CN101045555A - Method for modifying titanium dioxide film by heterocyclic compound - Google Patents
Method for modifying titanium dioxide film by heterocyclic compound Download PDFInfo
- Publication number
- CN101045555A CN101045555A CNA2006100664493A CN200610066449A CN101045555A CN 101045555 A CN101045555 A CN 101045555A CN A2006100664493 A CNA2006100664493 A CN A2006100664493A CN 200610066449 A CN200610066449 A CN 200610066449A CN 101045555 A CN101045555 A CN 101045555A
- Authority
- CN
- China
- Prior art keywords
- film
- titanium dioxide
- preparation
- dioxide film
- heterocyclic compound
- 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.)
- Granted
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
A process for modifying TiO2 film by heterocyclic compound includes such steps as pre-treating TiO2 film in vacuum heating condition, vacuum modifying reaction between the low-boiling micro-molecular heterocyclic compound containing N or S and the high-activity suspended bonds on the surface of TiO2 film, flushing with absolute alcohol, and vacuum drying.
Description
Technical field
The present invention relates to the functionalization preparation method of semiconductor film material.Particularly to the modifying method of titanium deoxid film.
Background technology
Can realize effective control of physics, chemistry and optical property to the regulation and control of semi-conductor nano-material surface structure, thereby widen the scope of application of material, make material obtain more effectively utilizing semiconductor material.The nano titania semiconductor material is because it is nontoxic, low price, have very high redox ability and superpower chemical physical stability simultaneously, in the oxidative degradation of organic pollutant, the aqueous solution, obtained aspect metal ion or organic reduction and the solar energy photoelectric conversion using widely.Utilize titanium dioxide surface to exist the characteristic of active hydroxyl a lot of at present to the research that titanium dioxide granule carries out finishing, as document " Surface Complexation of Colloidal Semiconductors Strongly Enhances InterfacialElectron-Transfer Rates ", J.Moser, S.Punchihewa, P.P.Infleta, M.Gratzel, Langmuir 7 (1991), 3012-3018 has reported and has utilized M-nitro benzoic acid, phthalic acid, m-phthalic acid, terephthalic acid and Whitfield's ointment etc. form the titanic chelate structure with the hydroxyl reaction of titanium dioxide surface; People such as Rajh successively utilize the organo-functional group that halfcystine, vitamins C, xitix, pyrocatechol etc. contain carboxyl or rare glycol to realize the finishing of titanium dioxide (is seen " Surface Modification of Small ParticleTiO
2Colloidal with Cysteine for Enhances Photochemical Reduction:An EPRStudy ", T.Rajh, A.E.Ostfin, O.I.Micic, D.M.Tiede, M.C.Thunnauer, 100 (1996), 4538-4545); Above-mentioned modifying method all is by titanium dioxide granule is immersed in the solution that includes its modifier, utilizes that carboxyl reaction realizes its particulate finishing (pickling process) in the hydroxyl of titanium dioxide surface and the organic molecule.And this method requires the modifier molecule to contain enediol base or carboxyl functional group, has limited the scope of decorating molecule.Compare with the titanium dioxide granule material, its film has bigger use value in actual applications, but at present the modification research of thin-film material is carried out seldom.Document " Surface Modification andPhotosensitization of TiO
2Nanocrystalline Film with Ascorbic Acid "; A.P.Xagas; M.C.Bernard; A.Hugot-Le Goff; N.Spyrellis; Z.Loizos, P.Falaras, J Photochem.Photobiol.A:Chem., 132 (2000), 115-120 discloses, people such as A.P.Xagas adopt the dipping method similar to above-mentioned titanium dioxide granule modification that xitix is modified the titanium deoxid film surface, make the absorption red shift of film, improved utilization, but this method is modified the photoelectrochemistry less stable of back titanium dioxide film materials solar spectrum.
Summary of the invention:
The invention provides a kind of method of modifying titanium dioxide film by heterocyclic compound, can make the titanium atom on titanium deoxid film surface and heterogeneous ring compound form stable electronics and grip system altogether, thereby improve the stability of titanium dioxide film materials photoelectrochemistry.
