CN106480470A - Al2O3The array TiO modifying2Nano wire and the method for photoelectrocatalysiss hydrogen production by water decomposition - Google Patents
Al2O3The array TiO modifying2Nano wire and the method for photoelectrocatalysiss hydrogen production by water decomposition Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 52
- 239000001257 hydrogen Substances 0.000 title claims abstract description 52
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 239000002070 nanowire Substances 0.000 claims abstract description 128
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 107
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 100
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 99
- 239000004744 fabric Substances 0.000 claims abstract description 98
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 71
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 71
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 71
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 230000008021 deposition Effects 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- 239000000758 substrate Substances 0.000 claims abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 62
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 60
- 238000002360 preparation method Methods 0.000 claims description 56
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 45
- 238000000231 atomic layer deposition Methods 0.000 claims description 38
- 238000000151 deposition Methods 0.000 claims description 34
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 29
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000004140 cleaning Methods 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 239000012159 carrier gas Substances 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 9
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 239000008151 electrolyte solution Substances 0.000 claims description 4
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 3
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical group [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 2
- 241000196324 Embryophyta Species 0.000 claims 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 4
- 229910052782 aluminium Inorganic materials 0.000 claims 4
- 241000209094 Oryza Species 0.000 claims 2
- 235000007164 Oryza sativa Nutrition 0.000 claims 2
- 235000012149 noodles Nutrition 0.000 claims 2
- 239000000047 product Substances 0.000 claims 2
- 235000009566 rice Nutrition 0.000 claims 2
- 239000006227 byproduct Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 8
- 239000007791 liquid phase Substances 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 59
- 239000011941 photocatalyst Substances 0.000 description 23
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 23
- 230000000694 effects Effects 0.000 description 18
- 230000001699 photocatalysis Effects 0.000 description 14
- 238000010792 warming Methods 0.000 description 12
- 238000007146 photocatalysis Methods 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- 229910052719 titanium Inorganic materials 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 230000004044 response Effects 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 229950000845 politef Drugs 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 238000006303 photolysis reaction Methods 0.000 description 3
- 230000015843 photosynthesis, light reaction Effects 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000003491 array Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000005622 photoelectricity Effects 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 229910003087 TiOx Inorganic materials 0.000 description 1
- 229910003077 Ti−O Inorganic materials 0.000 description 1
- NPNMHHNXCILFEF-UHFFFAOYSA-N [F].[Sn]=O Chemical compound [F].[Sn]=O NPNMHHNXCILFEF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000004845 hydriding Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
- C23C28/042—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material including a refractory ceramic layer, e.g. refractory metal oxides, ZrO2, rare earth oxides
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- 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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
- Ceramic Engineering (AREA)
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- Inorganic Compounds Of Heavy Metals (AREA)
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Abstract
The invention provides a kind of Al2O3The array TiO modifying2Nano wire and the method for photoelectrocatalysiss hydrogen production by water decomposition.The Al of the present invention2O3The array TiO modifying2Nano wire includes carbon cloth substrate, is grown in carbon cloth suprabasil array TiO2Nano wire and by array TiO2Nanowire surface carries out Al obtained from ald2O3Layer, and Al2O3The number of plies of layer is 1 20 layers.The present invention directly grows the homogeneous TiO of pattern using the method for liquid phase Hydrothermal Synthesiss on carbon cloth2Nano-wire array, then with TMA and H2O is as presoma in nanowire surface uniform deposition Al2O3Atomic layer, prepared material has good photoelectrocatalysiss hydrogen manufacturing performance.Additionally, present invention also offers a kind of utilize above-mentioned Al2O3The array TiO modifying2The method that nano wire carries out photoelectrocatalysiss hydrogen production by water decomposition as catalyst.
Description
Technical field
The present invention relates to a kind of Al2O3The array TiO modifying2Nano wire and preparation method thereof, further relates to a kind of photoelectrocatalysiss
The method of hydrogen production by water decomposition, belongs to photocatalysis technology field.
Background technology
Today's society, energy and environment problem is more and more prominent, and the regenerative resource of exploitation more cleaning is imperative, adopts
Clean the desirable route that reproducible solar energy electrocatalytic decomposition water hydrogen making is solve problem.1972, Japan Science
Family Fujishima and Honda finds TiO2Electrode can produce hydrogen by decomposition water under ultraviolet lighting, thus opens TiO2Light
The applied research of catalysis.TiO2It is the n-type semiconductor of scientist's research earliest, its low price, nontoxic and environmental friendliness, become
Preferable conductor photocatalysis object of study.
One-dimentional structure TiO2The characteristic that nano-wire array possesses makes it compared to TiO2Thin film has bigger specific surface area
And absorbability, for photoelectrocatalysiss, there is more preferable effect.Nano thread structure still falls within nanometer scale on certain dimension, and
Its unique structure makes it have border confinement effect, has more preferable transmission performance to light induced electron and hole.TiO2Nano wire
The defect of array surface and Ti-O dangling bonds can form photo-generated carrier complex centre so as to photocatalytic activity reduction, therefore must
Feasible method must be found and reduce photo-generated carrier being combined on surface.
In order to improve TiO2Photocatalytic activity, CN103354283A disclose one kind have golden nanometer particle modify branch
Shape titanic oxide nanorod array electrode and preparation method thereof and the application of photoelectrolysis water hydrogen manufacturing, this invention effectively inhibits two
In titanium oxide, electron-hole pair is compound, makes the extinction of material by surface plasma body resonant vibration (SPR) effect of gold nanocrystals
Range expansion, to visible region, improves photoelectrochemistrpool pool photolysis water hydrogen activity.CN102631909A discloses a kind of surface
Titanium dioxide nano thread microsphere catalysis material of hydrogenation and preparation method thereof, titanate radical nanopipe microsphere presoma is placed in quartz
In the quartz boat of tube hub, in sintering procedure, it is passed through hydrogen, can get the TiO of surface hydriding2Nano wire microsphere, this catalyst exists
Under full spectral illumination, there is enhanced photolysis water hydrogen efficiency.What CN102534781A proposed a kind of efficient photocatalytic water mixes stannum
TiO2Nano-wire array and its preparation method and application, with tetra-n-butyl titanate as titanium source, water is solvent to this preparation method, tetrachloro
Change stannum is Xi Yuan, and concentrated hydrochloric acid regulates and controls the speed of hydrolysis, and stannum two is mixed in growth on containing fluorine tin oxide (FTO) electro-conductive glass substrate
TiOx nano linear array, conventional photolytic water technology and photoelectric conversion technology are coupled by this invention, improve solar-electricity
Pond is to the absorption efficiency of light it is achieved that efficient photolysis water hydrogen and photoelectric conversion produce a one-step process of photoelectric current.
