CN106582876A - Metal or metalloid modified zinc cadmium sulfide-ethylenediamine photocatalyst and preparation method - Google Patents
Metal or metalloid modified zinc cadmium sulfide-ethylenediamine photocatalyst and preparation method Download PDFInfo
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- CN106582876A CN106582876A CN201611218397.7A CN201611218397A CN106582876A CN 106582876 A CN106582876 A CN 106582876A CN 201611218397 A CN201611218397 A CN 201611218397A CN 106582876 A CN106582876 A CN 106582876A
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- ethylenediamine
- photocatalyst
- modification
- metal
- aqueous solution
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 128
- 239000002184 metal Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 229910052752 metalloid Inorganic materials 0.000 title abstract description 8
- -1 metalloid modified zinc cadmium sulfide-ethylenediamine Chemical class 0.000 title abstract description 7
- 150000002738 metalloids Chemical class 0.000 title description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 239000011701 zinc Substances 0.000 claims description 174
- 239000007864 aqueous solution Substances 0.000 claims description 80
- 238000012986 modification Methods 0.000 claims description 62
- 230000004048 modification Effects 0.000 claims description 47
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- FOOFBKPXUKOLDO-UHFFFAOYSA-N C(CN)N.[Cd].[Zn].[S] Chemical compound C(CN)N.[Cd].[Zn].[S] FOOFBKPXUKOLDO-UHFFFAOYSA-N 0.000 claims description 40
- 239000012153 distilled water Substances 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 25
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 21
- 238000005119 centrifugation Methods 0.000 claims description 19
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000000247 postprecipitation Methods 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 14
- IGUWUAGBIVHKDA-UHFFFAOYSA-N cadmium;sulfanylidenezinc Chemical compound [Zn].[Cd]=S IGUWUAGBIVHKDA-UHFFFAOYSA-N 0.000 claims description 12
- 229910052961 molybdenite Inorganic materials 0.000 claims description 12
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 11
- 239000005864 Sulphur Substances 0.000 claims description 11
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 11
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims description 11
- 150000002171 ethylene diamines Chemical class 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 210000002700 urine Anatomy 0.000 claims description 11
- 239000003643 water by type Substances 0.000 claims description 11
- 239000004246 zinc acetate Substances 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 10
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 10
- 230000001699 photocatalysis Effects 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 9
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 9
- 229910003266 NiCo Inorganic materials 0.000 claims description 8
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 238000007146 photocatalysis Methods 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 230000036571 hydration Effects 0.000 claims description 5
- 238000006703 hydration reaction Methods 0.000 claims description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052724 xenon Inorganic materials 0.000 claims description 5
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011609 ammonium molybdate Substances 0.000 claims description 4
- 229940010552 ammonium molybdate Drugs 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 2
- 239000010931 gold Substances 0.000 claims 2
- 229910052737 gold Inorganic materials 0.000 claims 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims 1
- 229910021508 nickel(II) hydroxide Inorganic materials 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 150000002736 metal compounds Chemical class 0.000 abstract description 2
- 239000002135 nanosheet Substances 0.000 abstract 2
- 150000002737 metalloid compounds Chemical class 0.000 abstract 1
- 239000006104 solid solution Substances 0.000 description 31
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 22
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 11
- 229910052725 zinc Inorganic materials 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 229910021205 NaH2PO2 Inorganic materials 0.000 description 4
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000002186 photoactivation Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical compound [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- B01J35/39—
-
- 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
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
-
- 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
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
-
- 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
- C01B2203/1076—Copper or zinc-based 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 invention discloses a metal or metalloid modified zinc cadmium sulfide-ethylenediamine photocatalyst and a preparation method. The preparation method of the metal modified zinc cadmium sulfide-ethylenediamine photocatalyst comprises the following steps that (1) ZnxCd1-xS-ethylenediamine hybrid nanosheets are prepared; (2) metal ion modified ZnxCd1-xS-ethylenediamine hybrid nanosheets are prepared; and (3) the metal modified zinc cadmium sulfide-ethylenediamine photocatalyst is prepared. The method is simple in process, easy and convenient to operate and low in preparation cost, and the prepared metal or metalloid compound modified ZnxCd1-xS-ethylenediamine photocatalyst is highly dispersed in water and has high visible light catalysis water-splitting hydrogen production performance and good chemical stability.
Description
Technical field
The present invention relates to a kind of catalysis material and preparation method thereof, and in particular to what metal or metal compound were modified
Sulfur zinc cadmium (ZnxCd1-xS)-ethylenediamine photocatalyst and preparation method, belong to nano-photocatalyst material synthesis and photocatalysis technology
Field.
Background technology
Solar energy photocatalytic hydrogen manufacturing is one of focus of current energy field research.
CdS with Wurzite structure is a kind of most commonly used sulfide photocatalyst of research, because it has phase
To narrower energy gap (2.4eV), can absorbing wavelength<The sunlight of 510nm.The flat-band potential of-the 0.87V that it has
The reduction of water is especially suitable for, also can be by water oxygen on the valence band potential theory of 1.5V (vsNHE).By partly leading for CdS and broad stopband
Body ZnS is compound to prepare ZnxCd1-xS solid solution, can significantly improve its photocatalysis hydrolytic hydrogen production performance.However, traditional ZnxCd1-xS
Specific surface area that solid solution is present is little, in aqueous poor dispersion, photo-generate electron-hole recombination rate be high, photo-quantum efficiency is low and
The deficiencies such as photochemical stability difference, seriously limit its extensive application in photocatalysis field.
The content of the invention
It is an object of the invention to overcome the deficiencies in the prior art, there is provided a kind of sulfur zinc cadmium-ethylenediamine light of metal-modified
The preparation method of catalyst.
Second object of the present invention is to provide the sulfur zinc cadmium-ethylenediamine photocatalyst of metal-modified.
Third object of the present invention is to provide a kind of system of the sulfur zinc cadmium-ethylenediamine photocatalyst of metal boride modification
Preparation Method.
Fourth object of the present invention is to provide the sulfur zinc cadmium-ethylenediamine photocatalyst of a kind metal boride modification.
5th purpose of the present invention is to provide a kind of system of the sulfur zinc cadmium-ethylenediamine photocatalyst of metal phosphide modification
Preparation Method.
6th purpose of the present invention is to provide a kind of sulfur zinc cadmium-ethylenediamine photocatalyst of metal phosphide modification.
7th purpose of the present invention is to provide a kind of system of the sulfur zinc cadmium-ethylenediamine photocatalyst of metal sulfide modification
Preparation Method.