Preparation method of the present invention: earlier titanium deoxid film is carried out pre-treatment in the device that continues to vacuumize, pretreatment temperature is 300-450 ℃, time 4-12 hour, makes film surface form the active Ti key that dangles, continuing under the condition of vacuumizing then, naturally cooling to 60-100 ℃; Stop to vacuumize, organic ring-type small molecules heterogeneous ring compound lower boiling is nitrogenous or element sulphur enters in the pretreatment unit by evaporation, with the pretreated titanium deoxid film modification reaction of process with height reactive behavior, it is surperficial with the dehydrated alcohol flushing to take out modification back product after 20-120 minute, and vacuum-drying promptly gets the titanium deoxid film that heterogeneous ring compound is modified.
Described titanium deoxid film prepares with known method, the preferred porous material of forming by nanocrystal that adopts, and its surfaceness is 530～778, voidage is 36～37%.
Above-mentioned lower boiling organic ring-type small molecules heterogeneous ring compound nitrogenous or sulphur is the organic molecule heterogeneous ring compound that contains pyridine ring, pyrrole ring, imidazole ring or thiphene ring structure, can form stable electronics with the titanium atom of titanium dioxide surface and grip system altogether.
The above-mentioned vacuum tightness that continues to vacuumize should be not less than 2*10
-6Pa, vacuum tightness rises and more to help the dangle formation of key of the active Ti of film surface, and vacuum tightness reduces will prolong the vacuum heat treatment time.
The preferred temperature of above-mentioned pre-treatment is 300～400 ℃, be 4-6h heat-up time, naturally cools to 80-100 ℃, and prolonging film surface heat-up time, to form the active Ti key that dangles helpful, but because the active hydroxyl finiteness of film surface, undue prolongation will increase the cost of modifying.
The preferred temperature of reaction of above-mentioned modification reaction is 80-100 ℃, and the reaction times is 20-60 minute, and it is slow to make the decomposition that instead would not cause new product owing to temperature is high and temperature cross low reaction speed.
The present invention utilizes heterogeneous ring compound molecule and active Ti through the titanium dioxide surface of the vacuum pre-treatment key reaction of dangling, make the titanium atom of titanium dioxide surface and heterogeneous ring compound form stable electronics and grip system altogether, thereby improved the stability of modified electrode greatly, make the good titanium deoxid film decorative material of photochemical stability, utilize this film to be working electrode cyclic voltammetric test shows, remove Ti in the titanium deoxid film between the-1.0v-1.0v
4+With Ti
3+Transform beyond the redox peak mutually, newly do not add any redox peak, this has guaranteed that this modification film is in photoelectrochemistry is used, the xitix that similar existing pickling process makes can not take place modify in the film, cause the no actual value situation appearance in photoelectrochemistry is used of its film because the oxidation peak of organic decoration thing exists.And preparation method of the present invention is simple, and the modifier consumption is less, is easy to produce in enormous quantities.With modify before compare, modify the back titanium deoxid film and improved it and utilize sunlight efficient, (as shown in Figure 1), improved in aspect practicality such as thin-film solar cells, photochemical catalysis and photodissociation water.The flat-band potential of the titanium dioxide membrane electrode provided after modifying simultaneously and the electrode of unmodified relatively are moved, and the redox ability that has changed titanic oxide material makes it have bigger use value on photodissociation water, composite semiconductor material.
Description of drawings:
The titanium deoxid film that Fig. 1 is to use the present invention to prepare, with the base material conductive glass be reference, utilize Hitachi U3010 to record absorption spectrum.
Embodiment:
The present invention may be better understood by following representative embodiment, although provided these embodiment, also should comprise: do not departing under the scope of the invention condition, disclosed method is carried out the conspicuous various changes of those skilled in the art.
