CN107349937A - A kind of preparation method of graphene-based bimetallic sulfide nano composite photo-catalyst - Google Patents
A kind of preparation method of graphene-based bimetallic sulfide nano composite photo-catalyst Download PDFInfo
- Publication number
- CN107349937A CN107349937A CN201710508676.5A CN201710508676A CN107349937A CN 107349937 A CN107349937 A CN 107349937A CN 201710508676 A CN201710508676 A CN 201710508676A CN 107349937 A CN107349937 A CN 107349937A
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- China
- Prior art keywords
- salt compound
- graphene
- bimetallic sulfide
- catalyst
- cadmium
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Links
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 46
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 42
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 27
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002131 composite material Substances 0.000 claims abstract description 40
- -1 salt compound Chemical class 0.000 claims abstract description 39
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 53
- 239000001257 hydrogen Substances 0.000 claims description 53
- 229910052739 hydrogen Inorganic materials 0.000 claims description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 238000004519 manufacturing process Methods 0.000 claims description 34
- 239000011259 mixed solution Substances 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 10
- 238000013019 agitation Methods 0.000 claims description 9
- 238000004090 dissolution Methods 0.000 claims description 8
- 239000003643 water by type Substances 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000004310 lactic acid Substances 0.000 claims description 5
- 235000014655 lactic acid Nutrition 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 230000003287 optical effect Effects 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 5
- 238000010926 purge Methods 0.000 claims description 5
- 230000004044 response Effects 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- 238000005406 washing Methods 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
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- LTUDISCZKZHRMJ-UHFFFAOYSA-N potassium;hydrate Chemical compound O.[K] LTUDISCZKZHRMJ-UHFFFAOYSA-N 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims 2
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 claims 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 229910000831 Steel Inorganic materials 0.000 claims 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims 1
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 claims 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims 1
- 239000011609 ammonium molybdate Substances 0.000 claims 1
- 235000018660 ammonium molybdate Nutrition 0.000 claims 1
- 229940010552 ammonium molybdate Drugs 0.000 claims 1
- DAPUDVOJPZKTSI-UHFFFAOYSA-L ammonium nickel sulfate Chemical compound [NH4+].[NH4+].[Ni+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DAPUDVOJPZKTSI-UHFFFAOYSA-L 0.000 claims 1
- 235000014121 butter Nutrition 0.000 claims 1
- 229910052793 cadmium Inorganic materials 0.000 claims 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims 1
- 229910000011 cadmium carbonate Inorganic materials 0.000 claims 1
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims 1
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 claims 1
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 claims 1
- 229910000331 cadmium sulfate Inorganic materials 0.000 claims 1
- GKDXQAKPHKQZSC-UHFFFAOYSA-L cadmium(2+);carbonate Chemical compound [Cd+2].[O-]C([O-])=O GKDXQAKPHKQZSC-UHFFFAOYSA-L 0.000 claims 1
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 claims 1
- 238000003421 catalytic decomposition reaction Methods 0.000 claims 1
- 239000008139 complexing agent Substances 0.000 claims 1
- DKUYEPUUXLQPPX-UHFFFAOYSA-N dibismuth;molybdenum;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mo].[Mo].[Bi+3].[Bi+3] DKUYEPUUXLQPPX-UHFFFAOYSA-N 0.000 claims 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims 1
- 229940043237 diethanolamine Drugs 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims 1
- 229940078494 nickel acetate Drugs 0.000 claims 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims 1
- DITXJPASYXFQAS-UHFFFAOYSA-N nickel;sulfamic acid Chemical compound [Ni].NS(O)(=O)=O DITXJPASYXFQAS-UHFFFAOYSA-N 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 239000011684 sodium molybdate Substances 0.000 claims 1
- 235000015393 sodium molybdate Nutrition 0.000 claims 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims 1
- 239000010959 steel Substances 0.000 claims 1
- 239000004246 zinc acetate Substances 0.000 claims 1
- 239000011787 zinc oxide Substances 0.000 claims 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims 1
- 229910000368 zinc sulfate Inorganic materials 0.000 claims 1
- 229960001763 zinc sulfate Drugs 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000035484 reaction time Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 38
- 230000001699 photocatalysis Effects 0.000 description 18
- 229910005914 NiSx Inorganic materials 0.000 description 16
- 230000003301 hydrolyzing effect Effects 0.000 description 15
- 239000011701 zinc Substances 0.000 description 15
- 230000003197 catalytic effect Effects 0.000 description 13
- 230000000694 effects Effects 0.000 description 13
- 238000007146 photocatalysis Methods 0.000 description 11
- 238000000354 decomposition reaction Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 239000004065 semiconductor Substances 0.000 description 8
- 229910052961 molybdenite Inorganic materials 0.000 description 7
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 7
- 239000003426 co-catalyst Substances 0.000 description 6
- 239000004005 microsphere Substances 0.000 description 6
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 6
- 238000002604 ultrasonography Methods 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000006303 photolysis reaction Methods 0.000 description 4
