CN108654669A - A kind of doped zinc sulphide catalyst and preparation method for solar hydrogen making - Google Patents
A kind of doped zinc sulphide catalyst and preparation method for solar hydrogen making Download PDFInfo
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- CN108654669A CN108654669A CN201810396770.0A CN201810396770A CN108654669A CN 108654669 A CN108654669 A CN 108654669A CN 201810396770 A CN201810396770 A CN 201810396770A CN 108654669 A CN108654669 A CN 108654669A
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- 239000005083 Zinc sulfide Substances 0.000 title claims abstract description 76
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 title claims abstract description 73
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000001257 hydrogen Substances 0.000 title claims abstract description 59
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 59
- 239000003054 catalyst Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 47
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 41
- 239000000463 material Substances 0.000 claims abstract description 30
- 230000001699 photocatalysis Effects 0.000 claims abstract description 28
- 238000007146 photocatalysis Methods 0.000 claims abstract description 27
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000005864 Sulphur Substances 0.000 claims abstract description 15
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004246 zinc acetate Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 34
- 239000007789 gas Substances 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 17
- 229960001484 edetic acid Drugs 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 15
- 238000000576 coating method Methods 0.000 claims description 15
- 238000013019 agitation Methods 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 13
- 239000011521 glass Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 238000012545 processing Methods 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 239000007767 bonding agent Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 5
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 239000000440 bentonite Substances 0.000 claims description 4
- 229910000278 bentonite Inorganic materials 0.000 claims description 4
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 4
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 4
- 229940071125 manganese acetate Drugs 0.000 claims description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 26
- 230000003197 catalytic effect Effects 0.000 abstract description 19
- 238000010521 absorption reaction Methods 0.000 abstract description 14
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 11
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 230000007704 transition Effects 0.000 abstract description 4
- 238000000862 absorption spectrum Methods 0.000 abstract description 3
- 238000005036 potential barrier Methods 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 description 16
- 125000004429 atom Chemical group 0.000 description 13
- 238000012360 testing method Methods 0.000 description 10
- 229910052724 xenon Inorganic materials 0.000 description 10
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 10
- 238000000354 decomposition reaction Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- 238000001507 sample dispersion Methods 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- 229920000615 alginic acid Polymers 0.000 description 4
- 239000000783 alginic acid Substances 0.000 description 4
- 229960001126 alginic acid Drugs 0.000 description 4
- 235000010443 alginic acid Nutrition 0.000 description 4
- 150000004781 alginic acids Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 229910052793 cadmium Inorganic materials 0.000 description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000002803 fossil fuel Substances 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- 238000006303 photolysis reaction Methods 0.000 description 3
- 230000015843 photosynthesis, light reaction Effects 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910052984 zinc sulfide Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005247 gettering Methods 0.000 description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- XOCUXOWLYLLJLV-UHFFFAOYSA-N [O].[S] Chemical compound [O].[S] XOCUXOWLYLLJLV-UHFFFAOYSA-N 0.000 description 1
- YRONBDGIQLUFNV-UHFFFAOYSA-L [Zn].Cl[Fe]Cl Chemical compound [Zn].Cl[Fe]Cl YRONBDGIQLUFNV-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/349—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of flames, plasmas or lasers
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1088—Non-supported catalysts
-
- 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
Abstract
The present invention proposes a kind of doped zinc sulphide catalyst and preparation method for solar hydrogen making, using zinc acetate as zinc ion source, doped source is as doped raw material, after chelating, using thiocarbamide as sulphur source, pass through plasma bombardment material surface, the present invention is inserted into impurity band by metal ion mixing in forbidden band, reduces electron transition potential barrier, to make the absorption spectrum Einstein shift of zinc sulphide, catalytic efficiency is improved, N S keys are generated by the introducing of nitrogen-atoms, key is larger by force, it can inhibit the desulphurization reaction in catalytic process, improve the stability of catalyst.The present invention offer above method overcomes current zinc sulphide catalyst modification scheme and can not while preferably improve zinc sulphide catalytic stability and extend its visible wavelength absorption region defect, the present invention improves photocatalysis hydrogen production efficiency and stability by extending zinc sulphide for the selectivity of visible wavelength.
Description
Technical field
The present invention relates to photocatalysis hydrogen production technical fields, and in particular to a kind of doped zinc sulphide for solar hydrogen making is urged
Agent and preparation method.
