CN106480470B - Al2O3The array TiO of modification2The method of nano wire and photoelectrocatalysis hydrogen production by water decomposition - Google Patents
Al2O3The array TiO of modification2The method of nano wire and photoelectrocatalysis hydrogen production by water decomposition Download PDFInfo
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- 239000002070 nanowire Substances 0.000 title claims abstract description 133
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 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 49
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 238000000354 decomposition reaction Methods 0.000 title description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 107
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 99
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 99
- 239000004744 fabric Substances 0.000 claims abstract description 96
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 53
- 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 52
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 52
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 52
- 239000003054 catalyst Substances 0.000 claims abstract description 46
- 230000003197 catalytic effect Effects 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract 17
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract 16
- 239000002243 precursor Substances 0.000 claims abstract 7
- 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
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 42
- 238000002360 preparation method Methods 0.000 claims description 41
- 238000000151 deposition Methods 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 30
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 29
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 20
- 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
- 238000004140 cleaning Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 230000008021 deposition Effects 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 239000012159 carrier gas Substances 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- 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
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [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
- 239000011259 mixed solution Substances 0.000 claims 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims 1
- 229910052938 sodium sulfate Inorganic materials 0.000 claims 1
- 235000011152 sodium sulphate Nutrition 0.000 claims 1
- 238000004506 ultrasonic cleaning Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 9
- 239000007791 liquid phase Substances 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 59
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 50
- 238000012986 modification Methods 0.000 description 37
- 239000000047 product Substances 0.000 description 19
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 18
- 230000000694 effects Effects 0.000 description 16
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 15
- 229960000935 dehydrated alcohol Drugs 0.000 description 13
- 238000010792 warming Methods 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 description 10
- 230000001699 photocatalysis Effects 0.000 description 9
- 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
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 6
- -1 polytetrafluoroethylene Polymers 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000835 fiber 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
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 238000003491 array Methods 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification 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
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 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
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 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
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000004845 hydriding Methods 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
- 238000002156 mixing 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
- 239000012071 phase Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 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
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 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
- 239000002351 wastewater Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
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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
- 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
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- 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
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- 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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- 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
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- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
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Abstract
本发明提供了一种Al2O3修饰的阵列TiO2纳米线与光电催化分解水制氢的方法。本发明的Al2O3修饰的阵列TiO2纳米线包括碳布基底、生长在碳布基底上的阵列TiO2纳米线、以及通过在阵列TiO2纳米线表面进行原子层沉积而得到的Al2O3层，并且Al2O3层的层数为1‑20层。本发明采用液相水热合成的方法直接在碳布上生长出形貌均一的TiO2纳米线阵列，继而以TMA和H2O作为前驱体在纳米线表面均匀沉积Al2O3原子层，所制备的材料具有很好的光电催化制氢性能。此外，本发明还提供了一种利用上述Al2O3修饰的阵列TiO2纳米线作为催化剂进行光电催化分解水制氢的方法。
The invention provides an array of TiO 2 nanowires modified by Al 2 O 3 and a method for photoelectric catalytic splitting of water to produce hydrogen. The Al 2 O 3 modified array TiO 2 nanowires of the present invention include carbon cloth substrates, array TiO 2 nanowires grown on the carbon cloth substrate, and Al 2 obtained by atomic layer deposition on the surface of the array TiO 2 nanowires O 3 layers, and the number of Al 2 O 3 layers is 1-20 layers. The invention adopts the liquid-phase hydrothermal synthesis method to directly grow the TiO2 nanowire array with uniform morphology on the carbon cloth, and then uses TMA and H2O as precursors to uniformly deposit the Al2O3 atomic layer on the surface of the nanowire. The prepared material has good photoelectric catalytic hydrogen production performance. In addition, the present invention also provides a method for using the above-mentioned Al 2 O 3 modified array TiO 2 nanowires as a catalyst for photoelectric catalytic water splitting to produce hydrogen.
Description
Technical field
The present invention relates to a kind of Al2O3The array TiO of modification2Nano wire and preparation method thereof further relates to a kind of photoelectrocatalysis
The method of hydrogen production by water decomposition belongs to photocatalysis technology field.
Background technique
Today's society, energy and environment problem is more and more prominent, and the more clean renewable energy of exploitation is imperative, uses
Cleaning reproducible solar energy electrocatalytic decomposition water hydrogen making is the desirable route solved the problems, such as.1972, Japan Science
Family Fujishima and Honda has found TiO2Electrode can decompose water under ultraviolet lighting and generate hydrogen, thus open TiO2Light
The application study of catalysis.TiO2It is the n-type semiconductor that scientist studies earliest, it is cheap, nontoxic and environmental-friendly, become
Ideal conductor photocatalysis research object.
One-dimentional structure TiO2The characteristic that nano-wire array has makes it compared to TiO2Film has bigger specific surface area
And adsorption capacity, there is better effect for photoelectrocatalysis.Nanowire structure still falls within nanometer scale on certain dimension, and
Its unique structure makes it have boundary confinement effect, has better transmission performance to light induced electron and hole. TiO2Nano wire
The defect and Ti-O dangling bonds of array surface will form photo-generated carrier complex centre, make the reduction of its photocatalytic activity, therefore must
Feasible method must be found and reduce photo-generated carrier in the compound of surface.