CN102107850B discloses a kind of rutile single crystals TiO of coated with carbon bed2The preparation side of nuclear shell structure nano linear array
Method, the method first prepares the rutile single crystals TiO of surface polyphenyl phenolic compounds cladding2Nano-wire array, then by its high warm
Solution is obtained the rutile single crystals TiO of coated with carbon bed2Nuclear shell structure nano linear array, this catalyst is remarkably improved TiO2Receive
The quantum yield of nanowire arrays, improves solar energy utilization ratio.
Ald (Atomic layer deposition：ALD) technology can in catalyst surface in layer
Deposition and atomic monofilm, and the growth of thin film or nano-particle can be controlled on atomic level.Repaiied by ald
Decorations semiconductor material surface, can reduce the compound of photo-generated carrier.The material of ALD deposition is also varied, such as Al2O3、TiO2、
ZnO etc., can significantly improve the photoelectric transformation efficiency of semi-conducting material by atomic layer passivating technique.Hwang etc. (Yun J H,
Hahn C,Liu B,et al.Photoelectrochemical properties of TiO2nanowire arrays:a
Study of the dependence on length and atomic layer deposition coating, Acs
Nano,2012,6(6):5060-9.) in rutile TiO2Nanowire surface deposited TiO2Shell, and have studied ALD TiO2Shell
The TiO to different length for the layer2The impact of nanowire photodiode stream.(Xu Z, Lin Y, Yin M, the et such as Xu
al.Understanding the enhancement mechanisms of surface plasmon-mediated
photoelectrochemical electrodes:a case study on Au nanoparticle decorated
TiO2Nanotubes.Advanced Materials Interfaces, 2015,2 (13) .) have extensively studied TiO2Nanotube
(TONT), Au nanoparticle, Al2O3Different electric charge transporting mechanism under the different configuration of passivation layer three.
CN103736500A disclose a kind of preparation method of Titanium dioxide/cadmium sulfide/titanium dioxide composite film and its
Application, in TiO2CdS nano-particle ALD deposition TiO again is deposited first with SILAR method on nanometer stick array2
Layer, this catalyst has good visible ray organic wastewater degraded effect.CN104923261A is disclosed and is existed using ALD technique
The CdS nano grain surface of Hydrothermal Synthesiss deposited the protective layer (TiO of one layer of 1-10A2、ZnO、Al2O3Deng), higher in guarantee
The catalytic life of CdS nanoparticle is extended on the premise of catalytic efficiency.
In sum, TiO2It is preferable photochemical catalyzing material, the development through decades has had various
Modified method improves its catalytic efficiency, and ALD technique has been used in the study on the modification of photocatalyst, and can improve photocatalysis
Efficiency, but by ALD technique in TiO2Nanowire surface depositing Al2O3Atomic layer, is efficiently improved by surface passivation effect
TiO2The photoelectrocatalysiss decomposition water hydrogen producing of nano wire does not have special report.
Content of the invention
For solving above-mentioned technical problem, it is an object of the invention to provide a kind of Al2O3The array TiO modifying2Nano wire and
Its preparation method and the method for photoelectrocatalysiss hydrogen production by water decomposition.This Al2O3The array TiO modifying2The preparation side of nano wire
Method utilizes technique for atomic layer deposition in TiO2Nanowire surface depositing Al2O3Layer, can greatly improve the photoelectrocatalysiss of titanium dioxide
Hydrogen production by water decomposition performance.
For reaching above-mentioned purpose, present invention firstly provides a kind of Al2O3The array TiO modifying2Nano wire, it includes carbon
Cloth substrate, it is grown in carbon cloth suprabasil array TiO2Nano wire and by array TiO2Nanowire surface carries out atomic layer
Al obtained from deposition2O3Layer；And described TiO2The length of nano wire is 500nm-1 μm, a diameter of 20-50nm, described Al2O3
The number of plies of layer is 1-20 layer.
Specific embodiment according to the present invention is it is preferable that described Al2O3The array TiO modifying2Nano wire be by with
Lower step prepares：
Step one：Carbon cloth is dipped in the hexane solution of titanium tetrachloride, standing a period of time；Then take out carbon cloth, in
500 DEG C -550 DEG C constant temperature 30-60 minutes, prepared length plants well the carbon cloth of layer；
Step 2：With 10:(1-2):(1-2):(0.1-5) volume ratio is by toluene, butyl titanate, concentrated hydrochloric acid (i.e. matter
The concentrated hydrochloric acid of amount concentration 37%), titanium tetrachloride is mixed and stirred for uniformly, obtaining a mixed liquor；It is highly preferred that step 2 is：?