Background technology
With the progress of Science and Technology, the raising of industrial expansion and human living standard, global energy nearly ten years
It is 1.9% to consume average year increasing value, wherein 80% energy comes from fossil fuel, fossil fuel formation need to undergo more than one hundred million years,
Belong to non-renewable energy resources.A large amount of burnings of fossil fuel will produce more hydrocarbon, oxygen sulfur compound and nitrogen oxidation
The pernicious gases such as object are closed, serious air pollution and greenhouse effects are caused.Develop and utilize cleaning, lasting, regenerative resource is
Realize the top priority of human social.Hydrogen Energy is simple etc. with combustion heat value height, clean environment firendly, and preparation method
Advantage is recyclable one of high-grade energy clean energy resource, is increasingly valued by people.
Solar energy is cleaning and inexhaustible natural energy resources the most, photolysis water hydrogen be solar energy chemical conversion with
The optimal path of storage, just by the extensive concern of scientific research personnel.Photoelectrochemistrpool pool is absorbed by photocatalyst powder or electrode
About 3% ultraviolet light in sunlight generates electronics and flows to cathode by external circuit, and water is electronically generated hydrogen in cathode receiving.Light is urged
It is to influence one of the principal element of efficiency of photocatalysis hydrogen production to change semi-conducting material catalytic activity.Conductor photocatalysis hydrogen production reaction
Basic process be photon that semiconductor absorber energy is equal to or more than energy gap, electronics will occur from valence band to conduction band
Transition, this light absorption are known as Intrinsic Gettering.Intrinsic Gettering generates hole in valence band, and electronics, this photoproduction electricity are generated in conduction band
Son-hole by the redox reaction that it is tended to act to very strong reduction and oxidation activity, being known as light-catalyzed reaction.
Current photochemical catalyst mainly has two kinds of wide-band gap material and small gap material.Wide-band gap material is using zinc sulphide as generation
Table can quickly generate photo-generate electron-hole pair under light illumination since ZnS has suitable band structure, and its to environment without
Evil, it is cheap, it is considered to be a kind of potential catalysis material is widely used in photocatalytic hydrogen production by water decomposition, light drop
Solve the fields such as organic pollution.But that there are forbidden bands is wider for the application in terms of zinc sulphide photocatalysis, is only capable of absorbing ultraviolet band light,
Greatly constrain the deficiency of its photolysis water hydrogen ability.And it in catalytic process, sulphion is easily detached from hydrogen ion knot
It closes and generates hydrogen sulfide severe toxicity gas, reduce catalyst activity and generate foreign gas.Therefore, therefore being modified to zinc sulphide makes
It is necessary with visible absorption and raising zinc sulphide stability.
Chinese invention patent application number 201310428774.X discloses a kind of with visible light catalysis activity, high stability
N doping zinc sulphide preparation method and applications, weigh zinc source and sulphur source be dissolved in distilled water respectively, obtain sulphur source solution
With zinc source solution；Sulphur source solution is added in the solution of zinc source, continues to stir to get zinc sulphide solid；Zinc sulphide solid is spent
Ion water washing, is then centrifuged for, and collects solid formation, then be washed with deionized, and then carries out alcohol washing, collects solid formation, obtains
Then zinc sulphide after to drying grinds to obtain powder zinc sulphide through mortar；The porcelain boat for filling zinc sulphide powder is put into tubular type
It in stove, is handled under ammonia atmosphere, obtains the N doping zinc sulphide with visible light catalysis activity high stability.However, the party
Light absorption can be greatly improved in 300-350nm ultraviolet regions by N doping in case, but it is visible in visible light 400-800nm
In optical range, absorption intensity only improves a little, it is seen that light area utilizes limited efficacy.Chinese invention patent application number
201110150679.9 disclose a kind of synthetic method of the nano-zinc sulfide cadmium with visible light catalysis activity, by zinc acetate,
Cadmium acetate, thioacetamide and neopelex, which are dissolved in alcoholic solvent, obtains mixed liquor, then mixed liquor is placed in microwave
Reaction synthesis obtains nano-zinc sulfide cadmium particle, is adulterated by cadmium, can improve suction of the zinc sulphide in the visible above smooth areas 400nm
Intensity is received, however the desulphurization reaction in catalytic process but can not be controlled effectively.
It is above-mentioned that can not zinc sulphide catalytic stability preferably be improved simultaneously to vulcanization zinc modification scheme and extend its visible light wave
Long absorption region, it is therefore proposed that a kind of catalytic stability that can improve zinc sulphide inhibits the generation of hydrogen sulfide impurities gas, and
And the scheme for improving catalyst in visible region optical absorption intensity is can be achieved at the same time, to improving zinc sulphide photocatalysis liberation of hydrogen efficiency
With important theory significance and practical value.
Invention content
Zinc sulphide catalytic stability and extension can not be preferably improved simultaneously for current zinc sulphide catalyst modification scheme
Its visible wavelength absorption region defect, the present invention propose a kind of for the doped zinc sulphide catalyst of solar hydrogen making and preparation
Method, to realize that zinc sulphide improves photocatalysis hydrogen production efficiency for the selectivity of visible wavelength while improving zinc sulphide
Catalytic stability.
