CN102380364A - Preparation method of TiO2/graphene composite film - Google Patents
Preparation method of TiO2/graphene composite film Download PDFInfo
- Publication number
- CN102380364A CN102380364A CN2011102580506A CN201110258050A CN102380364A CN 102380364 A CN102380364 A CN 102380364A CN 2011102580506 A CN2011102580506 A CN 2011102580506A CN 201110258050 A CN201110258050 A CN 201110258050A CN 102380364 A CN102380364 A CN 102380364A
- Authority
- CN
- China
- Prior art keywords
- tio
- graphene
- graphene oxide
- film
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Abstract
The invention provides a preparation method of a layered TiO2/graphene composite film. The preparation method comprises the following steps: 1, a graphene oxide is prepared with a chemical peeling method (also known as a graphite reduction oxidation method); 2, the large area uniform graphene oxide and a TiO2 nanofilm are sequentially prepared with a rotary coating technology; and 3, the prepared layered composite film is irradiated by placing it under an ultraviolet lamp, and the graphene oxide is reduced into graphene by photoproduced electrons produced by TiO2 in the irradiation process to form the TiO2/graphene composite film. The preparation method of the invention can be applied to the photocatalytic purification field. Compared with the TiO2 nanofilm, the layered composite film has an obviously improved absorption efficiency to visible light, and has a substantially improved degradation efficiency on organic pollutants.
Description
Technical field
The present invention relates to a kind of titanium dioxide (TiO
2The preparation method of)/Graphene laminated film belongs to nano material and photocatalysis field.
Background technology
As a kind of application photocatalyst material the most widely, TiO
2Played the part of the key player at aspects such as environmental pollution improvement and solar energy utilizations.At present, at TiO
2Aspects such as preparation very big breakthrough has been arranged, but since its energy gap be 3.2
(anatase, Anatase), can only absorbing wavelength less than the ultraviolet light of 387nm, photocatalysis efficiency is very low.Therefore, a lot of scientists concentrate on TiO with the emphasis of research
2The visible light modification with improve on the catalytic efficiency.At present, the method that is used for the visible light modification mainly contains mixes and compound.This wherein, carbon nanomaterial is because its unique physical and chemical performance, makes itself and TiO
2The Photocatalytic Performance Study of composite becomes a popular direction.
Cellular lattice structure of the bidimensional that Graphene is made up of the carbon hexatomic ring (2D) cycle; It can warpage becomes the fullerene (fullerene) of zero dimension (0D); Be rolled into CNT (the carbon nanotube of one dimension (1D); So Graphene is the elementary cell that constitutes other graphite materials CNT) or be stacked to the graphite (graphite) of three-dimensional (3D).Research shows that the theoretical specific area of Graphene is up to 2600 m
2g
-1Have outstanding heat conductivility (3000 Wm-1K-1)) and mechanical property (1060 GPa); And at a high speed electron mobility (15000cm2V-1s-1) under the room temperature); The Graphene particular structural, a series of character such as electrical conductivity that make it have perfect quantum tunneling effect, half integral quantum hall effect, never disappear.These special nature can make that all Graphene produces active influence to light-catalyzed reaction.Therefore, for other carbon nanomaterial, Graphene and TiO
2Compound possibly be even more ideal catalysis material.
At present, preparation TiO
2Mainly contain two kinds of hydro-thermal method, sol-gel processes with the method for graphene composite material.The characteristics of these methods are with TiO
2Nano particle and Graphene carry out compound.For example:
Hydro-thermal method: at first the graphite powder oxidation processes is become graphene oxide, then with itself and TiO
2Nano particle mixes and to carry out hydro-thermal reaction (120 ℃ are following 3 hours), last graphene oxide through in the process of hydrothermal reduction with TiO
2Nano particle is realized compound.The method
Advantage: TiO
2Directly form good Xiao Tuoji with Graphene and contact, even the formation chemical bonding, stoped compound problem in the right body in photocatalytic process light induced electron hole well, make photocatalysis performance be improved significantly.
Shortcoming: owing to compoundly concentrate on the position that the graphene oxide surface functional group exists, make TiO
2Nano particle can not all be distributed in the Graphene surface, is difficult to better shift fast TiO thus
2Photo-generated carrier through the illumination generation.In addition,, there is problems such as recycling and reclaim difficulty in actual applications, its photocatalysis efficiency and life-span are brought very big influence because this composite photo-catalyst is the powder of micro-nano-scale.