In reactor, it is added dropwise over toluene, butyl titanate, concentrated hydrochloric acid (i.e. the concentrated hydrochloric acid of mass concentration 37%), titanium tetrachloride successively,
Stir, wherein toluene, butyl titanate, concentrated hydrochloric acid, the volume ratio of titanium tetrachloride are 10:(1-2):(1-2):(0.1-5),
It is particularly preferably 10:1:1:(0.1-5)；
Step 3：The carbon cloth inclination certain angle that the length that step one is obtained plants well layer is placed in the mixed liquor that step 2 obtains
In (angle of inclination be preferably 40-60 °, this angle refers to the angle with described mixed liquor liquid level), in 180 DEG C of -220 DEG C of hydro-thermals
Reaction 20-25 hour；After cooling, by the product cleaning obtaining (washes of absolute alcohol can be used), then in 500 DEG C of -550 DEG C of perseverances
Warm 2-4 hour, prepared growth has array TiO2The carbon cloth of nano wire；
Step 4：The growth that step 3 is obtained has array TiO2The carbon cloth of nano wire is placed in atomic layer deposition system,
With trimethyl aluminium (TMA) and H2O is as presoma, N2As carrier gas, presoma is controlled to be passed through a timing under certain depositing temperature
Between, and make trimethyl aluminium and H2The partial pressure of O is 0.1-0.2Torr, and chamber pressure is 1-2Torr, above exists as a cycle
Array TiO2Nanowire surface depositing Al2O3Atomic layer, and make Al2O3The deposition number of plies of atomic layer is that (a cycle deposits 1-20
One layer of Al2O3Atomic layer), prepare described Al2O3The array TiO modifying2Nano wire.
In the present invention, described carbon cloth is carbon cloth, and it is the fabric of carbon fiber, is a kind of high tenacity, high flexibility
Conductive material.Described carbon cloth can be fine selected from polyacrylonitrile (PAN) base carbon fibre cloth, viscose base carbon fibre cloth, pitch base carbon
The combination of one or more in Wei Bu etc., the weaving mode for this carbon cloth and size are simultaneously not particularly limited, permissible
Selected according to actual needs by those skilled in the art.
Specific embodiment according to the present invention is it is preferable that in above-mentioned Al2O3The array TiO modifying2The preparation of nano wire
In step, the carbon cloth adopting in step one is the carbon cloth after cleaning, and the cleaning of carbon cloth is successively in acetone, distilled water, no
It is cleaned by ultrasonic in water-ethanol.
Specific embodiment according to the present invention is it is preferable that in above-mentioned Al2O3The array TiO modifying2The preparation of nano wire
In step, the concentration of the hexane solution of the titanium tetrachloride in step one is 0.01-0.1mol/L.
Specific embodiment according to the present invention is it is preferable that in above-mentioned Al2O3The array TiO modifying2The preparation of nano wire
In step, the time that carbon cloth is dipped in step one standing in the hexane solution of titanium tetrachloride is 5-15 hour.
Specific embodiment according to the present invention is it is preferable that in above-mentioned Al2O3The array TiO modifying2The preparation of nano wire
In step, in step one in 500 DEG C -550 DEG C constant temperature 30-60 minutes be to put into carbon cloth in tube furnace, with 3-6 DEG C/min's
Heating rate by room temperature to 500 DEG C -550 DEG C, then in 500 DEG C -550 DEG C constant temperature 30-60 minutes.
Specific embodiment according to the present invention is it is preferable that in above-mentioned Al2O3The array TiO modifying2The preparation of nano wire
In step, the reactor in step 2 can be ptfe autoclave, the ptfe autoclave of such as 200ml.
Specific embodiment according to the present invention is it is preferable that in above-mentioned Al2O3The array TiO modifying2The preparation of nano wire
In step, in step 3 is to put in tube furnace by the product after cleaning in 500 DEG C -550 DEG C constant temperature 2-4 hours, with 3-6
DEG C/heating rate of min by room temperature to 500 DEG C -550 DEG C, then in 500 DEG C -550 DEG C constant temperature 2-4 hours.
Specific embodiment according to the present invention is it is preferable that in above-mentioned Al2O3The array TiO modifying2The preparation of nano wire
In step, in step 4, the depositing temperature of presoma is 100-500 DEG C.
Specific embodiment according to the present invention is it is preferable that in above-mentioned Al2O3The array TiO modifying2The preparation of nano wire
In step, in step 4, the time that is passed through of presoma is 10-300s.
Present invention also offers a kind of above-mentioned Al2O3The array TiO modifying2The preparation method of nano wire, it includes following step
Suddenly：
Step one：Carbon cloth is dipped in the hexane solution of titanium tetrachloride, standing a period of time；Then take out carbon cloth, in
500 DEG C -550 DEG C constant temperature 30-60 minutes, prepared length plants well the carbon cloth of layer；
Step 2：With 10:(1-2):(1-2):(0.1-5) volume ratio is by toluene, butyl titanate, concentrated hydrochloric acid (i.e. matter
The concentrated hydrochloric acid of amount concentration 37%), titanium tetrachloride is mixed and stirred for uniformly, obtaining a mixed liquor；It is highly preferred that step 2 is：?
In reactor, it is added dropwise over toluene, butyl titanate, concentrated hydrochloric acid (i.e. the concentrated hydrochloric acid of mass concentration 37%), titanium tetrachloride successively,
Stir, wherein toluene, butyl titanate, concentrated hydrochloric acid, the volume ratio of titanium tetrachloride are 10:(1-2):(1-2):(0.1-5),
It is particularly preferably 10:1:1:(0.1-5)；
Step 3：The carbon cloth inclination certain angle that the length that step one is obtained plants well layer is placed in the mixed liquor that step 2 obtains
In (angle of inclination be preferably 40-60 °, this angle refers to the angle with described mixed liquor liquid level), in 180 DEG C of -220 DEG C of hydro-thermals
Reaction 20-25 hour；After cooling, by the product cleaning obtaining (washes of absolute alcohol can be used), then in 500 DEG C of -550 DEG C of perseverances
Warm 2-4 hour, prepared growth has array TiO2The carbon cloth of nano wire；
Step 4：The growth that step 3 is obtained has array TiO2The carbon cloth of nano wire is placed in atomic layer deposition system,
With trimethyl aluminium (TMA) and H2O is as presoma, N2As carrier gas, presoma is controlled to be passed through a timing under certain depositing temperature
Between, and make trimethyl aluminium and H2The partial pressure of O is 0.1-0.2Torr, and chamber pressure is 1-2Torr, above exists as a cycle
Array TiO2Nanowire surface depositing Al2O3Atomic layer, and make Al2O3The deposition number of plies of atomic layer is that (a cycle deposits 1-20
One layer of Al2O3Atomic layer), prepare described Al2O3The array TiO modifying2Nano wire.