Embodiment 1
(1) silica tube is placed among the tube furnace, an end links to each other with the filter flask of vacuum pump, and the other end links to each other with the there-necked flask that the 10ml heterogeneous ring compound is housed apart from piston by joint;
(2) titanium deoxid film is placed silica tube, began logical rare gas element argon gas or high purity nitrogen 2 hours, to remove the oxygen in the whole device; Used titanium deoxid film prepares in order to the below method: at first under intense agitation, with the mixing solutions of different third oxygen alcohol titanium of 24ml and Virahol (1: 1), dropwise join temperature and be about 0 ℃, in the 100ml aqueous acetic acid of pH=2.Stir to clarify under the room temperature, get clear solution.After the hydrolysis, violent stirring under 80 ℃ condition makes the Virahol volatilization in the solution complete.Treat that the cold slightly back of solution adds 20ml pH=2 aqueous acetic acid and stirs 12h.Then above-mentioned solution is transferred in the autoclave and and handled 12 hours, obtain the titanium dioxide white precipitation at 250 ℃ of constant temperature.Cooling back ultra-sonic dispersion 1 hour constantly stirs evaporation down at 120 ℃ at last, obtains solid content and be 15% colloidal tio 2.The colloidal tio 2 that makes is uniformly coated on glass rod mixes fluorine SnO
2On the conductive glass, in air, dry the back naturally and heat-treated 30 minutes at 450 ℃.Repeat said process, obtain double-layer transparent film electrode (the about 8 μ m of thickness).The gained film is based on Detitanium-ore-type, and the porous material of being made up of the nanocrystal that a spot of rutile exists, and its surfaceness is about 714, and voidage is 37%.
(3) close joint apart from piston, begin to vacuumize and heat, continue to vacuumize after 400 ℃ and constant temperature 4 hours;
(4) continuing under the condition of vacuumizing, stopping heating and make device naturally cool to 100 ℃;
(5) stop to vacuumize, open joint, make the heterogeneous ring compound pyridine enter in the silica tube and handle titanium deoxid film and react by evaporation apart from piston;
Take out after (6) 20 minutes and modify the back product, with dehydrated alcohol flushing surface, vacuum-drying promptly gets modifying titanium dioxide film by heterocyclic compound of the present invention.
Modification film with preparation, with the base material conductive glass is reference, utilize Hitachi U3010 to record absorption spectrum as shown in Figure 1, curve 7 is represented the unmodified titanium deoxid film, curve 1 is a film of representing the present embodiment preparation, as can be seen from the figure curve 1 is compared with curve 7, and its absorption value is all high at different wave length, thereby utilizes sunlight efficient obviously to increase; As working electrode, saturated calomel electrode is a reference electrode with the modification film for preparing, and platinum electrode is a counter electrode, and used electrolytic solution is 0.1M KSCN solution.Sweep velocity is 100mV/s, and light source is under the 500W xenon lamp condition, utilizes Electrochemical interfaceSolartron1287 to carry out electrochemistry, and gained zero current electromotive force is 1 corresponding flat-band potential in the table.
Implementation step is identical with embodiment 1, and temperature is 300 ℃ in the step (3), and other processing condition make the titanium dioxide pyridine and modify thin-film material with embodiment 1.With getting film after the modification of preparation, be reference with the base material conductive glass, utilize Hitachi U3010 to record absorption spectrum shown in Fig. 1 curve 2, as can be seen from the figure utilize sunlight efficient obviously to increase; As working electrode, saturated calomel electrode is a reference electrode with the modification film for preparing, and platinum electrode is a counter electrode, and used electrolytic solution is 0.1M KSCN solution.Sweep velocity is 100mV/s, and light source is under the 500W xenon lamp condition, utilizes Electrochemical interfaceSolartron1287 to carry out electrochemistry, and gained zero current electromotive force is 2 corresponding flat-band potentials in the table.