Sol-gal process: at first utilize chemical stripping method (claiming reduction-oxidation graphite method again) to prepare Graphene, again Graphene, butyl titanate, alcohol, acetate and distilled water are mixed with out colloidal sol successively, and dry down at 80 ℃; Then the presoma of preparing (in air or nitrogen atmosphere) under 450 ℃ was calcined 2 hours, obtained TiO at last
2/ graphene composite material.This method
Advantage: direct growth goes out TiO on the Graphene surface
2Nano particle, composite effect is even, helps the separation of photo-generated carrier; Simultaneously, owing to directly utilize Graphene, can more accurately control Graphene proportion in composite as presoma.
Shortcoming: the experimentation very complicated needs the time cycle long.In addition, identical with hydro-thermal method, the composite for preparing is a nanometer powder, and the recycling difficulty is difficult to functionalization and device.
In recent years, the life problems of catalysis material and device thereof are used a research direction that is.It is generally acknowledged and on matrix, prepare TiO
2The method of film can overcome TiO
2The deficiency that nano particle brought.Prepare TiO at present
2The method of film has pulsed laser deposition (PLD), magnetron sputtering method (sputtering), differential arc oxidation method (MAO) etc.For example:
Pulsed laser deposition (PLD): the high intensity pulses laser beam that utilizes excimer pulse laser to produce focuses on TiO
2Target material surface makes target material surface produce high temperature and corrode, and further produces the HTHP plasma, and the directed local of plasma expands to launch and on substrate, deposit and forms TiO
2Film.
Advantage: the growth parameter(s) of pulsed laser deposition is independent adjustable, is easy to TiO
2The growth for Thin Film process is accurately controlled, and can prepare uniform nanoscale TiO
2Film.
Shortcoming: the TiO that pulsed laser deposition is prepared
2Film is many to be existed with amorphous form, need heat-treat annealing, TiO
2Crystal formation is difficult to obtain fine control, especially with the material with carbon element compound tense because the crystallized temperature of amorphous carbon is higher than TiO far away
2Phase transition temperature (anatase-rutile).
Magnetron sputtering method: the cation that utilizes gas discharge to produce bombards the TiO as negative electrode at a high speed under electric field action
2Target material surface makes atom or molecule in the target penetrate from the surface and deposits to the surface of workpiece to be plated, forms needed film.
Advantage: the TiO that is obtained
2Film purity is high, and is better with substrate bonded, can on large-area substrates, prepare the uniform film of thickness.Simultaneously, in target, add various dopants, be easy to prepare the TiO of even doping
2Film is a kind of preparation doped Ti O
2The effective way of catalysis material.
Shortcoming: factors such as the temperature in the sputter procedure, air pressure are very high to the requirement of substrate, and sputtering technology is comparatively complicated, and its application is brought limitation.The parameter difference such as sputtering technology, film deposition rate and depositing temperature of different targets are bigger, therefore, are difficult to prepare TiO
2The base composite photocatalysis film.
Differential arc oxidation method: valve metal such as Ti or its alloy are placed electrolyte solution, utilize electrochemical method, in the micropore on surface, produce the spark discharge spot, generation TiO under heat chemistry, plasma chemistry and electrochemical acting in conjunction
2Ceramic membrane.
Advantage: the TiO that differential arc oxidation is prepared
2Film combines with titanium alloy substrate closely, and the film outermost layer is porous, anatase phase TiO
2, help giving full play to of photocatalysis performance.
Shortcoming: substrate surface temperature is up to 2000 ℃ in the micro-arc discharge process, and therefore, differential arc oxidization technique can only be confined to photocatalysis TiO
2Film carry out metal or metal oxide compound, and be difficult to carry out effectively compound with material with carbon element.
Comprehensive TiO
2The preparation method of photocatalysis film can find out that immobilized photocatalysis film material has overcome the difficult problem that photocatalytic nanometer particle in traditional suspension system is difficult to Separation and Recovery, has played great impetus to the application of catalysis material.Yet these masking techniques are for chemical preparation method, and technological requirement is more complicated, particularly are difficult to realize the compound of TiO and material with carbon element.Therefore, up to the present, about preparation TiO
2The method of/Graphene laminated film also is not reported.