- 230000015843 photosynthesis, light reaction Effects 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
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- 206010013786 Dry skin Diseases 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
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- 238000001035 drying Methods 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000002060 nanoflake Substances 0.000 description 3
- 238000005580 one pot reaction Methods 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
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- 230000008878 coupling Effects 0.000 description 2
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- 230000007547 defect Effects 0.000 description 2
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- 239000006185 dispersion Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000031068 symbiosis, encompassing mutualism through parasitism Effects 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- OISMQLUZKQIKII-UHFFFAOYSA-L dichlorocadmium;hydrate Chemical compound O.[Cl-].[Cl-].[Cd+2] OISMQLUZKQIKII-UHFFFAOYSA-L 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 239000002090 nanochannel Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 235000007686 potassium Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- NASFKTWZWDYFER-UHFFFAOYSA-N sodium;hydrate Chemical compound O.[Na] NASFKTWZWDYFER-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- KHMOASUYFVRATF-UHFFFAOYSA-J tin(4+);tetrachloride;pentahydrate Chemical class O.O.O.O.O.Cl[Sn](Cl)(Cl)Cl KHMOASUYFVRATF-UHFFFAOYSA-J 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- JGPSMWXKRPZZRG-UHFFFAOYSA-N zinc;dinitrate;hexahydrate Chemical class O.O.O.O.O.O.[Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O JGPSMWXKRPZZRG-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
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- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- 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
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- 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
- B01J37/341—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 electric or magnetic fields, wave energy or particle radiation
- B01J37/343—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 electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- 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
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Abstract
The invention discloses a kind of preparation method of graphene-based bimetallic sulfide nano composite photo-catalyst, a series of graphene-based bimetallic sulfide composite photocatalyst synthesized by simple gentle one step hydro thermal method, by controlling hydrothermal temperature, reaction time, the content of graphene addition and metal salt compound in compound system to regulate and control the appearance and size size of bimetallic sulfide and the oriented growth in graphenic surface；In addition, preparation method technological operation of the present invention is simple, low in raw material price, it is adapted to scale industrial production.
Description
Technical field
The invention belongs to photocatalysis technology field, and in particular to a kind of bimetallic sulfide nanometer using graphene as carrier
Composite photo-catalyst and preparation method thereof and photocatalysis hydrolytic hydrogen production application.
Background technology
Environmental pollution and energy shortage turn into the severe challenge that 21 century human society faces.Therefore, one is developed
Kind is new, free of contamination, and economic regenerative resource has far reaching significance to human social.Hydrogen is one
Kind of ultra-clean secondary energy sources, have the advantages that energy density it is high, it is renewable, pollution-free, can store, can transport.In addition, hydrogen is made
For a kind of important industrial chemicals and industrial protection gas, be widely used in metallurgical industry, Minute Organic Synthesis, Aero-Space,
Petroleum chemical industry etc..And the source of Hydrogen Energy is mainly water-gas conversion, hydrocarbon cracking, water electrolysis hydrogen production etc. at present, these sides
Method consumes substantial amounts of non-renewable resources, and also creates pollution.The economy of Hydrogen Energy, green production turn into a kind of urgent
Technical need.From 1972, Japanese scholars Fujishima and Honda successfully utilized TiO2Water is catalytically decomposed light anode material
Into H2And O2Since, solar energy photocatalytic hydrogen production by water decomposition has turned into current most one of hydrogen producing technology of application prospect, has pole
Big social economic value.Therefore, it is current to greatly develop high-performance, low cost, green solar energy photocatalytic material
One of solar energy photocatalytic hydrogen production by water decomposition technical field key subject urgently to be resolved hurrily.In past nearly half a century, people
Have developed a variety of semiconductor lights such as oxide, sulfide, phosphide, halide and nitride with production hydrogen activity and urge
Change material.However, existing for these semi-conducting materials itself the defects of physicochemical properties, such as：Material forbidden band itself is wide
Spend larger, photo-generate electron-hole easy compound and catalyst is difficult to reclaim, cause conductor photocatalysis material catalyst difficult
Effectively to utilize sunshine and photocatalysis hydrolytic hydrogen production activity is not high, and then its reality in large-scale industrial production is limited
Using.Therefore, realize that the key of the large-scale industrial application of photocatalysis hydrolytic hydrogen production is to develop to obtain with high sunshine profit
With the novel photocatalyst of rate and bloom quantum conversion.
