CN101026200A - Method for preparing nitrogen-doped modified TiO2 film under ammonia regulation and high pressure reaction device - Google Patents
Method for preparing nitrogen-doped modified TiO2 film under ammonia regulation and high pressure reaction device Download PDFInfo
- Publication number
- CN101026200A CN101026200A CNA2007100719310A CN200710071931A CN101026200A CN 101026200 A CN101026200 A CN 101026200A CN A2007100719310 A CNA2007100719310 A CN A2007100719310A CN 200710071931 A CN200710071931 A CN 200710071931A CN 101026200 A CN101026200 A CN 101026200A
- Authority
- CN
- China
- Prior art keywords
- tio
- film
- nitrogen
- doped modified
- lid
- 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
- 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
This invention relates to a preparation method for ammonia controlled N doped modified TiO2 films and a high pressure reacting device including the following steps: 1, mixing a reactant, 2, bathing it, 3, filtering, 4, adding secondary distilled water, 5, bathing it, 6, processing a TiO2 nm serum, 7, adding emulsion agent into it and grinding it, 8, coating a film and sintering to get a TiO2 film, 9, penetrating ammonia of 99.99wt% and reacting for 5min-4h, in which, the top surface of a sleeve is fixedly connected with the top surface of a cover, a thermocouple is placed in the sleeve along the axial direction, the outlet of a connecting pipe is connected with the inlet of a gas meter, and the inlet of the pipe is connected with the outlet of the drum.
Description
Technical field
The present invention relates to a kind of TiO
2The preparation method of modified film and reaction unit.
Background technology
DSSC is a kind of novel solar battery that new development is in recent years got up, and the TiO of one of part
2Membrane structure and conduction level have determined the overall performance of DSSC.TiO
2It is a kind of wide bandgap semiconductor.Pure TiO
2Powder and film narrow to the absorption region of light, have only the energy could the exciting light catalytic reaction, and ultraviolet ray only accounts for about the 3-5% of sun natural daylight radiation more than or equal to the ultraviolet ray of energy gap; Simultaneously, electronics and hole are compound easily, and the productive rate of charge carrier is lower, directly have influence on light-catalysed efficient and effect.Therefore people expand TiO by the whole bag of tricks
2To the utilizing scope and suppress electronics and hole compound of light, generally be to adopt various materials to TiO
2Carry out modification.
Domestic a lot of people proposes by to TiO
2The modification of electrode improves the performance of DSSC.At present, about TiO
2The method of the modification of film is a lot.Mainly comprise: reduce crystallite dimension, doped transition metal ions, nonmetallic ion-doped, semiconductor is compound, area load, surface light sensitization, the surface is super-strong acidified and precious metal surface deposition etc.Studies show that: adopt nonmetalloid TiO
2Carry out doping vario-property, can make TiO with nonmetal alternative a spot of Lattice Oxygen
2Band gap narrow down, under not reducing ultraviolet light active in, can effectively must expand TiO
2Spectral response range, improve its utilance to visible light.The nonmetalloid that research at present is used for doping vario-property has N, C, S, F, Cl, Br etc.In the research with nitrogen doped Ti O
2That studies is the most extensive, but still exists the not high problem of visible light activity.
Report N doping vario-property TiO at present
2Method mainly contain following several: high-temperature heat treatment method, magnetron sputtering method, pulsed laser deposition, wet method preparation and mechanochemical reaction.More than each method, by nitrogen doping less than 1%, to TiO
2The film energy gap reduces scope between 3.2～3.0eV, though wet method prepare itrogen content of getter with nitrogen doped can be up to more than 0.5%, easily contain more hydrone in nanocrystalline; Though the high-temperature heat treatment method can address this problem, itrogen content of getter with nitrogen doped is not high; Mechanochemical reaction is difficult to the uniformity of controlled doping; Magnetron sputtering method, pulsed laser deposition have improved this situation, but itrogen content of getter with nitrogen doped is not high yet, all less than 1%. Be used to prepare nitrogen doped Ti O at present
2Nitrogenous source mainly contain N
2, NH
3, organic amine salt, inorganic ammonium salt and nitrogenous TiO
2Predecessor.For the selection of nitrogenous source, generally adopt N
2(40%)/and the mist of Ar, NH
3/ Ar gaseous mixture, concentrated ammonia liquor, purity is not high, and the content that causes N to mix is little; And can not control the forbidden band size.