To solve the above problems, the present invention uses following technical scheme：
A kind of preparation method of doped zinc sulphide catalyst for solar hydrogen making is mixed using zinc acetate as zinc ion source
Miscellaneous source is as doped raw material, and using thiocarbamide as sulphur source, by plasma bombardment material surface, specific preparation process is as follows：
（1）Zinc acetate and doped source are mixed, appropriate amount of deionized water is added, by 0.5 ~ 3h of mechanical agitation, obtain zinc ion with
The mixed solution of doped metal ion, a concentration of 1.8 ~ 3.0 mol/L of zinc ion, the doped metal ion wherein in solution
A concentration of 0.66 ~ 0.20mol/L；Doped source includes the one or more of nickel acetate, copper acetate, ferric acetate, manganese acetate；
（2）Ethylenediamine tetra-acetic acid is added in the mixed solution of the zinc ion and doped metal ion, it is small by ultrasound 1 ~ 5
When, the zinc ion and doped metal ion solution chelated, wherein the ethylenediamine tetra-acetic acid and the zinc ion and doping
The mass ratio of the mixed solution of metal ion is 1 ~ 5:200；
（3）It is 1 by mass ratio:1~5:200 flocculant, the zinc ion of bonding agent and chelating and doped metal ion solution are mixed
It closes, and stirs 1~5h, after standing filtering, obtain chelating presoma, the chelating presoma is coated on substrate material surface,
The coating thickness is 10 ~ 50 μm, is placed in vacuum drying chamber, 1 ~ 2 hour dry, obtains photocatalysis predecessor；
（4）The photocatalysis predecessor is placed in plasma environment, thiocarbamide steam is passed through and sulphur source is provided, plasma is carried out and bangs
Processing is hit, metal atom doped sheet ZnS-film is obtained, wherein the plasma is microwave electron cyclotron resonance etc.
Gas ions, plasma glow gas are the nitrogen mixture source of the argon gas and 5% volume of 95% volume.
Preferably, the flocculant include aluminum sulfate, aluminium chloride, ferric sulfate, iron chloride, polyacrylamide, citric acid and
The combination of one or more of bentonite.
The binder selects common aqueous thickening binder, such as polyvinyl alcohol, chitosan, alginic acid.
Preferably, the substrate material is the electro-conductive glass of FTO or ITO coating, and the sheet resistance of electro-conductive glass is 3 ~ 10 Ω.
Preferably, the thiocarbamide is heated to distilling at 150 ~ 160 DEG C under vacuum, obtains thiocarbamide steam.
Preferably, the temperature of the vacuum drying chamber is 40 ~ 80 DEG C, and chamber pressure is 10 ~ 50kPa.
Preferably, the plasma power is 0.5-2 kW.
Preferably, the synusia thickness of the sheet zinc sulphide is 8 ~ 20nm, and piece diameter is 0.6 ~ 20 μm.
Further provide for a kind of doped zinc sulphide catalyst for solar hydrogen making being prepared by the above method, light
Spectrum response range is 340 ~ 800nm, and liberation of hydrogen efficiency is up to 410-480 mmolh-1·g-1。
That there are forbidden bands is wider for application in terms of zinc sulphide photocatalysis, is only capable of absorbing ultraviolet band light, greatly constrains it
The deficiency of photolysis water hydrogen ability.And it in catalytic process, sulphion, which is easily detached to combine in hydrogen ion, generates hydrogen sulfide play
Poisonous gas reduces catalyst activity and generates foreign gas.For current zinc sulphide catalyst modification scheme can not simultaneously compared with
Zinc sulphide catalytic stability is improved well and extends its visible wavelength absorption region defect.In consideration of it, the present invention proposes a kind of use
It is added using zinc acetate and doped source solution as raw material in the doped zinc sulphide catalyst and preparation method of solar hydrogen making
Ethylenediamine tetra-acetic acid（EDTA）Chelation treatment is carried out, flocculant and binder is then added, it is after standing filtering, chelate is uniform
Coated on substrate material surface, corona treatment is carried out.Plasma air source uses 95% volume argon gas and 5% volume nitrogen
Air source is mixed, load thiocarbamide steam is reacted, and metal atom doped sheet ZnS-film is obtained.The present invention passes through metal
Ion doping is inserted into impurity band in forbidden band, reduces electron transition potential barrier and is carried to make the absorption spectrum Einstein shift of zinc sulphide
High catalytic efficiency.N-S keys are generated by the introducing of nitrogen-atoms, key is larger by force, can inhibit the desulphurization reaction in catalytic process,
Improve the stability of catalyst.