In numerous semiconductor catalysis materials, sulfide, particularly CdS, turn into the most commonly used photochemical catalyst of research.
Due to its narrower energy gap, under visible light illumination, CdS has higher hydrogen production activity.But it is in photolysis water hydrogen
Photoetch and automatic oxidation reaction phenomenon easily occur in course of reaction, and then causes the Activity and stabill of whole photocatalytic system
It is not high, it significantly limit the CdS application in light hydrolytic hydrogen production field.Hydrolyzed by furtheing investigate conductor photocatalysis material
The reaction mechanism of hydrogen manufacturing and the internal factor for influenceing catalytic activity, it has been found that a variety of effective ways solve above-mentioned limitation
The bottleneck problem that photocatalysis efficiency improves, including single ionic doping or codope, the semiconductors coupling based on band theory,
Surface sensitization and carried noble metal co-catalyst, the purpose is to build the compound semiconductor photocatalytic material with narrow band gap,
Efficiently separating and forming substantial amounts of chain carrier in catalyst surface for photoproduction life electron-hole pair is realized, it is final to improve
The photolysis water hydrogen catalytic activity of catalyst.However, comprehensive lot of documents report shows, the sulphur based on the synthesis of above-mentioned improved method
Compound semiconductor light-catalyst does not show significant photocatalytic hydrogen production by water decomposition activity.Further, since a large amount of noble metals help
Catalyst such as Pt, Au etc. use, the preparation cost of sulfide semiconductor photochemical catalyst is increased on the contrary, is unfavorable for scale chemical industry
Industry application.
Therefore, by multicomponent semiconductor nano material and graphene it is compound be improve photochemical catalyst visible region photocatalysis water
Solve one of available strategy of hydrogen manufacturing.This is due to that graphene not only has the performances such as more excellent conduction and heat conduction, its surface
Numerous oxy radicals and defect be present can not only bring many chemical active sites, also can provide positioning of anchor for metal ion
Point；In addition, graphene can play structural support and conductive channel effect in photochemical catalyst system, and then greatly improve light and urge
The directional separation and efficiency of transmission of photogenerated charge in change system.Finally, the big specific surface area of graphene and good stability is also
The efficiency of light absorption and service life of catalyst can be effectively improved.
The content of the invention
An object of the present invention is using the excellent two-dimensional material graphene of electric conductivity as substrate, is given birth in its surface in situ
Long bimetallic sulfide, and then construct graphene-based bimetallic sulfide nano composite photo-catalyst.By coupling graphene
Bigger serface and high conductivity, the high carrier mobility of the heterojunction material of different dimensions capture and absorbed energy with strong photon
Power, establishes the nanochannel of photo-generated carrier high-speed transfer, and then constructs new and effective photocatalytic system, realizes the system light
Raw separation of charge efficiency and visible region quantum efficiency significantly improve.
The second object of the present invention there is provided a kind of simple, gentle, efficient and suitable large-scale production graphene-based
Bimetallic sulfide nano composite photo-catalyst preparation method.Compared with existing graphene-based method for preparing catalyst, reaction temperature
Spend relatively low, the reaction time is short, and bimetallic sulfide is dispersed in graphenic surface and size is adjustable, whole building-up process
Green is controllable.In addition, the present invention replaces noble metal pt, Au etc. using cheap non-noble metal sulfided thing, urged being greatly lowered
While agent production cost, the photolysis water hydrogen catalytic activity of photochemical catalyst is also significantly increased.In addition, prepared by the present invention
Graphene-based bimetallic sulfide composite photocatalyst show excellent recycling performance, have potentially commercially melt
Hair prospect.