Summary of the invention
The objective of the invention is in order to solve present modification TiO
2The uppity problem of energy gap size of film provides a kind of ammonia regulation nitrogen-doped modified TiO
2The preparation method of film and high pressure reaction assembly.
The nitrogen-doped modified TiO of ammonia regulation of the present invention
2The step of method for manufacturing thin film is as follows: one, under room temperature and the speed stirring condition with 90～120r/min, it is 0.08～0.15mol/L HCl or HNO that 20～50ml isopropyl titanate is added drop-wise to 100～200ml concentration
3Mixing in the solution, reaction 30min～2h; Two, in 50～90 ℃ of water-baths, the speed of mixed liquor with 90～120r/min is stirred reaction 5～10h; Three, reacting liquid filtering that will be after step 2 is handled; Four, in above-mentioned filtrate, add redistilled water, make TiO
2The weight percent concentration of solution is 2～10%; Five, in 180～250 ℃ of water-baths, the reactant liquor that step 4 is handled reacts 10～15h; Six, the reactant liquor after distilation steps five is handled makes TiO
2The weight percent concentration of solution is 5～15%, obtains nano-TiO
2Slurries; Seven, to nano-TiO
2Add emulsifying agent in the slurries and grind 0.5～2h, obtain pastel, wherein nano-TiO
2The weight ratio of slurries and emulsifying agent is 2～4: 1; Eight, the pastel that step 7 is obtained is filmed, and under 300～800 ℃ of conditions, sintering 5min～1h obtains TiO in Muffle furnace again
2Film; Nine, with TiO
2Film is placed in the high pressure reaction assembly, under 300～500 ℃ of temperature, 0.1～2MPa reaction condition, feeds high-purity ammonia in reaction vessel, and reaction 5min～4h obtains nitrogen-doped modified TiO
2Film.
The nitrogen-doped modified TiO of ammonia regulation among the present invention
2The high pressure reaction assembly of film is made up of the air inlet pipe that has intake valve, thermocouple, the escape pipe that has air outlet valve, lid, bolt, cylindrical shell, sleeve pipe, packing ring, the feed tube that has the feed liquor valve, air gauge and tube connector; Fixedly connected with the upper surface of lid in the upper surface of sleeve pipe, prolong in the sleeve pipe and axially be placed with thermocouple, the central shaft of the relative lid with the escape pipe that has air outlet valve of air inlet pipe that has intake valve is to being symmetrical arranged, the central shaft of the relative lid with tube connector of feed tube that has the feed liquor valve is to being symmetrical arranged, the air inlet pipe that has intake valve, having the escape pipe of air outlet valve and the lower surface of tube connector fixedlys connected with the lower surface of lid respectively, the feed tube that has the feed liquor valve stretches into the bottom of cylindrical shell, have the outer wall of feed tube of feed liquor valve and lid on, the lower surface welding, the groove of the upper end of cylindrical shell is provided with packing ring, lid connects to the bolt of symmetry by relative lid central shaft with cylindrical shell, the gas outlet of tube connector is communicated with barometric air inlet, and the air inlet of tube connector is communicated with the gas outlet of cylindrical shell.
The nitrogen-doped modified TiO that the inventive method obtains
2The film general formula is TiO
2-xN
x, X=0.05 in the formula～2, nitrogen-doped modified TiO
2The energy gap of film is 2.0～3.2eV, nitrogen-doped modified TiO
2Film is 5～15% to visible light electric current conversion ratio, nitrogen-doped modified TiO
2The thickness of film is 8～10 μ m.
The nitrogen-doped modified TiO of the present invention
2Film is to visible light electric current conversion ratio height, and the present invention controls TiO by the addition of control ammonia
2Film energy gap size.
Description of drawings
Fig. 1 is that master of the present invention looks cross-sectional view, and Fig. 2 is the A-A profile of Fig. 1, and Fig. 3 is the B-B profile of Fig. 1, and Fig. 4 is the nitrogen-doped modified TiO of ammonia regulation that embodiment one obtains
2The thickness SEM figure of film, Fig. 5 is the nitrogen-doped modified TiO of ammonia regulation that embodiment one obtains
2Film amplifies 100,000 times of SEM figure, and Fig. 6 is the nitrogen-doped modified TiO of ammonia regulation that embodiment one obtains
2The standard x RD figure of film.