8th purpose of the present invention is to provide a kind of sulfur zinc cadmium-ethylenediamine photocatalyst of metal sulfide modification.
9th purpose of the present invention is to provide a kind of sulfur zinc cadmium-ethylenediamine photocatalyst, the metal of above-mentioned metal-modified
Sulfur zinc cadmium-ethylenediamine photocatalyst or metal that the sulfur zinc cadmium-ethylenediamine photocatalyst of boride modification, metal phosphide are modified
The sulfur zinc cadmium-ethylenediamine photocatalyst applications of sulfide modification.
Technical scheme is summarized as follows：
A kind of preparation method of the sulfur zinc cadmium-ethylenediamine photocatalyst of metal-modified, comprises the following steps：
(1) by cadmium acetate, zinc acetate and sulphur urine in molar ratio 1:(1.5-9):(8-30) ratio is mixed to get mixture,
Take mixture 5-10g to add in 100ml ethylenediamines, stirring obtains clear solution, hydro-thermal 12- under the conditions of 180 DEG C -220 DEG C
48h, is cooled to room temperature, centrifugation, and solid distilled water wash, drying obtain ZnxCd1-xS- ethylenediamine hybridized nanometer pieces, it is described
ZnxCd1-xS is the molecular formula of sulfur zinc cadmium；
(2) by 1g：The ratio of 1ml, the Zn that step (1) is obtainedxCd1-xS- ethylenediamine hybridized nanometer pieces, are scattered in 0.2-
0.5M NiCl2Aqueous solution is scattered in 0.2-0.5M CoCl2Aqueous solution is scattered in that molar concentration is equal and concentration is 0.2-
The NiCl of 0.5M2And CoCl2Mixed aqueous solution in, be uniformly dispersed, in 60-80 DEG C of evaporating water, Metal Ions Modification is obtained
ZnxCd1-xS- ethylenediamine hybridized nanometer pieces；
(3) Zn of the Metal Ions Modification for obtaining 2-5g steps (2)xCd1-xS- ethylenediamine hybridized nanometer pieces are dispersed in
In 50ml deionized waters, it is 11-13 to add NaOH to adjust pH, is heated to 60-80 DEG C, adds 0.1-0.5g hydration hydrazine reaction 1-
3h, reaction postprecipitation is centrifuged, and with distilled water wash, drying, obtains the sulfur zinc cadmium-ethylenediamine photocatalysis of metal-modified
Agent, the sulfur zinc cadmium-ethylenediamine photocatalyst of the metal-modified is Ni/ZnxCd1-xS- ethylenediamines photocatalyst or Co/ZnxCd1- xS- ethylenediamines photocatalyst or NiCo/ZnxCd1-xS- ethylenediamine photocatalysts, wherein X=0.6-0.9.
The sulfur zinc cadmium-ethylenediamine photocatalyst of metal-modified prepared by said method.
A kind of preparation method of the sulfur zinc cadmium-ethylenediamine photocatalyst of metal boride modification, comprises the following steps：
(1) by cadmium acetate, zinc acetate and sulphur urine in molar ratio 1:(1.5-9):(8-30) ratio is mixed to get mixture,
Take mixture 5-10g to add in 100ml ethylenediamines, stirring obtains clear solution, hydro-thermal 12- under the conditions of 180 DEG C -220 DEG C
48h, is cooled to room temperature, centrifugation, and solid distilled water wash, drying obtain ZnxCd1-xS- ethylenediamine hybridized nanometer pieces, it is described
ZnxCd1-xS is the molecular formula of sulfur zinc cadmium；
(2) by 1g：The ratio of 1ml, the Zn that step (1) is obtainedxCd1-xS- ethylenediamine hybridized nanometer pieces are scattered in 0.2-
0.5M NiCl2Aqueous solution is scattered in 0.2-0.5M CoCl2Aqueous solution is scattered in that molar concentration is equal and concentration is 0.2-
The NiCl of 0.5M2And CoCl2Mixed aqueous solution in, be uniformly dispersed, in 60-80 DEG C of evaporating water, Metal Ions Modification is obtained
ZnxCd1-xS- ethylenediamine hybridized nanometer pieces；
(3) Zn of the Metal Ions Modification for obtaining 2-5g steps (2)xCd1-xS- ethylenediamine hybridized nanometer pieces are dispersed in
In 50ml deionized waters, it is 11-13 to add NaOH to adjust pH, is heated to 60-80 DEG C, adds 0.5-5ml 1M KBH4Aqueous solution
Reaction 1-3h, reaction postprecipitation is centrifuged, and with distilled water wash, drying, obtains the sulfur zinc cadmium-second of metal boride modification
Diamidogen photocatalyst, the sulfur zinc cadmium-ethylenediamine photocatalyst of the metal boride modification is NiB/ZnxCd1-xS- ethylenediamines are urged
Agent or CoB/ZnxCd1-xS- ethylenediamines photocatalyst or NiCoB2/ZnxCd1-xS- ethylenediamine photocatalysts, wherein X=0.6-
0.9。
The sulfur zinc cadmium-ethylenediamine photocatalyst of metal boride modification prepared by said method.
A kind of preparation method of the sulfur zinc cadmium-ethylenediamine photocatalyst of metal phosphide modification, comprises the following steps：
(1) by cadmium acetate, zinc acetate and sulphur urine in molar ratio 1:(1.5-9):(8-30) ratio is mixed to get mixture,
Take mixture 5-10g to add in 100ml ethylenediamines, stirring obtains clear solution, hydro-thermal 12- under the conditions of 180 DEG C -220 DEG C
48h, is cooled to room temperature, centrifugation, and solid distilled water wash, drying obtain ZnxCd1-xS- ethylenediamine hybridized nanometer pieces, it is described
ZnxCd1-xS is the molecular formula of sulfur zinc cadmium；
(2) by 1g：The ratio of 1ml, the Zn that step (1) is obtainedxCd1-xS- ethylenediamine hybridized nanometer pieces, are scattered in 0.2-
0.5M NiCl2Aqueous solution is scattered in 0.2-0.5M CoCl2Aqueous solution is scattered in that molar concentration is equal and concentration is 0.2-
The NiCl of 0.5M2And CoCl2Mixed aqueous solution in, be uniformly dispersed, in 60-80 DEG C of evaporating water, Metal Ions Modification is obtained
ZnxCd1-xS- ethylenediamine hybridized nanometer pieces；
(3) Zn of the Metal Ions Modification for obtaining 2-5g steps (2)xCd1-xS- ethylenediamine hybridized nanometer pieces are dispersed in
In 50ml deionized waters, 0.5-5ml 1M NaH are added2PO2, it is 9-11 that NaOH adjusts pH, after being heated to 60-80 DEG C, is added
0.05-0.2ml 1M KBH4Aqueous solution, reacts 1-3h, reacts postprecipitation centrifugation, is that 5% ammonia will be heavy with volumetric concentration
Ni (OH) in shallow lake2Wash away, distillation is washed to neutrality, be dried, obtain the sulfur zinc cadmium-ethylenediamine photocatalysis of metal phosphide modification
Agent, the sulfur zinc cadmium-ethylenediamine photocatalyst of the metal phosphide modification is NiP/ZnxCd1-xS- ethylenediamines photocatalyst or
CoP/ZnxCd1-xS- ethylenediamines photocatalyst or NiCoP2/ZnxCd1-xS- ethylenediamine photocatalysts, wherein X=0.6-0.9.
