CN104338546A - A semiconductor material photocatalyst based on a layered structure and hydrogen production applications thereof - Google Patents

A semiconductor material photocatalyst based on a layered structure and hydrogen production applications thereof Download PDF

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CN104338546A
CN104338546A CN201310330319.6A CN201310330319A CN104338546A CN 104338546 A CN104338546 A CN 104338546A CN 201310330319 A CN201310330319 A CN 201310330319A CN 104338546 A CN104338546 A CN 104338546A
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photochemical catalyst
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metallic element
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李�灿
贾玉帅
韩洪宪
蒋宗轩
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Dalian Institute of Chemical Physics of CAS
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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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Abstract

The invention relates to a semiconductor material photocatalyst based on a layered structure and hydrogen production applications thereof. The photocatalyst and the applications are characterized in that: a semiconductor material comprises a group-IIA metal element, a metal element in the IB group, a group-VIB or group-VIIB or group-IIB or group-IIIA metal element, and one or two group-VIA nonmetal element. A hydrogen production reaction under visible light is performed by adopting the semiconductor material as the photocatalyst, with or without a small amount of a transition metal and a precious metal supported on the catalyst surface by in-situ photodeposition as a cocatalyst. The semiconductor material can be compounded with a known n type semiconductor to form a p-n heterojunction water decomposition system, and can be adopted as a photocathode material for a photoelectrochemistry water decomposition system.

Description

A kind of based on layer structure semi-conducting material photochemical catalyst and the application of product hydrogen thereof
Technical field
The present invention relates to solar energy photocatalytic and produce hydrogen application, be specifically related to not support for catalyst using the semi-conducting material of layer structure or only support a small amount of transition metal, noble metal as co-catalyst, under realizing optical excitation, produce H-H reaction.This semi-conducting material can construct p-n hetero-junctions decomposition water system with known n-type semiconductors coupling, also can be used as photocathode material and is applied to Optical Electro-Chemistry decomposition water system.
Background technology
Energy problem is the global problem of restriction 21 century socio-economic development.The current problem such as greenhouse effects, environmental pollution caused due to the use of fossil energy more and more becomes the critical problem affecting China's sustainable development.Therefore, no matter be from the energy or environmental, we need the reproducible energy of alternative fossil fuel, and this is the huge challenge of this century and later long-time interior human survival thereof.Utilize decomposing water with solar energy hydrogen manufacturing to be considered to one of desirable route not solving the energy and environmental problem, be just subject to worldwide extensive concern (Energy Environmental Science, 2011,4,2467-2481.).
Up to the present there have been many semiconductor catalysts to be in the news to be applied to photochemical catalyzing and sacrificed reagent and existed in lower product hydrogen product oxygen half-reaction (Chemical Reviews, 2010,110,6503-6570.).But these semiconductor catalyst major parts reported are all n-type semiconductor, this is mainly because utilizable p-type semiconductor is very limited in the material of exploitation at present, even if also still there is the following problem in some p-type semiconductor material with photocatalytic activity that document has been reported: (1) some p-type material (CoO, Co known 2o 3, Co 3o 4; NiO, Ni 2o 3) performance not having photochemical catalyzing own, can only use as co-catalyst; (2) some the p-type materials be in the news can only realize producing hydrogen half-reaction, thermodynamically cannot meet requirement (International Journal of Hydrogen Energy, 2005,30, the 693-699 of decomposition water; Solar Energy, 2006,80,272-280; Energy Conversion and Management, 2009,50,62-68.); (3) although little some p-type materials (Cu 2o, CaFe 2o 4) meet the requirement of decomposition water in theory but consider the overpotential problem in Water oxidize process, valence band thermodynamically actual requirement (Chemical Communications, 1999, the 1069-1070 that cannot meet decomposition water of these materials; Journal of Physical Chemistry, 1994,98,2950-2951.).