A kind of preparation method of graphene-based bimetallic sulfide nano composite photo-catalyst of the present invention, including following step
Suddenly：
Step 1, graphite oxide powder is prepared using modified Hummer's methods first, then weigh 0.1-1.0g's
Above-mentioned graphite oxide powder is distributed in water, and it is 1-10mg ﹒ mL to be configured to concentration-1Graphite oxide solution, pass through ultrasound peel off
Method prepares dispersed graphene oxide (GO) nanometer sheet suspension, wherein, ultrasonic power 100-800W, when ultrasonic
Between be 2-8h；
Step 2, by the metal salt presoma of bimetallic sulfide：Pink salt compound and cadmium salt compound (or molybdenum salt chemical combination
Thing and cadmium salt compound；Or nickel salt compound, zinc salt compound and cadmium salt compound) be added separately to according to certain mol ratio
In 60mL deionized waters；The GO aqueous solution for measuring 1-10mL again is added drop-wise in above-mentioned hybrid metal saline solution, and ultrasonic disperse is equal
It is even, form mixed solution A；Afterwards, 0-0.6mg monohydrate potassium, 0-0.8mg are separately added into above-mentioned mixed solution A
DEXTROSE ANHYDROUS, 0-1mg polyvinylpyrrolidone and 0-0.6mg cetyl trimethylammonium bromide, it is molten to form mixing
Liquid B；Finally, it is stand-by by mixed solution B magnetic agitation 6 hours at normal temperatures；
Wherein, the metal salt presoma cadmium salt compound of the bimetallic sulfide described in step 2 and pink salt compound
Molar ratio range is 6~1:3；The molar ratio range of molybdenum salt compound and cadmium salt compound is 0.01~0.3:1；Nickel salt chemical combination
The molar ratio range of thing, zinc salt compound and cadmium salt compound is 0.05~1:1:4.
Step 3, the Cys for weighing 1.0-8.0mmoL are added in the mixed solution B in step 2, ultrasonic dissolution,
Form mixed solution C and at normal temperatures magnetic agitation 1h；It is polytetrafluoroethylene (PTFE) that mixed solution C is transferred into 100mL liners afterwards
Stainless steel cauldron in, the hydro-thermal reaction 1-20h at 120-220 DEG C, question response terminate and reaction temperature naturally cool to room
Temperature, by obtained corresponding graphene-based bimetallic sulfide nano composite photo-catalyst in rotating speed on 4000r/min centrifuges
5min is centrifuged, and product is repeatedly washed with water and ethanol respectively, the product after centrifuge washing is separated is done at 60 DEG C
Dry 24h, finally give corresponding graphene-based bimetallic sulfide nano composite photo-catalyst.
Step 4, weigh the graphene-based bimetallic sulfide composite photocatalyst ultrasound point synthesized in 0.05g step 3
It is scattered in 50mL water, the organic acid or organic amine for adding 5-20mL purge 5min as hole sacrifice agent, nitrogen；With 300W's
Xenon lamp filters out ultraviolet light and extreme ultraviolet light of the wavelength less than 420nm as light source, while using optical filter, carries out visible ray and urges
Change hydrogen production by water decomposition reaction, hydrogen growing amount is detected using gas chromatograph.
Wherein, organic acid can be any one in lactic acid, malic acid or citric acid, and organic amine can be diethanol
Any one in amine, n-propanolamine or triethanolamine；And the addition of hole sacrifice agent and the volume range of water are 0.1
~0.5:1.
