CN102500352A - Preparation method for crystal face controllable titanium dioxide/graphene compound nanophase materials - Google Patents
Preparation method for crystal face controllable titanium dioxide/graphene compound nanophase materials Download PDFInfo
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- CN102500352A CN102500352A CN2011103596643A CN201110359664A CN102500352A CN 102500352 A CN102500352 A CN 102500352A CN 2011103596643 A CN2011103596643 A CN 2011103596643A CN 201110359664 A CN201110359664 A CN 201110359664A CN 102500352 A CN102500352 A CN 102500352A
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- titanium dioxide
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Abstract
The invention relates to a preparation method for crystal face controllable titanium dioxide/graphene compound nanophase materials. The method comprises the following steps: dispersing graphene oxide into deionized water, then ultrasonically dispersing into evenly dispersed precursor solution in which the concentration of graphene oxide is 0.1 to 0.3 mg/ml, then adding (NH4) 2TiF6 into the solution for uniform stirring so as to enable the concentration of the (NH4) 2TiF6 in mixed solution to be 0.01 to 0.05 mol/L, adding the mixed solution into a high pressure kettle with a polytetrafluoroethylene inner liner, and then preparing through reaction performing under 150 to 170 DEG C for 4 to 24 h. In the titanium dioxide/ graphene compound nano-composite material prepared by the method, the titanium dioxide nano particles are evenly dispersed on the surface of graphene, the crystalline phase is anatas titanium dioxide, the titanium dioxide nano particles have crystal planes (001) and (100) to be exposed, or planes (001) and (101) to be exposed, and the catalytic activity is higher.
Description
Technical field
The present invention relates to the preparation method of the controlled titanium dioxide of a kind of crystal face/Graphene composite nano materials, can be used for the environmental protection and the energy technology field of ultraviolet degradation organic pollution and hydrogen production by water decomposition.
Technical background
Continuous development along with human society; People constantly consume fossil energy; Through millions upon millions of years formed fossil energy approach exhaustions, on the other hand, the natural environment that the waste water that energy resource consumption produced, waste gas are depended on for existence to people caused huge pollution on the one hand.One of main problem that the energy and environmental problem have become present human society and faced.Photocatalysis technology is a kind of a kind of emerging technology of utilizing solar energy source degraded environment noxious pollutant or producing regenerative resources such as hydrogen, is the effective ways that solve the present energy and environmental problem.In numerous conductor photocatalysis materials, titanium dioxide makes it become most widely used catalysis material because it has numerous advantages such as photocatalytic activity height, nontoxic, physicochemical properties be stable.Yet from the commercialization angle, the photocatalytic activity of titanium dioxide awaits further to improve.And people's research in the recent period shows, because each diversity of crystal of anatase titania makes its different crystal face show different reactivities, can improve its photocatalytic activity greatly through crystal face and the ratio thereof of controlling titanium dioxide nanocrystalline.
Graphene is a kind of mono-layer graphite with laminated structure, because the special construction that itself had makes it have special nature in electricity, calorifics and mechanical properties, and has potential using value in various fields.Because its special physicochemical characteristic, the research Graphene is with the compound focus that becomes recent material science research of other materials.In the recent period, it is found that Graphene compoundly, can effectively promote the separation of photo-generated carrier, thereby improve the activity of catalysis material greatly with conductor photocatalysis material.Titanium dioxide/Graphene composite nano materials is by extensive studies, and proof titanium dioxide is with the compound photocatalytic activity that can improve titanium dioxide effectively of Graphene.Yet still there are some problems in the titanium dioxide of being reported/Graphene composite nano materials, as: the crystal face regulation and control that titanium dioxide is prone to reunion, titanium dioxide are relatively more difficult, etc.Greatly reduce the specific area of composite system like this, influenced its photocatalytic activity.Therefore, preparation has the controlled titanium dioxide of crystal face/Graphene composite nano materials, to the photocatalysis property of further raising titanium dioxide nano material, promotes its application in real life to have important Research Significance and using value.