Embodiment 3
Implementation step is identical with embodiment 1, and modifier uses 10ml 1-Methylimidazole in the step (1), and other processing condition make the titanium dioxide Methylimidazole and modify thin-film material with embodiment 1.With getting film after the modification of preparation, be reference with the base material conductive glass, utilize Hitachi U3010 to record absorption spectrum shown in Fig. 1 curve 3, as can be seen from the figure utilize sunlight efficient obviously to increase; As working electrode, saturated calomel electrode is a reference electrode with the modification film for preparing, and platinum electrode is a counter electrode, and used electrolytic solution is 0.1MKSCN solution.Sweep velocity is 100mV/s, and light source is under the 500W xenon lamp condition, utilizes Electrochemicalinterface Solartron1287 to carry out electrochemistry, and gained zero current electromotive force is 2 corresponding flat-band potentials in the table.
Embodiment 4
Basic implementation step and processing condition are identical with embodiment 1, and the heterogeneous ring compound of modifying usefulness is 10ml pyrroles, promptly gets titanium dioxide pyrroles of the present invention and modifies thin-film material.With getting film after the modification of preparation, be reference with the base material conductive glass, utilize Hitachi U3010 to record absorption spectrum shown in Fig. 1 curve 4.As can be seen from the figure utilize sunlight efficient obviously to increase; As working electrode, saturated calomel electrode is a reference electrode with the modification film for preparing, and platinum electrode is a counter electrode, and used electrolytic solution is 0.1M KSCN solution.Sweep velocity is 100mV/s, and light source is under the 500W xenon lamp condition, utilizes Electrochemical interfaceSolartron1287 to carry out electrochemistry, and gained zero current electromotive force is 2 corresponding flat-band potentials in the table.
Implementation step is substantially with embodiment 1, and the heterogeneous ring compound of modifying usefulness is the 10ml thiophene, step 3 pretreatment time 6 hours, and other implementation step and processing condition are identical with embodiment 1, promptly get titanium dioxide thiophene of the present invention and modify thin-film material.With getting film after the modification of preparation, be reference with the base material conductive glass, utilize Hitachi U3010 to record absorption spectrum shown in Fig. 1 curve 5, as can be seen from the figure utilize sunlight efficient obviously to increase; As working electrode, saturated calomel electrode is a reference electrode with the modification film for preparing, and platinum electrode is a counter electrode, and used electrolytic solution is 0.1M KSCN solution.Sweep velocity is 100mV/s, and light source is under the 500W xenon lamp condition, utilizes Electrochemical interface Solartron1287 to carry out electrochemistry, and gained zero current electromotive force is 2 corresponding flat-band potentials in the table.
Implementation step is identical with embodiment 1, and step 3 is constant temperature 12h, and step 4 is for being cooled to 60 ℃, and step 6 is to take out after 120 minutes.Other processing condition make the titanium dioxide pyridine and modify thin-film material with embodiment 1.With getting film after the modification of preparation, be reference with the base material conductive glass, utilize Hitachi U3010 to record absorption spectrum shown in Fig. 1 curve 6, as can be seen from the figure utilize sunlight efficient obviously to increase; As working electrode, saturated calomel electrode is a reference electrode with the modification film for preparing, and platinum electrode is a counter electrode, and used electrolytic solution is 0.1M KSCN solution.Sweep velocity is 100mV/s, and light source is under the 500W xenon lamp condition, utilizes Electrochemical interface Solartron1287 to carry out electrochemistry, and gained zero current electromotive force is 6 corresponding flat-band potentials in the table.
Flat-band potential by the modification film of embodiment of the invention 1-6 preparation is as shown in table 1.
Table I
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 |
| Flat-band potential U (V) | -0.279 | -0.330 | -0.233 | -0.168 | -0.196 | -0.282 |
Embodiment 7
Implementation step is identical with embodiment 1, titanium deoxid film is to prepare with following method in the step (2): get the butanol solution that 0.7594g ethyl cellulose, 3.0375g P25 (commercially available) and 15ml propyl carbinol are mixed with 20% P25, stir this solution 2h it is mixed; Add 0.46g Terpineol 350,0.92g 361 and 0.92g TX-100 then, utilize silk screen printing mixing fluorine SnO after fully mixing
2On the conductive glass, in air, dry the back naturally and heat-treated 30 minutes, repeat above-mentioned screen printing process, obtain the P25 film at 450 ℃.Other processing condition promptly make the titanium dioxide pyridine and modify thin-film material with embodiment 1.