In view of the foregoing, we attempt to prepare TiO through simple spin coating method
2/ Graphene stratiform is compound, and (layer-by-layer, LBL) film, this layered composite film can be good at overcoming that nano particle is difficult to Separation and Recovery and thin-film material is difficult to carry out a compound difficult problem with Graphene.The material that it is advantageous that different performance can be worked in coordination with together well, displays one's respective advantages most possibly.And combine between rete and matrix closely to have strengthened TiO
2The photocatalysis performance of/graphene composite material and cycle life have good prospect in the application facet of functionalization and device.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of TiO
2The preparation method of/Graphene laminated film.
The present invention solves the problems of the technologies described above the technical scheme that is provided to be: at first adopt chemical stripping method (claiming reduction-oxidation graphite method again) preparation graphene oxide, mainly comprise the pre-oxidation (removing carbon nano-particle) and secondary oxidation (graphite layers the is inserted functional group) process of graphite; Adopt the rotation paint-on technique to prepare uniform graphene oxide film of thickness and nano-TiO successively afterwards
2Film; At last the layered composite film for preparing is positioned over irradiation under the uviol lamp, in this process, TiO
2The light induced electron that produces is reduced into Graphene with graphene oxide, forms TiO
2/ Graphene stratiform laminated film.
Technique scheme specifically comprises the steps:
1, the preparation of graphene oxide: the existing method according to well known in the art prepares, like the chemical stripping method.
2, rotation applies: respectively with graphene oxide and TiO
2Nano particle is dissolved in organic solvent, is made into suspension, and its mass concentration is respectively 0.1 ~ 1 mg/ml, 1 ~ 10 mg/ml; Adopt spin coating method to prepare graphene oxide film and nano-TiO successively
2Film, 2500 ~ 3000 rev/mins of rotating speeds, every layer of coating time is 30 ~ 60 seconds, the feed liquor amount is 1 ~ 2 ml, and is dry under 40 ~ 60 ℃ after applying, and carries out behind the even dry film to be formed applying next time again, finally forms TiO
2/ graphene oxide layered composite film;
3. the reduction of graphene oxide: with the above-mentioned graphene oxide/TiO for preparing
2The ultraviolet light that layered composite film is put into 254 ~ 325nm wavelength band shone 2 ~ 5 hours down, in this process, and TiO
2The light induced electron that produces is reduced into Graphene with graphene oxide, promptly obtains TiO
2/ Graphene stratiform laminated film.
The process that described chemical stripping legal system is equipped with graphene oxide is: with 0.3 g graphite powder, 0.5 g K
2S
2O
4With 0.5 g P
2O
5Be mixed to join 2 ~ 4 ml 98% in, 80 ℃ of following constant temperature stirred 4 hours, obtained dark blue solution.After the filtration head product joined the dense H of the mass concentration 98% of 12 ml
2SO
4In, slowly add 1.5 g KMnO
4, make the mixed solution temperature be no more than 20 ℃, 35 ℃ of following constant temperature stirred 2 hours then, and solution is yellowish-brown.Add 25 ml distilled water continued and stir, add 70 ml distilled water and 2 ml mass concentrations after 2 hours once more and be 30% H
2O
2, reduce the not KMnO of complete reaction
4, solution becomes glassy yellow.Filter successively again, pickling, washing, drying, promptly obtain graphene oxide.
The TiO that the inventive method is prepared
2/ Graphene stratiform laminated film can be used for the light catalytic purifying field.
The inventive method is at first prepared number of plies graphene oxide seldom, and successively with graphene oxide and TiO
2Nano particle is rotated to apply prepares graphene oxide/TiO
2Layered composite film utilizes TiO at last under the irradiation of ultraviolet light
2The light induced electron that produces reduces graphene oxide, obtains Graphene/TiO
2Layered composite film.This layered composite film has improved photochemical catalyst greatly and has treated the adsorption capacity of degradation product and the transfer efficiency of photo-generated carrier, thereby has improved photocatalysis performance.Pure TiO with the rotation coating
2Nano thin-film is compared, and layered composite film obviously improves ultraviolet light and absorption of visible light efficient, and the degradation efficiency of degraded organic contamination significantly improves.The inventive method technology is simple in addition, and the preparation process is easy to control, and production efficiency is high, and environmental pollution is little, simultaneously, impetus has been played in the device development of photochemical catalyst.In a word, the present invention has useful effect.