The Zn of metal phosphide modification prepared by said methodxCd1-xS- ethylenediamine photocatalysts.
A kind of preparation method of the sulfur zinc cadmium-ethylenediamine photocatalyst of metal sulfide modification, comprises the following steps：
(1) by cadmium acetate, zinc acetate and sulphur urine in molar ratio 1:(1.5-9):(8-30) ratio is mixed to get mixture,
Take mixture 5-10g to add in 100ml ethylenediamines, stirring obtains clear solution, hydro-thermal 12- under the conditions of 180 DEG C -220 DEG C
48h, is cooled to room temperature, centrifugation, and solid distilled water wash, drying obtain ZnxCd1-xS- ethylenediamine hybridized nanometer pieces, it is described
ZnxCd1-xS is the molecular formula of sulfur zinc cadmium；
(2) by 1g：The ratio of 1ml, the Zn that step (1) is obtainedxCd1-xS- ethylenediamine hybridized nanometer pieces and 0.2-0.5M
Four thio ammonium molybdate aqueous solution or tetrathio ammonium tungstate aqueous solution, add 50ml volumetric concentrations to be 10%-30% ethanol waters
In, it is uniformly dispersed, the oxygen that high-purity Ar gas is removed in solution is passed through, solution reacts 2-4h, solid Jing under the irradiation of 300W xenon lamps
Centrifugation, distilled water wash is used, 60-80 DEG C of drying obtains the sulfur zinc cadmium-ethylenediamine photocatalyst of metal sulfide modification,
The sulfur zinc cadmium-ethylenediamine photocatalyst of the metal sulfide modification is MoS2/ZnxCd1-xS- ethylenediamines photocatalyst or WS2/
ZnxCd1-xS- ethylenediamine photocatalysts, the X is 0.6-0.9.
The Zn of metal sulfide modification prepared by said methodxCd1-xS- ethylenediamine photocatalysts.
Above-mentioned photocatalyst is in visible ray or the application of sunlight photocatalysis water decomposition hydrogen manufacturing.
It is an advantage of the current invention that process is simple, easy to operate, preparation cost are low, prepared metal or metalloid chemical combination
Thing modifies ZnxCd1-xS- ethylenediamines photocatalyst disperses in water camber, with higher visible light catalytic water decomposition hydrogen manufacturing
Energy and good chemical stability.Metal or the Zn of metalloid modificationxCd1-xMetal or metalloid in S- ethylenediamine photocatalysts
Compound quality percentage composition is 1%-5%, ZnxCd1-xS solid solution weight/mass percentage composition be 74.8%-86.4%, ethylenediamine
Weight/mass percentage composition is 10.9%-24%.
Description of the drawings
Fig. 1 is Zn prepared by the step of embodiment 3 (1)0.8Cd0.2The XRD spectra of S- ethylenediamine hybridized nanometer pieces, shows in figure
The crystalline phase of composite photo-catalyst consist of Zn0.8Cd0.2S- ethylenediamine hybrid materials.
Fig. 2 is Zn prepared by the step of embodiment 3 (1)0.8Cd0.2The SEM photograph of S- ethylenediamine hybridized nanometer pieces.
Fig. 3 is embodiment 1：Ni/Zn0.6Cd0.4The SEM photograph of S- ethylenediamines (1%Ni) photocatalyst.
Fig. 4 is embodiment 5：CoB/Zn0.9Cd0.1The SEM photograph of S- ethylenediamines (2.4%CoB) photocatalyst.
Fig. 5 is embodiment 9：NiCoP2/Zn0.8Cd0.2S- ethylenediamine (7.4%NiCoP2) photocatalyst SEM photograph.
Fig. 6 is embodiment 12：MoS2/Zn0.8Cd0.2S- ethylenediamine (2.5%MoS2) photocatalyst SEM photograph.
Specific embodiment
Below by specific embodiment, the present invention is further illustrated.
The ZnxCd1-xS is the molecular formula of sulfur zinc cadmium；
The sulfur zinc cadmium (Ni/Zn of the nickel of embodiment 1 modification0.6Cd0.4The preparation method of S)-ethylenediamine photocatalyst, including with
Lower step：
(1) by cadmium acetate, zinc acetate and sulphur urine in molar ratio 1:1.5:8 ratio is mixed to get mixture, takes mixture
5g is added in 100ml ethylenediamines, and stirring obtains clear solution, and hydro-thermal 12h under the conditions of 180 DEG C is cooled to room temperature, centrifugation, Gu
Body distilled water wash, drying, obtain Zn0.6Cd0.4S- ethylenediamine hybridized nanometer pieces；
(2) by 2gZn0.6Cd0.4S- ethylenediamine hybridized nanometer pieces are scattered in 2ml 0.2M NiCl2In aqueous solution, dispersion is equal
It is even, in 60 DEG C of evaporating waters, Ni is obtained2+The Zn of modification0.6Cd0.4S- ethylenediamine hybridized nanometer pieces；
(3) Ni for obtaining 2g steps (2)2+The Zn of modification0.6Cd0.4S- ethylenediamine hybridized nanometer pieces be dispersed in 50ml go from
In sub- water, it is 11 to add NaOH to adjust pH, is heated to 60 DEG C, adds 0.1g hydration hydrazine reaction 3h, the Jing centrifugations point of reaction postprecipitation
From, with distilled water wash, dry, obtain Ni/Zn0.6Cd0.4S- ethylenediamine photocatalysts.
Ni/Zn0.6Cd0.4Ni mass contents are 1%, Zn in S- ethylenediamine photocatalysts0.6Cd0.4S solid solution mass contents
For 75%, ethylenediamine mass content is 24%.