Claims (6)
1, a kind of preparation method of heterocyclic organic compounds modifying titanium dioxide film, it is characterized in that, earlier titanium deoxid film is carried out pre-treatment in the device that continues to vacuumize, under vacuum condition, carry out pre-treatment, pretreatment temperature is 300-450 ℃, time 4-12 hour, continuing under the condition of vacuumizing then, device naturally cools to 60-100 ℃, stop to vacuumize, organic ring-type small molecules heterogeneous ring compound lower boiling is nitrogenous or element sulphur enters in the pretreatment unit by evaporation, with the pretreated titanium deoxid film modification reaction of process, take out after 20-120 minute and modify the back product,, make the titanium deoxid film that heterogeneous ring compound is modified after the vacuum-drying with dehydrated alcohol flushing surface.
2, according to the preparation method of right 1 described modifying titanium dioxide film by heterocyclic compound, it is characterized in that, the porous material that adorned titanium deoxid film is made up of nanocrystal, its surfaceness is 530～778, porosity is 36～37%.
3, according to the preparation method of right 1 described modifying titanium dioxide film by heterocyclic compound, it is characterized in that lower boiling organic ring-type small molecules heterogeneous ring compound nitrogenous or sulphur is the heterogeneous ring compound that contains pyridine ring, pyrrole ring, imidazole ring or thiphene ring structure.
According to the preparation method of right 1 described modifying titanium dioxide film by heterocyclic compound, it is characterized in that 4, pretreated vacuum tightness should be not less than 2*10
-6Pa.
According to the preparation method of right 1 described modifying titanium dioxide film by heterocyclic compound, it is characterized in that 5, pretreatment temperature is 300～400 ℃, be 4-6h heat-up time.
According to the preparation method of right 1 described modifying titanium dioxide film by heterocyclic compound, it is characterized in that 6, the modification reaction temperature is 80-100 ℃, the reaction times is 20-60 minute.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100664493A CN100460332C (en) | 2006-03-31 | 2006-03-31 | Method for modifying titanium dioxide film by heterocyclic compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100664493A CN100460332C (en) | 2006-03-31 | 2006-03-31 | Method for modifying titanium dioxide film by heterocyclic compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101045555A true CN101045555A (en) | 2007-10-03 |
| CN100460332C CN100460332C (en) | 2009-02-11 |
Family
ID=38770519
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100664493A Expired - Fee Related CN100460332C (en) | 2006-03-31 | 2006-03-31 | Method for modifying titanium dioxide film by heterocyclic compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100460332C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101195094B (en) * | 2007-12-24 | 2010-06-02 | 吉林大学 | Visible light activated titanium dioxide porphyrin nano composite catalyst and method for producing the same |
| CN102491459A (en) * | 2011-12-02 | 2012-06-13 | 北京化工大学 | Nonmetal doped titanium-based film electrode as well as preparation method and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6994837B2 (en) * | 2001-04-24 | 2006-02-07 | Tekna Plasma Systems, Inc. | Plasma synthesis of metal oxide nanopowder and apparatus therefor |
| CN1118322C (en) * | 2001-05-16 | 2003-08-20 | 中国科学院化学研究所 | Process for preparing modified titanium dioxide nano photocatalysis material |
| CN1296550C (en) * | 2004-10-22 | 2007-01-24 | 上海工程技术大学 | Modified nano oxide compound, its application and use thereof |
-
2006
- 2006-03-31 CN CNB2006100664493A patent/CN100460332C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101195094B (en) * | 2007-12-24 | 2010-06-02 | 吉林大学 | Visible light activated titanium dioxide porphyrin nano composite catalyst and method for producing the same |