Embodiment
Embodiment one: the nitrogen-doped modified TiO of ammonia regulation in the present embodiment
2Preparation method's step of film is as follows: one, under room temperature and the speed stirring condition with 90～120r/min, it is 0.08～0.15mol/L HCl or HNO that 20～50ml isopropyl titanate is added drop-wise to 100～200ml concentration
3Mixing in the solution, reaction 30min～2h; Two, in 50～90 ℃ of water-baths, the speed of mixed liquor with 90～120r/min is stirred reaction 5～10h; Three, reacting liquid filtering that will be after step 2 is handled; Four, in above-mentioned filtrate, add redistilled water, make TiO
2The weight percent concentration of solution is 2～10%; Five, in 180～250 ℃ of water-baths, the reactant liquor that step 4 is handled reacts 10～15h; Six, the reactant liquor after distilation steps five is handled makes TiO
2The weight percent concentration of solution is 5～15%, obtains nano-TiO
2Slurries; Seven, to nano-TiO
2Add emulsifying agent in the slurries and grind 0.5～2h, obtain pastel, wherein nano-TiO
2The weight ratio of slurries and emulsifying agent is 2～4: 1; Eight, the pastel that step 7 is obtained is filmed, and under 300～800 ℃ of conditions, sintering 5min～1h obtains TiO in Muffle furnace again
2Film; Nine, with TiO
2Film is placed in the high pressure reaction assembly 15, under 300～500 ℃ of temperature, 0.1～2MPa reaction condition, feeds high-purity ammonia in reaction vessel, and reaction 5min～4h obtains nitrogen-doped modified TiO
2Film.
The nitrogen-doped modified TiO that present embodiment obtains
2The film general formula is TiO
2-xN
x, X=0.05 in the formula～2, nitrogen-doped modified TiO
2The energy gap of film is 2.0～3.2eV, nitrogen-doped modified TiO
2Film is 5～15% to visible light electric current conversion ratio.
The nitrogen-doped modified TiO that (referring to Fig. 4) present embodiment obtains
2The thickness of film is 8～10 μ m.
The nitrogen-doped modified TiO that (referring to Fig. 5) obtains present embodiment
2The electrode surface of film is observed, and its surperficial particle size distribution is more even, and is nanoscale, and has the duct to be distributed in its surface.
The nitrogen-doped modified TiO that (referring to Fig. 6) present embodiment obtains
2The characteristic peak of film is the standard feature peak, the nitrogen-doped modified TiO that present embodiment is synthetic
2Film is a Detitanium-ore-type.
The nitrogen-doped modified TiO that present embodiment is obtained
2Photovoltaic spectrum (SPS) analysis is carried out on the surface of film, draws to draw a conclusion: with N/TiO
2With TiO
2SPS contrast, for TiO
2, its absworption peak showed tangible red shift phenomenon after its peak response wavelength mixed through N.
The nitrogen-doped modified TiO that present embodiment is obtained
2XPS analysis is carried out on the surface of film, draws to draw a conclusion: there are 2 absworption peaks in N1s among the chemical state composition XPS about 400eV and 396eV.
Embodiment two: present embodiment is HCl or HNO in step 1
3The concentration of solution is 0.1mol/L.Other is identical with embodiment one.
Embodiment three: present embodiment is used magnetic stirring apparatus in step 1 and step 2.Other is identical with embodiment one.
Embodiment four: present embodiment heats 12h in step 5.Other is identical with embodiment one.
Embodiment five: the emulsifying agent in step 7 is emulsifier op-10, Emulsifier MOA-10 or polyethylene glycol.Other is identical with embodiment one.
Embodiment six: present embodiment is nano-TiO in step 7
2The weight ratio of slurries and emulsifying agent is 2: 1.Other is identical with embodiment one.
Embodiment seven: present embodiment is nano-TiO in step 7
2The weight ratio of slurries and emulsifying agent is 3: 1.Other is identical with embodiment one.
Embodiment eight: present embodiment is nano-TiO in step 7
2The weight ratio of slurries and emulsifying agent is 4: 1.Other is identical with embodiment one.
