, at this, the described TiO that contains ₂The macro nanometer structure in the environment that does not contain the matrix that comprises Ti, generate.

In one embodiment, this contains TiO ₂The macro nanometer structure generally comprise to have and be approximately the contain TiO of 20nm to the representative diameter of 150nm ₂Macro nanometer fiber and TiO ₂-B structure, the wherein said TiO that contains ₂The macro nanometer fiber be thereby that part is twined and to be formed a plurality of spaces there at least.

The thickness range of described free standing structure film is micron from tens of to hundreds of.Described free standing structure film is a porous, permeable and the class zeolite, chemically inert, biological compatible and/or heat-staple.

Aspect another, the present invention relates to a kind of method that directly prepares the 3D structure from nanostructured.In one embodiment, said method comprising the steps of: a plurality of TiO of containing are provided ₂The macro nanometer structure; With described a plurality of TiO that contain ₂The macro nanometer structure be cast on the template, to form the 3D structure on template, at this, described template has the structure corresponding to the 3D structure that will form, and the 3D structure a period of time on the described template of certain temperature drying.The described TiO that contains ₂The macro nanometer structure comprise nanofiber, nanotube, nano wire or their any combination.

Described method further comprises the step that removes dried 3D structure from described template, at this, describedly removes the step that step is included in the dried 3D structure on the described template of calcining in 300-600 ℃ the temperature range.In one embodiment, described template to small part is processed by ashless filter paper and polyethylene film.

In one embodiment, the described step that is cast into comprises the following steps: to contain TiO with more than first ₂The macro nanometer structure be cast on the template film; The individual TiO that contains of on the template film described more than first will be cast into ₂Macro nanometer structure dry first period in RT; Then the macro nanometer structure of at least one additional amount is cast into more than the first individual TiO that contain of the described drying of template film ₂The macro nanometer structure on; And will be cast into dried first described a plurality of TiO of containing on the described template film ₂The macro nanometer structure of additional amount dry second period in RT of macro nanometer structure, described second period is identical with described a period of time or different fully.

In one embodiment, the thickness range that has to small part 3D structure is tens of to hundreds of microns.To small part 3D structure be porous, permeable and class zeolite.In one embodiment, described 3D structure is chemically inert, biological compatible and/or heat-staple.

In one aspect, the present invention relates to 3D structure according to method for preparing.To the described 3D structure of small part be multilayer.

On the other hand, the present invention relates to a kind of 3D structure.In one embodiment, described 3D structure comprises a plurality of TiO of containing ₂The layer of macro nanometer structure.Can synthesize this like this and contain TiO ₂The macro nanometer structure: with a large amount of TiO ₂Powder mixes with the alkali metal or the alkaline solution of certain volume, to form mixture; And, contain TiO with formation being higher than heating described mixture a period of time under 160 ℃ the temperature ₂The macro nanometer structure, at this, the described TiO that contains ₂The macro nanometer structure in the environment that does not contain the matrix that comprises Ti, generate.This contains TiO ₂The macro nanometer structure generally comprise to have and be approximately the contain TiO of 20nm to the representative diameter of 150nm ₂Macro nanometer fiber and TiO ₂-B structure wherein, contains TiO described in each layer ₂The macro nanometer fiber be thereby that part twine to form the 3D structure at least.

In one embodiment, to the described 3D structural thickness of small part scope micron from tens of to hundreds of.To the described 3D structure of small part be porous, permeable and class zeolite.Described 3D structure is chemically inert and/or heat-staple.

By following description, specific embodiment, more in conjunction with the accompanying drawings, can more in depth understand various aspects of the present invention.Can carry out various changes or equivalence to these features and embodiment replaces and does not exceed protection scope of the present invention.

Description of drawings

The accompanying drawing illustration one or more embodiment of the present invention, and principle of the present invention has been described with associated description.In the case of any possible, same Reference numeral is used to represent identical parts or intimate parts in the accompanying drawing in each width of cloth accompanying drawing, wherein:

Fig. 1 schematically shows the preparation process of nanofiber cup according to an embodiment of the invention;

Fig. 2 shows according to the enforcement of the present invention flexible FSM based on nanofiber and the picture of the cup of preparation: (a) plane FSM and folding FSM (illustration) and (b) go up the FSM cup of preparation in filter paper template and plastic formwork (illustration);

Fig. 3 shows the picture of the SEM of nanofiber FSM (SEM), FESEM (field emission scanning electron microscope) and TEM (transmission electron microscope) according to an embodiment of the invention: (a) SEM of described nanofiber FSM figure, it shows described nanofiber FSM sandwich construction, (b) the high-resolution FESEM of described nanofiber FSM figure, it shows the winding nanofiber of described nanofiber FSM and (c) the TEM figure of the nanofiber of described nanofiber FSM;

Fig. 4 shows SEM, FESEM and the TEM figure of the nanofiber FSM after the calcining according to an embodiment of the invention: (a) SEM of the cross section of described nanofiber FSM figure, it shows the sandwich construction after about 700 ℃ of calcinings, (b) the high-resolution FESEM of described nanofiber FSM figure, it shows the TiO after described winding nanofiber after 700 ℃ of calcinings and the calcining ₂The TEM of the nanofiber figure (illustration) and (c) the X-ray diffraction patterns of the titanate nanofiber paper before and after 700 ℃ of calcinings 3 hours;

Fig. 5 shows high-resolution FESEM figure (a) and the nanofiber cup of described nanofiber FSM preparation and the picture of pipe with the nanofiber FSM that twines nanofiber according to an embodiment of the invention;

Fig. 6 shows and writes-wipe light supplementary information (photoassisted information) on nanofiber FSM paper according to an embodiment of the invention and the standard printing paper: (a) use information that the crystal violet ink writes in the information of writing for the 4th time on the nanofiber FSM paper with in the first time on the printing paper and (b) adopt UV to shine information after wiping for the 4th time;

Fig. 7 show degraded nerve toxicant analog (NAS) according to two embodiment of the present invention (a) and (b) contain TiO ₂Under the effect of FSM, in RT in water photocatalytic degradation;

Fig. 8 shows the TiO that contains that (a) has winding ₂Nanofiber with the picture of the nanofiber FSM that forms porous network and (b) schematically shows bacterial spore filter according to an embodiment of the invention;

Fig. 9 schematically shows the TiO of containing according to an embodiment of the invention ₂The cup photocatalysis of nano fibrous membrane and infiltration comprehensive function;

Figure 10 shows the TiO of containing according to an embodiment of the invention ₂The medicine release concentration of nanofiber medicine release; With

Figure 11 schematically show to small part by the TiO of containing according to an embodiment of the invention ₂Underwear/the overcoat of macro nanometer scrim preparation.

The specific embodiment

By following example will present invention is described in more detail, those skilled in the art are conspicuous can to obtain embodiment after a plurality of changes or the conversion according to these examples.Now each embodiment of the present invention is done in more detail and introduce.With reference to Fig. 1-11, identical numeral refers to identical parts in all figure.Herein, except clearly indicating in context, " one " and " this " that use in specification and the claim comprise plural number.Same, except in context, clearly indicating, in this specification and claim, use " ... interior " comprise " ... interior " and " ... on ".In addition, title that adopts in the specification and subhead are for the ease of readers ' reading, do not influence protection scope of the present invention.In addition, specially some terms of usefulness are in this manual clearly defined below.

Definition

In the context of the present invention, use in the present invention in the specific context of these terms, the term that uses in this specification has its general implication in the art.