Separation and transmission that its active very important factor is electron-hole is affected in photochemical catalyzing process." knot " that research shows to construct energy level and Lattice Matching between semiconductor effectively can improve the separative efficiency of electron-hole thus promote photocatalytic activity (Chemistry of Materials, 2005,17,3255-3261; Journal of the American Chemical Society, 2008,130,7176-7177; Journal of Physical Chemistry C, 2010,114,1963-1968; Journal of Physical Chemistry C, 2010,114,12818-12822.).TiO is reported before us 2and Ga 2o 3what " the out-phase knot " constructed on molecule with nano-level between respective different crystalline phase effectively can promote photo-generated carrier is separated (Angewandte Chemie-International Edition, 2008,47,1766-1769; Angewandte Chemie-International Edition, 2012,51,13089-13092.).We also studied Sr in the recent period 2tiO 4/ SrTiO 3(La, what Cr) " n-n hetero-junctions " can realize electronics and hole under optical excitation is effectively separated and transmission thus product hydrogen activity (the Journal of Materials Chemistry A that improve under its visible ray, 2013, DOI:10.1039/C3TA11326D.).Surface tie mutually with heterojunction photocatalyst in due to two components between the driving force that is separated of the electron-hole that provides of different level of energy relatively little, and the transmission separately of electronics and hole also can be subject to the impact of interfacial resistance between two components.
Driving force is separated and obtains higher carrier separation efficiency that between p-type semiconductor and n-type semiconductor, construct " p-n junction " be a kind of desirable selection in order to provide relatively large electron-hole.There is bibliographical information this " p-n junction " composite photo-catalyst can separate electronic and hole thus significantly improve ability (the Angewandte Chemie-International Edition of photocatalysis and photoelectrocatalysis decomposition water efficiently, 2005,44,4585-4589; Chemical Communications, 2009,5889-5891; Journal of the American Chemical Society, 2013,135,5375-5383.).Chinese patent CN102125858A, CN102125859A, CN102423709A etc. report preparation method and the application of p-n composite semiconductor light-catalyst.Given this design and select suitable p-type and n-type semiconductor to be the key of constructing " p-n junction ", because known a large portion semi-conducting material is that therefore n-type semiconductor is constructing the restriction being in fact subject to available p-type semiconductor material in " p-n junction " compound system process.So find and exploitation narrow band gap and the suitable decomposition water p-type semiconductor material of level of energy just seems particularly crucial.
A kind of p-type layer shape semi-conducting material is applied in Photocatalyzed Hydrogen Production reaction by the present invention first, a small amount of transition metal or noble metal promoted agent support the hydrogen production potential that can significantly improve photochemical catalyst.This material is compared with the p-type Photocatalyzed Hydrogen Production material of known report: process for synthetic catalyst is relatively simple; There is good visible absorption performance (absorbing band edge at about 550nm); Conduction band valence band location thermodynamically meets the requirement of decomposition water.This semi-conducting material can construct p-n hetero-junctions decomposition water system with known n-type semiconductors coupling, also can be used as photocathode material and is applied to Optical Electro-Chemistry decomposition water system.
Summary of the invention
The present invention aims to provide a kind of catalyst being applied to Photocatalyzed Hydrogen Production reaction, and supporting of a small amount of transition metal or noble metal promoted agent, can significantly improve the hydrogen production potential of photochemical catalyst.In addition, the invention provides a kind of p-type semiconductor material being suitable for constructing p-n hetero-junctions decomposition water system, also provide a kind of photocathode material be applied in Optical Electro-Chemistry decomposition water system.
For achieving the above object, the invention provides following aspect:
A kind of based on layer structure semi-conducting material photochemical catalyst, this semi-conducting material is by a kind of IIA race metallic element, a kind of IB race metallic element, a kind of group vib or VIIB race or VIII or IIB race or IIIA race metallic element, add the layer structure semi-conducting material that one or both VIA race nonmetalloids form jointly in addition.Wherein the mol ratio of IIA race metallic element and IB race metallic element is 2:1 or 1:1, the mol ratio of IIA race metallic element and group vib or VIIB race or VIII or IIB race or IIIA race metallic element is the mol ratio of 2:1, IIA race metallic element and VIA race nonmetalloid is 1:2.
This photochemical catalyst is layered distribution along C direction of principal axis on crystal structure, specifically comprise three-decker and be respectively (1) IIA race metal cation layer, (2) layer of the nonmetal composition of I B-group metal and VIA race, the layer of (3) group vibs or VIIB race or VIII or the arbitrary metal of IIB race or IIIA race and the nonmetal composition of VIA race.
Wherein said IIA race metal is selected from Sr, I B-group metal is selected from Cu, group vib or VIIB race or VIII or IIB race or IIIA race metallic element are selected from the one in Cr, Mn, Fe, Co, Zn, Ga, In, VIA race nonmetalloid be selected from O and S one or both.