Embodiment nine: the nitrogen-doped modified TiO of ammonia regulation in the present embodiment
2The high pressure reaction assembly 15 of film is made up of the air inlet pipe 1 that has intake valve 2, thermocouple 3, the escape pipe 5 that has air outlet valve 4, lid 6, bolt 7, cylindrical shell 8, sleeve pipe 9, packing ring 10, the feed tube 12 that has feed liquor valve 11, air gauge 13 and tube connector 14; Fixedly connected with the upper surface of lid 6 in the upper surface of sleeve pipe 9, prolong in the sleeve pipe 9 and axially be placed with thermocouple 3, the central shaft of the air inlet pipe 1 that has an intake valve 2 and the escape pipe that has air outlet valve 45 relative lids 6 is to being symmetrical arranged, the central shaft of the feed tube 12 that has a feed liquor valve 11 and tube connector 14 relative lids 6 is to being symmetrical arranged, the air inlet pipe 1 that has intake valve 2, having the escape pipe 5 of air outlet valve 4 and the lower surface of tube connector 14 fixedlys connected with the lower surface of lid respectively, the feed tube 12 that has feed liquor valve 11 stretches into cylindrical shell 8 bottoms, have the outer wall of feed tube 12 of feed liquor valve 11 and lid on, the lower surface welding, be provided with packing ring 10 in the groove of the upper end of cylindrical shell 8, lid 6 connects by the bolt 7 of relative lid 6 central shafts to symmetry with cylindrical shell 8, the gas outlet of tube connector 14 is communicated with the air inlet of air gauge 13, and the air inlet of tube connector 14 is communicated with the gas outlet of cylindrical shell 8.
Embodiment ten: the material of present embodiment middle cover 6 and cylindrical shell 8 is a stainless steel, and the thickness of lid 6 and cylindrical shell 8 is 8～15mm.Other is identical with embodiment nine.
Embodiment 11: the center of present embodiment middle sleeve 9 and lid 6 overlaps.Other is identical with embodiment nine.
Embodiment 12: the material of the air inlet pipe 1 of intake valve 2, the escape pipe 5 that has air outlet valve 4, bolt 7, sleeve pipe 9, the feed tube 12 that has feed liquor valve 11 and tube connector 14 is a stainless steel in the present embodiment.Other is identical with embodiment nine.
Embodiment five: the material of present embodiment middle washer 10 is an aluminium alloy, and the thickness of pad is 2～5mm.Other is identical with embodiment nine.
Claims (10)
1, the nitrogen-doped modified TiO of a kind of ammonia regulation
2The preparation method of film is characterized in that the nitrogen-doped modified TiO of ammonia regulation
2Preparation method's step of film is as follows: one, under room temperature and the speed stirring condition with 90～120r/min, it is 0.08～0.15mol/L HCl or HNO that 20～50ml isopropyl titanate is added drop-wise to 100～200ml concentration
3Mixing in the solution, reaction 30min～2h; Two, in 50～90 ℃ of water-baths, the speed of mixed liquor with 90～120r/min is stirred reaction 5～10h; Three, reacting liquid filtering that will be after step 2 is handled; Four, in above-mentioned filtrate, add redistilled water, make TiO
2The weight percent concentration of solution is 2～10%; Five, in 180～250 ℃ of water-baths, the reactant liquor that step 4 is handled reacts 10～15h; Six, the reactant liquor after distilation steps five is handled makes TiO
2The weight percent concentration of solution is 5～15%, obtains nano-TiO
2Slurries; Seven, to nano-TiO
2Add emulsifying agent in the slurries and grind 0.5～2h, obtain pastel, wherein nano-TiO
2The weight ratio of slurries and emulsifying agent is 2～4: 1; Eight, the pastel that step 7 is obtained is filmed, and under 300～800 ℃ of conditions, sintering 5min～1h obtains TiO in Muffle furnace again
2Film; Nine, with TiO
2Film is placed in the high pressure reaction assembly (15), under 300～500 ℃ of temperature, 0.1～2MPa reaction condition, feeds high-purity ammonia in reaction vessel, and reaction 5min～4h obtains nitrogen-doped modified TiO
2Film.
2, the nitrogen-doped modified TiO of ammonia regulation according to claim 1
2The preparation method of film is characterized in that HCl or HNO in step 1
3The concentration of solution is 0.1mol/L.
3, the nitrogen-doped modified TiO of ammonia regulation according to claim 1
2The preparation method of film is characterized in that using magnetic stirrer in step 1 and step 2.
4, the nitrogen-doped modified TiO of ammonia regulation according to claim 1
2The preparation method of film is characterized in that the emulsifying agent in step 7 is emulsifier op-10, Emulsifier MOA-10 or polyethylene glycol.