It is demonstrated experimentally that using 0.5M NiCl2Aqueous solution substitutes the 0.2M NiCl of the present embodiment2Aqueous solution, other are with this enforcement
Example, prepares Ni/Zn0.6Cd0.4S- ethylenediamine photocatalysts, wherein Ni mass contents are 2.5%, Zn0.6Cd0.4S solid solution body constitution
Amount content is 74%, and ethylenediamine mass content is 23.5%.
The sulfur zinc cadmium (Co/Zn of the cobalt of embodiment 2 modification0.9Cd0.1The preparation of S)-ethylenediamine photocatalyst
(1) by cadmium acetate, zinc acetate and sulphur urine in molar ratio 1:9:30 ratio is mixed to get mixture, takes mixture 8g
In adding 100ml ethylenediamines, stirring obtains clear solution, and hydro-thermal 36h under the conditions of 200 DEG C is cooled to room temperature, centrifugation, solid
With distilled water wash, drying, Zn is obtained0.9Cd0.1S- ethylenediamine hybridized nanometer pieces；
(2) by 3gZn0.9Cd0.1S- ethylenediamine hybridized nanometer pieces are scattered in 3ml 0.4M CoCl2In aqueous solution, dispersion is equal
It is even, in 70 DEG C of evaporating waters, Co is obtained2+The Zn of modification0.9Cd0.1S- ethylenediamine hybridized nanometer pieces；
(3) by 3gCo2+The Zn of modification0.9Cd0.1S- ethylenediamine hybridized nanometer pieces are dispersed in 50ml deionized waters, are added
It is 13 that NaOH adjusts pH, is heated to 70 DEG C, adds 0.3g hydration hydrazine reaction 2h, reaction postprecipitation to be centrifuged, and uses distilled water
Washing, drying, obtain Co/Zn0.9Cd0.1S- ethylenediamine photocatalysts.
Co/Zn0.9Cd0.1Co mass contents are 2%, Zn in S- ethylenediamine photocatalysts0.9Cd0.1S solid solution mass contents
For 80%, ethylenediamine mass content is 18%.
It is demonstrated experimentally that using 0.2M CoCl2Aqueous solution substitutes the 0.4M CoCl of the present embodiment2Aqueous solution, other are with this enforcement
Example, prepares Co/Zn0.9Cd0.1S- ethylenediamine photocatalysts, wherein Co mass contents are 1%, Zn0.9Cd0.1S solid solution weights
Content is 80.8%, and ethylenediamine mass content is 18.2%.
Use 0.5M CoCl2Aqueous solution substitutes the 0.4M CoCl of the present embodiment2Aqueous solution, other same the present embodiment, prepares
Co/Zn0.9Cd0.1S- ethylenediamine photocatalysts, wherein Co mass contents are 2.5%, Zn0.9Cd0.1S solid solution mass contents are
79.8%, ethylenediamine mass content is 17.7%.
The NiCo/Zn of embodiment 30.8Cd0.2The preparation of S- ethylenediamine photocatalysts
(1) by cadmium acetate, zinc acetate and sulphur urine in molar ratio 1:4:15 ratio is mixed to get mixture, takes mixture
10g is added in 100ml ethylenediamines, and stirring obtains clear solution, and hydro-thermal 48h under the conditions of 220 DEG C is cooled to room temperature, centrifugation, Gu
Body distilled water wash, drying, obtain Zn0.8Cd0.2S- ethylenediamine hybridized nanometer pieces；
(2) by 5gZn0.8Cd0.2S- ethylenediamine hybridized nanometer pieces are scattered in 5ml 0.5M NiCl2And 0.5MCoCl2Mixing
In aqueous solution, it is uniformly dispersed, in 80 DEG C of evaporating waters, Ni is obtained2+-Co2+The Zn of modification0.8Cd0.2S- ethylenediamine hybridized nanometers
Piece.
(3) Ni for obtaining 5g steps (2)2+-Co2+The Zn of modification0.8Cd0.2S- ethylenediamine hybridized nanometer pieces are dispersed in
In 50ml deionized waters, it is 12 to add NaOH to adjust pH, is heated to 80 DEG C, adds 0.5g hydration hydrazine reaction 1h, reacts postprecipitation
It is centrifuged, with distilled water wash, drying, obtains NiCo/Zn0.8Cd0.2S- ethylenediamine photocatalysts.
NiCo/Zn0.8Cd0.2NiCo mass contents are 5%, Zn in S- ethylenediamine photocatalysts0.8Cd0.2S solid solution weights
Content is 85%, and ethylenediamine mass content is 10%.
Use 0.2M NiCl2And 0.2MCoCl2Mixed aqueous solution substitutes the 0.5M NiCl of the present embodiment2With 0.5M CoCl2
Mixed aqueous solution, other same the present embodiment, prepares NiCo/Zn0.8Cd0.2S- ethylenediamine photocatalysts, wherein NiCo mass contains
Measure as 2%, Zn0.8Cd0.2S solid solution mass content is 87.6%, and ethylenediamine mass content is 10.4%.
The NiB/Zn of embodiment 40.6Cd0.4The preparation of S- ethylenediamine photocatalysts
(1) with the step of embodiment 1 (1)；
(2) with the step of embodiment 1 (2)；
(3) Ni for obtaining 2g steps (2)2+The Zn of modification0.6Cd0.4S- ethylenediamine hybridized nanometer pieces be dispersed in 50ml go from
In sub- water, it is 11 to add NaOH to adjust pH, is heated to 60 DEG C, adds 0.5ml 1M KBH4Reactant aqueous solution 3h, reacts postprecipitation
It is centrifuged, with distilled water wash, drying, obtains NiB/Zn0.6Cd0.4S- ethylenediamine photocatalysts.
NiB/Zn0.6Cd0.4NiB mass contents are 1.2%, Zn in S- ethylenediamine photocatalysts0.6Cd0.4S solid solution weights
Content is 74.9%, and ethylenediamine mass content is 23.9%.
It is demonstrated experimentally that using 0.5M NiCl2Aqueous solution substitutes the 0.2M NiCl of the present embodiment2Aqueous solution, uses 1.2ml 1M
KBH4Aqueous solution replaces the present embodiment 0.5ml 1M KBH4Aqueous solution, other same the present embodiment, prepares NiB/Zn0.6Cd0.4S-
Ethylenediamine photocatalyst, wherein NiB mass contents are 3%, Zn0.6Cd0.4S solid solution mass content is 73.6%, ethylenediamine matter
Amount content is 23.4%.