Described photochemical catalyst is the material with layer structure formed by the additional another kind of metal of strontium copper oxygen sulphur, another kind of metal specifically refer to Cr, Mn, Fe, Co, Zn, Ga, In one of them.
Described photochemical catalyst is with this semi-conducting material for carrier, does not support or supports one or two or more kinds the original position light deposition in a small amount of transition metal, noble metal in catalyst surface as co-catalyst.The loading of transition metal and noble metal is the 0.01-5.0wt% of photochemical catalyst.
The preparation method of described photochemical catalyst: raw material (reaction raw materials is the metal simple-substance of required metallic element, in metal or bimetallic oxide, metal or bimetallic sulfide one or two or more kinds) is placed in quartz ampoule; under argon gas atmosphere protective condition; the arbitrary temperature within the scope of 500-1200 DEG C is heated in tube furnace; reaction 5-20h, obtains photochemical catalyst.
Original position Photodeposition is adopted to be supported in photocatalyst surface one or two or more kinds in transition metal and noble metal Ni, Pd, Pt, Ru, Rh.The process that specifically supports to add containing photochemical catalyst and electron donor reagent (Organic Alcohol of C1-C4 or the organic acid of C1-C4 or alkali metal sulphide, alkali metal sulfite respectively containing the solvable presoma of one or two or more kinds (chloride or nitrate or carbonyls) in above-mentioned transition metal and noble metal Ni, Pd, Pt, Ru, Rh, wherein Organic Alcohol and organic acid concentration range are 1vol% ~ 99vol%, and the concentration range of alkali metal sulphide and alkali metal sulfite is 1mM ~ 10M) the aqueous solution in.Under illumination condition, realize Pt respectively, the in-situ impregnation of one or two or more kinds in Ni, Pd, Rh, Ru.The loading of transition metal and noble metal is the 0.01-5.0wt% of added photochemical catalyst in reaction.
The product hydrogen application of described photochemical catalyst: with described semi-conducting material for photochemical catalyst does not support, or the product H-H reaction carried out in catalyst surface as co-catalyst using described semi-conducting material for one or two or more kinds the original position light deposition in transition metal, noble metal supports by carrying body under visible ray, or this semi-conducting material can construct p-n hetero-junctions decomposition water system with known n-type semiconductors coupling, or this semi-conducting material also can be used as photocathode material and is applied to Optical Electro-Chemistry decomposition water system.
To not support or the catalyst of only supported transition metal and noble metal joins containing electron donor reagent (Organic Alcohol of C1-C4 or the organic acid of C1-C4 or alkali metal sulphide, alkali metal sulfite, wherein Organic Alcohol and organic acid concentration range are 1vol% ~ 99vol%, and the concentration range of alkali metal sulphide and alkali metal sulfite is 1mM ~ 10M) the aqueous solution in.Under agitation reaction system is found time, keep reaction temperature 5-50 DEG C, adopt suitable sources (xenon lamp, mercury lamp, xenon-mercury lamp, iodine-tungsten lamp and sunshine) to irradiate and react, the amounts of hydrogen produced by online gas chromatographic analysis.
The constructing of p-n hetero-junctions decomposition water system is referred to and is assembled by suitable synthetic method (hydro-thermal method, solid phase method, magnetron sputtering method or atomic layer deposition method etc.) as p-type semiconductor material and n-type semiconductor known at present by the catalyst in the present invention, builds the photocatalysis system with obvious carrier separation effect.Optical Electro-Chemistry decomposition water system refers to and is combined with anode material known at present as negative electrode by the semi-conducting material in the present invention, employing suitable sources is irradiated, and does not add or only add the while that a small amount of (0v ~ 1.0v) bias voltage realizing negative electrode producing hydrogen anode produces oxygen.
The preparation of photocathode material is mainly through electrophoretic deposition, magnetron sputtering method, atomic layer deposition method or scrape embrane method etc. and realize.
Light source comprises one or two or more kinds in xenon lamp, mercury lamp, xenon-mercury lamp, iodine-tungsten lamp and sunshine, light source send the wavelength optimum range 190-700nm of light.
The present invention, compared with known technology, has following characteristics:
1. the type catalyst application reacts in Photocatalyzed Hydrogen Production by the present invention first.
2. this catalyst has the characteristic of typical p-type semiconductor, absorbs band edge at about 550nm, and adopts different metallic elements and different synthesis conditions absorption band edge to be expected to further expansion.
3. the band gap of this semiconductor meets the requirement of decomposition water under visible light conditions, and position of energy band thermodynamically also meets the requirement of decomposition water.