5, the nitrogen-doped modified TiO of ammonia regulation according to claim 1
2The preparation method of film is characterized in that nano-TiO in step 7
2The weight ratio of slurries and emulsifying agent is 2: 1.
6, the nitrogen-doped modified TiO of ammonia regulation according to claim 1
2The preparation method of film is characterized in that nano-TiO in step 7
2The weight ratio of slurries and emulsifying agent is 3: 1.
7, the high pressure reaction assembly that uses of method according to claim 1 is characterized in that it is made up of the air inlet pipe that has intake valve (2) (1), thermocouple (3), the escape pipe (5) that has air outlet valve (4), lid (6), bolt (7), cylindrical shell (8), sleeve pipe (9), packing ring (10), the feed tube (12) that has feed liquor valve (11), air gauge (13) and tube connector (14); Fixedly connected with the upper surface of lid (6) in the upper surface of sleeve pipe (9), prolong in the sleeve pipe (9) and axially be placed with thermocouple (3), the central shaft that has the relative lid with the escape pipe that has air outlet valve (4) (5) of the air inlet pipe (1) of intake valve (2) (6) is to being symmetrical arranged, the central shaft that has the relative lid with tube connector (14) of the feed tube (12) of feed liquor valve (11) (6) is to being symmetrical arranged, the air inlet pipe (1) that has intake valve (2), having the escape pipe (5) of air outlet valve (4) and the lower surface of tube connector (14) fixedlys connected with the lower surface of lid respectively, the feed tube (12) that has feed liquor valve (11) stretches into the bottom of cylindrical shell (8), have the outer wall of feed tube (12) of feed liquor valve (11) and lid on, the lower surface welding, be provided with packing ring (10) in the groove of the upper end of cylindrical shell (8), lid (6) connects to the bolt (7) of symmetry by relative lid (6) central shaft with cylindrical shell (8), the gas outlet of tube connector (14) is communicated with the air inlet of air gauge (13), and the air inlet of tube connector (14) is communicated with the gas outlet of cylindrical shell (8).
8, the nitrogen-doped modified TiO of ammonia regulation according to claim 7
2The high pressure reaction assembly of film is characterized in that the material of lid (6) and cylindrical shell (8) is a stainless steel, and the thickness of lid (6) and cylindrical shell (8) is 8～15mm.
9, the nitrogen-doped modified TiO of ammonia regulation according to claim 7
2The high pressure reaction assembly of film, it is characterized in that sleeve pipe (9) and the lid (6) central lines.
10, the nitrogen-doped modified TiO of ammonia regulation according to claim 7
2The high pressure reaction assembly of film, the material that it is characterized in that packing ring (10) is an aluminium alloy, the thickness of pad is 2～5mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100719310A CN100536175C (en) | 2007-03-23 | 2007-03-23 | Method for preparing nitrogen-doped modified TiO2 film under ammonia regulation and high pressure reaction device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100719310A CN100536175C (en) | 2007-03-23 | 2007-03-23 | Method for preparing nitrogen-doped modified TiO2 film under ammonia regulation and high pressure reaction device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101026200A true CN101026200A (en) | 2007-08-29 |
| CN100536175C CN100536175C (en) | 2009-09-02 |
Family
ID=38744271
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007100719310A Expired - Fee Related CN100536175C (en) | 2007-03-23 | 2007-03-23 | Method for preparing nitrogen-doped modified TiO2 film under ammonia regulation and high pressure reaction device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100536175C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101354971B (en) * | 2008-09-12 | 2011-04-06 | 中国科学院化学研究所 | Method for preparing dye sensitization TiO2 nano-crystalline film photoelectric electrode doping with metal |
| CN103386291A (en) * | 2013-08-13 | 2013-11-13 | 广州利确节能科技有限公司 | Synergistic reactor for improving fuel gas energy of novel energy sources |
| CN104138766A (en) * | 2014-08-11 | 2014-11-12 | 中国建材国际工程集团有限公司 | Preparation method of N-doped TiO2 film capable of achieving visible light catalysis |
| CN107723678A (en) * | 2017-10-09 | 2018-02-23 | 复旦大学 | A kind of method that high pressure ammonia passivation improves titanium oxide photochemical catalyst efficiency |