Below or in other positions of this specification, some is used to describe term of the present invention discusses, so that in description, and to providing additional guidance to the technical staff in the use of these method and apparatus apparatus and method of the present invention.For the ease of reading, some term has been carried out mark, such as adopting italic and/or quotation marks.The use of these marks does not influence the scope and the meaning of this term, and the scope of this term is identical with meaning, and in a part, no matter whether this term is labeled, and its implication is the same.Should be appreciated that same incident can have multiple saying.Therefore, can be with any one or a plurality of term of replacing that term and synonym be used for discussing in this place, no matter term is preparation or mistake discussed herein, it does not have any special implication.The synonym of some term also is provided.Other synon uses are not got rid of in one or more synon narrations.The embodiment of Shi Yonging (example that comprises any term discussed herein) in the present invention is only used for exemplaryly, is not limited to scope of the present invention and implication or any term that exemplifies out.Same, the embodiment that the present invention is not limited to provide in the specification.In addition, subhead can be used for helping the reader of specification to read over whole specification, yet the use of subhead does not influence scope of the present invention.

As using herein, " approximately " or " being similar to " refers generally in set-point or scope 20 percentage points, and in preferred 10 percentage points, the best is to be positioned in 5 percentage points.The quantity that herein provides is similar to, and means that term " approximately " or " being similar to " can be derived if clearly do not explain.

As use herein, term " photocatalysis " is meant and the accelerator that photochemical catalyst is light reaction occurring.When photochemical catalyst TiO2 caught ultraviolet light (UV) from sunlight or fluorescence, it was with water or airborne oxygen forms active oxygen.This process is similar to photosynthesis, and in photosynthesis, chlorophyll is caught from the oxygen in the sunlight to convert water and carbon dioxide to oxygen and glucose.The oxidisability of the active oxygen that forms is enough to oxidation and decomposes organic material, polluter or foul smell and killing bacteria.

Integral viewpoint of the present invention

In many nano material systems, prepare large scale, multi-functional, paper shape FSM and all be challenging work from long inorganic functional nano wire fully based on the visible equipment of 3D naked eyes of FSM.The invention discloses a kind of method of synthetic macro nanometer structure and use described macro nanometer structure directly to prepare FSM and based on the method for the 3D equipment of FSM, and disclose its in photocatalysis, write-wipe-written information, micro porous filtration (microfiltration), medicine discharge may using and similar application of controlling again.

To be described in conjunction with embodiments of the invention and accompanying drawing 1-11.According to purpose of the present invention,, in one aspect of the invention, relate to a kind of synthetic TiO that contains as concrete and general description at this ₂The method of macro nanometer structure, described nanostructured comprises nanofiber, nanotube, nano wire or their any combination.

According to the present invention, in one embodiment, can prepare TiO like this ₂The macro nanometer structure: with a large amount of TiO ₂Powder mixes with the alkali metal or the alkaline solution of certain volume, to form mixture, this mixture is placed in the container, and heats putting into baker after the described seal of vessel, then, contain TiO with formation being higher than heating described mixture a period of time under 160 ℃ the temperature ₂The macro nanometer structure.In one embodiment, described mixture heats in 180-300 ℃ temperature range, and heat time heating time, scope was in 3-960 hour.Then adopt the TiO that contains of distilled water or weak acid scrubbing formation ₂The macro nanometer structure.

The mixture that this alkali metal soln can comprise a kind of following material or make up arbitrarily in them: NaOH, KOH, LiOH, RbOH and CsOH.The mixture that this alkaline solution can comprise a kind of following material or make up arbitrarily in them: Mg (OH) ₂, Ca (OH) ₂, Sr (OH) ₂And Ba (OH) ₂

According to the present invention, the described TiO that contains ₂The macro nanometer structure in the environment that does not contain the matrix that comprises Ti, generate.Like this, this contains TiO ₂The macro nanometer structure generally comprise and have that to be approximately 20nm be hundreds of microns to several millimeters nanofibers (for example, shown in Fig. 3 and 4) to the representative diameter of 150nm and length range.This nanofiber generally is TiO ₂-B phase or metatitanic acid salt face.

By convention, can obtain to contain TiO like this ₂Nanostructured: in about 150 ℃ [10] or lower temperature, in the NaOH concentrated solution, handle TiO ₂Powder.At inoculation TiO ₂Form nanostructured on the matrix of powder.He Cheng nanostructured generally comprises nanotube like this, and the length of described nanotube generally is a few to tens of microns.

Yet, according to the TiO that contains of the present invention ₂The macro nanometer structure need a period of times contain TiO being higher than 160 ℃ of heating with generation ₂The macro nanometer structure, therefore, cause generating length and be hundreds of microns to several millimeters the TiO that contains ₂The macro nanometer structure, at this, the described TiO that contains ₂The macro nanometer structure do not contain comprise can with TiO ₂Generate in the environment of the matrix of inoculation.For example, in one embodiment, can synthesize the macro nanometer structure like this, at first will about 0.3g TiO ₂Powder (Degussa P25) adds in 40ml10M alkali metal or the alkaline solution, and these mixtures are put into capacity is 150ml teflon liner autoclaving container.Seal described container and put it in the baker heating 1-7 days, heating-up temperature be 160 ℃ for the growth of macro nanometer on length.Also can adopt other containers to implement the present invention.After reaction (growth), adopt the synthetic nanofiber of distilled water washing.Should be white and be pulpous state by synthetic nanofiber, and can be used to form FSM and/or 3D structure, this 3D structure comprises cup-shaped and tubular structure.

On the other hand, the present invention relates to according to said method synthetic contain TiO ₂The macro nanometer structure.

On the other hand, the present invention relates to a kind of synthesis of nano structure.This synthesis of nano structure comprises the chemical reaction product according to following reaction equation:

2NaOH+3TiO ₂＝Na ₂Ti ₃O ₇+H ₂O，

Wherein, this chemical reaction reacts a period of time being higher than under 160 ℃ the temperature, so that product forms, and chemical reaction carries out in the environment that does not contain the matrix that comprises Ti.In one embodiment, this chemical reaction carries out in closed container.The effecting reaction temperature range is between about 180-300 ℃.The effective reaction time scope is between about 3-960 hour.

Provide the described first reactant TiO with form of powder ₂, and described second reactant comprises inorganic group, and provide with the form of solution.In one embodiment, second reactant comprises NaOH, and product comprises that chemical formula is Na ₂Ti ₃O ₇Compound.Described chemical formula is Na ₂Ti ₃O ₇Compound be form with nanofiber, its representative diameter scope is that 20nm is to 150nm.

Synthetic nanofiber can be used to form 2D FSM and/or 3D structure, described this 3D structure comprises cup-shaped and tubular structure.

For example, can adopt the following step preparation two dimension (2D) FSM: at first provide a plurality of TiO of containing ₂The macro nanometer structure.Then with described a plurality of TiO that contain ₂The macro nanometer structure be cast on the template film on the template film, to form free standing structure film.Then, in the certain described free standing structure film of temperature drying a period of time.Described baking temperature is generally in 0-180 ℃ scope.Drying time, section was generally in about 0.5-30 hour scope.Can dried free standing structure film be removed from described template film by the free standing structure film on the described template film of calcining in 300-600 ℃ temperature range at last, described template film is to be made or made by polyethylene film by ashless filter paper.This template film generally is 2D.

The described step that is cast into comprises more than the first individual TiO that contain ₂The macro nanometer structure be cast on the template film; The individual TiO that contains of on the template film described more than first will be cast into ₂Macro nanometer structure dry first period in RT; Then the macro nanometer structure with at least one additional amount is cast into the individual TiO that contains of dried more than first on the template film ₂The macro nanometer structure on; And will be cast into the individual TiO that contains of dried described more than first on the described template film ₂The macro nanometer structure of additional amount dry second period in RT of macro nanometer structure, described second period and described a period of time are identical or different.