Description of drawings
Fig. 1 is the TiO of embodiment 1 preparation
2The high-resolution-ration transmission electric-lens of/graphene composite material (HRTEM) figure;
Fig. 2 is the TiO of embodiment 2 preparations
2Raman spectrum (Raman) figure of/Graphene stratiform laminated film;
Fig. 3 is the TiO of embodiment 3 preparations
2ESEM (SEM) profile of/Graphene stratiform laminated film;
Fig. 4 is the TiO of Comparative Examples and embodiment 4 preparations
2Ultraviolet-visible (UV-Vis) the absorption spectrum comparison diagram of/Graphene stratiform laminated film;
Fig. 5 is the TiO of Comparative Examples and embodiment 4 preparations
2/ Graphene stratiform laminated film is to the degradation effect comparison diagram of rhodamine-B solution.
The specific embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is further set forth, but therefore do not limit the present invention within the described scope of embodiments.
Embodiment 1:
With 0.3 g graphite powder, 0.5 g K
2S
2O
4With 0.5 g P
2O
5The mass fraction that is mixed to join 2 ~ 4 ml is 98% dense H
2SO
4In, 80 ℃ of following constant temperature stirred 4 hours, obtained dark blue solution.The mass fraction that after the filtration head product is joined 12 ml is 98% dense H
2SO
4In, slowly add 1.5 g KMnO
4, make the mixed solution temperature be no more than 20 ℃, 35 ℃ of following constant temperature stirred 2 hours then, and solution is yellowish-brown.Add 25 ml distilled water continued and stir, add 70 ml distilled water and 2 ml mass fractions after 2 hours once more and be 30% H
2O
2, reduce the not KMnO of complete reaction
4, solution becomes glassy yellow.Filter successively again, pickling, washing, drying, promptly obtain graphene oxide.
Dispose graphene oxide and TiO respectively
2The alcohol suspension of nano particle, its mass concentration is respectively 0.1 mg/ml, 1 mg/ml.Adopt spin coating method to prepare graphene oxide film and TiO successively
2Nano thin-film, rotating speed are 2500 rev/mins, and the time is 30 seconds, and the feed liquor amount is 1 ml, and each back that applies is dry under 60 ℃, carries out applying next time again, finally forms TiO
2/ graphene oxide layered composite film.With the above-mentioned TiO for preparing
2The ultraviolet light that/graphene oxide layered composite film is put into 254 ~ 325nm wavelength band shone 2 hours down, in this process, and TiO
2The light induced electron that produces is reduced into Graphene with graphene oxide, promptly obtains Graphene/TiO
2Layered composite film.
Graphene/the TiO of embodiment 1 preparation
2(HRTEM) is as shown in Figure 1 for the high-resolution-ration transmission electric-lens of composite, and by finding out among the figure: the graphene oxide number of plies that makes is less, TiO
2Nano particle is evenly distributed on the Graphene surface.
Embodiment 2: with 0.3 g graphite powder, 0.5 g K
2S
2O
4With 0.5 g P
2O
5Be mixed to join 2 ~ 4 ml mass fractions and be 98% dense H
2SO
4In, 80 ℃ of following constant temperature stirred 4 hours, obtained dark blue solution.After the filtration head product being joined 12 ml mass fractions is 98% dense H
2SO
4In, slowly add 1.5 g KMnO
4, make the mixed solution temperature be no more than 20 ℃, 35 ℃ of following constant temperature stirred 2 hours then, and solution is yellowish-brown.Add 25 ml distilled water continued and stir, add 70 ml distilled water and 2 ml mass concentrations after 2 hours once more and be 30% H
2O
2, reduce the not KMnO of complete reaction
4, solution becomes glassy yellow.Filter successively again, pickling, washing, drying, promptly obtain graphene oxide.
Dispose graphene oxide and TiO respectively
2The acetone suspension of nano particle, its mass concentration is respectively 0.4 mg/ml, 4mg/ml.Adopt spin coating method to prepare graphene oxide film and TiO successively
2Nano thin-film, rotating speed are 2500 rev/mins, and the time is 40 seconds, and the feed liquor amount is 1.5 ml, and each back that applies is dry under 60 ℃, carries out applying next time again, finally forms TiO
2/ graphene oxide layered composite film.With the above-mentioned TiO for preparing
2The ultraviolet light that/graphene oxide layered composite film is put into 254 ~ 325nm wavelength band shone 3 hours down, finally obtained Graphene/TiO
2Layered composite film.