The present invention has advantages below compared with prior art：
(1) preparation method of graphene-based bimetallic sulfide nano composite photo-catalyst is easy and effective and with pervasive
Property.A series of graphene-based bimetallic sulfide composite photocatalyst is synthesized by simple gentle one step hydro thermal method, passed through
Control hydrothermal temperature, reaction time, the content of graphene addition and metal salt compound in compound system regulate and control
The appearance and size size of bimetallic sulfide and the oriented growth in graphenic surface；In addition, preparation method of the present invention
Technological operation is simple, low in raw material price, is adapted to scale industrial production；
(2) mentality of designing of graphene-based bimetallic sulfide nano composite photo-catalyst is rationally novel.The present invention combines
The study hotspot and difficulties of current photocatalysis hydrolytic hydrogen production, from band theory, using crystallographic theory as
Point of penetration, led to using the GO with bigger serface and high conductivity and rich in oxygen-containing functional group as conductive substrates and electric transmission
Road, dispersed bimetallic sulfide composite photocatalyst is grown in its surface anchoring.Light caused by light absorbs activated centre
Excite electronics to turn finally to move on to electron acceptor through electron propagation ducts graphene, realize the space point of photo-generate electron-hole pair
From and transfer, to greatest extent improve composite catalyst light hydrolytic hydrogen production activity；In addition, strategy restriction metal sulfide
Reunion during the course of the reaction and photoetch phenomenon, it is ensured that the Stability Analysis of Structures of graphene-based bimetallic sulfide composite photocatalyst
Property and efficient catalytic cycle activity；
(3) by introducing a small amount of non-noble metal sulfided thing (such as：Sn2S3, NiS, Ni3S4, Ni7S6, MoS2With ZnS etc.) take
The precious metals pt, Au etc. that generation is commonly used is used as co-catalyst, not only increases the photocatalysis performance of catalyst, to a certain extent greatly
The big preparation cost for having saved catalyst, is advantageous to the series of products and realizes scale photolysis water hydrogen practical application.
Brief description of the drawings
Fig. 1 (a) is Sn prepared by the present invention2S3The SEM figures of-CdS/rGO composite Nano thin slice photochemical catalysts；
Fig. 1 (b) is Sn prepared by the present invention2S3The TEM figures of-CdS/rGO composite Nano thin slice photochemical catalysts；
Fig. 2 is pure Sn prepared by hydro-thermal method of the present invention2S3, pure CdS and Sn2S3- CdS/rGO composite Nano thin slice photocatalysis
The XRD of agent；
Fig. 3 (a) is the visible ray hydrolytic hydrogen production rate diagram (λ that hydro-thermal method of the present invention prepares catalyst sample>420nm)；
Fig. 3 (b) is Sn prepared by the present invention2S3- CdS/rGO composite Nano thin slice visible rays hydrolytic hydrogen production circulation activity figure
(λ>420nm)；
Fig. 4 (a) is NiSx/Cd prepared by the present invention0.8Zn0.2The SEM figures of S/rGO composite Nano thin slices；
Fig. 4 (b) is NiSx/Cd prepared by the present invention0.8Zn0.2The TEM figures of S/rGO composite Nano thin slices；
Fig. 5 (a) is the XRD of NiSx/rGO samples prepared by hydro-thermal method of the present invention；
Fig. 5 (b) is NiSx/Cd prepared by hydro-thermal method of the present invention0.8Zn0.2The XRD of S/rGO samples；
Fig. 5 (c) is Cd prepared by hydro-thermal method of the present invention0.8Zn0.2S sample XRDs；
Fig. 6 (a) is the visible ray hydrolytic hydrogen production rate diagram (λ that hydro-thermal method of the present invention prepares catalyst sample>420nm)；
Fig. 6 (b) is NiSx/Cd prepared by the present invention0.8Zn0.2S/rGO composite Nano thin slice visible rays hydrolytic hydrogen production circulates
Activity figure (λ>420nm)；
Fig. 7 (a) is MoS prepared by the present invention2The SEM figures of/CdS/rGO composite Nano foil catalysts；
Fig. 7 (b) is MoS prepared by the present invention2The TEM figures of/CdS/rGO composite Nano foil catalysts；
Fig. 8 (a) is MoS prepared by hydro-thermal method of the present invention2The XRD of/CdS/rGO samples；
Fig. 8 (b) is the XRD of pure CdS samples prepared by hydro-thermal method of the present invention；
Fig. 8 (c) is pure MoS prepared by hydro-thermal method of the present invention2Sample XRD；
Fig. 9 (a) is the visible ray hydrolytic hydrogen production activity figure (λ that hydro-thermal method of the present invention prepares catalyst sample>420nm)；
Fig. 9 (b) is MoS prepared by the present invention2/ CdS/rGO composite Nano thin slice visible rays hydrolytic hydrogen production circulation activity figure
(λ>420nm).
Embodiment
The system of graphene-based bimetallic sulfide nano composite photo-catalyst is further described below by embodiment
Preparation Method.But the scope that this should not be interpreted as to the above-mentioned theme of the present invention is only limitted to following embodiment, all based on the present invention
The technology that the above is realized belongs to the scope of the present invention.