The CoB/Zn of embodiment 50.9Cd0.1The preparation of S- ethylenediamine photocatalysts
(1) with the step of embodiment 2 (1)；
(2) with the step of embodiment 2 (2)；
(3) Co for obtaining 3g steps (2)2+The Zn of modification0.9Cd0.1S- ethylenediamine hybridized nanometer pieces be dispersed in 50ml go from
In sub- water, it is 12 to add NaOH to adjust pH, is heated to 70 DEG C, adds 1.5ml 1M KBH4Reactant aqueous solution 2h, reacts postprecipitation
It is centrifuged, with distilled water wash, drying, obtains CoB/Zn0.9Cd0.1S- ethylenediamine photocatalysts.
CoB/Zn0.9Cd0.1CoB mass contents are 2.4%, Zn in S- ethylenediamine photocatalysts0.9Cd0.1S solid solution weights
Content is 79.8%, and ethylenediamine mass content is 17.8%.
It is demonstrated experimentally that using 0.5M CoCl2Aqueous solution substitutes the 0.4M CoCl of the present embodiment2Aqueous solution, uses 1.8ml 1M
KBH4Aqueous solution replaces the present embodiment 1.5ml 1M KBH4Aqueous solution, other same the present embodiment, prepares CoB/Zn0.9Cd0.1S-
Ethylenediamine photocatalyst, wherein CoB mass contents are 3%, Zn0.9Cd0.1S solid solution mass content is 79.3%, ethylenediamine matter
Amount content is 17.7%..
Use 0.2M CoCl2Aqueous solution substitutes the 0.4M CoCl of the present embodiment2Aqueous solution, with 0.8ml 1M KBH4Aqueous solution
Replace the present embodiment 1.5ml 1M KBH4Aqueous solution, other same the present embodiment, prepares CoB/Zn0.9Cd0.1S- ethylenediamine light is urged
Agent, wherein CoB mass contents are 1.2%, Zn0.9Cd0.1S solid solution mass content is 80.6%, and ethylenediamine mass content is
18.2%.
The NiCoB of embodiment 62/Zn0.8Cd0.2The preparation of S- ethylenediamine photocatalysts
(1) with the step of embodiment 3 (1)；
(2) with the step of embodiment 3 (2)；
(3) by Ni obtained in 5g steps (2)2+-Co2+The Zn of modification0.8Cd0.2S- ethylenediamine hybridized nanometer pieces are dispersed in
In 50ml deionized waters, it is 13 to add NaOH to adjust pH, after solution is heated to 80 DEG C, adds 5ml 1MKBH4Reactant aqueous solution
1h, reaction postprecipitation is centrifuged, and with distilled water wash, drying, obtains NiCoB2/Zn0.8Cd0.2S- ethylenediamine photocatalysis
Agent.
NiCoB2/Zn0.8Cd0.2NiCoB in S- ethylenediamine photocatalysts2Mass content is 5.9%, Zn0.8Cd0.2S solid solution
Mass content is 84.2%, and ethylenediamine mass content is 9.9%.
Use 0.2M NiCl2And 0.2MCoCl2Mixed aqueous solution substitutes the 0.5M NiCl of the present embodiment2With 0.5M CoCl2
Mixed aqueous solution, with 2ml 1M KBH4Aqueous solution replaces the present embodiment 5ml 1M KBH4Aqueous solution, other same the present embodiment, system
It is standby go out NiCoB2/Zn0.8Cd0.2S- ethylenediamine photocatalysts, wherein NiCoB2Mass content is 2.4%, Zn0.8Cd0.2S solid solution
Mass content is 87.3%, and ethylenediamine mass content is 10.3%.
The NiP/Zn of embodiment 70.6Cd0.4The preparation of S- ethylenediamine photocatalysts
(1) with the step of embodiment 1 (1)；
(2) with the step of embodiment 1 (2)；
(3) 2g steps (2) are obtained into Ni2+The Zn of modification0.6Cd0.4S-- ethylenediamine hybridized nanometer pieces be dispersed in 50ml go from
In sub- water, 0.5ml 1M NaH are added2PO2, it is 9 that NaOH adjusts pH, after being heated to 60 DEG C, adds 0.05ml 1M KBH4It is water-soluble
Liquid, reacts 3h, reacts postprecipitation centrifugation, is 5% ammonia by the Ni (OH) in precipitation with volumetric concentration2Wash away, distilled water
Neutrality is washed till, is dried, obtain NiP/Zn0.6Cd0.4S- ethylenediamine photocatalysts.
NiP/Zn0.6Cd0.4NiP mass contents are 1.5%, Zn in S- ethylenediamine photocatalysts0.6Cd0.4S solid solution weights
Content is 74.8%, and ethylenediamine mass content is 23.7%.
It is demonstrated experimentally that using 0.5M NiCl2Aqueous solution substitutes the 0.2M NiCl of the present embodiment2Aqueous solution, uses 1.2ml 1M
NaH2PO2Substitute the 0.5ml 1M NaH of the present embodiment2PO2, with 0.13ml 1M KBH4Aqueous solution replaces the present embodiment
0.05ml 1M KBH4Aqueous solution, other same the present embodiment, prepares NiP/Zn0.6Cd0.4S- ethylenediamine photocatalysts, wherein
NiP mass contents are 3.8%, Zn0.6Cd0.4S solid solution mass content is 73.1%, and ethylenediamine mass content is 23.1%.
The CoP/Zn of embodiment 80.9Cd0.1The preparation of S- ethylenediamine photocatalysts
(1) with the step of embodiment 2 (1)；
(2) with the step of embodiment 2 (2)；
(3) 3g steps (2) are obtained into Co2+The Zn of modification0.9Cd0.1S- ethylenediamine hybridized nanometer pieces are dispersed in 50ml deionizations
In water, 1.5ml 1M NaH are added2PO2, it is 10 that NaOH adjusts pH, after being heated to 70 DEG C, adds 0.1ml 1MKBH4Aqueous solution,
Reaction 2h, reacts postprecipitation centrifugation, is 5% ammonia by the Ni (OH) in precipitation with volumetric concentration2Wash away, distillation is washed to
Neutrality, is dried, and obtains CoP/Zn0.9Cd0.1S- ethylenediamine photocatalysts.
CoP/Zn0.9Cd0.1CoP mass contents are 3%, Zn in S- ethylenediamine photocatalysts0.9Cd0.1S solid solution weights contain
Measure as 79.3%, ethylenediamine mass content is 17.7%.