TiO by embodiment 2 preparations
2The Raman spectrum of/Graphene stratiform laminated film is as shown in Figure 2, therefrom can find out: TiO
2Clear with the Raman peaks of Graphene, Graphene and TiO promptly are described
2Nano particle is compound good.
Embodiment 3: with 0.3 g graphite powder, 0.5 g K
2S
2O
4With 0.5 g P
2O
5Be mixed to join 2 ~ 4 ml mass fractions and be 98% dense H
2SO
4In, 80 ℃ of following constant temperature stirred 4 hours, obtained dark blue solution.After the filtration head product being joined 12 ml mass fractions is 98% dense H
2SO
4In, slowly add 1.5 g KMnO
4, make the mixed solution temperature be no more than 20 ℃, 35 ℃ of following constant temperature stirred 2 hours then, and solution is yellowish-brown.Add 25 ml distilled water continued and stir, add 70 ml distilled water and 2 ml mass concentrations after 2 hours once more and be 30% H
2O
2, reduce the not KMnO of complete reaction
4, solution becomes glassy yellow.Filter successively again, pickling, washing, drying, promptly obtain graphene oxide.
Dispose graphene oxide and TiO respectively
2The alcohol suspension of nano particle, its mass concentration is respectively 0.7 mg/ml, 7 mg/ml.Adopt spin coating method to prepare graphene oxide film and TiO successively
2Nano thin-film, rotating speed are 3000 rev/mins, and the time is 50 seconds, and the feed liquor amount is 2 ml, and each back that applies is dry under 60 ℃, carries out applying next time again, finally forms TiO
2/ graphene oxide layered composite film.With the above-mentioned TiO for preparing
2The ultraviolet light that/graphene oxide layered composite film is put into 254 ~ 325nm wavelength band shone 4 hours down, promptly obtained Graphene/TiO
2Layered composite film.
TiO by embodiment 3 preparations
2ESEM (SEM) profile of/Graphene stratiform laminated film is as shown in Figure 3,
Embodiment 4: with 0.3 g graphite powder, 0.5 g K
2S
2O
4With 0.5 g P
2O
5Be mixed to join 2 ~ 4 ml mass fractions and be 98% dense H
2SO
4In, 80 ℃ of following constant temperature stirred 4 hours, obtained dark blue solution.After the filtration head product being joined 12 ml mass fractions is 98% dense H
2SO
4In, slowly add 1.5 g KMnO
4, make the mixed solution temperature be no more than 20 ℃, 35 ℃ of following constant temperature stirred 2 hours then, and solution is yellowish-brown.Add 25 ml distilled water continued and stir, add 70 ml distilled water and 2 ml mass concentrations after 2 hours once more and be 30% H
2O
2, reduce the not KMnO of complete reaction
4, solution becomes glassy yellow.Filter successively again, pickling, washing, drying, promptly obtain graphene oxide.
Dispose graphene oxide and TiO respectively
2The nano particle alcohol suspension, its mass concentration is respectively 1 mg/ml, 10 mg/ml.Adopt spin coating method to prepare graphene oxide film and TiO successively
2Nano thin-film, rotating speed are 3000 rev/mins, and the time is 60 seconds, and the feed liquor amount is 2 ml, and each back that applies is dry under 60 ℃, carries out applying next time again, finally forms TiO
2/ graphene oxide layered composite film.With the above-mentioned TiO for preparing
2The ultraviolet light that/graphene oxide layered composite film is put into 254 ~ 325nm wavelength band shone 5 hours down, promptly obtained Graphene/TiO
2Layered composite film.
Comparative Examples: the TiO that disposes 10 mg/ml
2The nano particle alcohol suspension adopts spin coating method to prepare TiO
2Nano thin-film, rotating speed are 3000 rev/mins, and the time is 60 seconds, and the feed liquor amount is 2 ml, promptly obtain TiO after the drying
2Nano thin-film.