Therefore, described 2D FSM has sandwich construction, and the thickness range that has is tens of to hundreds of microns.The thickness of 2D FSM is by the TiO that contains that is cast on the template film ₂The amount of macro nanometer structure determine.In every layer, contain TiO ₂Nanofiber to small part is twined, and therefore forms the space at this.As described below, this 2D FSM porous, permeable and the class zeolite, chemically inert, bioactive and/or heat-staple.

Above-mentioned disclosed process can be used for directly preparing the 3D structure from nanostructured.In this case, can use the template of 3D structure to replace the 2D film with corresponding 3D structure.Therefore, this 3D structure has the wall portion that multilayer forms.Contain TiO in each layer ₂Nanofiber be that part is twined at least, therefore form the space at this.The thickness range of the wall of this 3D structure is micron from tens of to hundreds of.To the described 3D structure of small part be porous, permeable and class zeolite.Described 3D structure is chemically inert, biological compatible and/or heat-staple.

With reference to Fig. 1, schematically show the process 100 of the nanofiber cup 150 that forms according to embodiments of the invention.At first, provide the 3D structure that as seen naked eyes have expectation and the template or the model 110 of size, described template or model 110 are by ashless filter paper, polyethylene film or other materials manufacturing.Then will be cast on described template or the model 110 according to the synthetic macro nanometer fiber of disclosed method in the specification.In about 0-180 ℃ temperature range, in baker, heat the described nanofiber cup that is cast into 150 about 0.5-30 hours of being cast on described macroscopic template or the model 110.Thereafter, by manually removing described plastic formwork or, to remove template or model 110 simply, so that form the nanofiber cup 150 of inorganic nano-fiber preparation by the filter paper template of burning in about 500 ℃ of calcinings.The wall of described nanofiber cup 150 (film) thickness range is from 10 to hundreds of microns, and its thickness depends on the amount of the nanofiber of use.

On the one hand, the present invention relates to a kind of nanostructured.In one embodiment, this synthesis of nano structure comprises the chemical reaction product according to following reaction equation, and described reaction is carried out according to following order:

(a)2NaOH+3TiO ₂→Na ₂Ti ₃O ₇；

(b) Na ₂Ti ₃O ₇+ 2H ⁺→ 2Na ⁺+ H ₂Ti ₃O ₇With

(c)H ₂Ti ₃O ₇→H ₂O+TiO ₂-B，

In one embodiment, chemical reaction (a) carries out in airtight container at least.Chemical reaction (b) is H generally 180-300 ℃ can take place a period of time to allow chemical formula ₂Ti ₃O ₇Compound generate with the form of macro nanometer fiber.Chemical reaction (c) carries out in calcination process, and at this, described calcination process comprises a step that heats in the air and a step of burning in air in 300-600 ℃ temperature range in smelting furnace.

Chemical reaction (c) makes that chemical formula is TiO ₂The compound of-B becomes the form of macro nanometer fiber, and wherein, the chemical formula of the form of described macro nanometer fiber is TiO ₂The representative diameter scope of the compound of-B is that 20nm is to 150nm.

In addition, the present invention can find the application of broad range in the art, as:

(1) film catalysis (adhesive-free/carrier (supports)/dirty separation (down-streamseparation)),

(2) catalytic carrier (film porous carrier catalysed particulate),

(3) catalytic decomposition pollutant, for instance, the effect of decomposing the nerve toxin under ultraviolet ray in the water is commercial TiO ₂About 12 times of powder,

(4) drug delivery (with DNA, protein and organic drug be stored in the space or mesoporous in be used for slowly or control discharges),

(5) tissue reconstruction (histocyte can be grown in the compatible space at biology),

(6) solar cell and water photon cracking (water photo-splitting),

(7) oil-breaking,

(8) be fuel cell preparation and storage hydrogen,

(9) information write-wipe-write again,

(10) make and to be used for nanometer medicine, battlefield and belligerent multi-functional underwear/overcoat etc., and

(11) make doughnut.

Below these and other aspects of the present invention are described further.

Realization of the present invention and embodiment

Show typical method and its correlated results according to an embodiment of the invention below, the scope that these embodiment are not intended to limit the invention.It should be noted that title or the subhead used in an embodiment all are for convenience of the reader, is not to limit scope of invention by any way.In addition, mention and disclose some theories since then, yet no matter these theoretical correctness are not to limit the scope of the invention by any way, can implement the present invention according to description of the invention fully like this and need not to consider any specific theory or arrangement of the exercise.

Embodiment 1

The synthetic TiO that contains ₂Macro nanometer fiber/nano wire and preparation FSM and 3D equipment: according to the present invention, disclose a kind of be higher than 160 ℃ effective temperature hydrothermal solution synthetic (hydrothermal synthesis) one period effective time contain TiO ₂The synthetic method of macro nanometer fiber/nano wire.

In this exemplary embodiments, will about 0.3g TiO ₂Powder (Degussa P25) adds in 40ml 10M alkali metal or the alkaline solution, and these mixtures are put into capacity is 150ml teflon liner autoclaving container.Seal described container and put it in the baker and heated 7 days.Collect the TiO that contains of white pulpous state ₂The macro nanometer fiber product, and adopt distilled water or weak acid scrubbing.The TiO that contains with the white pulpous state after the washing ₂The product of macro nanometer fiber be cast on the macroscopic template (adopting ashless filter paper (watt is graceful) or polyethylene film to make), then dry in RT.Described being cast into-dry run is repeated in RT several times, then in baker, heated (heating-up temperature is 0-180 ℃) about 0.5-30 hour.Thereby, adopt the described TiO that contains ₂The macro nanometer fiber on the naked eyes template, form 2D FSM and 3D cup.Then described macroscopic template is removed from described 2D FSM and 3D cup.In this embodiment, macroscopic template comprises plastic plate or cup.

With reference to Fig. 2 a and 2b, show figure and nano fibrous membrane cup 250 and 260 of nanofiber FSM 210 and 220 respectively.Fig. 2 a shows plane FSM 210 and folding FSM 220.The size of film is from several centimetres to tens of centimetres, and this depends on the amount of the nanofiber of use.In actual applications, it should be noted, slowly the FSM of deposition damages in avoiding repeatedly bending easily and folding, this has shown generally the robustness of the paper shape FSM that is made by long and flexible fiber, and points out to adopt the long time that nanofiber deposition (being cast into) will significantly be increased the robustness of FSM on template.Relation between the elasticity of sedimentation time and film (or robustness) show the FSM forming process be accompanied by nanofiber from body assembling (selfassembly).Sedimentation time can be by the ratio of water in the nanofiber or by the temperature of the described nanofiber of drying, or they both control jointly.Illustration proof plane FSM 210 among Fig. 2 a is folded to form folding FSM 220 as a piece of paper easily, and this has reacted the flexible characteristic of the FSM that is formed by length (large scale) nanofiber.The 1D nanofiber has been shown among Figure 14 to be assembled from body.For relatively, also show the picture of a coin-dividing 230 among Fig. 2 a.

The system research of conversion being made parameter shows, can control the flexibility of FSM paper like this: optimize the ratio of nano wire and water in (a) paper pulp and (b) time of dry described nano wire paper pulp.Shown in Fig. 2 b, the preparation of Jian Zhuan FSM can make like this, under the help of 3D template or mould, can directly long nano wire be cast in the macroscopic 3D equipment (as pipe, bowl and cup).This nano wire film device, each heavily about 0.2-0.3g also has wall thickness near 500pm, and is easy to hand-held and adopts scissors to prune, and this is that produce in RT for the first time can be for the 3D pottery that contains pure inorganic nano-fiber of scissor cut.