It is demonstrated experimentally that using 0.2M CoCl2Aqueous solution substitutes the 0.4M CoCl of the present embodiment2Aqueous solution, uses 0.8ml 1M
NaH2PO2Replace the 1.5ml 1M NaH of the present embodiment2PO2, use 0.05ml 1MKBH4Aqueous solution replaces the present embodiment
0.1ml1MKBH4Aqueous solution, other same the present embodiment, prepares CoP/Zn0.9Cd0.1S- ethylenediamine photocatalysts, wherein CoP matter
Amount content is 1.5%, Zn0.9Cd0.1S solid solution mass content is 80.5%, and ethylenediamine mass content is 18%.
Use 0.5M CoCl2Aqueous solution substitutes the 0.4M CoCl of the present embodiment2Aqueous solution, with 1.8ml 1M NaH2PO2Generation
For the 1.5ml 1M NaH of the present embodiment2PO2, use 0.12ml 1MKBH4Aqueous solution replaces the 0.1ml 1MKBH of the present embodiment4Water
Solution, with other same the present embodiment, prepares CoP/Zn0.9Cd0.1S- ethylenediamine photocatalysts, wherein CoP mass contents are
3.7%, Zn0.9Cd0.1S solid solution mass content is 78.7%, and ethylenediamine mass content is 17.6%.
The NiCoP of embodiment 92/Zn0.8Cd0.8The preparation of S- ethylenediamine photocatalysts
(1) with the step of embodiment 3 (1)；
(2) with the step of embodiment 3 (2)；
(3) 5g steps (2) are obtained into Ni2+-Co2+The Zn of modification0.8Cd0.2S- ethylenediamine hybridized nanometer pieces are dispersed in 50ml
In deionized water, 5ml 1M NaH are added2PO2, it is 11 that NaOH adjusts pH, after solution is heated to 80 DEG C, adds 0.2ml 1MKBH4
Aqueous solution, reacts 1h, reacts postprecipitation centrifugation, is 5% ammonia by the Ni (OH) in precipitation with volumetric concentration2Wash away, then
Neutrality is washed to distillation, is dried, obtain NiCoP2/Zn0.8Cd0.8S- ethylenediamine photocatalysts.
NiCoP2/Zn0.8Cd0.2NiCoP in S- ethylenediamine photocatalysts2Mass content is 7.4%, Zn0.8Cd0.2S solid solution
Mass content is 83%, and ethylenediamine mass content is 9.6%.
Use 0.2M NiCl2And 0.2MCoCl2Mixed aqueous solution substitutes the 0.5M NiCl of the present embodiment2And 0.5MCoCl2It is mixed
Heshui solution, with 2ml 1M NaH2PO2Aqueous solution replaces the 5ml 1M NaH of the present embodiment2PO2, use 0.08ml 1MKBH4It is water-soluble
Liquid replaces the present embodiment 0.2ml 1MKBH4Aqueous solution, other same the present embodiment, prepares NiCoP2/Zn0.8Cd0.2S- ethylenediamines
Photocatalyst, wherein NiCoP2Mass content is 3%, Zn0.8Cd0.2S solid solution mass content is 86.8%, and ethylenediamine quality contains
Measure as 10.2%.
The MoS of embodiment 102/Zn0.6Cd0.4The preparation of S- ethylenediamine photocatalysts
(1) with the step of embodiment 1 (1)；
(2) Zn for obtaining 2g steps (1)0.6Cd0.4S- ethylenediamine hybridized nanometer pieces and 2ml 0.2M four thio ammonium molybdates
Aqueous solution, adds 50ml volumetric concentrations to be in 10% ethanol water, to be uniformly dispersed, and is passed through the oxygen that high-purity Ar gas is removed in solution
Gas, solution reacts 2h under the irradiation of 300W xenon lamps, and solid is centrifuged, uses distilled water wash, 60 DEG C of dryings to obtain MoS2/
Zn0.6Cd0.4S-- ethylenediamine photocatalysts.
MoS2/Zn0.6Cd0.4MoS in S- ethylenediamine photocatalysts2Mass content is 1.3%, Zn0.6Cd0.4S solid solution weights
Content is 74.9%, and ethylenediamine mass content is 23.8%.
It is demonstrated experimentally that the 0.2M four thio ammonium molybdates for substituting the present embodiment with 0.5M four thio ammonium molybdate aqueous solutions are water-soluble
Liquid, is to replace volumetric concentration in the present embodiment to be 10% ethanol water in 20% ethanol water with volumetric concentration, and other are same
The present embodiment, prepares MoS2/Zn0.6Cd0.4S- ethylenediamine photocatalysts, wherein MoS2Mass content is 3.3%, Zn0.6Cd0.4S
Solid solution mass content is 73.4%, and ethylenediamine mass content is 23.3%.
The WS of embodiment 112/Zn0.9Cd0.1The preparation of S- ethylenediamine photocatalysts
(1) with the step of embodiment 2 (1)；
(2) Zn for obtaining 3g steps (1)0.9Cd0.1S- ethylenediamine hybridized nanometer pieces and 3ml 0.4M tetrathio ammonium tungstates
Aqueous solution, adds 50ml volumetric concentrations to be in 20% ethanol water, to be uniformly dispersed, and is passed through the oxygen that high-purity Ar gas is removed in solution
Gas, solution reacts 3h under the irradiation of 300W xenon lamps, and solid is centrifuged, uses distilled water wash, 70 DEG C of dryings to obtain WS2/
Zn0.9Cd0.1S- ethylenediamine photocatalysts.
WS2/Zn0.9Cd0.1WS in S- ethylenediamine photocatalysts2Mass content is 5%, Zn0.9Cd0.1S solid solution mass contents
For 77.5%, ethylenediamine mass content is 17.5%.
It is demonstrated experimentally that the 0.4M tetrathio ammonium tungstates for substituting the present embodiment with 0.5M tetrathio ammonium tungstate aqueous solutions are water-soluble
Liquid, it is 20% ethanol water to replace the present embodiment volumetric concentration for 25% ethanol water with volumetric concentration, and other are with this reality
Example is applied, WS is prepared2/Zn0.9Cd0.1S- ethylenediamine photocatalysts, wherein WS2Mass content is 6%, Zn0.9Cd0.1S solid solution body constitution
Amount content is 76.7%, and ethylenediamine mass content is 17.3%.