Shown in Figure 4 is the TiO of embodiment 4 preparations
2The TiO of/Graphene stratiform laminated film and Comparative Examples preparation
2The ultraviolet-visible of nano thin-film (UV-Vis) absorption spectrum comparison diagram, therefrom can find out: the layered composite film of embodiment 4 preparations improves the absorption intensity of visible light wave range, and the red shift phenomenon has taken place.
With two samples of embodiment 4 and Comparative Examples be used to degrade contrast experiment of rhodamine B solution, the concentration of rhodamine B solution is 12 mg/litre in the experiment, and the light source that adopts is a high-pressure sodium lamp.Contrast and experiment is as shown in Figure 5, can be drawn by Fig. 5: layered composite film to the degradation rate of rhodamine B solution with respect to TiO
2Nano thin-film obviously improves.
Claims (2)
1. TiO
2The preparation method of laminated film is characterized in that, at first adopts the chemical stripping legal system to be equipped with graphene oxide; Adopt the rotation paint-on technique to prepare uniform graphene oxide film of thickness and nano-TiO successively afterwards
2Film; At last the layered composite film for preparing is positioned over irradiation under the uviol lamp, in this process, TiO
2The light induced electron that produces is reduced into Graphene with graphene oxide, forms TiO
2/ Graphene stratiform laminated film.
2. preparation method as claimed in claim 1 is characterized in that, specifically comprises the steps:
1) preparation of graphene oxide;
2) rotation applies: respectively with graphene oxide and TiO
2Nano particle is dissolved in organic solvent, is made into suspension, and its mass concentration is respectively 0.1 ~ 1 mg/ml, 1 ~ 10 mg/ml; Adopt spin coating method to prepare graphene oxide film and nano-TiO successively
2Film, 2500 ~ 3000 rev/mins of rotating speeds, every layer of coating time is 30 ~ 60 seconds, the feed liquor amount is 1 ~ 2 ml, and is dry under 40 ~ 60 ℃ after applying, and carries out behind the even dry film to be formed applying next time again, finally forms TiO
2/ graphene oxide layered composite film;
3) reduction of graphene oxide: with the above-mentioned graphene oxide/TiO for preparing
2The ultraviolet light that layered composite film is put into 254 ~ 325nm wavelength band shone 2 ~ 5 hours down, in this process, and TiO
2The light induced electron that produces is reduced into Graphene with graphene oxide, promptly obtains TiO
2/ Graphene stratiform laminated film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102580506A CN102380364A (en) | 2011-09-02 | 2011-09-02 | Preparation method of TiO2/graphene composite film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102580506A CN102380364A (en) | 2011-09-02 | 2011-09-02 | Preparation method of TiO2/graphene composite film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102380364A true CN102380364A (en) | 2012-03-21 |
Family
ID=45820438
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011102580506A Pending CN102380364A (en) | 2011-09-02 | 2011-09-02 | Preparation method of TiO2/graphene composite film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102380364A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103207222A (en) * | 2013-04-12 | 2013-07-17 | 中国科学院山西煤炭化学研究所 | Method for preparing graphene nano-material electrochemical sensor by atomic layer deposition process |
| CN103203252A (en) * | 2013-04-23 | 2013-07-17 | 武汉大学 | Three-dimensional net structure composite material, and preparation method and application |
| CN103360109A (en) * | 2013-06-28 | 2013-10-23 | 东南大学 | Method for preparing structural color film based on layer-by-layer assembly technology and product and application thereof |
| CN104596994A (en) * | 2014-12-15 | 2015-05-06 | 浙江大学 | Europium-doped titanium dioxide/graphene oxide composite film and preparation method thereof |
| CN104624220A (en) * | 2015-02-10 | 2015-05-20 | 济南大学 | Preparation method of TiO2/rGO composite |
| CN105181770A (en) * | 2015-09-09 | 2015-12-23 | 上海大学 | Preparation method of manganese dioxide/graphene/titanium dioxide-modified glassy carbon electrode for electrochemical detection of hydrogen peroxide and application of preparation method |