Shown in Fig. 2 b, can make the visible film nanofiber of

naked eyes cup

250 and 260 by on the template of ashless filter paper and polyethylene film, being cast into nanofiber respectively.Can separate this plastic formwork with hand.Yet the filter paper template need be burned by open flame at about 500 ℃ temperature lower calcination or in air and be removed.The visible film nanofiber of these

naked eyes cup

250 and 260 is a white, heavily about 0.3g.Such inorganic nano-fiber container is different from that those traditional ceramics engineering process build, and is being close to or higher than those containers that baking is come out under 1000 ℃ the temperature.In order to compare, the picture of a coin-dividing 240 has been shown among Fig. 2 b.

The form and the spatial organization of nanofiber depended in the successful casting of FSM or 3D equipment.This long nanofiber can be assembled into healthy and strong FAM and 3D film device from body, and nano particle or short nanofiber then can not.Further, can determine the robustness of 3D film device to the control of the assembling of nanofiber.

Adopt TEM (transmission electron microscope), SEM (SEM), FESEM (field emission scanning electron microscope), energy dispersion X-ray detector (EDX) and X-ray diffraction (XRD) equipment to characterize the free standing structure film and the 3D equipment of the configuration of surface of the macro nanometer structure that contains TiO2 according to an embodiment of the invention and transversary, this nanofiber respectively.Described SEM and EDX operate on the ESEMXL30 microscope of Philip and carry out.Adopt Philip X ' Pert X-ray diffraction meter to gather the XRD data.TEM research is carried out on JEOLX-100 microscope and JEOL 2010 FEG STEW/TEM.

Fig. 3 a-3c shows SEM, FESEM and the TEM figure of the wall portion of described according to an embodiment of the invention nanofiber cup respectively.Shown in Fig. 3 a, the wall portion of nanofiber cup is that a plurality of layers by the nanofiber of assembling from body constitute.The number of plies is identical with the number of times that nanofiber adds on the template.The sandwich construction of this glass film shows that the air dry run is accompanied by the spontaneity of nanofiber from the body assembling process.Nanofiber shown in Fig. 3 a is fewer than those assembling number of times of the report in the document [5,8].But, can be contemplated that and can at high temperature carry out the longer time or adopt specific technology from the body assembling by permission, improve the assembling of nanofibers as nanometer carrying (nano-logging) [11], magnetic field calibration [12] etc.

The high-resolution FESEM photo of the wall of cup portion shown in Fig. 3 b has disclosed the precise and tiny details of the nanofiber that twines in the cup film, and the 3D space that forms there.This nanofiber has the diameter range of about 50nm to about 100nm, and its length is mostly near 1mm or longer.Yet some nanofiber has tens of length that arrive hundreds of microns, and this may be owing to common lasting crystallization and/or inhomogeneous growth in the long-time hydrothermal solution heating process.Nanofiber in the wall of cup portion twines, and therefore forms 3D porous FSM, and the THICKNESS CONTROL of this FSM is at about 0.1mm.This thickness changes along with the change of the nanofiber amount of using.Size is that 0.5 to 10 micron 3D space is optimal, and it can make nanofiber extend in heating process or move towards periphery with the response mechanical pressure, improve heat endurance and the mechanical strength of FSM like this.In fact, the 3D large aperture can be used for a large amount of fast the transmission and the atmosphere storage in bigger temperature range in the catalytic action, and therefore, it is different from those FSM that had reported elsewhere.

Fig. 3 c is the TEM figure of the nanofiber of the wall of cup portion shown in Fig. 3 b.Shown in Fig. 3 c, the average diameter of this nanofiber is about 60nm.In addition, under TEM, do not see the nanotube that other are arranged in sample.Report in this result and the document when heating-up temperature is higher than 160 ℃, general nanofiber rather than nanotube [13] unanimity of generating in hydrothermal solution is synthetic.As discussed above, adopting the hydrothermal solution heating-up temperature that is higher than 160 ℃ in the present invention is in order to form paper pulp shape and long nanofiber.

The XRD figure case of nanofiber confirms 1D nano wire sampling similar titanate [13] on lattice structure.These XRD data show that the nano wire that processes like this will be the metatitanic acid salt face, and can adopt following lattice parameter to characterize: [2 θ=9.8 ° (001), 11.2 ° (200), 24.4 ° (110) and 29.7 ° (003), (JCPDS card number: 47-0561)].The essential structure unit of this titanate structure is TiO ₂-octahedra [22].Should be total to limit (TiO ₆) octahedron will form negative electrical charge layer structure.Its counter cation (countercations) (Na for instance, ⁺) be positioned at adjacent layer (adjacent layer), will cause depending on the variable interlayer distance of cationic size and hydration levels like this, this can explain the flexibility [23] of long nanofiber.

Can by in air to be higher than 500 ℃ the about heat endurance of studying nanofiber FSM in 3 hours of temperature heating film.Fig. 4 a was presented in the air with 700 ℃ smelting furnace calcining after 3 hours, and described inorganic nano-fiber FSM still keeps its typical sandwich construction.Fig. 4 b has showed the FESEM figure of the inorganic nano-fiber FSM after 700 ℃ of calcinings, and is identical among the fiber nanostructured that it demonstrates and Fig. 3 b.From the sampling after 600 ℃ of calcinings, also obtain same result.TEM figure in the illustration of Fig. 4 b confirms that the FSM after the calcining generally is made up of the nanofiber shown in Fig. 3 c.Yet after three hours, the film nanofiber becomes than shorter thicker in the past, makes FSM no longer have flexibility, thereby shows that nanofibrous structures has experienced phase transformation at about 800 ℃ 800 ℃ of calcinings.

As shown in Figs. 4a and 4b, after three hours, the wall portion of 3D object still keeps the sandwich construction of the typical nanofiber that twines 700 ℃ of calcinings.Yet after 800 ℃ of calcinings, the wall film becomes frangible.This is because original nano wire form changes over typical 20 μ m length and 100-400nm is wide.Its XRD data show that this nano wire is TiO after 700 ℃ of calcinings ₂-B phase, and adopt following lattice parameter to characterize: (a=12.1787, b=3.7412,

β=107.0548 °), then 800 ℃ of calcinings, generate TiO ₂The mixture of-B phase and anatase.The XRD parameter all meets results reported in the document [24].With other paper shape material different [6-8], the visible nano wire paper of these naked eyes is very useful in high-temperature catalytic.Fig. 4 c shows and contains TiO ₂The paper of long nanofiber is at 700 ℃ of calcinings (410) and back X-ray powder diffraction pattern of (420) before about 3 hours.

Fig. 5 a shows the high-resolution FESEM figure of the nanofiber FSM of the nanofiber with winding.Fig. 5 b shows according to the comparison diagram of various 3D structures of the present invention (nanofiber cup 550,560 and manage 570) with a coin-dividing 530.

In brief, except other incident, the present invention also discloses a kind of synthetic TiO that contains ₂The macro nanometer structure method and make heat-staple, healthy and strong and multi-functional 2D paper and 3D equipment (pipe, bowl, cup etc. for instance) based on FSM near naked eyes visible size and shape.directly cast healthy and strong 2D FSM from the 1D nano material, the most important thing is to make long 1D nanostructured, then they are suitably made up.Inorganic 1D nanostructured is white, heat-staple, chemically inert, biological compatible, and can form the long nanofiber of flexible mm-, and the diameter of described nanofiber is generally less than 100nm.Such inorganic nano-fiber can form the projection film on macroscopic template or mould, the size of these templates and mould can be the virtually any size that design is fit to casting naked eyes visual cell and instrument.Because it may use (comprising chemical sensitisation, photocatalysis, opto-electronic conversion, rheostat, gas sensor and solar cell) a large amount of fields, nanofiber is subjected to extensive concern [9].Because that its use is cheap rough TiO ₂Material can scale up nanofiber FSM and cup-like containers easily, and is fit to a large amount of production.Because known heat endurance and chemical inertness, these inorganic nano-fibers FSM catalyst reusable edible also can be in wider temperature range recycling.Can use inorganic nano-fiber FSM, container and the instrument of casting in every field, for example: hydrogen storage [18] and generate [19], clean environment [20], sensing [21], catalysis water-splitting and oil-breaking, making protective cover and anti-armor, make flame-retardant textile, filter bacterium, light helps rewriting, control medicine release and regeneration and similar field.