Doped zinc sulphide catalyst prepared by the present invention is with undoped zinc sulphide, N doping zinc sulphide in same technique
Under the conditions of using gas chromatography test hydrogen manufacturing performance, as shown in table 1.
Table 1：
The present invention provides a kind of doped zinc sulphide catalyst and preparation method for solar hydrogen making, compared with prior art,
Its feature protruded and excellent effect are：
1, the present invention is inserted into impurity band in forbidden band, reduces electron transition potential barrier using by metal ion mixing zinc sulphide,
To make the absorption spectrum Einstein shift of zinc sulphide, catalytic efficiency is improved, while the present invention generates N-S keys by the introducing of nitrogen-atoms,
Its key is larger by force, can inhibit the desulphurization reaction in catalytic process, improves the stability of catalyst, overcomes existing zinc sulphide and changes
Property scheme cannot achieve to improve and zinc sulphide catalytic stability while preferably extending its visible wavelength absorption region defect.
2, the present invention adulterates nitrogen-atoms by corona treatment, compared with chemical doping, plasma doping processing
With very high doping rate, and the structural stability of doped zinc sulphide can be improved.
3, raw material type needed for preparation method of the present invention is few, inexpensively easily obtains, easy to operate controllable.
Specific implementation mode
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
（1）By zinc acetate and doped source nickel acetate, appropriate amount of deionized water is added, by mechanical agitation 0.5h, obtain zinc ion with
The mixed solution of doped metal ion, a concentration of 1.8 mol/L of zinc ion wherein in solution, the doped metal ion it is dense
Degree is 0.20mol/L；
（2）Ethylenediamine tetra-acetic acid is added in the mixed solution of the zinc ion and doped metal ion, by 2 hours ultrasonic,
The zinc ion and doped metal ion solution chelated, wherein the ethylenediamine tetra-acetic acid and the zinc ion and doping metals
The mass ratio of the mixed solution of ion is 1:200；
（3）It is by mass ratio：1:4:200 flocculant aluminum sulfate, the zinc ion of bonding agent polyvinyl alcohol and chelating and doping
Metal ion solution mixes, and stirs 5h, after standing filtering, obtains chelating presoma, the chelating presoma is coated on side
Resistance is 4 Ω, and the Conducting Glass material surface of FTO coating, the coating thickness is 10 μm, is placed in vacuum drying chamber, very
The temperature of empty drying chamber is 45 DEG C, chamber pressure 10kPa, 1 hour dry, obtains photocatalysis predecessor；
（4）The photocatalysis predecessor is placed in microwave electron cyclotron resonance plasma environment, plasma power 0.5
KW, plasma glow gas are the nitrogen mixture source of the argon gas and 5% volume of 95% volume, heat thiocarbamide under vacuum
It distils when to 155 DEG C, obtains thiocarbamide steam and reative cell offer sulphur source is provided, carry out plasma bombardment processing, obtain metallic atom
The sheet zinc sulphide of the sheet ZnS-film of doping, the metallic atom and nitrogen atom doping, obtains described after stripping
Stratiform zinc sulphide, synusia thickness are 20nm, and piece diameter is 20 μm.
The catalysis material prepared in the embodiment of the present invention is tested：With UV2550 ultraviolet-uisible spectrophotometers
Collect the doped zinc sulphide material for showing to test present embodiment preparation has strong absorption in 490nm or so, is demonstrated by
It is good visible light-responded.The Photocatalyzed Hydrogen Production of sample is tested under normal temperature and pressure in the three-necked flask that volume is 100 m L
It carries out, the opening of three-necked flask is sealed with silica gel plug.It is the xenon lamp of 350W as light source to use power, light source with react
The distance between device is 20 cm, and the visible light of transmission is then used as light source to be used for exciting light-catalyzed reaction.Prepared by 50 mg
Sample dispersion in distilled water, be transferred in three-necked flask.Later, three-necked flask is irradiated with xenon lamp, passes through optical filtering
Piece（λ>400nm）Time is 20 min, in Photocatalyzed Hydrogen Production experiment, carries out magnetic agitation to solution, catalyst granules is made to begin
It is evenly dispersed in system eventually, the amount of photocatalysis Decomposition aquatic products anger body, production hydrogen speed is tested using GC-14C gas chromatographs
Rate has reached 410 mmolh-1·g-1, show higher hydrogen-producing speed.