| CN110289179A (en) * | 2019-05-29 | 2019-09-27 | 南京源恒能源科技有限公司 | Reactive metal oxides-carbonization bacteria cellulose electrode material preparation method |
-
2007
- 2007-03-23 CN CNB2007100719310A patent/CN100536175C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101354971B (en) * | 2008-09-12 | 2011-04-06 | 中国科学院化学研究所 | Method for preparing dye sensitization TiO2 nano-crystalline film photoelectric electrode doping with metal |
| CN103386291A (en) * | 2013-08-13 | 2013-11-13 | 广州利确节能科技有限公司 | Synergistic reactor for improving fuel gas energy of novel energy sources |
| CN103386291B (en) * | 2013-08-13 | 2015-09-02 | 广州利确节能科技有限公司 | A kind of enhanced reaction of modification device for promoting new energy gas energy |
| CN104138766A (en) * | 2014-08-11 | 2014-11-12 | 中国建材国际工程集团有限公司 | Preparation method of N-doped TiO2 film capable of achieving visible light catalysis |
| CN107723678A (en) * | 2017-10-09 | 2018-02-23 | 复旦大学 | A kind of method that high pressure ammonia passivation improves titanium oxide photochemical catalyst efficiency |
| CN110289179A (en) * | 2019-05-29 | 2019-09-27 | 南京源恒能源科技有限公司 | Reactive metal oxides-carbonization bacteria cellulose electrode material preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100536175C (en) | 2009-09-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106914264B (en) | The preparation method of composite visible light catalyst | |
| US10773247B2 (en) | Hollow porous carbon nitride nanospheres composite loaded with AgBr nanoparticles, preparation method thereof, and its application in dye degradation | |
| CN106391089B (en) | A kind of carbonitride load iron oxide photocatalyst of efficient degradation p-nitrophenol | |
| CN100536175C (en) | Method for preparing nitrogen-doped modified TiO2 film under ammonia regulation and high pressure reaction device | |
| CN101792117B (en) | Method for preparing tungsten-doped anatase type nano titanium dioxide composite powder | |
| CN103240073B (en) | Zn<2+>-doped BiVO4 visible-light-driven photocatalyst and preparation method thereof | |
| CN113680372B (en) | Heat-assisted preparation method and application of graphite-phase carbon nitride nanosheets | |
| Shafiq et al. | The construction of a highly efficient pn heterojunction Bi2O3/BiVO4 for hydrogen evolution through solar water splitting | |
| CN110721698A (en) | Bismuth vanadate/copper vanadate composite photocatalyst and preparation method and application thereof | |
| CN107649118B (en) | BiVO4Supported mixed crystalline phase TiO2Preparation method of visible light composite photocatalyst | |
| CN109675604A (en) | Nickel hydroxide/thin layer carbonitride compounded visible light photocatalyst and preparation method thereof | |
| CN110102328A (en) | Cryogenic fluid phase technology prepares flower pattern carbon quantum dot/nitridation carbon quantum dot/super oxygen waltherite Three-element composite photocatalyst | |
| CN106362742A (en) | Ag/ZnO nano-composite, preparation method thereof and application of composite | |
| CN104226320B (en) | The preparation method of vanadium boron codope titanium dioxide and nickel oxide composite photo-catalyst | |
| CN109174156A (en) | Semiconductors coupling catalysis material of N doping black titanium dioxide and preparation method thereof | |
| CN106975509B (en) | Preparation method and application of nitrogen and iron co-doped bismuth vanadate visible-light-driven photocatalyst | |
| CN112023974A (en) | P-CeO2/g-C3N4Heterojunction material, preparation method and application thereof | |
| CN111790431A (en) | With Al2O3Modified g-C3N4Preparation method of photocatalytic material | |
| CN105817241B (en) | A kind of preparation method of phosphotungstic acid copper titanium dioxide core shell structural nano material | |
| CN105195203B (en) | A kind of visible light-responded Nb2O5/g‑C3N4The preparation method and purposes of heterojunction material | |
| CN106964388B (en) | A kind of wolframic acid stannous adulterates the preparation method of two-dimentional graphite phase carbon nitride composite photo-catalyst | |
| CN104741112A (en) | Preparation method for TiO2/WO3 composite powder | |
| CN111558389A (en) | BiVO4Protonated g-C3N4AgI ternary composite photocatalyst and preparation method thereof | |
| Khachane et al. | High photocatalytic activity for the degradation of rhodamine B in water | |
| Chen et al. | Constructing dual Z-scheme WO3/Cu-g-C3N4/AgBr composite photocatalyst with enhanced photocatalytic performance under visible light irradiation |
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: 20090902 Termination date: 20120323 |