In order to improve TiO2Photocatalytic activity, CN103354283A, which is disclosed, a kind of there is gold nanoparticle to modify branch
The application of shape titanic oxide nanorod array electrode and preparation method thereof and photoelectrolysis water hydrogen manufacturing, the invention effectively inhibit two
Electron-hole pair is compound in titanium oxide, and the extinction of material is made by surface plasma body resonant vibration (SPR) effect of gold nanocrystals
Range expands to visible region, improves photoelectrochemistrpool pool photolysis water hydrogen activity.CN102631909A discloses a kind of surface
Titanate radical nanopipe microballoon presoma is placed in quartz by titanium dioxide nano thread microballoon catalysis material of hydrogenation and preparation method thereof
In the quartz boat of tube hub, it is passed through hydrogen in sintering procedure, the TiO of surface hydriding can be obtained2Nano wire microballoon, the catalyst exist
There is the photolysis water hydrogen efficiency of enhancing under full spectral illumination.What CN102534781A proposed a kind of efficient photocatalytic water mixes tin
TiO2Nano-wire array and its preparation method and application, for the preparation method using tetra-n-butyl titanate as titanium source, water is solvent, tetrachloro
Change tin is tin source, and concentrated hydrochloric acid regulates and controls the rate of hydrolysis, is mixing tin two containing growth in fluorine tin oxide (FTO) electro-conductive glass substrate
TiOx nano linear array, the invention couple conventional photolytic water technology and photoelectric conversion technology, improve solar-electricity
Pond realizes efficient photolysis water hydrogen and photoelectric conversion generates a one-step process of photoelectric current to the absorption efficiency of light.
CN102107850B discloses a kind of rutile single crystals TiO of coated with carbon bed2The preparation side of nuclear shell structure nano linear array
Method, this method first prepare the rutile single crystals TiO of surface polyphenyl phenolic compounds cladding2Then nano-wire array warms its height
Solve the rutile single crystals TiO that coated with carbon bed is made2Nuclear shell structure nano linear array, the catalyst are remarkably improved TiO2It receives
The quantum yield of nanowire arrays improves solar energy utilization ratio.
Atomic layer deposition (Atomic layer deposition:ALD) technology can be in catalyst surface in layer
Deposition and atomic monofilm, and the growth of film or nano particle can be controlled in atomic level.It is repaired by atomic layer deposition
Semiconductor material surface is adornd, the compound of photo-generated carrier can be reduced.The material of ALD deposition is also varied, such as Al2O3、TiO2、
ZnO etc. can significantly improve the photoelectric conversion efficiency of semiconductor material by atomic layer passivating technique.Hwang etc. (Yun J H,
Hahn C,Liu B,et al.Photoelectrochemical properties of TiO2 nanowire 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
TiO of the layer to different length2The influence of nanowire photodiode stream.(Xu Z, Lin Y, the Yin M, 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 charge transporting mechanism under the different configuration of passivation layer three.
CN103736500A disclose a kind of Titanium dioxide/cadmium sulfide/titanium dioxide composite film preparation method and its
Using in TiO2CdS nano particle ALD depositing Ti O again is deposited first with SILAR method on nanometer stick array2
Layer, this catalyst have good visible light organic wastewater degraded effect.CN104923261A is disclosed to be existed using ALD technique
The CdS nano grain surface of hydrothermal synthesis deposited the protective layer (TiO of one layer of 1-10A2、ZnO、Al2O3Deng), it is higher in guarantee
The catalytic life of CdS nanoparticle is extended under the premise of catalytic efficiency.
In conclusion TiO2It is ideal photochemical catalyzing material, has had after decades of development various
Modified method improves its catalytic efficiency, and ALD technique has been used in the study on the modification of photochemical catalyst, and photocatalysis can be improved
Efficiency, but by ALD technique in TiO2Nanowire surface depositing Al2O3Atomic layer is acted on by surface passivation and efficiently being improved
TiO2The photoelectrocatalysis of nano wire decomposes aquatic products hydrogen, and there is no special reports.
Summary of the invention
In order to solve the above technical problems, the purpose of the present invention is to provide a kind of Al2O3The array TiO of modification2Nano wire and
Preparation method and method for photoelectrocatalysis hydrogen production by water decomposition.The Al2O3The array TiO of modification2The preparation side of nano wire
Method is using technique for atomic layer deposition in TiO2Nanowire surface depositing Al2O3Layer, can greatly improve the photoelectrocatalysis of titanium dioxide
Hydrogen production by water decomposition performance.
In order to achieve the above objectives, present invention firstly provides a kind of Al2O3The array TiO of modification2Nano wire comprising carbon
Cloth substrate, the array TiO being grown in carbon cloth substrate2Nano wire and by array TiO2Nanowire surface carries out atomic layer
Al obtained from deposition2O3Layer；And the TiO2The length of nano wire is 500nm-1 μm, diameter 20-50nm, the Al2O3
The number of plies of layer is 1-20 layers.