Embodiment 1
(1) the graphite oxide powder ultrasonic for weighing 60mg dryings is dispersed in 20mL deionized waters, uses power as 800W
Ultrasonic Cell Disruptor ultrasound 4h, be made concentration be 3mg ﹒ mL-1Graphene oxide water solution；
(2) weigh respectively 0.2g glucose, 0.11g Tin tetrachloride pentahydrates and the chloride hydrate cadmiums of 0.24g 2.5 be placed in it is clean
In net 100mL small beakers, then add thereto in 60mL deionized waters, ultrasonic dissolution, form mixed solution A；Afterwards, upwards
State and 4mL 3mg ﹒ mL are added in mixed solution A-1Graphene oxide water solution, magnetic agitation 4h under normal temperature, form mixed solution
B；
(3) Cys for weighing 0.56g are added in above-mentioned mixed solution B, ultrasonic dissolution, form mixed solution
C and at normal temperatures magnetic agitation 1h；Mixed solution C is transferred to the stainless steel reaction that 100mL liners are polytetrafluoroethylene (PTFE) afterwards
In kettle, the hydro-thermal reaction 2h at 180 DEG C.Question response is terminated and reaction temperature naturally cools to room temperature, and obtained sediment is existed
Rotating speed is to centrifuge 5min on 4000r/min centrifuges, and product is repeatedly washed with water and ethanol respectively, by centrifuge washing
Product after separation dries 24h at 60 DEG C, finally gives Sn2S3- CdS/rGO composite Nano thin slice photochemical catalysts；
(4) Sn of synthesis in 0.05g steps (3) is weighed2S3- CdS/rGO composite Nano thin slice photochemical catalysts ultrasonic disperse is extremely
In 50mL water, then it is separately added into above-mentioned suspension 5mL lactic acid and Pt that mass fraction is 3.0% is as hole sacrifice agent
And co-catalyst；Nitrogen purges 5min, using 300W xenon lamp as light source, while filters out wavelength using optical filter and is less than
420nm ultraviolet light and extreme ultraviolet light, visible light catalytic hydrogen production by water decomposition reaction is carried out, using gas chromatograph detection hydrogen life
Cheng Liang.
" island " Sn of Fig. 1 display synthesis2S3- CdS symbiosis nanocrystals are dispersed in redox graphene (rGO)
Nano flake surface, Sn2S3The size of-CdS symbiosis nanocrystals is between 16.7nm to 27.8nm.
Height of specimen crystallization prepared by the display of Fig. 2 XRD spectrums, and the CdS synthesized is hexagonal crystal phase, and Sn2S3For iris
Phase.In addition, the figure further shows that successfully synthesizes Sn by simple one pot of hydro-thermal method2S3- CdS/rGO composite Nanos are thin
Piece photochemical catalyst.
Fig. 3 a show：With pure Sn2S3、Sn2S3/ rGO and CdS/rGO composite nano materials are compared, the Sn of synthesis2S3-
CdS/rGO composite Nano thin slice photochemical catalysts have highest visible light catalytic hydrogen production by water decomposition ability, it is seen that light irradiation 6h, its
Hydrogen output is up to 994.4 μm of olg-1.In addition, Sn can be seen that by Fig. 3 b2S3- CdS/rGO composite Nanos thin slice, which has, to be continued
Increased hydrogen manufacturing circulation activity, it is seen that light irradiation 60h, its hydrogen-producing speed are still up to 1671 μm of olh-1·g-1, show Sn2S3-
CdS/rGO composite Nano thin slices have excellent visible light catalytic hydrolytic hydrogen production performance and high stability.