| CN106317976A (en) * | 2016-09-08 | 2017-01-11 | 上海理工大学 | Preparation method of graphene/titanium dioxide transparent anticorrosive coating |
| CN106745481A (en) * | 2016-12-23 | 2017-05-31 | 哈尔滨工业大学 | One kind fills the continuous photocatalysis method of Graphene/P25 laminated films based on secondary groups |
| CN107159178A (en) * | 2016-12-19 | 2017-09-15 | 广东工业大学 | A kind of TiO of graphene modified2The preparation method of membranaceous compound and its application in photocatalysis degradation organic contaminant |
| CN107819123A (en) * | 2017-10-31 | 2018-03-20 | 南京旭羽睿材料科技有限公司 | A kind of graphene combination electrode material |
| CN108043394A (en) * | 2017-12-15 | 2018-05-18 | 长春理工大学 | A kind of preparation method of Ag doped with nano stick laminated film for the VOCs that degrades |
| CN108854540A (en) * | 2018-07-06 | 2018-11-23 | 江西博鑫精陶环保科技有限公司 | A kind of large-scale photocatalysis inorganic titanium plate membrane reaction bed for sewage treatment |
| CN114023963A (en) * | 2021-10-26 | 2022-02-08 | 陕西科技大学 | MXene @ TiS2-TiO2Flexible composite film and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101474899A (en) * | 2009-01-16 | 2009-07-08 | 南开大学 | Grapheme-organic material layered assembling film and preparation method thereof |
| CN101658786A (en) * | 2009-09-25 | 2010-03-03 | 上海大学 | Method for preparing graphene-based titanium dioxide composite photocatalyst by radiation of electron beams |
-
2011
- 2011-09-02 CN CN2011102580506A patent/CN102380364A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101474899A (en) * | 2009-01-16 | 2009-07-08 | 南开大学 | Grapheme-organic material layered assembling film and preparation method thereof |
| CN101658786A (en) * | 2009-09-25 | 2010-03-03 | 上海大学 | Method for preparing graphene-based titanium dioxide composite photocatalyst by radiation of electron beams |
Non-Patent Citations (1)
| Title |
|---|
| KIRAN K M ET AL.: "Multilayer hybrid films consisting of alternating grapheme and titania nanosheets with ultrafast electron transfer and photoconversion properties", 《说明书第3-4页实施例2》 * |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103207222A (en) * | 2013-04-12 | 2013-07-17 | 中国科学院山西煤炭化学研究所 | Method for preparing graphene nano-material electrochemical sensor by atomic layer deposition process |
| CN103207222B (en) * | 2013-04-12 | 2015-03-25 | 中国科学院山西煤炭化学研究所 | Method for preparing graphene nano-material electrochemical sensor by atomic layer deposition process |
| CN103203252A (en) * | 2013-04-23 | 2013-07-17 | 武汉大学 | Three-dimensional net structure composite material, and preparation method and application |
| CN103360109A (en) * | 2013-06-28 | 2013-10-23 | 东南大学 | Method for preparing structural color film based on layer-by-layer assembly technology and product and application thereof |
| CN103360109B (en) * | 2013-06-28 | 2015-07-15 | 东南大学 | Method for preparing structural color film based on layer-by-layer assembly technology and product and application thereof |
| CN104596994A (en) * | 2014-12-15 | 2015-05-06 | 浙江大学 | Europium-doped titanium dioxide/graphene oxide composite film and preparation method thereof |
| CN104596994B (en) * | 2014-12-15 | 2017-05-03 | 浙江大学 | Europium-doped titanium dioxide/graphene oxide composite film and preparation method thereof |
| CN104624220B (en) * | 2015-02-10 | 2016-09-07 | 济南大学 | One prepares TiO2the method of/rGO composite |
| CN104624220A (en) * | 2015-02-10 | 2015-05-20 | 济南大学 | Preparation method of TiO2/rGO composite |
| CN105181770A (en) * | 2015-09-09 | 2015-12-23 | 上海大学 | Preparation method of manganese dioxide/graphene/titanium dioxide-modified glassy carbon electrode for electrochemical detection of hydrogen peroxide and application of preparation method |
| CN106317976A (en) * | 2016-09-08 | 2017-01-11 | 上海理工大学 | Preparation method of graphene/titanium dioxide transparent anticorrosive coating |
| CN107159178A (en) * | 2016-12-19 | 2017-09-15 | 广东工业大学 | A kind of TiO of graphene modified2The preparation method of membranaceous compound and its application in photocatalysis degradation organic contaminant |