Summary of the invention
The purpose of this invention is to provide the preparation method of the controlled titanium dioxide of a kind of crystal face/Graphene composite nano materials, in this kind composite nano materials, titanium dioxide has the crystal face controllability, and has polymolecularity on the Graphene surface.
The preparation method of titanium dioxide/Graphene composite nano materials that a kind of crystal face is controlled comprises that step is following:
(1) with having the graphene oxide that general chemical oxidation graphite legal system is equipped with laminated structure now;
(2) get graphene oxide and be scattered in the deionized water, ultrasonic dispersion obtained finely dispersed precursor solution in 20-40 minute, and graphene oxide concentration is 0.1～0.3mg/ml in the precursor solution, in this solution, added (NH then
4)
2TiF
6, stir, make (NH
4)
2TiF
6Concentration is 0.01～0.05mol/L in mixed solution; Mixed solution put into have the teflon-lined autoclave; React 4～24h down at 150～170 ℃; Naturally cool to room temperature, after products therefrom was spent deionised water, filters, vacuum drying must have the titanium dioxide/Graphene composite nano materials of particular crystal plane.
Described chemical oxidation graphite method preferably adds graphite flake and KMnO with the concentrated sulfuric acid and SPA
4Oxidation.
The titanium dioxide that above-mentioned preparation method obtains/Graphene composite nano materials; Titania nanoparticles is dispersed in the Graphene surface; Crystalline phase is an anatase titania, titania nanoparticles have 001} with the 100} crystal face appears, perhaps 001} with { the 101} crystal face appears.
The crystal face kind that titanium dioxide appeared can be regulated and control through the control reaction time, and in titanium dioxide/Graphene composite nano materials, the ratio of each crystal face that titania nanoparticles is showed can be through control initial reactant (NH
4)
2TiF
6Concentration regulate and control.
Prepared titanium dioxide/Graphene the composite nano materials of the present invention has the following advantages:
1, titania nanoparticles has specific crystal face, is of a size of 200～600 nanometers, and crystalline phase is an anatase titania, and crystal face and ratio thereof are controlled;
2, titanium dioxide has polymolecularity on the Graphene surface, and this structure can provide more avtive spot in catalytic reaction, thereby has more high catalytic activity;
3, therefore titanium dioxide help titanium dioxide with the charge transfer between the Graphene with being combined by firm chemical bond between the Graphene, thereby promote carrier separation, improves catalytic activity;
4, the preparation method of this composite nano materials is simple, and the preparation productive rate is high, has great industrialization prospect.
Photocatalytic activity test to material of the present invention proposes is carried out with the following method:
(cross section 30cm is carried out in the test of photocatalytically degradating organic dye in glass beaker
2, high 5cm) carry out under the normal temperature and pressure.Light source is selected the 300W xenon lamp for use, comes the photocatalytic activity of assess sample with methylene blue dye.Weighing the 10mg sample dispersion is in the methylene blue solution of 10mg/L in 60mL concentration.Before the light-catalyzed reaction, lucifuge stirred 30 minutes, made dye molecule reach adsorption equilibrium at sample surfaces, and every separated 10min gets the 3mL sample behind the logical light, and centrifugation is got supernatant liquor and used the measurement of ultraviolet-visible spectrophotometer absorbance.As a comparison, the P25 graphene composite material (English: P25graphene) measure and under equal conditions to carry out photocatalysis dyestuff degraded test that has identical content of titanium dioxide.
Through the photocatalysis test; Crystal face is adjustable, and titanium dioxide/Graphene composite nano materials can have been degraded methylene blue dye in 40min; And the P25 graphene composite material needs 60min to show that the adjustable titanium dioxide of this crystal face/Graphene composite nano materials has higher photocatalysis efficiency than the P25 Graphene composite nano materials of identical content of titanium dioxide with the methylene blue degraded fully.