Embodiment 2
（1）By zinc acetate and doped source manganese acetate, appropriate amount of deionized water is added, by mechanical agitation 1.5h, obtain zinc ion with
The mixed solution of doped metal ion, 2.0 mol/L of concentration of zinc ion, the concentration of the doped metal ion wherein in solution
For 0.13mol/L；
（2）Ethylenediamine tetra-acetic acid is added in the mixed solution of the zinc ion and doped metal ion, by 4 hours ultrasonic,
The zinc ion and doped metal ion solution chelated, wherein the ethylenediamine tetra-acetic acid and the zinc ion and doping metals
The mass ratio of the mixed solution of ion is 3:200；
（3）It is 1 by mass ratio：3：200 flocculant iron chloride, the zinc ion and doping metals of bonding agent chitosan and chelating
Solion mixes, and stirs 4h, after standing filtering, obtains chelating presoma, is coated on sheet resistance by the chelating presoma
The Conducting Glass material surface of 10 Ω, ITO coating, the coating thickness are 35 μm, are placed in vacuum drying chamber, vacuum
The temperature of drying chamber is 70 DEG C, chamber pressure 50kPa, 2 hours dry, obtains photocatalysis predecessor；
（4）The photocatalysis predecessor is placed in microwave electron cyclotron resonance plasma environment, plasma power 1.5
KW, plasma glow gas are the nitrogen mixture source of the argon gas and 5% volume of 95% volume, heat thiocarbamide under vacuum
It distils when to 155 DEG C, obtains thiocarbamide steam and reative cell offer sulphur source is provided, carry out plasma bombardment processing, obtain metallic atom
The sheet zinc sulphide of the sheet ZnS-film of doping, the metallic atom and nitrogen atom doping after stripping, obtains described
Stratiform zinc sulphide, synusia thickness are 8nm, and piece diameter is 15 μm.
The catalysis material prepared in the embodiment of the present invention is tested：With UV2550 ultraviolet-uisible spectrophotometers
Collect the doped zinc sulphide material for showing to test present embodiment preparation has strong absorption in 510nm or so, is demonstrated by
It is good visible light-responded.The Photocatalyzed Hydrogen Production of sample is tested under normal temperature and pressure in the three-necked flask that volume is 100 m L
It carries out, the opening of three-necked flask is sealed with silica gel plug.It is the xenon lamp of 350W as light source to use power, light source with react
The distance between device is 20 cm, and the visible light of transmission is then used as light source to be used for exciting light-catalyzed reaction.Prepared by 50 mg
Sample dispersion in distilled water, be transferred in three-necked flask.Later, three-necked flask is irradiated with xenon lamp, passes through optical filtering
Piece（λ>400nm）Time is 20 min, in Photocatalyzed Hydrogen Production experiment, carries out magnetic agitation to solution, catalyst granules is made to begin
It is evenly dispersed in system eventually, the amount of photocatalysis Decomposition aquatic products anger body, production hydrogen speed is tested using GC-14C gas chromatographs
Rate has reached 430 mmolh-1·g-1, show higher hydrogen-producing speed.
Embodiment 3
（1）By zinc acetate and doped source ferric acetate, appropriate amount of deionized water is added and obtains zinc ion by mechanical agitation 2h and mixes
The mixed solution of miscellaneous metal ion, a concentration of 2.8mol/L of zinc ion, the concentration of the doped metal ion wherein in solution
For 0.20mol/L；
（2）Ethylenediamine tetra-acetic acid is added in the mixed solution of the zinc ion and doped metal ion, by 4 hours ultrasonic,
The zinc ion and doped metal ion solution chelated, wherein the ethylenediamine tetra-acetic acid and the zinc ion and doping metals
The mass ratio of the mixed solution of ion is 5:200；
（3）It is 1 by mass ratio: 5:Mixing, bonding agent alginic acid and the chelating of 200 flocculant ferric sulfate and iron chloride
Zinc ion and the mixing of doped metal ion solution, and 1h is stirred, after standing filtering, chelating presoma is obtained, before the chelating
It is 8 Ω to drive body and be coated on sheet resistance, and the Conducting Glass material surface of FTO or ITO coating, the coating thickness is 50 μm, is set
In vacuum drying chamber, the temperature for being dried in vacuo chamber is 80 DEG C, chamber pressure 15kPa, 2 hours dry, obtains photocatalysis
Predecessor；
（4）The photocatalysis predecessor is placed in microwave electron cyclotron resonance plasma environment, plasma power 1.2
KW, plasma glow gas are the nitrogen mixture source of the argon gas and 5% volume of 95% volume, heat thiocarbamide under vacuum
It distils when to 160 DEG C, obtains thiocarbamide steam and reative cell offer sulphur source is provided, carry out plasma bombardment processing, obtain metallic atom
The sheet zinc sulphide of the sheet ZnS-film of doping, the metallic atom and nitrogen atom doping after stripping, obtains described
Stratiform zinc sulphide, synusia thickness are 10nm, and piece diameter is 18 μm.