The carbon cloth adopting in above-mentioned preparation method it is preferable that in step one is the carbon cloth after cleaning, and carbon cloth is clear
Wash is to be cleaned by ultrasonic in acetone, distilled water, dehydrated alcohol successively.
The concentration of the hexane solution of titanium tetrachloride in above-mentioned preparation method it is preferable that in step one is 0.01-
0.1mol/L.
Above-mentioned preparation method stands it is preferable that in step one being dipped in carbon cloth in the hexane solution of titanium tetrachloride
Time be 5-15 hour.
In above-mentioned preparation method it is preferable that in step one in 500 DEG C -550 DEG C constant temperature 30-60 minutes be by carbon cloth
Put in tube furnace, with the heating rate of 3-6 DEG C/min by room temperature to 500 DEG C -550 DEG C, then in 500 DEG C of -550 DEG C of perseverances
Warm 30-60 minute.
Reactor in above-mentioned preparation method it is preferable that in step 2 can be ptfe autoclave, for example
The ptfe autoclave of 200ml.
In above-mentioned preparation method it is preferable that in step 3 is will be after cleaning in 500 DEG C -550 DEG C constant temperature 2-4 hours
Product put in tube furnace, with the heating rate of 3-6 DEG C/min by room temperature to 500 DEG C -550 DEG C, then in 500 DEG C -
550 DEG C of constant temperature 2-4 hours.
In above-mentioned preparation method it is preferable that in step 4, the depositing temperature of presoma is 100-500 DEG C.
In above-mentioned preparation method it is preferable that in step 4, the time that is passed through of presoma is 10-300s.
On the other hand, present invention also offers a kind of method of photoelectrocatalysiss hydrogen production by water decomposition, the method is with above-mentioned
Al2O3The array TiO modifying2Nano wire, as catalyst, comprises the following steps：
Using 0.01-1mol/L metabisulfite solution as electrolyte solution, with area as 1-10cm2Al2O3The array modified
TiO2Nano-wire catalyst, as working electrode, is platinized platinum to electrode, and reference electrode is silver chloride electrode, by connecting electrochemistry
Work station applies the bias of 0.1-1V to three electrode reactors；
Then three electrode reactors are placed in the reaction unit of sealing, and evacuation is carried out to reaction unit, reach negative
After one atmospheric pressure, then with light source, working electrode is irradiated so that producing hydrogen in reaction unit.
It is preferable that the light source being adopted is xenon source in the method for above-mentioned photoelectrocatalysiss hydrogen production by water decomposition.
In the method for above-mentioned photoelectrocatalysiss hydrogen production by water decomposition it is preferable that during the course of the reaction, at described electrolyte solution
Under continuous stirring.
The invention provides a kind of Al2O3The array TiO modifying2Nano wire, its preparation method is on flexible carbon fibre cloth
Growth array TiO2Nano wire, then utilizes technique for atomic layer deposition (ALD) in array TiO2Nanowire surface depositing Al2O3Layer,
Obtain the ALD Al on carbon cloth2O3/TiO2Nano-wire array, wherein, ald Al2O3The number of plies of layer is 1-20 layer.Tool
For body, the present invention directly grows the homogeneous TiO of pattern using the method for liquid phase Hydrothermal Synthesiss on carbon cloth2Nanometer linear array
Row, then with trimethyl aluminium (TMA) and H2O is as presoma in nanowire surface uniform deposition Al2O3Atomic layer, prepared
Material has good photoelectrocatalysiss hydrogen manufacturing performance.The Al of the present invention2O3The array TiO modifying2The processing technology letter of nano wire
Single, repeatability is very good, can serve as light-catalyzed reaction, solaode, photoelectricity flexible device etc., is suitable for high-volume exploitation life
Produce.Additionally, present invention also offers a kind of utilize above-mentioned Al2O3The array TiO modifying2Nano wire carries out photoelectricity as catalyst
The method of catalytic decomposition water hydrogen manufacturing.The ALD Al that the present invention provides2O3/TiO2Nano wire photocatalyst has very high photocatalysis
Activity, with simple TiO2Nano wire is compared, and hydrogen-producing speed significantly improves.
Technical scheme provided by the present invention has the advantages that：
1.TiO2Nano wire is compared to the TiO of other structures2Produce hydrogen for photoelectrocatalysiss and there is more preferable effect, array
TiO2The convenient hydrogen producing in the environment of biasing of nano wire；Nano thread structure has stronger mechanical strength, and necessarily empty
Between larger surface area is provided；TiO2Nano thread structure still falls within nanometer scale on certain dimension, and its unique structure makes
It has border confinement effect, has more preferable transmission performance to light induced electron and hole.
2. the Al that the present invention provides2O3The array TiO modifying2Nano wire photocatalyst, Al2O3The passivation of layer can press down
TiO processed2Compound, the separation efficiency of raising electron hole pair of nano wire photo-generated carrier, substantially increases TiO2The light of nano wire
Catalytic performance, photoelectrocatalysiss decomposition water hydrogen-producing speed is all greatly improved.
Brief description
Fig. 1 is the Al of embodiment 2 preparation2O3The array TiO modifying2The stereoscan photograph of nano wire photocatalyst；
Fig. 2 is the Al of embodiment 2 preparation2O3The array TiO modifying2The transmission electron microscope photo of nano wire photocatalyst；
Fig. 3 is the Al of embodiment 1 preparation2O3The array TiO modifying2The photoelectrocatalysiss of nano wire photocatalyst decompose Aquatic product
Hydrogen amount and time curve；
Fig. 4 is the Al of embodiment 2 preparation2O3The array TiO modifying2The photoelectrocatalysiss of nano wire photocatalyst decompose Aquatic product
Hydrogen amount and time curve；
Fig. 5 is the Al of embodiment 3 preparation2O3The array TiO modifying2The photoelectrocatalysiss of nano wire photocatalyst decompose Aquatic product
Hydrogen amount and time curve；
Fig. 6 is the Al of embodiment 4 preparation2O3The array TiO modifying2The photoelectrocatalysiss of nano wire photocatalyst decompose Aquatic product
Hydrogen amount and time curve；
Fig. 7 is the Al of embodiment 5 preparation2O3The array TiO modifying2The photoelectrocatalysiss of nano wire photocatalyst decompose Aquatic product
Hydrogen amount and time curve；
Fig. 8 is the array TiO of comparative example 1 preparation2The photoelectrocatalysiss decomposition water hydrogen output of nano wire photocatalyst and time
Relation curve；
Fig. 9 is embodiment 1-5 and the photoelectrocatalysiss decomposition water hydrogen output of photocatalyst of comparative example 1 preparation and the time closes
It is curve comparison figure.