4. this catalyst can be used as p-type semiconductor material and uses in the constructing of p-n hetero-junctions decomposition water system.
5. this catalyst can be used as the cathode material use of Optical Electro-Chemistry decomposition water system.
Accompanying drawing explanation
The Sr synthesized under Fig. 1 different temperatures 2cuInO 3xRD spectra (a) 1073K of S, (b) 1123K, (C) 1173K, (d) 1223K;
The Sr synthesized under Fig. 2 different temperatures 2cuInO 3ultravioletvisible absorption figure (a) 1073K of S, (b) 1123K, (C) 1173K, (d) 1223K;
Fig. 3 scanning electron microscopic picture (a)-(d) Sr 2cuInO 3s, (e) and (f) 0.5wt%Rh/Sr 2cuInO 3s;
Fig. 4 Sr 2cuInO 3s supports the hydrogen-producing speed (0.5wt%) of different co-catalyst;
Fig. 5 Sr 2cuInO 3s hydrogen-producing speed is with the change of Rh loading;
Fig. 6 Sr 2cuInO 3the crystal structure figure of S.
Detailed description of the invention
Below by embodiment, the present invention will be further described, but embodiments of the present invention are not limited thereto, and can not be interpreted as limiting the scope of the invention.Such as, only Sr is listed for brevity here 2cuInO 3the embodiment of S, but and do not mean that phosphide element just can not realize the present invention after being replaced by other metallic elements.
Embodiment 1
Solid phase synthesis Sr 2cuInO 3s.Take 0.03mol strontium sulfide, 0.03mol strontium oxide strontia, 0.015mol cuprous oxide, 0.015mol indium sesquioxide, above-mentioned raw materials fully to be ground in the quartzy hanging basket of rear loading and to be placed in quartz ampoule.Pass into argon gas to rise to temperature required (1073K or 1123K or 1173K or 1223K) from room temperature under argon gas atmosphere protection, heating rate 5 DEG C/min, and keep 10 hours at such a temperature, be finally cooled to room temperature, obtain photochemical catalyst.Synthesis obtains the XRD spectra of photochemical catalyst and ultraviolet-visible absorption spectroscopy figure respectively as depicted in figs. 1 and 2.
Embodiment 2
Original position Photodeposition supported co-catalyst.By H 2ptCl 66H 2o (0.36mg Pt/mL), Ni (NO 3) 26H 2o (0.30mg Ni/mL), (NH 4) 2pdCl 4(0.50mg Pd/mL), RhCl 33H 2o (0.20mg Rh/mL) and RuCl 3nH 2o (0.30mg Ru/mL) adds 200mL respectively and contains 0.2g Sr 2cuInO 3the vulcanized sodium of S and mixed solution (the 0.01M Na of sodium sulfite 2s and 0.01M Na 2sO 3) in, under illumination condition (wavelength is greater than 420nm for 300W xenon lamp, electric current 20A), realize Pt respectively, NiS 2, PdS, Rh, RuS 2in-situ impregnation, the loading of co-catalyst is 0.5wt%.Support electromicroscopic photograph before and after Rh as shown in Figure 3.
Embodiment 3
Sr 2cuInO 3s investigates as the product H-H reaction of photochemical catalyst.0.2g catalyst joins 200mL0.01M Na 2s and 0.01M Na 2sO 3solution in, the condition that supports of co-catalyst is with embodiment 2.Under agitation reaction system is found time, keep reaction temperature 13 DEG C.Excitation source is xenon lamp, electric current 20A, installs 420nm optical filter and reacts (Kenko, L-42 under visible light illumination; λ >420nm), the amounts of hydrogen produced by online gas chromatographic analysis.The hydrogen output of reaction as shown in Figure 4 and Figure 5.
Embodiment 4
Ball-milling method synthesis p-n heterojunction photocatalyst.By 0.5g Sr 2cuInO 3s and 0.5g Sm 2ti 2s 2o 5jointly put into ball grinder, fully grinding 8 hours (having 12 minutes intervals every a hour).After grinding, biased sample is put into quartz ampoule, keep 5 hours at 500 DEG C under argon gas atmosphere protection, finally slowly cool to room temperature.