Embodiment 2

Contain TiO ₂The direct application of macro nanometer fiber be that the writing function of the writing-wipe of information storage-again is provided under the help of UV irradiation.TiO ₂Be commonly used for cheap and nontoxic photocatalysis.After being subjected to the UV rays excite, TiO ₂But catalysis dyestuff degraded [25].

In this embodiment, 4 characters " UARK " of hydration ink (1.0 * 1mol/L crystal violet) are write according to the TiO of containing of the present invention ₂The FSM paper 610 made of macro nanometer fiber on.The FSM paper 610 that will have the written information of " UARK " exposes to the open air in air under the UV ray.Expose 15 minutes to the open air in the UV ray after, described 4 characters " UARK " disappear, shown in Fig. 6 b.In the present embodiment, can on this FSM paper 610 (21.4mg), repeat this to write-erase cycles 4 times.After exposing to the open air in the UV ray, all 4 characters " UARK " all are wiped free of at every turn, shown in Fig. 6 b.Yet for conventional printing paper 620 (49.0mg), each UV irradiation only causes in circulation for the first time in the submit a written statement to a higher authority slight variation of four characters writing out of conventional printing paper 620.In addition, such inorganic nano-fiber paper also has may use in adverse circumstances (when being lower than 700 ℃).

The annual whole world has 9.5 hundred ten thousand hectares forest to be cut down, and wherein 35% commercial timber is used for papermaking [26].So use can rewrite, can wipe and the inorganic nano-fiber or the nano wire paper of heat resistanceheat resistant will be saved the forest that is disappearing.

Embodiment 3

Contain TiO ₂The Another Application of macro nanometer fiber be photocatalysis.Confirmed TiO ₂The photocatalytic activity of-B phase is better than other TiO ₂Phase [27].Because its large aperture character, these stalwartnesses based on the nano wire film catalyst have the photocatalysis Decomposition effect [15] of unique organic pollution.As nerve toxicant analog (NAS) [15], for instance, (C2H5O) 2P (O) (H2CSC6H5) (Ao Erdeli (Aldrich)).

In typical embodiment, will be according to the TiO that contains of the present invention ₂The 10mg FSM that makes of macro nanometer fiber in RT, be immersed in about 10mL 1mol/L Mg (NO ₃) ₂In 12 hours.FSM behind the dipping is dry in RT, then in air, heated about 3 hours to be higher than 100 ℃.FSM after then will heating is placed in the solution that comprises a plurality of organic pollutions.In this embodiment, organic pollution comprises NAS.The 5mm position is provided with UV lamp (Entella, B100AP/R type) above solution, this FSM is carried out the UV irradiation.Adopt UV visible spectrometer (as HP (Hewlett-Packard) 8453) measuring N AS concentration (C _t).

The solution that has nano wire FSM in UV irradiation is after 15 minutes, the concentration (C of NAS _t) from original content (C ₀, original content is 4.5 * 10 ^-7Mol/L, 50mL) decline 67.8% (1-C _t/ C ₀).The square 712 of Fig. 7 a shows the resolution ratio (1-C of NAS concentration _t/ C ₀), it is different from describes in the document [17].

In HP 8453, carry out the spectroscopy measurements of NAS concentration.Under the situation of the catalysis that does not have FSM, under same UV irradiation, NAS concentration descends less than detectability.Another skip test, use FSM, but do not adopt the UV irradiation, this makes the concentration of NAS about 1.0% (shown in square among Fig. 7 a 718) that descend, this means that 66.8% (67.8%-1.0%) that NAS concentration descends generally depends on photocatalysis Decomposition, rather than the absorption of the surface of catalyst.

In TEM/SEM/XRD research, on nano-fiber catalyst, do not have the MgO nano particle.Yet EDX studies show that, has the Mg that mass fraction is 8.5wt% in this catalyst.These results point out that the Mg atom may exist with the form of high dispersive cluster, and this exciting technique personnel carry out HRTEM work to discern its shape/size, then analyze to contain the role of Mg particle in photocatalysis.

P25 and anatase TiO that use etc. are heavy ₂Powder (325 holes, Alfa Aesar) carries out parallel testing, the concentration that obtains NAS 35.0% and 8.0% (shown in the square 714 and 716 among Fig. 7 a) that descend respectively.In NAS light decomposed, the FSM film obviously was better than P25 and anatase powder, and this explanation nano wire FSM film can be used as outstanding new photochemical catalyst.In the process of UV irradiation, the solution temperature increase is insignificant.In heterogeneous catalysis (heterogeneous catalysis), use such nano wire FSM catalyst can minimize (i) downstream separation and catalyst weight loss, the (ii) use of catalytic carrier and adhesive (iii) can be reclaimed catalyst easily by calcining, reduces cost.

Embodiment 4

As disclosed among the embodiment 3, TiO ₂Be fabulous [15] aspect the photocatalysis Decomposition organic pollution (nerve toxicant analog (NAS) [15]).This is different from the catalysis [16] of the activated carbon of black.In addition, when existing, can strengthen TiO at Mg (II) greatly ₂Photocatalytic activity [17].In this cross-section study, at the NAS aqueous solution photocatalytic activity of RT research nanofiber FSM, described NAS is that (phenylthiomethylphosphonate is called for short DPTMP, C to phenyl sulfo-methoxyl group phosphonic acids ₁₁H ₁₇O ₃PS, Alfa Aesar).

Before catalysis, nanofiber FSM in RT, is immersed in 1mol/L Mg (NO ₃) ₂In 12 hours, then dry and be higher than in 100 ℃ of air heating about 3 hours at RT.Can prepare NAS solution like this: 45 μ m DPTMP are dissolved in the 100mL water of the FSM that contains the 10mg preparation.From the lamp that is arranged on 5mm position above the solution (mineralising light UVGL-58, h=254nm) after 15 minutes the UV irradiation, the concentration (C of the NAS in the solution _t) 98% (1-C descends _t/ C ₀), shown in the square 722 of Fig. 7 b.UV visible spectrometer (as HP (Hewlett-Packard) 8453) measuring N AS concentration (C).The FSM of same weight is adopted in skip test, but do not adopt the UV irradiation, this makes the concentration of NAS about 1.0% (shown in square among Fig. 7 b 728) that descend, and what this means that NAS concentration descends 98% generally depends on photocatalysis Decomposition, rather than the absorption of the surface on the nanofiber.In parallel laboratory test, heavy anatase TiO such as use ₂Powder (325 holes, Alfa Aesar) carries out the preliminary treatment identical with this catalyst, and it causes concentration decline 8% (shown in the square 726 among Fig. 7 a) of NAS.After the UV irradiation, do not observe the change of solution temperature.

Can pass through to optimize reaction temperature, UV irradiation time and intensity, and described 98% catalytic conversion rate is further improved in the structure of Mg element, form and position.98% of the quick photocatalysis Decomposition of NAS conversion ratio is pointed out may using of nanofiber FSM catalyst in the water under RT, as making the mask in the civil defense application.Compare with heterogeneous catalysis commonly used, use such nanofiber FSM catalyst can minimize downstream separation and catalyst weight loss, eliminate simultaneously and use catalyst carrier and adhesive.In addition, the property ignored of the more effective use on the surface of each catalytic nanometer fiber, catalyst weight and to reclaim catalyst by high-temperature calcination also be to be worth expectation.To the structure of Mg element, size with distribute and can develop the inorganic nano fiber film catalyst that makes new advances, to be used for various important catalysis related application to the further improvement of the porous control of FSM.