Specific embodiment according to the present invention, it is preferable that the Al2O3The array TiO of modification2Nano wire be by with
What lower step was prepared:
Step 1: carbon cloth is dipped in the hexane solution of titanium tetrachloride, stands a period of time；Carbon cloth is then taken out, in
500 DEG C -550 DEG C of constant temperature 30-60 minutes, the carbon cloth of long good kind of layer is made；
Step 2: with 10:(1-2): (1-2): the volume ratio of (0.1-5) is by toluene, butyl titanate, concentrated hydrochloric acid (i.e. matter
Measure the concentrated hydrochloric acid of concentration 37%), titanium tetrachloride is mixed and stirred for uniformly, obtaining a mixed liquor；It is highly preferred that step 2 are as follows:
In reaction kettle, toluene, butyl titanate, concentrated hydrochloric acid (i.e. the concentrated hydrochloric acid of mass concentration 37%), titanium tetrachloride is successively added dropwise,
Stir evenly, wherein toluene, butyl titanate, concentrated hydrochloric acid, titanium tetrachloride volume ratio be 10:(1-2): (1-2): (0.1-
It 5) is particularly preferably, 10:1:1:(0.1-5)；
Step 3: the carbon cloth for the good kind of layer of length that step 1 obtains is tilted a certain angle the mixed liquor for being placed in step 2 and obtaining
In (inclined angle is preferably 40-60 °, which refers to the angle with the mixed liquor liquid level), in 180 DEG C of -220 DEG C of hydro-thermals
Reaction 20-25 hours；After cooling, by obtained product cleaning (washes of absolute alcohol can be used), then in 500 DEG C -550 DEG C
Constant temperature 2-4 hours, obtained growth had 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 under certain depositing temperature and is passed through a timing
Between, and make trimethyl aluminium and H2The partial pressure of O is 0.1-0.2Torr, chamber pressure 1-2Torr, above to exist as a cycle
Array TiO2Nanowire surface depositing Al2O3Atomic layer, and make Al2O3The deposition number of plies of atomic layer is 1-20 (a cycle deposition
One layer of Al2O3Atomic layer), the Al is prepared2O3The array TiO of modification2Nano wire.
In the present invention, the carbon cloth is carbon cloth, is the fabric of carbon fiber, is a kind of high tenacity, high flexibility
Conductive material.The carbon cloth can be selected from polyacrylonitrile (PAN) base carbon fibre cloth, viscose base carbon fibre cloth, asphaltic base carbon fiber
One or more of combination in Wei Bu etc., weaving mode and size for the carbon cloth are simultaneously not particularly limited, can be with
It is selected according to actual needs by those skilled in the art.
Specific embodiment according to the present invention, it is preferable that in above-mentioned Al2O3The array TiO of modification2The preparation of nano wire
In step, the carbon cloth used in step 1 is the carbon cloth after cleaning, and the cleaning of carbon cloth is successively in acetone, distilled water, nothing
It is cleaned by ultrasonic in water-ethanol.
Specific embodiment according to the present invention, it is preferable that in above-mentioned Al2O3The array TiO of modification2The preparation of nano wire
In step, the concentration of the hexane solution of the titanium tetrachloride in step 1 is 0.01-0.1mol/L.
Specific embodiment according to the present invention, it is preferable that in above-mentioned Al2O3The array TiO of modification2The preparation of nano wire
It is 5-15 hours that carbon cloth is dipped in the time stood in the hexane solution of titanium tetrachloride in step, in step 1.
Specific embodiment according to the present invention, it is preferable that in above-mentioned Al2O3The array TiO of modification2The preparation of nano wire
In step, in step 1 in 500 DEG C -550 DEG C of constant temperature 30-60 minutes be that carbon cloth is put into tube furnace, with 3-6 DEG C/min
Heating rate by room temperature to 500 DEG C -550 DEG C, then in 500 DEG C -550 DEG C of constant temperature 30-60 minutes.
Specific embodiment according to the present invention, it is preferable that in above-mentioned Al2O3The array TiO of modification2The preparation of nano wire
In step, the reaction kettle in step 2 can be ptfe autoclave, such as the ptfe autoclave of 200ml.
Specific embodiment according to the present invention, it is preferable that in above-mentioned Al2O3The array TiO of modification2The preparation of nano wire
In step, in step 3-550 DEG C of constant temperature 2-4 hours is that the product after cleaning is put into tube furnace in 500 DEG C, 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 of constant temperature 2-4 hours.
Specific embodiment according to the present invention, it is preferable that in above-mentioned Al2O3The array TiO of modification2The preparation of nano wire
In step, the depositing temperature of presoma is 100-500 DEG C in step 4.
Specific embodiment according to the present invention, it is preferable that in above-mentioned Al2O3The array TiO of modification2The preparation of nano wire
In step, the time that is passed through of presoma is 10-300s in step 4.