The 0.4M tetrathio ammonium tungstate aqueous solutions of the present embodiment are substituted with 0.2M tetrathio ammonium tungstate aqueous solutions, 50ml bodies are used
It is 20% ethanol water that product concentration replaces the present embodiment 50ml volumetric concentrations for 10% ethanol water, and other are with this enforcement
Example, prepares WS2/Zn0.9Cd0.1S- ethylenediamine photocatalysts, wherein WS2Mass content is 2.5%, Zn0.9Cd0.1S solid solution body constitution
Amount content is 79.5%, and ethylenediamine mass content is 18%.
The MoS of embodiment 122/Zn0.8Cd0.2The preparation of S- ethylenediamine photocatalysts
(1) with the step of embodiment 3 (1)；
(2) Zn for obtaining 5g steps (1)0.8Cd0.2S- ethylenediamine hybridized nanometer pieces and 5ml 0.5M four thio ammonium molybdates
Aqueous solution, adds 50ml volumetric concentrations to be in 30% ethanol water, to be uniformly dispersed, and is passed through the oxygen that high-purity Ar gas is removed in solution
Gas, solution reacts 4h under the irradiation of 300W xenon lamps, and solid is centrifuged, uses distilled water wash, 80 DEG C of dryings to obtain MoS2/
Zn0.8Cd0.2S- ethylenediamine photocatalysts.
MoS2/Zn0.8Cd0.2MoS in S- ethylenediamine photocatalysts2Mass content is 2.5%, Zn0.8Cd0.2S solid solution weights
Content is 86.4%, and ethylenediamine mass content is 11.1%.
It is demonstrated experimentally that the 0.5M four thio ammonium molybdates for substituting the present embodiment with 0.2M four thio ammonium molybdate aqueous solutions are water-soluble
Liquid, with 15% ethanol water 30% ethanol water is replaced, other same the present embodiment, prepares MoS2/Zn0.8Cd0.2S- second
Diamidogen photocatalyst, wherein MoS2Mass content is 1%, Zn0.8Cd0.2S solid solution mass content is 87.7%, ethylenediamine quality
Content is 11.3%.
Hydrogen-producing speed is calculated with below equation：
Wherein：H2% (v/v) is the volume ratio by shared by hydrogen in the gas-phase product of chromatography；mcFor institute in course of reaction
The quality of photoactivation agent.
Each embodiment photocatalytic water hydrogen-producing speed (visible ray) situation is as shown in table 1.
Table 1
The foregoing is only preferred embodiments of the present invention, all impartial changes done according to scope of the present invention patent with
Modification, all belongs to the covering scope of the present invention.
Claims (9)
1. a kind of preparation method of the sulfur zinc cadmium-ethylenediamine photocatalyst of metal-modified, is characterized in that comprising the following steps：
(1) by cadmium acetate, zinc acetate and sulphur urine in molar ratio 1:(1.5-9):(8-30) ratio is mixed to get mixture, takes mixed
Compound 5-10g is added in 100ml ethylenediamines, and stirring obtains clear solution, and hydro-thermal 12-48h under the conditions of 180 DEG C -220 DEG C is cold
But to room temperature, centrifugation, solid distilled water wash, drying obtain ZnxCd1-xS- ethylenediamine hybridized nanometer pieces, the ZnxCd1-xS
For the molecular formula of sulfur zinc cadmium；
(2) by 1g：The ratio of 1ml, the Zn that step (1) is obtainedxCd1-xS- ethylenediamine hybridized nanometer pieces, are scattered in 0.2-0.5M
NiCl2Aqueous solution is scattered in 0.2-0.5M CoCl2Aqueous solution is scattered in that molar concentration is equal and concentration is for 0.2-0.5M's
NiCl2And CoCl2Mixed aqueous solution in, be uniformly dispersed, in 60-80 DEG C of evaporating water, Metal Ions Modification is obtained
ZnxCd1-xS- ethylenediamine hybridized nanometer pieces；
(3) Zn of the Metal Ions Modification for obtaining 2-5g steps (2)xCd1-xS- ethylenediamine hybridized nanometer pieces are dispersed in 50ml
In ionized water, it is 11-13 to add NaOH to adjust pH, is heated to 60-80 DEG C, adds 0.1-0.5g hydration hydrazine reaction 1-3h, reaction
Postprecipitation is centrifuged, and with distilled water wash, drying, obtains the sulfur zinc cadmium-ethylenediamine photocatalyst of metal-modified, the gold
The sulfur zinc cadmium-ethylenediamine photocatalyst of category modification is Ni/ZnxCd1-xS- ethylenediamines photocatalyst or Co/ZnxCd1-xS- ethylenediamines
Photocatalyst or NiCo/ZnxCd1-xS- ethylenediamine photocatalysts, wherein X=0.6-0.9.
2. claim 1 method prepare metal-modified sulfur zinc cadmium-ethylenediamine photocatalyst.
3. a kind of preparation method of the sulfur zinc cadmium-ethylenediamine photocatalyst of metal boride modification, is characterized in that including following step
Suddenly：
(1) by cadmium acetate, zinc acetate and sulphur urine in molar ratio 1:(1.5-9):(8-30) ratio is mixed to get mixture, takes mixed
Compound 5-10g is added in 100ml ethylenediamines, and stirring obtains clear solution, and hydro-thermal 12-48h under the conditions of 180 DEG C -220 DEG C is cold
But to room temperature, centrifugation, solid distilled water wash, drying obtain ZnxCd1-xS- ethylenediamine hybridized nanometer pieces, the ZnxCd1-xS
For the molecular formula of sulfur zinc cadmium；
(2) by 1g：The ratio of 1ml, the Zn that step (1) is obtainedxCd1-xS- ethylenediamine hybridized nanometer pieces are scattered in 0.2-0.5M
NiCl2Aqueous solution is scattered in 0.2-0.5M CoCl2Aqueous solution is scattered in that molar concentration is equal and concentration is for 0.2-0.5M's
NiCl2And CoCl2Mixed aqueous solution in, be uniformly dispersed, in 60-80 DEG C of evaporating water, Metal Ions Modification is obtained
ZnxCd1-xS- ethylenediamine hybridized nanometer pieces；
(3) Zn of the Metal Ions Modification for obtaining 2-5g steps (2)xCd1-xS- ethylenediamine hybridized nanometer pieces are dispersed in 50ml
In ionized water, it is 11-13 to add NaOH to adjust pH, is heated to 60-80 DEG C, adds 0.5-5ml 1M KBH4Reactant aqueous solution 1-
3h, reaction postprecipitation is centrifuged, and with distilled water wash, drying, obtains the sulfur zinc cadmium-ethylenediamine light of metal boride modification
Catalyst, the sulfur zinc cadmium-ethylenediamine photocatalyst of the metal boride modification is NiB/ZnxCd1-xS- ethylenediamines catalyst or
CoB/ZnxCd1-xS- ethylenediamines photocatalyst or NiCoB2/ZnxCd1-xS- ethylenediamine photocatalysts, wherein X=0.6-0.9.