Embodiment 5

Can in filtering, particle be applied according to nanofiber FSM of the present invention and 3D equipment.In this embodiment, provide and comprise that diameter is that the polystyrene latex droplet hydration suspension of A Faaisha (AlfaAesar) microballoon of 0.75,1.2 and 2.5 μ m is studied described nano wire permeability of the membrane [5].The concentration of each hydration suspension is 0.0025% (mass fraction).This micro porous filtration is used and is contained TiO ₂The nanofiber cup operated about 5 minutes.Detect and find, the 1mL after filtration samples (hydration suspension), does not have the microballoon of 2-μ m.Yet in parallel laboratory test, the microballoon of 0.75 and 1 μ m passes the wall of filter, and this explanation 3D equipment has the size distinction effect in micron-sized particulate filtration.

In addition, contain TiO ₂Nano fibrous membrane can be used for filtration, the clean environment of the bacterial spore in the civil defence, the nerve growth base that is used to repair impaired spinal cord, treatment Alzheimer disease and Parkinson's, the reparation of intravascular injection bone, portable MEMS (microelectronic mechanical sensor), biology sensor and membrance chemistry sensor.Fig. 8 shows has the TiO of containing ₂Nanofiber with the picture of the nanofiber FSM that forms the porous net, it is used for micro particle filtering.Fig. 8 b schematically shows the bacterial spore filter that uses the nanofiber that twines.

Embodiment 6

As shown in Figure 9, obtained confirmation according to the permeability of nano fibrous membrane cup 910 of the present invention and the unique combination of photocatalytic at present embodiment.In the present embodiment, according to method pre-preparation Mg (II) solution in embodiments of the

invention

3 and 4, then fill with NAS solution 920.As shown in Figure 9, adopt the UV ray of UV lamp (Entella, B100AP/R type) emission from the described nano fibrous membrane cup 910 that comprises NAS solution 920 of side irradiation.After 15 minutes UV irradiation, collect about 3ml infiltration catalytic solution, the NAS of (32.0+/-1.0) % is decomposed rapidly.If existing UV lamp is to can be used for around described cup 920, its concentration descend can with shown in Fig. 7 b (FSMIUV) quite.Its result has confirmed this 3D equipment under different temperatures, may use in industrial Continuous Flow-filtration-catalysis, and wherein, be restricted the time of contact of described reactant and catalyst.

Embodiment 7

Macropore 3D equipment adopts folding nano wire/nanofiber as wall, can be used for controlling medicine and discharges [29].In an exemplary embodiments, will contain TiO ₂Nanofiber FSM (74.0mg) be immersed in about 100ml in advance and contain in the crystal violet of 0.001mol/L, at room temperature flooded 12 hours, then at room temperature be placed in the 10mL fresh water.Adopting HP 8453UV visible spectrometer to detect controlled medicine discharges.Behind each 24 hours of medicine release, this is contained TiO ₂Nanofiber FSM transfer in the 10mL fresh water.Figure 10 shows and contains TiO in the solution ₂The drug concentration that discharges of nanofiber FSM, it is presented at about 24 hours, controlled medicine discharges and reaches peak, and at least 4 days effectively.

Embodiment 8

In addition, after being coated with the last layer HGH, the described TiO that contains ₂The 3D foldable structure of nanofiber/line very useful on the stem cell growth in guiding, this makes it have possibility in regenerative medicine and uses [30,31].

Embodiment 9

Pottery titanate nano wire (NW) be eco-friendly, biological compatible, chemically inert, be easy to surface-functionalized, cheap and be heat-staple.In this embodiment, synthesized the new compound that can be used for making tire.This new compound comprises the TiO that contains of mixed rubber polymer ₂Macro nanometer fiber/nano wire.Compare with rubber compound based on carbon black, NW-rubber can be greyish white on color, and a kind of novel tire can be provided, it more engages with polymer backbone and has oil consumption lighter or better on higher mechanical strength, the weight in the highland, and easier control on wet and slippery road surface.

In tire was made, NW was changeable, and this depends on and uses needs.Short NW can make at about 150-160 ℃ in several hours.The reaction temperature of long NW is more than 160 ℃, and the reaction time was longer than 1 day.

Embodiment 10

According to the TiO that contains of the present invention ₂The macro nanometer fiber can be used for being nanometer medicine, battlefield, sports ground, space station, fireman and similarly use and make multi-functional underwear/overcoat.Multi-functional underwear/overcoat 1300 to small part by containing TiO ₂The macro nanometer fiber make.For example, as shown in figure 11, described multi-functional underwear/overcoat 1300 has a plurality of by containing TiO ₂The macro nanometer fiber make the zone, as the preceding of multi-functional underwear/overcoat 1300 and after cloth 1310 and 1320.In described a plurality of zone each comprises that all one or more minimum intrusive mood Nano medications discharge heat release box 1134, electrochemical nano biology sensor 1336 and the analog of MEMS (minimum-invasion nanodrug delivery MEMS) 1332, Nano medication.The heat that described minimum intrusive mood Nano medication discharges MEMS, Nano medication discharges box 1134, control can be controlled or make up to electrochemical nano biology sensor 1336 separately.

Above-mentioned purpose of description to the preferred embodiments of the present invention is to illustrate for example and describe.These embodiment are not limits, that is to say that the present invention is not subjected to the restriction of disclosed precise forms, under instruction of the present invention or can obtain numerous modifications and variations to these embodiment from the practice of the present invention.

Selection and description to embodiment are for principle of the present invention and practical application thereof are made explanations, to enable those skilled in the art to utilizing the present invention in various embodiments and to serve as to cooperate specific use to carry out various modifications.Those skilled in the art know that in the alternative embodiment that does not break away from the principle and scope of the present invention.Therefore, scope of the present invention is by claim of the present invention and be equal to and limit, rather than the description of front and exemplary embodiments described herein.

The application submits to as the PCT international application with the name of Univ Arkansas Technology Dev F. (U.S. state-owned firm), application is All Countries except that the U.S., and is only applying for United States Patent (USP) on January 12nd, 2007 with the name of Ryan Tian (United States citizen).

The cross reference of relevant patent

The application benefits from applicant Z.Ryan Tian and Wenjun Dong according to united states patent law 35U.S.C.51 19 (e), proposes on January 12nd, 2006, and application number is 60/758,492, " TiO by name ₂Nano fibrous membrane and manufacture method thereof and application " and application number be 60/785,649, at " TiO by name on March 23rd, 2006 ₂Nanofiber, film and thin layer and manufacture method thereof and application " patent application, at this in conjunction with quoting, with for referencial use.

Quote and discussed some lists of references in the specification of the present invention, comprise patent, patent application and all kinds of publication.To these lists of references quote and discussion is only used for specification of the present invention clearly is described, be not to admit that these lists of references are indication of the present invention " prior aries ".The document of all references and discussion is quoted with same degree set at this in specification, just as the combination reference separately of these documents.Form with [] shows that it is the documents that a n piece of writing is quoted in the list of references tabulation hereinafter.For example, [10] are the 10th piece of list of references of quoting in list of documents, just, and Tian, Z.R., Voigt, J, A., Liu, J., Mckenzie, B., Xu, H., J.Am.Chem.Soc., 2003,125,12384.