| CN102491459A (en) * | 2011-12-02 | 2012-06-13 | 北京化工大学 | Nonmetal doped titanium-based film electrode as well as preparation method and application thereof |
| CN102491459B (en) * | 2011-12-02 | 2013-06-19 | 北京化工大学 | Nonmetal doped titanium-based film electrode as well as preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100460332C (en) | 2009-02-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | Enhanced photocatalysis on TiO2 nanotube arrays modified with molecularly imprinted TiO2 thin film | |
| Zarrin et al. | Photocatalytic activity of TiO2/Nb2O5/PANI and TiO2/Nb2O5/RGO as new nanocomposites for degradation of organic pollutants | |
| Yu et al. | Non-noble metal Bi deposition by utilizing Bi2WO6 as the self-sacrificing template for enhancing visible light photocatalytic activity | |
| Hunge | Sunlight assisted photoelectrocatalytic degradation of benzoic acid using stratified WO3/TiO2 thin films | |
| Liu et al. | Photoelectrocatalytic degradation of tetracycline by highly effective TiO2 nanopore arrays electrode | |
| Zhang et al. | Particle-size-dependent distribution of carboxylate adsorption sites on TiO2 nanoparticle surfaces: insights into the surface modification of nanostructured TiO2 electrodes | |
| Peiró et al. | Low-temperature deposition of TiO2 thin films with photocatalytic activity from colloidal anatase aqueous solutions | |
| Wang et al. | Enhanced photoelectrocatalytic activity for dye degradation by graphene–titania composite film electrodes | |
| CN104646037A (en) | BiOXs pholocatalyst, grapheme-compounded BiOXs pholocatalyst and preparation method thereof | |
| Liang et al. | In situ synthesis of g-C3N4/TiO2 with {001} and {101} facets coexposed for water remediation | |
| Wang et al. | Ultrasound-assisted synthesis and solar-light-driven photoelectrocatalytic activity of CdS sensitized TiO2 nanotube array photocatalysts | |
| CN110241439B (en) | Plasma treatment for preparing surface hydroxylation WO3Method for preparing thin film photoelectrode material | |
| Umadevi et al. | Enhanced photocatalytic, antimicrobial activity and photovoltaic characteristics of fluorine doped TiO2 synthesized under ultrasound irradiation | |
| CN103949234A (en) | Preparation method of boron-doped graphene/TiO2 nanorod photocatalytic material | |
| Mura et al. | Effect of a galvanostatic treatment on the preparation of highly ordered TiO2 nanotubes | |
| CN100342555C (en) | Low temp process for preparing TiO2 nano-crystal porous film electrode | |
| CN108579768B (en) | Few-layer MoS2Modified Ag-TiO2Preparation method of nano composite film | |
| Madhavi et al. | Hydrogen plasma-treated 1D/3D TiO2 nanorod array photoanode for efficient photoelectrochemical water splitting | |
| CN102276011B (en) | Simple method for preparing TiO2 membrane electrode | |
| Weerasinghe et al. | Efficiency enhancement of low-cost metal free dye sensitized solar cells via non-thermal atmospheric pressure plasma surface treatment | |
| Zhang et al. | One step in situ synthesis of Bi2S3/Bi2O2CO3/Bi3O4Cl ternary heterostructures with enhanced photocatalytic performance | |
| CN103551138A (en) | Preparation method of bismuth oxide sensitized titanium dioxide nanotube catalyst and application of bismuth oxide sensitized titanium dioxide nanotube catalyst in degrading organic pollutants | |
| CN100460332C (en) | Method for modifying titanium dioxide film by heterocyclic compound | |
| CN100400606C (en) | Method of preparing anatase type titanium dioxide dispersion at low temperature by hot-liquid method | |
| Gowthambabu et al. | Synthesis of anatase TiO 2 microspheres and their efficient performance in dye-sensitized solar cell |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090211 Termination date: 20120331 |