The present invention also provides a kind of above-mentioned Al2O3The array TiO of modification2The preparation method of nano wire comprising following step
It is rapid:
Step 1: carbon cloth is dipped in the hexane solution of titanium tetrachloride, stands a period of time；Carbon cloth is then taken out, in
500 DEG C -550 DEG C of constant temperature 30-60 minutes, the carbon cloth of long good kind of layer is made；
Step 2: with 10:(1-2): (1-2): the volume ratio of (0.1-5) is by toluene, butyl titanate, concentrated hydrochloric acid (i.e. matter
Measure the concentrated hydrochloric acid of concentration 37%), titanium tetrachloride is mixed and stirred for uniformly, obtaining a mixed liquor；It is highly preferred that step 2 are as follows:
In reaction kettle, toluene, butyl titanate, concentrated hydrochloric acid (i.e. the concentrated hydrochloric acid of mass concentration 37%), titanium tetrachloride is successively added dropwise,
Stir evenly, wherein toluene, butyl titanate, concentrated hydrochloric acid, titanium tetrachloride volume ratio be 10:(1-2): (1-2): (0.1-
It 5) is particularly preferably, 10:1:1:(0.1-5)；
Step 3: the carbon cloth for the good kind of layer of length that step 1 obtains is tilted a certain angle the mixed liquor for being placed in step 2 and obtaining
In (inclined angle is preferably 40-60 °, which refers to the angle with the mixed liquor liquid level), in 180 DEG C of -220 DEG C of hydro-thermals
Reaction 20-25 hours；After cooling, by obtained product cleaning (washes of absolute alcohol can be used), then in 500 DEG C -550 DEG C
Constant temperature 2-4 hours, obtained growth had 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 under certain depositing temperature and is passed through a timing
Between, and make trimethyl aluminium and H2The partial pressure of O is 0.1-0.2Torr, chamber pressure 1-2Torr, above to exist as a cycle
Array TiO2Nanowire surface depositing Al2O3Atomic layer, and make Al2O3The deposition number of plies of atomic layer is 1-20 (a cycle deposition
One layer of Al2O3Atomic layer), the Al is prepared2O3The array TiO of modification2Nano wire.
In the above preparation method, it is preferable that the carbon cloth used in step 1 is the carbon cloth after cleaning, and carbon cloth is clear
Wash is successively to be cleaned by ultrasonic in acetone, distilled water, dehydrated alcohol.
In the above preparation method, it is preferable that the concentration of the hexane solution of the titanium tetrachloride in step 1 is 0.01-
0.1mol/L。
In the above preparation method, it is preferable that carbon cloth is dipped in the hexane solution of titanium tetrachloride in step 1 and is stood
Time be 5-15 hours.
In the above preparation method, it is preferable that in step 1 in 500 DEG C -550 DEG C of constant temperature 30-60 minutes be by carbon cloth
It is put into 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
Constant temperature 30-60 minutes.
In the above preparation method, it is preferable that the reaction kettle in step 2 can be ptfe autoclave, such as
The ptfe autoclave of 200ml.
In the above preparation method, it is preferable that in step 3 in 500 DEG C -550 DEG C of constant temperature 2-4 hours be that will clean after
Product be put into 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 constant temperature 2-4 hours.
In the above preparation method, it is preferable that the depositing temperature of presoma is 100-500 DEG C in step 4.
In the above preparation method, it is preferable that the time that is passed through of presoma is 10-300s in step 4.
On the other hand, the present invention also provides a kind of method of photoelectrocatalysis hydrogen production by water decomposition, this method is with above-mentioned
Al2O3The array TiO of modification2Nano wire is as catalyst, comprising the following steps:
It is 1-10cm with area using 0.01-1mol/L metabisulfite solution as electrolyte solution2Al2O3The array of modification
TiO2Nano-wire catalyst is platinized platinum to electrode as working 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 reaction unit is vacuumized, reach negative
After one atmospheric pressure, then with light source working electrode is irradiated so as to generate hydrogen in reaction unit.
In the method for above-mentioned photoelectrocatalysis hydrogen production by water decomposition, it is preferable that used light source is xenon source.
In the method for above-mentioned photoelectrocatalysis hydrogen production by water decomposition, it is preferable that during the reaction, at the electrolyte solution
Under continuous stirring.