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Claims

1, a kind of method of synthetic macro nanometer structure is characterized in that, may further comprise the steps:

A is with a large amount of TiO ₂Powder mixes with the alkali metal or the alkaline solution of certain volume, to form mixture; With

B contains TiO being higher than heating described mixture a period of time under 160 ℃ the temperature with formation ₂The macro nanometer structure;

The described TiO that contains ₂The macro nanometer structure in the environment that does not contain the matrix that comprises Ti, generate.

According to the described method of claim 1, it is characterized in that 2, described mixture is placed in the closed container.

According to the described method of claim 2, it is characterized in that 3, described heating steps comprises the described airtight container that comprises mixture is put in the baker and heats.

According to the described method of claim 1, it is characterized in that 4, the temperature that heats this mixture is in 180-300 ℃ scope.

According to the described method of claim 1, it is characterized in that 5, heat time heating time is in about 3-960 hour scope.

6, according to the described method of claim 1, it is characterized in that, further comprise and adopt distilled water or the described TiO of containing of weak acid scrubbing ₂The step of macro nanometer structure.

7, according to the described method of claim 1, it is characterized in that the described TiO that contains ₂The macro nanometer structure comprise that the representative diameter scope is approximately the nanofiber of 20nm to 150nm.

According to the described method of claim 7, it is characterized in that 8, nanofiber generally is TiO ₂-B phase or metatitanic acid salt face.

9, according to the described method of claim 1, it is characterized in that the mixture that described alkali metal soln comprises a kind of following material or makes up arbitrarily in them: NaOH (NaOH), potassium hydroxide (KOH), lithium hydroxide (LiOH), rubidium hydroxide (RbOH), cesium hydroxide (CsOH).

10, according to the described method of claim 1, it is characterized in that the mixture that described alkaline solution comprises a kind of following material or makes up arbitrarily in them: magnesium hydroxide [Mg (OH) ₂], calcium hydroxide [Ca (OH) ₂], strontium hydroxide [Sr (OH) ₂] and barium hydroxide [Ba (OH) ₂].

11, according to the TiO that contains of the described method of claim 1 preparation ₂The macro nanometer structure.

12, a kind of synthesis of nano structure is characterized in that, described synthesis of nano structure comprises the chemical reaction product according to following reaction equation:

2NaOH+3TiO ₂＝Na ₂Ti ₃O ₇+H ₂O，

Wherein, this chemical reaction reacts a period of time under 160 ℃ that are higher than temperature, so that product formation, and at this, chemical reaction carries out in the environment that does not contain the matrix that comprises Ti.

13, according to the described synthesis of nano structure of claim 12, it is characterized in that described chemical reaction carries out in closed container.

According to the described synthesis of nano structure of claim 12, it is characterized in that 14, described effecting reaction temperature range is between 180-300 ℃.

According to the described synthesis of nano structure of claim 14, it is characterized in that 15, described effective reaction time scope is between 3-960 hour.

16, according to the described synthesis of nano structure of claim 15, it is characterized in that the described first reactant TiO ₂Be to provide, and described second reactant comprises inorganic group, and provide with the form of solution with form of powder.

17, according to the described synthesis of nano structure of claim 16, it is characterized in that second reactant comprises NaOH, and product comprises that chemical formula is Na ₂Ti ₃O ₇Compound.

According to the described synthesis of nano structure of claim 17, it is characterized in that 18, described chemical formula is Na ₂Ti ₃O ₇Compound be form with nanofiber, its representative diameter scope is that 20nm is to 150nm.

19, a kind of synthesis of nano structure is characterized in that, described synthesis of nano structure comprises the chemical reaction product according to following reaction equation, and described reaction is carried out according to following order:

(a)2NaOH+3TiO ₂→Na ₂Ti ₃O ₇；

(b) Na ₂Ti ₃O ₇+ 2H ⁺→ 2Na ⁺+ H ₂Ti ₃O ₇With

(c)H ₂Ti ₃O ₇→H ₂O+TiO ₂-B，

Wherein, chemical reaction (a) is being higher than reaction a period of time under 160 ℃ the temperature so that product forms at least, and this at least chemical reaction (a) in the environment that does not contain the matrix that comprises Ti, carry out.

According to the described synthesis of nano structure of claim 19, it is characterized in that 20, described at least chemical reaction (a) carries out in closed container.

According to the described synthesis of nano structure of claim 19, it is characterized in that 21, the range of reaction temperature of described at least chemical reaction (a) is between 180-300 ℃.

According to the described synthesis of nano structure of claim 21, it is characterized in that 22, the reaction time range of described at least chemical reaction (a) is between 3-960 hour.

23, according to the described synthesis of nano structure of claim 19, it is characterized in that the described first reactant TiO ₂Be to provide, and described second reactant comprises inorganic group, and provide with the form of solution with form of powder.

24, according to the described synthesis of nano structure of claim 23, it is characterized in that second reactant comprises NaOH, and product comprises that chemical formula is Na ₂Ti ₃O ₇Compound.

According to the described synthesis of nano structure of claim 24, it is characterized in that 25, described chemical formula is Na ₂Ti ₃O ₇Compound be form with nanofiber, its representative diameter scope is that 20nm is to 150nm.

According to the described synthesis of nano structure of claim 23, it is characterized in that 26, described second reactant comprises OH ^-

According to the described synthesis of nano structure of claim 26, it is characterized in that 27, described product comprises that chemical formula is H ₂Ti ₃O ₇Compound.

According to the described synthesis of nano structure of claim 27, it is characterized in that 28, described chemical formula is H ₂Ti ₃O ₇Compound be form with nanofiber, its representative diameter scope is that 20nm is to 150nm.

According to the described synthesis of nano structure of claim 28, it is characterized in that 29, described chemical reaction (b) generally between 180-300 ℃ takes place a period of time, so that chemical formula is H ₂Ti ₃O ₇Compound generate with the form of macro nanometer fiber.

According to the described synthesis of nano structure of claim 29, it is characterized in that 30, described chemical reaction (c) carries out in calcination process.

According to the described synthesis of nano structure of claim 30, it is characterized in that 31, described calcination process comprises a step that heats in the air in smelting furnace in 300-600 ℃ temperature range, or a step of in air, burning.

According to the described synthesis of nano structure of claim 31, it is characterized in that 32, described chemical reaction (c) makes that chemical formula is TiO ₂The compound of-B generates with the form of macro nanometer fiber.

According to the described synthesis of nano structure of claim 32, it is characterized in that 33, described chemical formula is TiO ₂The compound of-B is the form of macro nanometer fiber, and its representative diameter scope is that 20nm is to 150nm.

34, a kind of method that is used for synthetic macro nanometer structure, it is characterized in that, described method comprises the following steps: to heat a kind of reactant and a kind of solution a period of time to generate the macro nanometer structure based on described reactant in certain heating-up temperature, wherein, described macro nanometer structure based on reactant generates in the environment of the crystal seed that does not have described reactant.

According to the described method of claim 34, it is characterized in that 35, described solution and reactant are placed in the closed container.

According to the described method of claim 34, it is characterized in that 36, described reactant comprises TiO ₂Powder, and described solution comprises alkali metal or alkaline solution.

According to the described method of claim 36, it is characterized in that 37, described heating-up temperature is higher than 160 ℃.

According to the described method of claim 37, it is characterized in that 38, described heat time heating time, scope was between 3-960 hour.

According to the described method of claim 34, it is characterized in that 39, described macro nanometer structure comprises nanofiber, nanotube, nano wire or their any combination.

40, the macro nanometer structure of synthesizing according to the described method of claim 34.

41, a kind of method that is used to prepare free standing structure film comprises the following steps:

A provides a plurality of TiO of containing ₂The macro nanometer structure;

B is with described a plurality of TiO that contain ₂The macro nanometer structure be cast on the template film on described template film, to form free standing structure film;

C is in the certain described free standing structure film of temperature drying a period of time.