Description of drawings
Fig. 1 is the X-ray diffractogram of the embodiment of the invention 1 product;
Fig. 2 is the SEM figure of the embodiment of the invention 1 product;
Fig. 3 is the SEM figure of the embodiment of the invention 2 products;
Fig. 4 is the SEM figure of the embodiment of the invention 3 products;
Fig. 5 is the SEM figure of the embodiment of the invention 4 products.
The specific embodiment
Embodiment 1
At first be equipped with graphene oxide with general chemical oxidation graphite legal system: with the concentrated sulfuric acid and SPA according to 9: 1 mixed configuration 400mL of volume ratio solution.In solution, add 3g graphite flake and 18g KMnO
4, then 50 ℃ of insulated and stirred 12 hours.Reaction naturally cools to room temperature after finishing, and the gained mixture is poured into contained 3mL 30%H
2O
2Ice cube (400mL) in.Then said mixture is successively distinguished centrifuge washing twice with deionized water, 30% hydrochloric acid, ethanol, after products therefrom adds the dispersion of 200mL ether, filter the final vacuum drying and obtain graphene oxide.
With in 4mg graphene oxide dissolving and the 20mL deionized water, ultrasonic dispersion obtains finely dispersed precursor solution half an hour.In this solution, add 120mg (NH4) then
2TiF
6, stir, making its concentration is 0.03mol/L.Mixed solution put into have the teflon-lined autoclave; React 4h down at 160 ℃; Naturally cool to room temperature, after products therefrom was spent deionised water, filters, 60 ℃ of vacuum drying promptly get had { 001} and { titanium dioxide/Graphene composite nano materials that the 100} face is formed.
Accompanying drawing 1 is the X-ray diffractogram of present embodiment products therefrom, can know that by figure each diffraction maximum of this product is anatase TiO
2Accompanying drawing 2 is the SEM figure of present embodiment products therefrom, as can be seen from the figure prepared TiO
2Be the block nano particle in four directions, particle size is 250～300nm, this TiO
2Nano particle is by { 001} is with { the 100} crystal face is formed, and has the dispersiveness of height on the Graphene surface.
The result who more than detects and analyze proves that the resulting product of present embodiment is by { 001} is with { titanium dioxide of 100} crystal face expression evenly spreads to the formed composite nano materials in Graphene surface.Titanium dioxide show therefore { 001} is with { the 100} crystal face has high reaction activity and high, and polymolecularity can provide more reactivity site, in catalytic reaction, has higher activity, has potential using value.
Embodiment 2
At first prepare graphene oxide (with embodiment 1); With in 4mg graphene oxide dissolving and the 20mL deionized water, ultrasonic dispersion obtains finely dispersed precursor solution half an hour.In this solution, add 120mg (NH4) then
2TiF
6, stir, making its concentration is 0.03mol/L.Mixed solution put into have the teflon-lined autoclave; React 24h down at 160 ℃; Naturally cool to room temperature, after products therefrom was spent deionised water, filters, 60 ℃ of vacuum drying promptly get had titanium dioxide/Graphene composite nano materials that different facial is formed.
Accompanying drawing 3 is the SEM figure of the prepared product of present embodiment, can be known by figure, and the crystal face of titanium dioxide granule is { 101} and { 001} face in the product.Titania nanoparticles has higher dispersiveness on the Graphene surface simultaneously.
Embodiment 3
At first prepare graphene oxide (with embodiment 1); With in 4mg graphene oxide dissolving and the 20mL deionized water, ultrasonic dispersion obtains finely dispersed precursor solution half an hour.In this solution, add 40mg (NH then
4)
2TiF
6, stir, making its concentration is 0.01mol/L.Mixed solution put into have the teflon-lined autoclave; React 4h down at 160 ℃; Naturally cool to room temperature, after products therefrom was spent deionised water, filters, 60 ℃ of vacuum drying promptly get had titanium dioxide/Graphene composite nano materials that different facial is formed.