Specific embodiment
In order to be more clearly understood to the technical characteristic of the present invention, purpose and beneficial effect, attached referring now to description
Figure technical scheme is carried out described further below, but it is not intended that to the present invention can practical range restriction.
Embodiment 1
Present embodiments provide a kind of Al2O3The array TiO modifying2Nano wire photocatalyst, its preparation method specifically includes
Following steps：
Carbon cloth is cleaned by ultrasonic successively in acetone, distilled water, dehydrated alcohol.Compound concentration is the tetrachloro of 0.05mol/L
Change the hexane solution of titanium, the carbon cloth after cleaning is dipped in wherein, stands 10h；Take out carbon cloth put in tube furnace, with 4 DEG C/
Min is warming up to 500 DEG C by 30 DEG C, 500 DEG C of constant temperature 30min, and prepared length plants well the carbon cloth of layer.Anti- in the politef of 200ml
Answer in kettle, be added dropwise over toluene, butyl titanate, concentrated hydrochloric acid (i.e. the concentrated hydrochloric acid of mass concentration 37%), titanium tetrachloride successively, stir
Mix uniformly, wherein toluene, butyl titanate, concentrated hydrochloric acid, the volume ratio of titanium tetrachloride are 10:1:1:1.The carbon cloth planting layer will be grown
Tilt 40 ° about (angle of this inclination is the angle with mixed liquor liquid level in reactor) and put in aforesaid reaction vessel, 180 DEG C of water
Thermal response 22h；Natural cooling, the hydrothermal product obtaining absolute ethanol washing is then placed in tube furnace, with 4 DEG C/min
It is warming up to 550 DEG C by 30 DEG C, 550 DEG C of constant temperature 2h, prepared growth has array TiO2The carbon cloth of nano wire, TiO2The length of nano wire
It is about 1 μm, diameter is about 20-30nm.
Growth there is array TiO2The carbon cloth of nano wire is placed in atomic layer deposition system, from trimethyl aluminium (TMA) and
H2O is as presoma, N2As carrier gas, presoma is controlled to be passed through the time for 90s, TMA and H under 150 DEG C of depositing temperatures2O divides
Press as 0.1Torr, chamber pressure is 1Torr, above as a cycle depositing Al2O3Atomic layer, the circulation time of ald
Number is 1 (i.e. ald Al2O3The number of plies of layer is 1 layer), prepared ALD 1cycle Al2O3/TiO2Nano wire photocatalysis
Agent.
Embodiment 2
Present embodiments provide a kind of Al2O3The array TiO modifying2Nano wire photocatalyst, its preparation method specifically includes
Following steps：
Carbon cloth is cleaned by ultrasonic successively in acetone, distilled water, dehydrated alcohol.Compound concentration is the tetrachloro of 0.05mol/L
Change the hexane solution of titanium, the carbon cloth after cleaning is dipped in wherein, stands 10h；Take out carbon cloth put in tube furnace, with 4 DEG C/
Min is warming up to 500 DEG C by 30 DEG C, 500 DEG C of constant temperature 30min, and prepared length plants well the carbon cloth of layer.Anti- in the politef of 200ml
Answer in kettle, be added dropwise over toluene, butyl titanate, concentrated hydrochloric acid (i.e. the concentrated hydrochloric acid of mass concentration 37%), titanium tetrachloride successively, stir
Mix uniformly, wherein toluene, butyl titanate, concentrated hydrochloric acid, the volume ratio of titanium tetrachloride are 10:1:1:1.The carbon cloth planting layer will be grown
Tilt 50 ° about (angle of this inclination is the angle with mixed liquor liquid level in reactor) and put in aforesaid reaction vessel, 180 DEG C of water
Thermal response 22h；Natural cooling, the hydrothermal product obtaining absolute ethanol washing is then placed in tube furnace, with 4 DEG C/min
It is warming up to 550 DEG C by 30 DEG C, 550 DEG C of constant temperature 2h, prepared growth has array TiO2The carbon cloth of nano wire.
Growth there is array TiO2The carbon cloth of nano wire is placed in atomic layer deposition system, from trimethyl aluminium (TMA) and
H2O is as presoma, N2As carrier gas, presoma is controlled to be passed through the time for 90s, TMA and H under 150 DEG C of depositing temperatures2O divides
Press as 0.1Torr, chamber pressure is 1Torr, above as a cycle depositing Al2O3Atomic layer, the circulation time of ald
Number is 2 (i.e. ald Al2O3The number of plies of layer is 2 layers), prepared ALD 2cycles Al2O3/TiO2Nano wire photocatalysis
Agent.
Fig. 1 is Al manufactured in the present embodiment2O3The array TiO modifying2The stereoscan photograph of nano wire photocatalyst.Fig. 2
For Al manufactured in the present embodiment2O3The array TiO modifying2The transmission electron microscope photo of nano wire photocatalyst.Can be seen by Fig. 1-2
Go out, growth on carbon cloth has the homogeneous TiO of pattern2Nano-wire array, TiO2The length of nano wire is about 1 μm, and diameter is about 20-
30nm, and in array TiO2Nanowire surface uniform deposition has Al2O3Atomic layer, Al2O3The number of plies of atomic layer is 2 layers.