| CN106745481A (en) * | 2016-12-23 | 2017-05-31 | 哈尔滨工业大学 | One kind fills the continuous photocatalysis method of Graphene/P25 laminated films based on secondary groups |
| CN107819123A (en) * | 2017-10-31 | 2018-03-20 | 南京旭羽睿材料科技有限公司 | A kind of graphene combination electrode material |
| CN108043394A (en) * | 2017-12-15 | 2018-05-18 | 长春理工大学 | A kind of preparation method of Ag doped with nano stick laminated film for the VOCs that degrades |
| CN108854540A (en) * | 2018-07-06 | 2018-11-23 | 江西博鑫精陶环保科技有限公司 | A kind of large-scale photocatalysis inorganic titanium plate membrane reaction bed for sewage treatment |
| CN114023963A (en) * | 2021-10-26 | 2022-02-08 | 陕西科技大学 | MXene @ TiS2-TiO2Flexible composite film and preparation method thereof |
| CN114023963B (en) * | 2021-10-26 | 2022-09-13 | 陕西科技大学 | MXene @ TiS 2 -TiO 2 Flexible composite film and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102380364A (en) | Preparation method of TiO2/graphene composite film | |
| Wang et al. | Synthesis, modification and application of titanium dioxide nanoparticles: A review | |
| Ahmad et al. | Advancements in the development of TiO2 photoanodes and its fabrication methods for dye sensitized solar cell (DSSC) applications. A review | |
| Low et al. | Recent developments of graphene-TiO2 composite nanomaterials as efficient photoelectrodes in dye-sensitized solar cells: A review | |
| Peng et al. | (111) TiO2-x/Ti3C2: Synergy of active facets, interfacial charge transfer and Ti3+ doping for enhance photocatalytic activity | |
| Jia et al. | Graphitic carbon nitride films: emerging paradigm for versatile applications | |
| Kuai et al. | Rational construction of a CdS/reduced graphene oxide/TiO 2 core–shell nanostructure as an all-solid-state Z-scheme system for CO 2 photoreduction into solar fuels | |
| Guo et al. | Graphene-based materials for photoanodes in dye-sensitized solar cells | |
| Yang et al. | Cyano and potassium-rich gC 3 N 4 hollow tubes for efficient visible-light-driven hydrogen evolution | |
| Wei et al. | Spontaneous photoelectric field-enhancement effect prompts the low cost hierarchical growth of highly ordered heteronanostructures for solar water splitting | |
| Baynosa et al. | Solvent-driven morphology-controlled synthesis of highly efficient long-life ZnO/graphene nanocomposite photocatalysts for the practical degradation of organic wastewater under solar light | |
| Bandi et al. | Oxygen-deficient tungsten oxides | |
| Gnanamoorthy et al. | Photocatalytic properties of amine functionalized Bi2Sn2O7/rGO nanocomposites | |
| CN111992239B (en) | Silver/bismuth vanadate/carbon nitride heterojunction photocatalyst and preparation method and application thereof | |
| Pan et al. | In situ construction of g-C3N4/TiO2 heterojunction films with enhanced photocatalytic activity over magnetic-driven rotating frame | |
| Recepoglu et al. | Boron carbon nitride nanosheets in water and wastewater treatment: A critical review | |
| Zhang et al. | WO3/TiO2 heterojunction photocatalyst prepared by reactive magnetron sputtering for Rhodamine B dye degradation | |
| Wang et al. | Defect engineering in two-dimensional graphitic carbon nitride and application to photocatalytic air purification | |
| WO2022062228A1 (en) | Z-type heterojunction photoanode production method and z-type heterojunction photoanode | |
| Duan et al. | Elemental phosphorus for recent sustainable processes: rules and strategies in preparation and applications | |
| Qu et al. | Two-dimensional nanomaterials: synthesis and applications in photothermal catalysis | |
| Priya et al. | Construction of MoS2 nanoparticles incorporated TiO2 nanosheets heterojunction photocatalyst for enhanced visible light driven hydrogen production | |
| Kang et al. | Harmonious K–I–O co-modification of gC 3 N 4 for improved charge separation and photocatalysis | |
| Chen et al. | Manganese phosphorous trifulfide nanosheets and nitrogen doped carbon dot composites with manganese vacancies for a greatly enhanced hydrogen evolution | |
| CN107497427A (en) | A kind of silver/graphite alkene/zinc oxide composite preparation method of degradable formaldehyde |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120321 |