The present invention provides a kind of Al2O3The array TiO of modification2Nano wire, preparation method are on flexible carbon fibre cloth
Grow array TiO2Nano wire, then using technique for atomic layer deposition (ALD) in array TiO2Nanowire surface depositing Al2O3Layer,
Obtain the ALD Al on carbon cloth2O3/TiO2Nano-wire array, wherein atomic layer deposition Al2O3The number of plies of layer is 1-20 layers.Tool
For body, the present invention directly grows the uniform TiO of pattern using the method for liquid phase hydrothermal synthesis on carbon cloth2Nanometer linear array
Column, then with trimethyl aluminium (TMA) and H2O is as presoma in nanowire surface uniform deposition Al2O3Atomic layer, it is prepared
Material has good photoelectrocatalysis hydrogen manufacturing performance.Al of the invention2O3The array TiO of modification2The manufacture craft letter of nano wire
Single, repeatability is very good, may be used as light-catalyzed reaction, solar battery, photoelectricity flexible device etc., is suitble to high-volume exploitation life
It produces.In addition, utilizing above-mentioned Al the present invention also provides a kind of2O3The array TiO of modification2Nano wire carries out photoelectricity as catalyst
The method that water hydrogen manufacturing is catalytically decomposed.ALD Al provided by the invention2O3/TiO2Nano wire photochemical catalyst has very high photocatalysis
Activity, with simple TiO2Nano wire is compared, and hydrogen-producing speed significantly improves.
Technical solution provided by the present invention has the advantages that
1.TiO2TiO of the nano wire compared to other structures2Producing hydrogen for photoelectrocatalysis has better effect, array
TiO2Convenient hydrogen producing in the environment of biasing of nano wire；Nanowire structure has stronger mechanical strength, and certain empty
Between biggish surface area is provided；TiO2Nanowire structure still falls within nanometer scale on certain dimension, and its unique structure makes
It has better transmission performance with boundary confinement effect, to light induced electron and hole.
2. Al provided by the invention2O3The array TiO of modification2Nano wire photochemical catalyst, Al2O3The passivation of layer can press down
TiO processed2Nano wire photo-generated carrier it is compound, improve the separative efficiency of electron hole pair, substantially increase TiO2The light of nano wire
Catalytic performance, photoelectrocatalysis decompose water hydrogen-producing speed and are all greatly improved.
Detailed description of the invention
Fig. 1 is Al prepared by embodiment 22O3The array TiO of modification2The stereoscan photograph of nano wire photochemical catalyst；
Fig. 2 is Al prepared by embodiment 22O3The array TiO of modification2The transmission electron microscope photo of nano wire photochemical catalyst；
Fig. 3 is Al prepared by embodiment 12O3The array TiO of modification2The photoelectrocatalysis of nano wire photochemical catalyst decomposes aquatic products
Hydrogen amount and time curve；
Fig. 4 is Al prepared by embodiment 22O3The array TiO of modification2The photoelectrocatalysis of nano wire photochemical catalyst decomposes aquatic products
Hydrogen amount and time curve；
Fig. 5 is Al prepared by embodiment 32O3The array TiO of modification2The photoelectrocatalysis of nano wire photochemical catalyst decomposes aquatic products
Hydrogen amount and time curve；
Fig. 6 is Al prepared by embodiment 42O3The array TiO of modification2The photoelectrocatalysis of nano wire photochemical catalyst decomposes aquatic products
Hydrogen amount and time curve；
Fig. 7 is Al prepared by embodiment 52O3The array TiO of modification2The photoelectrocatalysis of nano wire photochemical catalyst decomposes aquatic products
Hydrogen amount and time curve；
Fig. 8 is array TiO prepared by comparative example 12The photoelectrocatalysis of nano wire photochemical catalyst decomposes aquatic products hydrogen amount and time
Relation curve；
The photoelectrocatalysis for the photochemical catalyst that Fig. 9 is embodiment 1-5 and prepared by comparative example 1 decomposes aquatic products hydrogen amount and the time closes
It is curve comparison figure.
Specific embodiment
It is attached referring now to specification in order to which technical characteristic of the invention, purpose and beneficial effect are more clearly understood
Figure carries out technical solution of the present invention described further below, but should not be understood as that limiting the scope of the invention.
Embodiment 1
Present embodiments provide a kind of Al2O3The array TiO of modification2Nano wire photochemical catalyst, preparation method specifically include
Following steps:
Carbon cloth is successively cleaned by ultrasonic in acetone, distilled water, dehydrated alcohol.Compound concentration is the tetrachloro of 0.05mol/L
Carbon cloth after cleaning is dipped in wherein, stands 10h by the hexane solution for changing titanium；Take out carbon cloth be put into tube furnace, with 4 DEG C/
Min is warming up to 500 DEG C, 500 DEG C of constant temperature 30min by 30 DEG C, and the carbon cloth of long good kind of layer is made.It is anti-in the polytetrafluoroethylene (PTFE) of 200ml
It answers in kettle, toluene, butyl titanate, concentrated hydrochloric acid (i.e. the concentrated hydrochloric acid of mass concentration 37%), titanium tetrachloride is successively added dropwise, stirs
Mix uniformly, wherein toluene, butyl titanate, concentrated hydrochloric acid, titanium tetrachloride volume ratio be 10:1:1:1.By the carbon cloth of long good kind of layer
40 ° or so of inclination (the inclined angle is the angle with mixed liquor liquid level in reaction kettle) is put into aforesaid reaction vessel, 180 DEG C of water
Thermal response 22h；Obtained hydrothermal product is washed with dehydrated alcohol, is then placed in tube furnace by natural cooling, with 4 DEG C/min
550 DEG C are warming up to by 30 DEG C, 550 DEG C of constant temperature 2h, obtained growth has array TiO2The carbon cloth of nano wire, TiO2The length of nano wire
About 1 μm, diameter is about 20-30nm.