Embodiment 3
Present embodiments provide a kind of Al2O3The array TiO modifying2Nano wire photocatalyst, its preparation method specifically includes
Following steps：
Carbon cloth is cleaned by ultrasonic successively in acetone, distilled water, dehydrated alcohol.Compound concentration is the tetrachloro of 0.01mol/L
Change the hexane solution of titanium, the carbon cloth after cleaning is dipped in wherein, stands 10h；Take out carbon cloth put in tube furnace, with 4 DEG C/
Min is warming up to 500 DEG C by 30 DEG C, 500 DEG C of constant temperature 30min, and prepared length plants well the carbon cloth of layer.Anti- in the politef of 200ml
Answer in kettle, be added dropwise over toluene, butyl titanate, concentrated hydrochloric acid (i.e. the concentrated hydrochloric acid of mass concentration 37%), titanium tetrachloride successively, stir
Mix uniformly, wherein toluene, butyl titanate, concentrated hydrochloric acid, the volume ratio of titanium tetrachloride are 10:1:1:4.The carbon cloth planting layer will be grown
Tilt 60 ° about (angle of this inclination is the angle with mixed liquor liquid level in reactor) and put in aforesaid reaction vessel, 180 DEG C of water
Thermal response 24h；Natural cooling, the hydrothermal product obtaining absolute ethanol washing is then placed in tube furnace, with 4 DEG C/min
It is warming up to 550 DEG C by 30 DEG C, 550 DEG C of constant temperature 2h, prepared growth has array TiO2The carbon cloth of nano wire, TiO2The length of nano wire
It is about 800 μm, diameter is about 20-30nm.
Growth there is array TiO2The carbon cloth of nano wire is placed in atomic layer deposition system, from trimethyl aluminium (TMA) and
H2O is as presoma, N2As carrier gas, presoma is controlled to be passed through the time for 90s, TMA and H under 150 DEG C of depositing temperatures2O divides
Press as 0.1Torr, chamber pressure is 1Torr, above as a cycle depositing Al2O3Atomic layer, the circulation time of ald
Number is 3 (i.e. ald Al2O3The number of plies of layer is 3 layers), prepared ALD 3cycles Al2O3/TiO2Nano wire photocatalysis
Agent.
Embodiment 4
Present embodiments provide a kind of Al2O3The array TiO modifying2Nano wire photocatalyst, its preparation method specifically includes
Following steps：
Carbon cloth is cleaned by ultrasonic successively in acetone, distilled water, dehydrated alcohol.Compound concentration is the tetrachloro of 0.01mol/L
Change the hexane solution of titanium, the carbon cloth after cleaning is dipped in wherein, stands 12h；Take out carbon cloth put in tube furnace, with 4 DEG C/
Min is warming up to 500 DEG C by 30 DEG C, 500 DEG C of constant temperature 30min, and prepared length plants well the carbon cloth of layer.Anti- in the politef of 200ml
Answer in kettle, be added dropwise over toluene, butyl titanate, concentrated hydrochloric acid (i.e. the concentrated hydrochloric acid of mass concentration 37%), titanium tetrachloride successively, stir
Mix uniformly, wherein toluene, butyl titanate, concentrated hydrochloric acid, the volume ratio of titanium tetrachloride are 10:1:1:1.The carbon cloth planting layer will be grown
Tilt 50 ° about (angle of this inclination is the angle with mixed liquor liquid level in reactor) and put in aforesaid reaction vessel, 180 DEG C of water
Thermal response 23h；Natural cooling, the hydrothermal product obtaining absolute ethanol washing is then placed in tube furnace, with 4 DEG C/min
It is warming up to 550 DEG C by 30 DEG C, 550 DEG C of constant temperature 2h, prepared growth has array TiO2The carbon cloth of nano wire, TiO2The length of nano wire
It is about 800 μm, diameter is about 20-30nm.
Growth there is array TiO2The carbon cloth of nano wire is placed in atomic layer deposition system, from trimethyl aluminium (TMA) and
H2O is as presoma, N2As carrier gas, presoma is controlled to be passed through the time for 90s, TMA and H under 150 DEG C of depositing temperatures2O divides
Press as 0.1Torr, chamber pressure is 1Torr, above as a cycle depositing Al2O3Atomic layer, the circulation time of ald
Number is 4 (i.e. ald Al2O3The number of plies of layer is 4 layers), prepared ALD 4cycles Al2O3/TiO2Nano wire photocatalysis
Agent.
Embodiment 5
Present embodiments provide a kind of Al2O3The array TiO modifying2Nano wire photocatalyst, its preparation method specifically includes
Following steps：
Carbon cloth is cleaned by ultrasonic successively in acetone, distilled water, dehydrated alcohol.Compound concentration is four chlorinations of 0.1mol/L
The hexane solution of titanium, the carbon cloth after cleaning is dipped in wherein, stands 5h；Take out carbon cloth put in tube furnace, with 4 DEG C/min by
30 DEG C are warming up to 500 DEG C, 500 DEG C of constant temperature 30min, and prepared length plants well the carbon cloth of layer.Ptfe autoclave in 200ml
In, it is added dropwise over toluene, butyl titanate, concentrated hydrochloric acid (i.e. the concentrated hydrochloric acid of mass concentration 37%), titanium tetrachloride successively, stirring is all
Even, wherein toluene, butyl titanate, concentrated hydrochloric acid, the volume ratio of titanium tetrachloride are 10:1:1:2.Tilt growing the carbon cloth planting layer
50 ° about (angle of this inclination is the angle with mixed liquor liquid level in reactor) put in aforesaid reaction vessel, 180 DEG C of hydro-thermals are anti-
Answer 22h；Natural cooling, the hydrothermal product obtaining absolute ethanol washing is then placed in tube furnace, with 4 DEG C/min by 30
DEG C it is warming up to 550 DEG C, 550 DEG C of constant temperature 2h, prepared growth has array TiO2The carbon cloth of nano wire, TiO2The length of nano wire is about 1
μm, diameter is about 20-30nm.