According to the described method of claim 41, it is characterized in that 42, the described step that provides comprises the following steps:

A is with a large amount of TiO ₂Powder mixes with the alkali metal or the alkaline solution of certain volume, with form mixture and

B contains TiO being higher than heating described mixture a period of time under 160 ℃ the temperature with formation ₂The macro nanometer structure,

At this, the described TiO that contains ₂The macro nanometer structure in the environment that does not contain the matrix that comprises Ti, generate.

43, according to the described method of claim 42, it is characterized in that the described TiO that contains ₂The macro nanometer structure generally comprise to have and be approximately the TiO of 20nm to the representative diameter of 150nm ₂-B phase nanofiber.

According to the described method of claim 43, it is characterized in that 44, described baking temperature is generally in 0-180 ℃ scope.

45, according to the described method of claim 44, it is characterized in that, in the generally about 0.5-30 hour scope of described drying time of scope.

According to the described method of claim 42, it is characterized in that 46, described template film comprises one of ashless filter paper and polyethylene film.

According to the described method of claim 46, it is characterized in that 47, described method further comprises the step that removes dried free standing structure film from described template film.

48, according to the described method of claim 47, it is characterized in that, describedly remove the step that step is included in the dried free standing structure film on the described template film of calcining in 300-600 ℃ the temperature range.

According to the described method of claim 42, it is characterized in that 49, the thickness range of described free standing structure film is the 10-1000 micron.

According to the described method of claim 42, it is characterized in that 50, described free standing structure film is porous, permeable and class zeolite.

According to the described method of claim 42, it is characterized in that 51, described free standing structure film is chemically inert.

According to the described method of claim 42, it is characterized in that 52, described free standing structure film is biological compatible.

According to the described method of claim 42, it is characterized in that 53, described free standing structure film is heat-staple.

According to the described method of claim 42, it is characterized in that 54, the described step that is cast into comprises the following steps:

A contains TiO with more than first ₂The macro nanometer structure be cast on the template film,

B will be cast into the individual TiO that contains of described more than first on the template film ₂Dry at room temperature first period of macro nanometer structure,

C then is cast into the individual TiO that contains of dried described more than first on the template film with the macro nanometer structure of at least one additional amount ₂The macro nanometer structure on,

D also will be cast into the individual TiO that contains of dried described more than first on the described template film ₂Macro nanometer structure dry second period at room temperature of additional amount of macro nanometer structure, described second period and described a period of time are identical or different.

According to the described method of claim 54, it is characterized in that 55, described free standing structure film has multilayer film.

56, the free standing structure film for preparing according to the described method of claim 54.

According to the described free standing structure film of claim 56, it is characterized in that 57, described template film generally is a two-dimensional structure, and the described free standing structure film of as above preparation generally is a two-dimensional structure.

58, a kind of free standing structure film has a plurality of TiO of containing ₂The macro nanometer structure sheaf, it is characterized in that the described TiO that contains ₂The macro nanometer structure synthetic like this:

A is with a large amount of TiO ₂Powder mixes with the alkali metal or the alkaline solution of certain volume, with the formation mixture, and

59, according to the described free standing structure film of claim 58, it is characterized in that the described TiO that contains ₂The macro nanometer structure generally comprise to have and be approximately the contain TiO of 20nm to the representative diameter of 150nm ₂Macro nanometer fiber and TiO ₂-B structure.

60, according to the described free standing structure film of claim 59, it is characterized in that the described TiO that contains in each layer ₂The macro nanometer fiber be thereby that part is twined and to be formed a plurality of spaces there at least.

According to the described free standing structure film of claim 60, it is characterized in that 61, described free standing structure film is porous, permeable and class zeolite.

According to the described free standing structure film of claim 60, it is characterized in that 62, described free standing structure film is chemically inert.

According to the described free standing structure film of claim 60, it is characterized in that 63, described free standing structure film is biological compatible.

According to the described free standing structure film of claim 60, it is characterized in that 64, described free standing structure film is heat-staple.

According to the described free standing structure film of claim 60, it is characterized in that 65, the thickness range of described free standing structure film is the 10-1000 micron.

66, a kind ofly directly prepare the method for three-dimensional structure, it is characterized in that described method comprises the following steps: from nanostructured

A provides a plurality of TiO of containing ₂The macro nanometer structure,

B is with described a plurality of TiO that contain ₂The macro nanometer structure be cast on the template, to form three-dimensional structure on template, wherein, described template has the structure corresponding to the three-dimensional structure that will form,

C three-dimensional structure a period of time on the described template of certain temperature drying.

According to the described method of claim 66, it is characterized in that 67, described baking temperature is generally in 0-180 ℃ scope.

According to the described method of claim 67, it is characterized in that 68, described drying time is generally in about 0.5-30 hour scope.

69, according to the described method of claim 66, it is characterized in that the described TiO that contains ₂The macro nanometer structure comprise nanofiber, nanotube, nano wire or their any combination.

According to the described method of claim 69, it is characterized in that 70, described template to small part is made by in ashless filter paper or the polyethylene film at least one.

According to the described method of claim 70, it is characterized in that 71, described method further comprises the step that removes dried three-dimensional structure from described template.

72, according to the described method of claim 71, it is characterized in that, describedly remove the step that step is included in the dried three-dimensional structure on the described template of calcining in 300-600 ℃ the temperature range.

73, according to the described method of claim 66, it is characterized in that the thickness range that has from tens of to hundreds of micron to the described three-dimensional structure of small part.

74, according to the described method of claim 66, it is characterized in that, described free standing structure film be porous with the class zeolite.

According to the described method of claim 66, it is characterized in that 75, described free standing structure film is chemically inert.

According to the described method of claim 66, it is characterized in that 76, described free standing structure film is biological compatible.

According to the described method of claim 66, it is characterized in that 77, described free standing structure film is heat-staple.

According to the described method of claim 66, it is characterized in that 78, the described step that is cast into comprises the following steps:

C then is cast into the individual TiO that contains of dried described more than first on the template film with the macro nanometer structure of at least one additional amount ₂The macro nanometer structure on, and

D will be cast into dried first described a plurality of TiO of containing on the described template film ₂The macro nanometer structure of additional amount dry second period in RT of macro nanometer structure, described second period and described first period are identical or different.

79, the three-dimensional structure for preparing according to the described method of claim 78.

According to the described three-dimensional structure of claim 79, it is characterized in that 80, at least a portion of described three-dimensional structure is to be made of multilayer.

81, a kind of three-dimensional structure comprises a plurality of TiO of containing ₂The layer of macro nanometer structure, it is characterized in that the described TiO that contains ₂The macro nanometer structure adopt the following step synthetic:

82,1 described three-dimensional structure according to Claim 8 is characterized in that the described TiO that contains ₂The macro nanometer structure generally comprise to have and be approximately the contain TiO of 20nm to the representative diameter of 150nm ₂Macro nanometer fiber and TiO ₂-B structure.

83,2 described three-dimensional structures according to Claim 8 is characterized in that the described TiO that contains in each layer ₂The macro nanometer fiber be thereby that part is twined and to be formed a plurality of spaces there at least.

84,3 described three-dimensional structures according to Claim 8 is characterized in that described three-dimensional structure is porous, permeable and class zeolite.

85,1 described three-dimensional structure according to Claim 8 is characterized in that described three-dimensional structure is chemically inert.

86,1 described three-dimensional structure according to Claim 8 is characterized in that, described three-dimensional structure is biological compatible.

87,1 described three-dimensional structure according to Claim 8 is characterized in that described three-dimensional structure is heat-staple.

88,1 described three-dimensional structure according to Claim 8 is characterized in that the thickness range of described three-dimensional structure is the 10-1000 micron.