Growth there is into array TiO2The carbon cloth of nano wire is placed in atomic layer deposition system, select trimethyl aluminium (TMA) and
H2O is as presoma, N2As carrier gas, presoma is controlled under 150 DEG C of depositing temperatures and is passed through the time as 90s, TMA and H2O's
Partial pressure is 0.1Torr, chamber pressure 1Torr, the above conduct a cycle depositing Al2O3Atomic layer, the circulation of atomic layer deposition
Number is 1 (i.e. atomic layer deposition Al2O3The number of plies of layer is 1 layer), ALD 1cycle Al is made2O3/TiO2Nanometer linear light is urged
Agent.
Embodiment 2
Present embodiments provide a kind of Al2O3The array TiO of modification2Nano wire photochemical catalyst, preparation method specifically include
Following steps:
Carbon cloth is successively cleaned by ultrasonic in acetone, distilled water, dehydrated alcohol.Compound concentration is the tetrachloro of 0.05mol/L
Carbon cloth after cleaning is dipped in wherein, stands 10h by the hexane solution for changing titanium；Take out carbon cloth be put into tube furnace, with 4 DEG C/
Min is warming up to 500 DEG C, 500 DEG C of constant temperature 30min by 30 DEG C, and the carbon cloth of long good kind of layer is made.It is anti-in the polytetrafluoroethylene (PTFE) of 200ml
It answers in kettle, toluene, butyl titanate, concentrated hydrochloric acid (i.e. the concentrated hydrochloric acid of mass concentration 37%), titanium tetrachloride is successively added dropwise, stirs
Mix uniformly, wherein toluene, butyl titanate, concentrated hydrochloric acid, titanium tetrachloride volume ratio be 10:1:1:1.By the carbon cloth of long good kind of layer
50 ° or so of inclination (the inclined angle is the angle with mixed liquor liquid level in reaction kettle) is put into aforesaid reaction vessel, 180 DEG C of water
Thermal response 22h；Obtained hydrothermal product is washed with dehydrated alcohol, is then placed in tube furnace by natural cooling, with 4 DEG C/min
550 DEG C are warming up to by 30 DEG C, 550 DEG C of constant temperature 2h, obtained growth has array TiO2The carbon cloth of nano wire.
Growth there is into array TiO2The carbon cloth of nano wire is placed in atomic layer deposition system, select trimethyl aluminium (TMA) and
H2O is as presoma, N2As carrier gas, presoma is controlled under 150 DEG C of depositing temperatures and is passed through the time as 90s, TMA and H2O's
Partial pressure is 0.1Torr, chamber pressure 1Torr, the above conduct a cycle depositing Al2O3Atomic layer, the circulation of atomic layer deposition
Number is 2 (i.e. atomic layer deposition Al2O3The number of plies of layer is 2 layers), ALD 2cycles Al is made2O3/TiO2Nanometer linear light is urged
Agent.
Fig. 1 is Al manufactured in the present embodiment2O3The array TiO of modification2The stereoscan photograph of nano wire photochemical catalyst.Fig. 2
For Al manufactured in the present embodiment2O3The array TiO of modification2The transmission electron microscope photo of nano wire photochemical catalyst.It can be seen by Fig. 1-2
Out, the TiO for having pattern uniform is grown on carbon cloth2Nano-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 of modification2Nano wire photochemical catalyst, preparation method specifically include
Following steps:
Carbon cloth is successively cleaned by ultrasonic in acetone, distilled water, dehydrated alcohol.Compound concentration is the tetrachloro of 0.01mol/L
Carbon cloth after cleaning is dipped in wherein, stands 10h by the hexane solution for changing titanium；Take out carbon cloth be put into tube furnace, with 4 DEG C/
Min is warming up to 500 DEG C, 500 DEG C of constant temperature 30min by 30 DEG C, and the carbon cloth of long good kind of layer is made.It is anti-in the polytetrafluoroethylene (PTFE) of 200ml
It answers in kettle, toluene, butyl titanate, concentrated hydrochloric acid (i.e. the concentrated hydrochloric acid of mass concentration 37%), titanium tetrachloride is successively added dropwise, stirs
Mix uniformly, wherein toluene, butyl titanate, concentrated hydrochloric acid, titanium tetrachloride volume ratio be 10:1:1:4.By the carbon cloth of long good kind of layer
60 ° or so of inclination (the inclined angle is the angle with mixed liquor liquid level in reaction kettle) is put into aforesaid reaction vessel, 180 DEG C of water
Thermal response is for 24 hours；Obtained hydrothermal product is washed with dehydrated alcohol, is then placed in tube furnace by natural cooling, with 4 DEG C/min
550 DEG C are warming up to by 30 DEG C, 550 DEG C of constant temperature 2h, obtained growth has array TiO2The carbon cloth of nano wire, TiO2The length of nano wire
About 800 μm, diameter is about 20-30nm.