Embodiment 5
Electrophoretic deposition prepares Sr 2cuInO 3s electrode.By 20mg elemental iodine and 75mg Sr 2cuInO 3s catalyst adds in 75mL acetone respectively, ultrasonic disperse 5min.The FTO glass cleaned up is connect negative pole, and platinized platinum connects positive pole, opens electrophoretic procedures, sedimentation time 3min.Close after first depositing one minute after voltage taking-up FTO glass is dried and deposit second minute again, close voltage taking-up FTO glass and continues to dry rear deposition the 3rd minute, so far whole deposition process is complete.Finally the electrode prepared is rinsed to be placed in clean culture dish with a large amount of absolute ethyl alcohol and intermediate water repeatedly and naturally dry.
Embodiment 6
Sr 2cuInO 3s tests as the Optical Electro-Chemistry decomposition water of photocathode, with Sr 2cuInO 3s is photocathode, and platinized platinum is to electrode, and saturated calomel electrode is reference electrode, at 0.1M Na 2sO 4measure in solution.Test starts to experiment terminal procedure, constantly to pass into bubbling argon front half an hour, discharges the air in whole reaction system.Excitation source is xenon lamp, reacts (Kenko, L-42 under adding 420nm optical filter radiation of visible light; λ >420nm), the hydrogen produced by online gas chromatographic analysis and amount of oxygen.
Embodiment 7
Sr 2cuInO 3the mensuration of S flat-band potential, utilizes the Mott-Schottky curve tested and obtain to obtain flat band potential value.With Sr 2cuInO 3s is working electrode, and platinized platinum is to electrode, and saturated calomel electrode is reference electrode, at 0.5M Na 2sO 4mott-Schottky curve is measured in solution.
Embodiment 8
Sr 2cuInO 3s has the space group P4/nmm in four directions, and its structure has typical Lamellar character along C direction of principal axis: Cu-S layer, In-O layer, Sr 2+cationic layer.Sr 2cuInO 3the crystal structure figure of S as shown in Figure 6.
In sum, the present invention first the p-type semiconductor material of stratiform is applied to Photocatalyzed Hydrogen Production reaction, a small amount of co-catalyst support the hydrogen-producing speed that can significantly improve catalyst.P-type semiconductor material provided by the invention both can construct the cathode material that p-n hetero-junctions decomposition water system also can be used as Optical Electro-Chemistry decomposition water system with known n-type semiconductor compound.

Claims (10)

1. one kind based on layer structure semi-conducting material photochemical catalyst, it is characterized in that: this semi-conducting material is by a kind of IIA race metallic element, a kind of IB race metallic element, a kind of group vib or VIIB race or VIII or IIB race or IIIA race metallic element, add the layer structure semi-conducting material that one or both VIA race nonmetalloids form jointly in addition;
Wherein the mol ratio of IIA race metallic element and IB race metallic element is 2: 1 or 1: 1, the mol ratio of IIA race metallic element and group vib or VIIB race or VIII or IIB race or IIIA race metallic element is the mol ratio of 2: 1, IIA race metallic element and VIA race nonmetalloid is 1: 2.
2. according to photochemical catalyst according to claim 1, it is characterized in that: this photochemical catalyst is layered distribution along C direction of principal axis on crystal structure, specifically comprise three-decker and be respectively (1) IIA race metal cation layer, (2) layer of the nonmetal composition of I B-group metal and VIA race, the layer of (3) group vibs or VIIB race or VIII or the arbitrary metal of IIB race or IIIA race and the nonmetal composition of VIA race.
3. according to photochemical catalyst according to claim 1, it is characterized in that: wherein said IIA race metal is selected from Sr, I B-group metal is selected from Cu, group vib or VIIB race or VIII or IIB race or IIIA race metallic element are selected from the one in Cr, Mn, Fe, Co, Zn, Ga, In, VIA race nonmetalloid be selected from O and S one or both.
4. according to photochemical catalyst described in claim 1, it is characterized in that: described photochemical catalyst is the material with layer structure formed by the additional another kind of metal of strontium copper oxygen sulphur, another kind of metal specifically refer to Cr, Mn, Fe, Co, Zn, Ga, In one of them.
5. according to the arbitrary described photochemical catalyst of claim 1-4, it is characterized in that: described photochemical catalyst is with this semi-conducting material for carrier, do not support or one or two or more kinds the original position light deposition in a small amount of transition metal, noble metal is supported in catalyst surface as co-catalyst; The loading of transition metal and noble metal is the 0.01-5.0wt% of photochemical catalyst.