The catalysis material prepared in the embodiment of the present invention is tested：With UV2550 ultraviolet-uisible spectrophotometers
Collect the doped zinc sulphide material for showing to test present embodiment preparation has strong absorption in 500nm or so, is demonstrated by
It is good visible light-responded.The Photocatalyzed Hydrogen Production of sample is tested under normal temperature and pressure in the three-necked flask that volume is 100 m L
It carries out, the opening of three-necked flask is sealed with silica gel plug.It is the xenon lamp of 350W as light source to use power, light source with react
The distance between device is 20 cm, and the visible light of transmission is then used as light source to be used for exciting light-catalyzed reaction.Prepared by 50 mg
Sample dispersion in distilled water, be transferred in three-necked flask.Later, three-necked flask is irradiated with xenon lamp, passes through optical filtering
Piece（λ>400nm）Time is 20 min, in Photocatalyzed Hydrogen Production experiment, carries out magnetic agitation to solution, catalyst granules is made to begin
It is evenly dispersed in system eventually, the amount of photocatalysis Decomposition aquatic products anger body, production hydrogen speed is tested using GC-14C gas chromatographs
Rate has reached 470 mmolh-1·g-1, show higher hydrogen-producing speed.
Embodiment 4
（1）By zinc acetate and doped source copper acetate, appropriate amount of deionized water is added and obtains zinc ion by mechanical agitation 3h and mixes
The mixed solution of miscellaneous metal ion, a concentration of 3.0 mol/L of zinc ion, the concentration of the doped metal ion wherein in solution
For 0.06mol/L；
（2）Ethylenediamine tetra-acetic acid is added in the mixed solution of the zinc ion and doped metal ion, by 1 hour ultrasonic,
The zinc ion and doped metal ion solution chelated, wherein the ethylenediamine tetra-acetic acid and the zinc ion and doping metals
The mass ratio of the mixed solution of ion is 5:200；
（3）It is 1 by mass ratio: 5:200 flocculant iron chloride, citric acid and bentonite mixtures, bonding agent polyvinyl alcohol
It is mixed with the zinc ion of chelating and doped metal ion solution, and stirs 1h, after standing filtering, chelating presoma is obtained, by institute
It is 10 Ω to state chelating presoma and be coated on sheet resistance, and the Conducting Glass material surface of ITO coating, the coating thickness is 50
μm, it is placed in vacuum drying chamber, the temperature for being dried in vacuo chamber is 80 DEG C, chamber pressure 50kPa, 2 hours dry, obtains light
Catalytic precursor；
（4）The photocatalysis predecessor is placed in microwave electron cyclotron resonance plasma environment, plasma power 0.5
KW, plasma glow gas are the nitrogen mixture source of the argon gas and 5% volume of 95% volume, heat thiocarbamide under vacuum
It distils when to 154 DEG C, obtains thiocarbamide steam and reative cell offer sulphur source is provided, carry out plasma bombardment processing, obtain metallic atom
The sheet zinc sulphide of the sheet ZnS-film of doping, the metallic atom and nitrogen atom doping, stripping, obtains the lamella
Shape zinc sulphide, synusia thickness are 8nm, and piece diameter is 0.6 μm.
The catalysis material prepared in the embodiment of the present invention is tested：With UV2550 ultraviolet-uisible spectrophotometers
Collect the doped zinc sulphide material for showing to test present embodiment preparation has strong absorption in 490nm or so, is demonstrated by
It is good visible light-responded.The Photocatalyzed Hydrogen Production of sample is tested under normal temperature and pressure in the three-necked flask that volume is 100 m L
It carries out, the opening of three-necked flask is sealed with silica gel plug.It is the xenon lamp of 350W as light source to use power, light source with react
The distance between device is 20 cm, and the visible light of transmission is then used as light source to be used for exciting light-catalyzed reaction.Prepared by 50 mg
Sample dispersion in distilled water, be transferred in three-necked flask.Later, three-necked flask is irradiated with xenon lamp, passes through optical filtering
Piece（λ>400nm）Time is 20 min, in Photocatalyzed Hydrogen Production experiment, carries out magnetic agitation to solution, catalyst granules is made to begin
It is evenly dispersed in system eventually, the amount of photocatalysis Decomposition aquatic products anger body, production hydrogen speed is tested using GC-14C gas chromatographs
Rate has reached 460 mmolh-1·g-1, show higher hydrogen-producing speed.