4. the sulfur zinc cadmium-ethylenediamine photocatalyst of the metal boride modification that prepared by the method for claim 3.
5. a kind of preparation method of the sulfur zinc cadmium-ethylenediamine photocatalyst of metal phosphide modification, is characterized in that including following step
Suddenly：
(1) by cadmium acetate, zinc acetate and sulphur urine in molar ratio 1:(1.5-9):(8-30) ratio is mixed to get mixture, takes mixed
Compound 5-10g is added in 100ml ethylenediamines, and stirring obtains clear solution, and hydro-thermal 12-48 h, cold under the conditions of 180 DEG C -220 DEG C
But to room temperature, centrifugation, solid distilled water wash, drying obtain ZnxCd1-xS- ethylenediamine hybridized nanometer pieces, the ZnxCd1-xS
For the molecular formula of sulfur zinc cadmium；
(2) by 1g：The ratio of 1ml, the Zn that step (1) is obtainedxCd1-xS- ethylenediamine hybridized nanometer pieces, are scattered in 0.2-0.5M
NiCl2Aqueous solution is scattered in 0.2-0.5M CoCl2Aqueous solution is scattered in that molar concentration is equal and concentration is for 0.2-0.5M's
NiCl2And CoCl2Mixed aqueous solution in, be uniformly dispersed, in 60-80 DEG C of evaporating water, Metal Ions Modification is obtained
ZnxCd1-xS- ethylenediamine hybridized nanometer pieces；
(3) Zn of the Metal Ions Modification for obtaining 2-5g steps (2)xCd1-xS- ethylenediamine hybridized nanometer pieces are dispersed in 50ml
In ionized water, 0.5-5ml 1M NaH are added2PO2, it is 9-11 that NaOH adjusts pH, after being heated to 60-80 DEG C, adds 0.05-
0.2ml 1M KBH4Aqueous solution, reacts 1-3h, reacts postprecipitation centrifugation, is 5% ammonia by precipitation with volumetric concentration
Ni(OH)2Wash away, distillation is washed to neutrality, be dried, obtain the sulfur zinc cadmium-ethylenediamine photocatalyst of metal phosphide modification, institute
The sulfur zinc cadmium-ethylenediamine photocatalyst for stating metal phosphide modification is NiP/ZnxCd1-xS- ethylenediamines photocatalyst or CoP/
ZnxCd1-xS- ethylenediamines photocatalyst or NiCoP2/ZnxCd1-xS- ethylenediamine photocatalysts, wherein X=0.6-0.9.
6. the Zn of the metal phosphide modification that prepared by the method for claim 5xCd1-xS- ethylenediamine photocatalysts.
7. a kind of preparation method of the sulfur zinc cadmium-ethylenediamine photocatalyst of metal sulfide modification, is characterized in that including following step
Suddenly：
(1) by cadmium acetate, zinc acetate and sulphur urine in molar ratio 1:(1.5-9):(8-30) ratio is mixed to get mixture, takes mixed
Compound 5-10g is added in 100ml ethylenediamines, and stirring obtains clear solution, and hydro-thermal 12-48h under the conditions of 180 DEG C -220 DEG C is cold
But to room temperature, centrifugation, solid distilled water wash, drying obtain ZnxCd1-xS- ethylenediamine hybridized nanometer pieces, the ZnxCd1-xS
For the molecular formula of sulfur zinc cadmium；
(2) by 1g：The ratio of 1ml, the Zn that step (1) is obtainedxCd1-xS- ethylenediamine hybridized nanometer pieces and 0.2-0.5M tetrathios
Ammonium molybdate aqueous solution or tetrathio ammonium tungstate aqueous solution, add 50ml volumetric concentrations to be dispersion in 10%-30% ethanol waters
Uniformly, the oxygen that high-purity Ar gas is removed in solution is passed through, solution reacts 2-4h, solid Jing centrifugations point under the irradiation of 300W xenon lamps
From, use distilled water wash, 60-80 DEG C of drying obtains the sulfur zinc cadmium-ethylenediamine photocatalyst of metal sulfide modification, the gold
The sulfur zinc cadmium-ethylenediamine photocatalyst of category sulfide modification is MoS2/ZnxCd1-xS- ethylenediamines photocatalyst or WS2/ZnxCd1- xS- ethylenediamine photocatalysts, the X is 0.6-0.9.
8. the Zn of the metal sulfide modification that prepared by the method for claim 7xCd1-xS- ethylenediamine photocatalysts.
9. the photocatalyst described in claim 2,4,6 or 8 is in visible ray or the application of sunlight photocatalysis water decomposition hydrogen manufacturing.
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| CN108722444A (en) * | 2018-06-04 | 2018-11-02 | 台州学院 | Porous C u2-xSe photochemical catalysts and preparation method |
| CN109046391A (en) * | 2018-09-07 | 2018-12-21 | 青岛科技大学 | A kind of composite material and preparation method and the application in visible photocatalysis aquatic products hydrogen |
| CN113731447A (en) * | 2021-08-31 | 2021-12-03 | 陕西科技大学 | Composite nano Ni-CdS material and preparation method and application thereof |
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| US20140213427A1 (en) * | 2013-01-31 | 2014-07-31 | Sunpower Technologies Llc | Photocatalyst for the Reduction of Carbon Dioxide |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107572581A (en) * | 2017-08-07 | 2018-01-12 | 中国科学技术大学 | The preparation method of metal sulfide/amine hybrid nano-material and nano metal sulfide material |
| CN108722444A (en) * | 2018-06-04 | 2018-11-02 | 台州学院 | Porous C u2-xSe photochemical catalysts and preparation method |
| CN108722444B (en) * | 2018-06-04 | 2020-09-01 | 台州学院 | Porous Cu2-xSe photocatalyst and preparation method thereof |
| CN109046391A (en) * | 2018-09-07 | 2018-12-21 | 青岛科技大学 | A kind of composite material and preparation method and the application in visible photocatalysis aquatic products hydrogen |
| CN109046391B (en) * | 2018-09-07 | 2022-02-15 | 青岛科技大学 | Composite material, preparation method thereof and application thereof in hydrogen production through visible light decomposition of water |
| CN113731447A (en) * | 2021-08-31 | 2021-12-03 | 陕西科技大学 | Composite nano Ni-CdS material and preparation method and application thereof |
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