6. the preparation method of the arbitrary described photochemical catalyst of claim 1-5; it is characterized in that: raw material (reaction raw materials is the metal simple-substance of required metallic element, in metal or bimetallic oxide, metal or bimetallic sulfide one or two or more kinds) is placed in quartz ampoule; under argon gas atmosphere protective condition; the arbitrary temperature within the scope of 500-1200 DEG C is heated in tube furnace; reaction 5-20h, obtains photochemical catalyst.
7. according to the preparation method of photochemical catalyst described in claim 6, it is characterized in that: adopt original position Photodeposition to be supported in photocatalyst surface one or two or more kinds in transition metal and noble metal Ni, Pd, Pt, Ru, Rh; The process that specifically supports to add containing photochemical catalyst and electron donor reagent (Organic Alcohol of C1-C4 or the organic acid of C1-C4 or alkali metal sulphide, alkali metal sulfite respectively containing the solvable presoma of one or two or more kinds (chloride of metal or nitrate or carbonyls) in above-mentioned transition metal and noble metal Ni, Pd, Pt, Ru, Rh, wherein Organic Alcohol and organic acid concentration range are respectively 1vol% ~ 99vol%, and the concentration range of alkali metal sulphide and alkali metal sulfite is 1mM ~ 10M) the aqueous solution in; The in-situ impregnation of one or two or more kinds in Pt, Ni, Pd, Rh, Ru is realized respectively under illumination condition; The loading of transition metal and noble metal is the 0.01-5.0wt% of added photochemical catalyst in reaction.
8. the product hydrogen application of the arbitrary described photochemical catalyst of claim 1-5, it is characterized in that: with described semi-conducting material for photochemical catalyst does not support, or the product H-H reaction carried out in catalyst surface as co-catalyst using described semi-conducting material for one or two or more kinds the original position light deposition in transition metal, noble metal supports by carrying body under visible ray, or this semi-conducting material can construct p-n hetero-junctions decomposition water system with known n-type semiconductors coupling, or this semi-conducting material also can be used as photocathode material and is applied to Optical Electro-Chemistry decomposition water system.
9. apply according to the product hydrogen of photochemical catalyst described in claim 8, it is characterized in that: will not support or the catalyst of only supported transition metal and noble metal joins containing electron donor reagent (Organic Alcohol of C1-C4 or the organic acid of C1-C4 or alkali metal sulphide, alkali metal sulfite, wherein Organic Alcohol and organic acid concentration range are 1vol% ~ 99vol%, and the concentration range of alkali metal sulphide and alkali metal sulfite is 1mM ~ 10M) the aqueous solution in; Under agitation reaction system is found time, keep reaction temperature 5-50 DEG C, adopt light source (in xenon lamp, mercury lamp, xenon-mercury lamp, iodine-tungsten lamp and sunshine one or two or more kinds) to irradiate to react, the amounts of hydrogen produced by online gas chromatographic analysis.
10. apply according to the product hydrogen of photochemical catalyst described in claim 8, it is characterized in that: the constructing of p-n hetero-junctions decomposition water system is referred to and assembled by suitable synthetic method (hydro-thermal method, solid phase method, magnetron sputtering method or atomic layer deposition method etc.) as p-type semiconductor material and n-type semiconductor known at present by the catalyst in the present invention, builds the photocatalysis system with obvious carrier separation effect;
Optical Electro-Chemistry decomposition water system refers to and is combined with anode material known at present as negative electrode by the semi-conducting material in the present invention, employing suitable sources is irradiated, and does not add or only add the while that a small amount of (0v ~ 1.0v) bias voltage realizing negative electrode producing hydrogen anode produces oxygen;
The preparation of photocathode material is mainly through electrophoretic deposition, magnetron sputtering method, atomic layer deposition method or scrape embrane method etc. and realize;
Light source comprises one or two or more kinds in xenon lamp, mercury lamp, xenon-mercury lamp, iodine-tungsten lamp and sunshine, light source send the wavelength optimum range 190-700nm of light.
CN201310330319.6A 2013-07-31 2013-07-31 A semiconductor material photocatalyst based on a layered structure and hydrogen production applications thereof Pending CN104338546A (en)

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CN109072456A (en) * 2016-01-04 2018-12-21 道达尔炼油化学公司 For photo-electrolyzing device photocathode, manufacture the method and photo-electrolyzing device of the photocathode
CN112588308A (en) * 2020-11-09 2021-04-02 中国科学院深圳先进技术研究院 SiP material and preparation method and application thereof
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