Embodiment 5
（1）By the mixing of zinc acetate and doped source manganese acetate, appropriate amount of deionized water is added, zinc is obtained by mechanical agitation 2.5h
The mixed solution of ion and doped metal ion, a concentration of 2.8mol/L of zinc ion wherein in solution, the doping metals from
A concentration of 0.08mol/L of son；
（2）Ethylenediamine tetra-acetic acid is added in the mixed solution of the zinc ion and doped metal ion, it is small by ultrasound 4.5
When, the zinc ion and doped metal ion solution chelated, wherein the ethylenediamine tetra-acetic acid and the zinc ion and doping
The mass ratio of the mixed solution of metal ion is 2:200；
（3）It is 1 by mass ratio:1.5:200 flocculant ferric sulfate and bentonite, the zinc ion of bonding agent alginic acid and chelating
It is mixed with doped metal ion solution, and stirs 2h, after standing filtering, obtained chelating presoma, the chelating presoma is applied
It is 6 Ω to be overlying on sheet resistance, and the Conducting Glass material surface of FTO coating, the coating thickness is 13 μm, is placed in vacuum drying chamber
In, the temperature for being dried in vacuo chamber is 64 DEG C, chamber pressure 35kPa, 1.8 hours dry, obtains photocatalysis predecessor；
（4）The photocatalysis predecessor is placed in microwave electron cyclotron resonance plasma environment, plasma power 2.0
KW, plasma glow gas are the nitrogen mixture source of the argon gas and 5% volume of 95% volume, heat thiocarbamide under vacuum
It distils when to 152 DEG C, obtains thiocarbamide steam and reative cell offer sulphur source is provided, carry out plasma bombardment processing, obtain metallic atom
The sheet zinc sulphide of the sheet ZnS-film of doping, the metallic atom and nitrogen atom doping, stripping obtain sheet sulphur
Change zinc, synusia thickness is 11nm, and piece diameter is 12 μm.
The catalysis material prepared in the embodiment of the present invention is tested：With UV2550 ultraviolet-uisible spectrophotometers
Collect the doped zinc sulphide material for showing to test present embodiment preparation has strong absorption in 460nm or so, is demonstrated by
It is good visible light-responded.The Photocatalyzed Hydrogen Production of sample is tested under normal temperature and pressure in the three-necked flask that volume is 100 m L
It carries out, the opening of three-necked flask is sealed with silica gel plug.It is the xenon lamp of 350W as light source to use power, light source with react
The distance between device is 20 cm, and the visible light of transmission is then used as light source to be used for exciting light-catalyzed reaction.Prepared by 50 mg
Sample dispersion in distilled water, be transferred in three-necked flask.Later, three-necked flask is irradiated with xenon lamp, passes through optical filtering
Piece（λ>400nm）Time is 20 min, in Photocatalyzed Hydrogen Production experiment, carries out magnetic agitation to solution, catalyst granules is made to begin
It is evenly dispersed in system eventually, the amount of photocatalysis Decomposition aquatic products anger body, production hydrogen speed is tested using GC-14C gas chromatographs
Rate has reached 480 mmolh-1·g-1, show higher hydrogen-producing speed.
Comparative example 1
The undoped zinc sulphide of same amount to be tested as photolytic hydrogen production catalyst, test condition is identical as embodiment 1-5,
Ultraviolet-uisible spectrophotometer collects the doped zinc sulphide material for showing to test present embodiment preparation in 310nm or so
Occur it is strong absorb, can only the shorter ultraviolet light of absorbing wavelength, further illustrate that it is relatively low to the utilization rate of sunlight.The light of sample
It is 90-115mmolh that catalysis production hydrogen experiment, which measures undoped zinc sulphide hydrogen-producing speed,-1·g-1, logical much smaller than in the present invention
Cross the hydrogen-producing speed of metal ion and nitrogen atom doping zinc sulphide.
Comparative example 2
Zinc acetate is added appropriate amount of deionized water, a concentration of 1.8 mol/L of zinc ion passes through mechanical agitation 0.5h in solution；It will
Ethylenediamine tetra-acetic acid is added in the zinc ion solution, by 2 hours ultrasonic, the zinc ion solution chelated；By mass ratio
Example is 1:4:200 flocculant aluminum sulfate, bonding agent alginic acid mix with the zinc ion solution of chelating, and stir 5h, stand
After filter, chelating presoma is obtained, it is 4 Ω, the Conducting Glass material of FTO coating that the chelating presoma, which is coated on sheet resistance,
Surface, the painting predecessor；The photocatalysis predecessor is placed in microwave electron cyclotron resonance plasma environment, plasma
Body glow gases are the nitrogen mixture source of the argon gas and 5% volume of 95% volume, when heating thiocarbamide to 155 DEG C under vacuum
Distillation obtains thiocarbamide steam and is passed through reative cell offer sulphur source, carries out plasma bombardment processing, obtain the sheet of nitrogen atom doping
ZnS-film.