Growth there is into array TiO2The carbon cloth of nano wire is placed in atomic layer deposition system, select trimethyl aluminium (TMA) and
H2O is as presoma, N2As carrier gas, presoma is controlled under 150 DEG C of depositing temperatures and is passed through the time as 90s, TMA and H2O's
Partial pressure is 0.1Torr, chamber pressure 1Torr, the above conduct a cycle depositing Al2O3Atomic layer, the circulation of atomic layer deposition
Number is 3 (i.e. atomic layer deposition Al2O3The number of plies of layer is 3 layers), ALD 3cycles Al is made2O3/TiO2Nanometer linear light is urged
Agent.
Embodiment 4
Present embodiments provide a kind of Al2O3The array TiO of modification2Nano wire photochemical catalyst, preparation method specifically include
Following steps:
Carbon cloth is successively cleaned by ultrasonic in acetone, distilled water, dehydrated alcohol.Compound concentration is the tetrachloro of 0.01mol/L
Carbon cloth after cleaning is dipped in wherein, stands 12h by the hexane solution for changing titanium；Take out carbon cloth be put into tube furnace, with 4 DEG C/
Min is warming up to 500 DEG C, 500 DEG C of constant temperature 30min by 30 DEG C, and the carbon cloth of long good kind of layer is made.It is anti-in the polytetrafluoroethylene (PTFE) of 200ml
It answers in kettle, toluene, butyl titanate, concentrated hydrochloric acid (i.e. the concentrated hydrochloric acid of mass concentration 37%), titanium tetrachloride is successively added dropwise, stirs
Mix uniformly, wherein toluene, butyl titanate, concentrated hydrochloric acid, titanium tetrachloride volume ratio be 10:1:1:1.By the carbon cloth of long good kind of layer
50 ° or so of inclination (the inclined angle is the angle with mixed liquor liquid level in reaction kettle) is put into aforesaid reaction vessel, 180 DEG C of water
Thermal response 23h；Obtained hydrothermal product is washed with dehydrated alcohol, is then placed in tube furnace by natural cooling, with 4 DEG C/min
550 DEG C are warming up to by 30 DEG C, 550 DEG C of constant temperature 2h, obtained growth has array TiO2The carbon cloth of nano wire, TiO2The length of nano wire
About 800 μm, diameter is about 20-30nm.
Growth there is into array TiO2The carbon cloth of nano wire is placed in atomic layer deposition system, select trimethyl aluminium (TMA) and
H2O is as presoma, N2As carrier gas, presoma is controlled under 150 DEG C of depositing temperatures and is passed through the time as 90s, TMA and H2O's
Partial pressure is 0.1Torr, chamber pressure 1Torr, the above conduct a cycle depositing Al2O3Atomic layer, the circulation of atomic layer deposition
Number is 4 (i.e. atomic layer deposition Al2O3The number of plies of layer is 4 layers), ALD 4cycles Al is made2O3/TiO2Nanometer linear light is urged
Agent.
Embodiment 5
Present embodiments provide a kind of Al2O3The array TiO of modification2Nano wire photochemical catalyst, preparation method specifically include
Following steps:
Carbon cloth is successively cleaned by ultrasonic in acetone, distilled water, dehydrated alcohol.Compound concentration is four chlorinations of 0.1mol/L
Carbon cloth after cleaning is dipped in wherein, stands 5h by the hexane solution of titanium；Take out carbon cloth be put into 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 the carbon cloth of long good kind of layer is made.In the ptfe autoclave of 200ml
In, toluene, butyl titanate, concentrated hydrochloric acid (i.e. the concentrated hydrochloric acid of mass concentration 37%), titanium tetrachloride is successively added dropwise, stirring is equal
It is even, wherein toluene, butyl titanate, concentrated hydrochloric acid, titanium tetrachloride volume ratio be 10:1:1:2.By the carbon cloth inclination of long good kind of layer
50 ° or so (the inclined angle is the angle with mixed liquor liquid level in reaction kettle) are put into aforesaid reaction vessel, and 180 DEG C of hydro-thermals are anti-
Answer 22h；Obtained hydrothermal product is washed with dehydrated alcohol, is then placed in tube furnace by natural cooling, with 4 DEG C/min by 30
DEG C 550 DEG C are warming up to, 550 DEG C of constant temperature 2h, obtained 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 into array TiO2The carbon cloth of nano wire is placed in atomic layer deposition system, select trimethyl aluminium (TMA) and
H2O is as presoma, N2As carrier gas, presoma is controlled under 150 DEG C of depositing temperatures and is passed through the time as 90s, TMA and H2O's
Partial pressure is 0.1Torr, chamber pressure 1Torr, the above conduct a cycle depositing Al2O3Atomic layer, the circulation of atomic layer deposition
Number is 5 (i.e. atomic layer deposition Al2O3The number of plies of layer is 5 layers), ALD 5cycles Al is made2O3/TiO2Nanometer linear light is urged
Agent.