Embodiment 2
(1) the graphite oxide powder ultrasonic for weighing 60mg dryings is dispersed in 20mL deionized waters, uses power as 520W
Ultrasonic Cell Disruptor ultrasound 6h, be made concentration be 3mg ﹒ mL-1Graphene oxide water solution；
(2) 0.2g glucose, 0.01g Nickelous nitrate hexahydrates, 0.06g zinc nitrate hexahydrates and 0.18g 2.5 are weighed respectively
Chloride hydrate cadmium is placed in the 100mL small beakers of cleaning, then is added thereto in 60mL deionized waters, ultrasonic dissolution, is formed mixed
Close solution A；Afterwards, 5mL 3mg ﹒ mL are added into above-mentioned mixed solution A-1Graphene oxide water solution, magnetic force stirs under normal temperature
6h is mixed, forms mixed solution B；
(3) Cys for weighing 0.54g are added in above-mentioned mixed solution B, ultrasonic dissolution, form mixed solution
C and at normal temperatures magnetic agitation 1h；Mixed solution C is transferred to the stainless steel reaction that 100mL liners are polytetrafluoroethylene (PTFE) afterwards
In kettle, the hydro-thermal reaction 2h at 160 DEG C.Question response is terminated and reaction temperature naturally cools to room temperature, and obtained sediment is existed
Rotating speed is to centrifuge 5min on 4000r/min centrifuges, and product is repeatedly washed with water and ethanol respectively, by centrifuge washing
Product after separation dries 24h at 60 DEG C, finally gives NiSx/Cd0.8Zn0.2S/rGO composite Nano thin slice photochemical catalysts；
(4) NiSx/Cd of synthesis in 0.05g steps (3) is weighed0.8Zn0.2S/rGO composite Nano thin slices photochemical catalyst ultrasound
It is dispersed in 50mL water, then 5mL lactic acid is separately added into as hole sacrifice agent into above-mentioned suspension；Nitrogen purges 5min,
Ultraviolet light and extreme ultraviolet light of the wavelength less than 420nm are filtered out using 300W xenon lamp as light source, while using optical filter, is carried out
Visible light catalytic hydrogen production by water decomposition is reacted, and hydrogen growing amount is detected using gas chromatograph.
The zero dimension NiSx/Cd of Fig. 4 display synthesis0.8Zn0.2S composite nano-microspheres are firmly anchored on redox graphene
(rGO) nano flake surface, NiSx/Cd0.8Zn0.2S composite nano-microspheres size uniformity and good dispersion, Microsphere Size size exist
Between 30nm to 60nm.
Height of specimen crystallization prepared by the display of Fig. 5 XRD spectrums, and the Cd synthesized0.8Zn0.2S is hexagonal crystal phase, and NiSx bags
Containing a cube crystalline phase Ni3S4With iris phase Ni7S6.Successfully closed by simple one pot of hydro-thermal method in addition, the figure further shows that
Into ternary NiSx/Cd0.8Zn0.2S/rGO composite Nano thin slice photochemical catalysts.
Fig. 6 shows：With pure NiSx, Cd0.8Zn0.2S, NiSx/rGO and Cd0.8Zn0.2S/rGO compares, NiSx/
Cd0.8Zn0.2S/rGO composite Nano thin slice photochemical catalysts have highest visible light catalytic hydrogen production by water decomposition ability, it is seen that illumination
5h is penetrated, its hydrogen-producing speed is up to 7.84mmolh-1·g-1, hence it is evident that higher than Cd0.8Zn0.2The hydrogen-producing speed of S/rGO+Pt catalyst
(5.84mmol·h-1·g-1), show that co-catalyst NiSx can substitute precious metals pt completely.Meanwhile NiSx/Cd0.8Zn0.2S/
RGO composite Nano thin slices photochemical catalyst has stable visible light catalytic hydrolytic hydrogen production performance, it is seen that light irradiation 25h, hydrogen output
Still it is up to 36.79mmolg-1。
Embodiment 3
(1) the graphite oxide powder ultrasonic for weighing 60mg dryings is dispersed in 20mL deionized waters, uses power as 520W
Ultrasonic Cell Disruptor ultrasound 6h, be made concentration be 3mg ﹒ mL-1Graphene oxide water solution；
(2) weigh respectively 0.2g glucose, 0.2g monohydrate potassiums, 0.2g cetyl trimethylammonium bromides,
The molybdic acid hydrate sodium of 0.072g bis- and the chloride hydrate cadmiums of 0.46g 2.5 are placed in the 100mL small beakers of cleaning, then are added thereto
In 60mL deionized waters, ultrasonic dissolution, mixed solution A is formed；Afterwards, 3mL 3mg ﹒ mL are added into above-mentioned mixed solution A-1's
Graphene oxide water solution, magnetic agitation 4h under normal temperature, form mixed solution B；
(3) Cys for weighing 0.54g are added in above-mentioned mixed solution B, ultrasonic dissolution, form mixed solution
C and at normal temperatures magnetic agitation 1h；Mixed solution C is transferred to the stainless steel reaction that 100mL liners are polytetrafluoroethylene (PTFE) afterwards
In kettle, the hydro-thermal reaction 12h at 200 DEG C.Question response is terminated and reaction temperature naturally cools to room temperature, and obtained sediment is existed
Rotating speed is to centrifuge 5min on 4000r/min centrifuges, and product is repeatedly washed with water and ethanol respectively, by centrifuge washing
Product after separation dries 24h at 60 DEG C, finally gives MoS2/ CdS/rGO composite Nano thin slice photochemical catalysts；
(4) MoS of synthesis in 0.05g steps (3) is weighed2/ CdS/rGO composite Nano thin slice photochemical catalysts ultrasonic disperse is extremely
In 50mL water, then 5mL lactic acid is separately added into as hole sacrifice agent and co-catalyst into above-mentioned suspension；Nitrogen purges
5min, ultraviolet light and far ultraviolet of the wavelength less than 420nm are filtered out using 300W xenon lamp as light source, while using optical filter
Light, visible light catalytic hydrogen production by water decomposition reaction is carried out, hydrogen growing amount is detected using gas chromatograph.