Growth there is array TiO2The carbon cloth of nano wire is placed in atomic layer deposition system, from trimethyl aluminium (TMA) and
H2O is as presoma, N2As carrier gas, presoma is controlled to be passed through the time for 90s, TMA and H under 150 DEG C of depositing temperatures2O divides
Press as 0.1Torr, chamber pressure is 1Torr, above as a cycle depositing Al2O3Atomic layer, the circulation time of ald
Number is 5 (i.e. ald Al2O3The number of plies of layer is 5 layers), prepared ALD 5cycles Al2O3/TiO2Nano wire photocatalysis
Agent.
Embodiment 6 photoelectrocatalysiss decomposition water activity rating
The evaluation that using Labsolar- II instrument of Bo Fei Lay company, catalyst is carried out with photoelectrocatalysiss decomposition water activity is real
Test, this evaluation experimental is carried out in such a way：
Producing area is 4cm2Catalyst as working electrode, be dipped in 0.1mol/L metabisulfite solution, to electrode
For platinized platinum, reference electrode is silver chloride electrode, and by connecting electrochemical workstation, three electrode reactors are applied with the bias of 0.2V；
Three electrode reactors and Labsolar- II system are connected, before the reaction starts to whole photocatalysis apparatus
Carry out evacuation process, negative one atmospheric pressure need to be reached；
Using xenon source direct irradiation on quartz reactor, the reactant in reactor is constantly in stirring
Under, within the response time of 2 hours, every sampling in 20 minutes once, the hydrogen component concentration in product passes through gas phase
On-line chromatographic analysis obtain.
According to above-mentioned steps, the catalyst ALD 1cycle Al to embodiment 1 preparation2O3/TiO2Nano wire is evaluated,
Obtain hydrogen output and the relation curve of time that catalyst is reacted with water, as shown in Figure 3.From in figure result, ALD
1Al2O3/TiO2The product hydrogen activity of nano wire sample is 40.63 μm of ol/ (h cm2).
According to above-mentioned steps, the catalyst ALD 2cycles Al to embodiment 2 preparation2O3/TiO2Nano wire is commented
Valency, obtains hydrogen output and the relation curve of time that catalyst is reacted with water, as shown in Figure 4.From in figure result, ALD
2Al2O3/TiO2The product hydrogen activity of nano wire sample is 42.46 μm of ol/ (h cm2).
According to above-mentioned steps, the catalyst ALD 3cycles Al to embodiment 3 preparation2O3/TiO2Nano wire is commented
Valency, obtains hydrogen output and the relation curve of time that catalyst is reacted with water, as shown in Figure 5.From in figure result, ALD
3Al2O3/TiO2The product hydrogen activity of nano wire sample is 36.05 μm of ol/ (h cm2).
According to above-mentioned steps, the catalyst ALD 4cycles Al to embodiment 4 preparation2O3/TiO2Nano wire is commented
Valency, obtains hydrogen output and the relation curve of time that catalyst is reacted with water, as shown in Figure 6.From in figure result, ALD
4Al2O3/TiO2The product hydrogen activity of nano wire sample is 32.0 μm of ol/ (h cm2).
According to above-mentioned steps, the catalyst ALD 5cycles Al to embodiment 5 preparation2O3/TiO2Nano wire is commented
Valency, obtains hydrogen output and the relation curve of time that catalyst is reacted with water, as shown in Figure 7.From in figure result, ALD
5Al2O3/TiO2The product hydrogen activity of nano wire sample is 26.65 μm of ol/ (h cm2).
Comparative example 1
This comparative example provides a kind of array TiO2Nano wire photocatalyst, its preparation method specifically includes following steps：
Carbon cloth is cleaned by ultrasonic successively in acetone, distilled water, dehydrated alcohol.Compound concentration is the tetrachloro of 0.05mol/L
Change the hexane solution of titanium, the carbon cloth after cleaning is dipped in wherein, stands 10h；Take out carbon cloth put in tube furnace, with 4 DEG C/
Min is warming up to 500 DEG C by 30 DEG C, 500 DEG C of constant temperature 30min, and prepared length plants well the carbon cloth of layer.Anti- in the politef of 200ml
Answer in kettle, be added dropwise over toluene, butyl titanate, concentrated hydrochloric acid (i.e. the concentrated hydrochloric acid of mass concentration 37%), titanium tetrachloride successively, stir
Mix uniformly, wherein toluene, butyl titanate, concentrated hydrochloric acid, the volume ratio of titanium tetrachloride are 10:1:1:1.The carbon cloth planting layer will be grown
Tilt 50 ° about (angle of this inclination is the angle with mixed liquor liquid level in reactor) and put in aforesaid reaction vessel, 180 DEG C of water
Thermal response 22h；Natural cooling, the hydrothermal product obtaining absolute ethanol washing is then placed in tube furnace, with 4 DEG C/min
It is warming up to 550 DEG C by 30 DEG C, 550 DEG C of constant temperature 2h, prepared growth has array TiO2The carbon cloth of nano wire, TiO2The length of nano wire
It is about 1 μm, diameter is about 20-30nm, as array TiO2Nano wire photocatalyst.
According to the evaluation methodology of embodiment 6, the TiO to comparative example 1 preparation2Nano wire photocatalyst is evaluated, and obtains
The hydrogen output that catalyst and water react and the relation curve of time, as shown in Figure 8.From in figure result, pure TiO2Nano wire
Product hydrogen activity be 6.38 μm of ol/ (h cm2).
Fig. 9 is embodiment 1-5 and the photoelectrocatalysiss decomposition water hydrogen output of photocatalyst of comparative example 1 preparation and the time closes
It is curve comparison figure, can be seen that the photocatalytic hydrogen production by water decomposition of embodiment 1-5 preparation with urging by Fig. 9 and the above results
Agent has than simple TiO2The high photocatalysis of nano wire divide hydrolytic hydrogen production efficiency.