The electrode material prepared in comparative example 2 is tested, test condition is identical as embodiment 1-5, UV, visible light point
Light photometer collects the doped zinc sulphide material for showing to test present embodiment preparation and strong absorption occurs in 340nm or so,
The shorter ultraviolet light of absorbing wavelength further illustrates that it is relatively low to the utilization rate of sunlight.The Photocatalyzed Hydrogen Production experiment of sample is surveyed
It is 280-350mmolh to obtain undoped zinc sulphide hydrogen-producing speed-1·g-1, it is much smaller than in the present invention and passes through metal ion and nitrogen
The hydrogen-producing speed of atom doped zinc sulphide.
It can be obtained by above-mentioned comparison, the suction of doped zinc sulphide catalyst nano-particles prepared by the present invention to sunlight
It receives range to increase, which has relatively stable hydrogen production by water decomposition performance, maintains higher hydrogen release speed during the reaction
Rate has preferable catalytic stability.
Claims (7)
1. a kind of preparation method of doped zinc sulphide catalyst for solar hydrogen making, which is characterized in that made using zinc acetate
For zinc ion source, doped source is as doped raw material, using thiocarbamide as sulphur source, by plasma bombardment material surface, specifically
Preparation process is as follows：
（1）Zinc acetate and doped source are mixed, appropriate amount of deionized water is added, by 0.5 ~ 3h of mechanical agitation, obtain zinc ion with
The mixed solution of doped metal ion, a concentration of 1.8 ~ 3.0 mol/L of zinc ion, the doped metal ion wherein in solution
A concentration of 0.06 ~ 0.20mol/L；The doped source includes the one or more of nickel acetate, copper acetate, ferric acetate, manganese acetate；
（2）Ethylenediamine tetra-acetic acid is added in the mixed solution of the zinc ion and doped metal ion, it is small by ultrasound 1 ~ 5
When, the zinc ion and doped metal ion solution chelated, wherein the ethylenediamine tetra-acetic acid and the zinc ion and doping
The mass ratio of the mixed solution of metal ion is 1 ~ 5:200；
（3）It is 1 by mass ratio:1~5:200 flocculant, the zinc ion of bonding agent and chelating and doped metal ion solution are mixed
It closes, and stirs 1~5h, after standing filtering, obtain chelating presoma, the chelating presoma is coated on substrate material surface,
The coating thickness is 10 ~ 50 μm, is placed in vacuum drying chamber, 1 ~ 2 hour dry, obtains photocatalysis predecessor；
（4）The photocatalysis predecessor is placed in plasma environment, thiocarbamide steam is passed through and sulphur source is provided, plasma is carried out and bangs
Processing is hit, metal atom doped sheet ZnS-film is obtained, wherein the plasma is microwave electron cyclotron resonance etc.
Gas ions, plasma glow gas are the nitrogen mixture source of the argon gas and 5% volume of 95% volume.
2. a kind of preparation method of doped zinc sulphide catalyst for solar hydrogen making according to claim 1, special
Sign is that the flocculant includes in aluminum sulfate, aluminium chloride, ferric sulfate, iron chloride, polyacrylamide, citric acid and bentonite
A combination of one or more.
3. a kind of preparation method of doped zinc sulphide catalyst for solar hydrogen making according to claim 1, special
Sign is that the substrate material is the electro-conductive glass of FTO or ITO coating, and the sheet resistance of electro-conductive glass is 3 ~ 10 Ω.
4. a kind of preparation method of doped zinc sulphide catalyst for solar hydrogen making according to claim 1, special
Sign is that the thiocarbamide is heated to distilling at 150 ~ 160 DEG C under vacuum, obtains thiocarbamide steam.
5. a kind of preparation method of doped zinc sulphide catalyst for solar hydrogen making according to claim 1, special
Sign is that the temperature of the vacuum drying chamber is 40 ~ 80 DEG C, and chamber pressure is 10 ~ 50kPa.
6. a kind of preparation method of doped zinc sulphide catalyst for solar hydrogen making according to claim 1, special
Sign is that the plasma power is 0.5-2 kW.
7. a kind of doped zinc sulphide catalyst for solar hydrogen making, using method as claimed in any one of claims 1 to 6
It is prepared.
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| CN115672397A (en) * | 2022-11-14 | 2023-02-03 | 中国科学院福建物质结构研究所 | Organic coated composite semiconductor material and preparation method and application thereof |
| CN116273064A (en) * | 2021-12-20 | 2023-06-23 | 中南大学 | Sphalerite-based photocatalytic material and preparation method and application thereof |
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| CN116273064A (en) * | 2021-12-20 | 2023-06-23 | 中南大学 | Sphalerite-based photocatalytic material and preparation method and application thereof |
| CN115672397A (en) * | 2022-11-14 | 2023-02-03 | 中国科学院福建物质结构研究所 | Organic coated composite semiconductor material and preparation method and application thereof |
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