6 photoelectrocatalysis of embodiment decomposes water activity rating
Photoelectrocatalysis is carried out to catalyst using II instrument of Labsolar- of Bo Fei Lay company and decomposes the active evaluation of water in fact
It tests, which carries out in the following 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, applies the inclined of 0.2V to three electrode reactors by connection electrochemical workstation
Pressure；
Three electrode reactors and II system of Labsolar- are connected, before the reaction starts to entire photocatalysis apparatus
Vacuumize process is carried out, 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 reaction time of 2 hours, primary every sampling in 20 minutes, the hydrogen component concentration in reaction product passes through gas phase
On-line chromatographic analysis obtains.
According to above-mentioned steps, catalyst ALD 1cycle Al prepared by embodiment 12O3/TiO2Nano wire is evaluated,
The relation curve of hydrogen output and time that catalyst is reacted with water is obtained, as shown in Figure 3.By result in figure it is found that ALD
1Al2O3/TiO2The production hydrogen activity of nano wire sample is 40.63 μm of ol/ (hcm2)。
According to above-mentioned steps, catalyst ALD 2cycles Al prepared by embodiment 22O3/TiO2Nano wire is commented
Valence obtains the relation curve of hydrogen output and time that catalyst is reacted with water, as shown in Figure 4.By result in figure it is found that ALD
2Al2O3/TiO2The production hydrogen activity of nano wire sample is 42.46 μm of ol/ (hcm2)。
According to above-mentioned steps, catalyst ALD 3cycles Al prepared by embodiment 32O3/TiO2Nano wire is commented
Valence obtains the relation curve of hydrogen output and time that catalyst is reacted with water, as shown in Figure 5.By result in figure it is found that ALD
3Al2O3/TiO2The production hydrogen activity of nano wire sample is 36.05 μm of ol/ (hcm2)。
According to above-mentioned steps, catalyst ALD 4cycles Al prepared by embodiment 42O3/TiO2Nano wire is commented
Valence obtains the relation curve of hydrogen output and time that catalyst is reacted with water, as shown in Figure 6.By result in figure it is found that ALD
4Al2O3/TiO2The production hydrogen activity of nano wire sample is 32.0 μm of ol/ (hcm2)。
According to above-mentioned steps, catalyst ALD 5cycles Al prepared by embodiment 52O3/TiO2Nano wire is commented
Valence obtains the relation curve of hydrogen output and time that catalyst is reacted with water, as shown in Figure 7.By result in figure it is found that ALD
5Al2O3/TiO2The production hydrogen activity of nano wire sample is 26.65 μm of ol/ (hcm2)。
Comparative example 1
This comparative example provides a kind of array TiO2Nano wire photochemical catalyst, preparation method specifically includes the following steps:
Carbon cloth is successively cleaned by ultrasonic in acetone, distilled water, dehydrated alcohol.Compound concentration is the tetrachloro of 0.05mol/L
Carbon cloth after cleaning is dipped in wherein, stands 10h by the hexane solution for changing titanium；Take out carbon cloth be put into tube furnace, with 4 DEG C/
Min is warming up to 500 DEG C, 500 DEG C of constant temperature 30min by 30 DEG C, and the carbon cloth of long good kind of layer is made.It is anti-in the polytetrafluoroethylene (PTFE) of 200ml
It answers in kettle, toluene, butyl titanate, concentrated hydrochloric acid (i.e. the concentrated hydrochloric acid of mass concentration 37%), titanium tetrachloride is successively added dropwise, stirs
Mix uniformly, wherein toluene, butyl titanate, concentrated hydrochloric acid, titanium tetrachloride volume ratio be 10:1:1:1.By the carbon cloth of long good kind of layer
50 ° or so of inclination (the inclined angle is the angle with mixed liquor liquid level in reaction kettle) is put into aforesaid reaction vessel, 180 DEG C of water
Thermal response 22h；Obtained hydrothermal product is washed with dehydrated alcohol, is then placed in tube furnace by natural cooling, with 4 DEG C/min
550 DEG C are warming up to by 30 DEG C, 550 DEG C of constant temperature 2h, obtained growth has array TiO2The carbon cloth of nano wire, TiO2The length of nano wire
About 1 μm, diameter is about 20-30nm, as array TiO2Nano wire photochemical catalyst.
According to the evaluation method of embodiment 6, TiO prepared by comparative example 12Nano wire photochemical catalyst is evaluated, and is obtained
The relation curve of hydrogen output and time that catalyst is reacted with water, as shown in Figure 8.By result in figure it is found that pure TiO2Nano wire
Production hydrogen activity be 6.38 μm of ol/ (hcm2)。
The photoelectrocatalysis for the photochemical catalyst that Fig. 9 is embodiment 1-5 and prepared by comparative example 1 decomposes aquatic products hydrogen amount 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 divides hydrolytic hydrogen production efficiency.
Claims (12)
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| CN108311131A (en) * | 2017-12-21 | 2018-07-24 | 安徽理工大学 | A kind of alundum (Al2O3) ultrathin membrane passivation titanic oxide nanorod array composite material and preparation method |
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