Claims (10)
1. a kind of Al2O3The array TiO modifying2Nano wire, it includes carbon cloth substrate, is grown in carbon cloth suprabasil array TiO2Receive
Rice noodle and by array TiO2Nanowire surface carries out Al obtained from ald2O3Layer；And described TiO2Receive
The length of rice noodle is 500nm-1 μm, a diameter of 20-50nm, described Al2O3The number of plies of layer is 1-20 layer.
2. Al according to claim 12O3The array TiO modifying2Nano wire, it is through the following steps that prepare：
Step one：Carbon cloth is dipped in the hexane solution of titanium tetrachloride, standing a period of time；Then take out carbon cloth, in 500
DEG C -550 DEG C of constant temperature 30-60 minutes, prepared length plants well the carbon cloth of layer；
Step 2：With 10:(1-2):(1-2):(0.1-5) volume ratio is by toluene, butyl titanate, concentrated hydrochloric acid, titanium tetrachloride
It is mixed and stirred for uniformly, obtaining a mixed liquor；
Step 3：The carbon cloth inclination certain angle that the length that step one is obtained plants well layer is placed in the mixed liquor that step 2 obtains,
In 180 DEG C -220 DEG C hydro-thermal reaction 20-25 hours；After cooling, by the product cleaning obtaining, then in 500 DEG C of -550 DEG C of constant temperature
2-4 hour, prepared growth has array TiO2The carbon cloth of nano wire, and described TiO2The length of nano wire is 500nm-1 μm, directly
Footpath is 20-50nm；Preferably, the angle of inclination is 40-60o；
Step 4：The growth that step 3 is obtained has array TiO2The carbon cloth of nano wire is placed in atomic layer deposition system, uses front three
Base aluminum and H2O is as presoma, N2As carrier gas, control presoma to be passed through certain time under certain depositing temperature, and make front three
Base aluminum and H2The partial pressure of O be 0.1-0.2Torr, chamber pressure be 1-2Torr, above as a cycle in array TiO2Nanometer
Line surface depositing Al2O3Atomic layer, and make Al2O3The deposition number of plies of atomic layer is 1-20, prepares described Al2O3Modify
Array TiO2Nano wire.
3. the Al described in a kind of claim 1 or 22O3The array TiO modifying2The preparation method of nano wire, it includes following step
Suddenly：
Step one：Carbon cloth is dipped in the hexane solution of titanium tetrachloride, standing a period of time；Then take out carbon cloth, in 500
DEG C -550 DEG C of constant temperature 30-60 minutes, prepared length plants well the carbon cloth of layer；
Step 2：With 10:(1-2):(1-2):(0.1-5) volume ratio is by toluene, butyl titanate, concentrated hydrochloric acid, titanium tetrachloride
It is mixed and stirred for uniformly, obtaining a mixed liquor；
Step 3：The carbon cloth inclination certain angle that the length that step one is obtained plants well layer is placed in the mixed liquor that step 2 obtains,
In 180 DEG C -220 DEG C hydro-thermal reaction 20-25 hours；After cooling, by the product cleaning obtaining, then in 500 DEG C of -550 DEG C of constant temperature
2-4 hour, prepared growth has array TiO2The carbon cloth of nano wire, and described TiO2The length of nano wire is 500nm-1 μm, directly
Footpath is 20-50nm；Preferably, the angle of inclination is 40-60o；
Step 4：The growth that step 3 is obtained has array TiO2The carbon cloth of nano wire is placed in atomic layer deposition system, uses front three
Base aluminum and H2O is as presoma, N2As carrier gas, control presoma to be passed through certain time under certain depositing temperature, and make front three
Base aluminum and H2The partial pressure of O be 0.1-0.2Torr, chamber pressure be 1-2Torr, above as a cycle in array TiO2Nanometer
Line surface depositing Al2O3Atomic layer, and make Al2O3The deposition number of plies of atomic layer is 1-20, prepares described Al2O3Modify
Array TiO2Nano wire.
4. preparation method according to claim 3, wherein, the carbon cloth adopting in step one is the carbon cloth after cleaning, and
The cleaning of carbon cloth is to be cleaned by ultrasonic in acetone, distilled water, dehydrated alcohol successively.
5. carbon cloth wherein, is dipped in the hexane solution of titanium tetrachloride by preparation method according to claim 3 in step one
The time of middle standing is 5-15 hour.
6. preparation method according to claim 3, wherein, in step one in 500 DEG C -550 DEG C constant temperature 30-60 minutes be
Carbon cloth is put in tube furnace, with the heating rate of 3-6 DEG C/min by room temperature to 500 DEG C -550 DEG C, then in 500 DEG C -
550 DEG C of constant temperature 30-60 minutes.
7. preparation method according to claim 3, wherein, in step 3 in 500 DEG C -550 DEG C constant temperature 2-4 hours be by
Product after cleaning is put in tube furnace, with the heating rate of 3-6 DEG C/min by room temperature to 500 DEG C -550 DEG C, Ran Houyu
500 DEG C -550 DEG C constant temperature 2-4 hours.
8. preparation method according to claim 3, wherein, in step 4, the depositing temperature of presoma is 100-500 DEG C；Step
In rapid four, the time that is passed through of presoma is 10-300s.
9. a kind of method of photoelectrocatalysiss hydrogen production by water decomposition, the method is with the Al described in claim 1 or 22O3The array modified
TiO2Nano wire, as catalyst, comprises the following steps：
Using 0.01-1mol/L metabisulfite solution as electrolyte solution, with area as 1-10cm2Al2O3The array TiO modifying2
Nano-wire catalyst, as working electrode, is platinized platinum to electrode, and reference electrode is silver chloride electrode, by connecting electrochemical operation
Stand and three electrode reactors are applied with the bias of 0.1-1V；
Then three electrode reactors are placed in the reaction unit of sealing, and evacuation is carried out to reaction unit, reach negative one
After atmospheric pressure, then with light source, working electrode is irradiated so that producing hydrogen in reaction unit.
10. the method for photoelectrocatalysiss hydrogen production by water decomposition according to claim 9, wherein, the light source being adopted is xenon lamp
Source；
During the course of the reaction, described electrolyte solution is under continuous stirring.
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