Accompanying drawing 4 is the SEM figure of the prepared product of present embodiment.
Embodiment 4
At first prepare graphene oxide (with embodiment 1); With in 4mg graphene oxide dissolving and the 20mL deionized water, ultrasonic dispersion obtains finely dispersed precursor solution half an hour.In this solution, add 200mg (NH then
4)
2TiF
6, stir, making its concentration is 0.05mol/L.Mixed solution put into have the teflon-lined autoclave; React 4h down at 160 ℃; Naturally cool to room temperature, after products therefrom was spent deionised water, filters, 60 ℃ of vacuum drying promptly get had titanium dioxide/Graphene composite nano materials that different facial is formed.
Accompanying drawing 5 is the SEM figure of the prepared product of present embodiment.
Claims (3)
1. the preparation method of the controlled titanium dioxide/Graphene composite nano materials of a crystal face is characterized in that, comprises that step is following:
(1) is equipped with graphene oxide with conventional chemical graphite oxide legal system;
(2) get graphene oxide and be scattered in the deionized water, ultrasonic dispersion obtains finely dispersed precursor solution, and graphene oxide concentration is 0.1～0.3mg/ml in the precursor solution, in this solution, adds (NH then
4)
2TiF
6, stir, make (NH
4)
2TiF
6Concentration is 0.01～0.05mol/L in mixed solution; Mixed solution put into have the teflon-lined autoclave; React 4～24h down at 150～170 ℃; Naturally cool to room temperature, after products therefrom was spent deionised water, filters, vacuum drying must have the titanium dioxide/Graphene composite nano materials of particular crystal plane.
2. titanium dioxide/Graphene composite nano materials of obtaining of the described preparation method of claim 1.
3. titanium dioxide according to claim 2/Graphene composite nano materials; It is characterized in that; Titania nanoparticles is dispersed in the Graphene surface; Crystalline phase is an anatase titania, titania nanoparticles have 001} with the 100} crystal face appears, perhaps 001} with { the 101} crystal face appears.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103143380A (en) * | 2013-03-21 | 2013-06-12 | 哈尔滨工业大学 | Solvent evaporation method for preparing graphite phase carbon nitride/{001} surface exposed anatase phase titanium dioxide nano composite material |
| CN107890861A (en) * | 2017-11-30 | 2018-04-10 | 新疆维吾尔自治区产品质量监督检验研究院 | One kind has the preparation method of the titanium dioxide lamella/graphene composite film of { 001 } crystal face |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101817552A (en) * | 2010-03-25 | 2010-09-01 | 山东大学 | Titanium dioxide micron tube material and preparation method thereof |
| CN101890344A (en) * | 2010-07-27 | 2010-11-24 | 华东理工大学 | Preparation method of graphene/titanium dioxide composite photocatalyst |
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2011
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101817552A (en) * | 2010-03-25 | 2010-09-01 | 山东大学 | Titanium dioxide micron tube material and preparation method thereof |
| CN101890344A (en) * | 2010-07-27 | 2010-11-24 | 华东理工大学 | Preparation method of graphene/titanium dioxide composite photocatalyst |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103143380A (en) * | 2013-03-21 | 2013-06-12 | 哈尔滨工业大学 | Solvent evaporation method for preparing graphite phase carbon nitride/{001} surface exposed anatase phase titanium dioxide nano composite material |
| CN107890861A (en) * | 2017-11-30 | 2018-04-10 | 新疆维吾尔自治区产品质量监督检验研究院 | One kind has the preparation method of the titanium dioxide lamella/graphene composite film of { 001 } crystal face |
| CN107890861B (en) * | 2017-11-30 | 2020-09-29 | 新疆维吾尔自治区产品质量监督检验研究院 | Preparation method of titanium dioxide lamella/graphene composite film with {001} crystal face |
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