The zero dimension MoS of Fig. 7 display synthesis2/ CdS composite nano-microspheres are firmly anchored on redox graphene (rGO)
Nano flake surface, MoS2/ CdS composite nano-microspheres size uniformity and good dispersion, Microsphere Size size arrive in 125nm
Between 235nm.
Height of specimen crystallization prepared by the display of Fig. 8 XRD spectrums, and the CdS synthesized is cube crystalline phase, and co-catalyst MoS2
For iris phase.In addition, the figure further shows that successfully synthesizes ternary MoS by simple one pot of hydro-thermal method2/CdS/
RGO composite Nano thin slice photochemical catalysts.
Fig. 9 shows：With pure MoS2, CdS compare, MoS2/ CdS/rGO composite Nano thin slice photochemical catalysts have highest
Visible light catalytic hydrogen production by water decomposition ability, it is seen that light irradiation 5h, its hydrogen output are up to 8.1mmolg-1.Meanwhile MoS2/CdS/
RGO composite Nano thin slices photochemical catalyst has stable visible light catalytic hydrolytic hydrogen production performance, it is seen that light irradiation 30h, hydrogen output
Still it is up to 7.7mmolg-1。
Claims (5)
- A kind of 1. preparation method of graphene-based bimetallic sulfide nano composite photo-catalyst, it is characterised in that preparation process It is as follows：(1) graphite oxide powder is prepared using modified Hummer's methods first, then weighs 0.1-1.0g above-mentioned oxidation Powdered graphite is distributed in water, and it is 1-10mgmL to be configured to concentration-1Graphite oxide solution, prepared by ultrasonic stripping means Dispersed graphene oxide (GO) nanometer sheet suspension, wherein, ultrasonic power 100-800W, ultrasonic time 2- 8h；(2) by the metal salt presoma of bimetallic sulfide：Pink salt compound and cadmium salt compound；Or molybdenum salt compound and cadmium salt Compound；Or nickel salt compound, zinc salt compound and cadmium salt compound are added separately in 60mL deionized waters according to mol ratio； The GO aqueous solution for measuring 1-10mL again is added drop-wise in above-mentioned hybrid metal saline solution, and ultrasonic disperse is uniform, forms mixed solution A；Afterwards, 0-0.6mg monohydrate potassium, 0-0.8mg DEXTROSE ANHYDROUS, 0- are separately added into above-mentioned mixed solution A 1mg polyvinylpyrrolidone and 0-0.6mg cetyl trimethylammonium bromide, form mixed solution B；Finally, will mix Solution B magnetic agitation 6 hours at normal temperatures, it is stand-by；(3) Cys for weighing 1.0-8.0mmoL are added in the mixed solution B in step (2), ultrasonic dissolution, are formed mixed Close solution C and at normal temperatures magnetic agitation 1h；Mixed solution C is transferred to 100mL liners as the stainless of polytetrafluoroethylene (PTFE) afterwards In steel reactor, the hydro-thermal reaction 1-20h at 120-220 DEG C, question response terminates and reaction temperature naturally cools to room temperature, will To corresponding graphene-based bimetallic sulfide nano composite photo-catalyst rotating speed be 4000r/min centrifuges on centrifuge 5min, and product is repeatedly washed with water and ethanol respectively, the product after centrifuge washing is separated is dried at 60 DEG C 24h, finally give corresponding graphene-based bimetallic sulfide nano composite photo-catalyst；(4) the middle graphene-based bimetallic sulfide composite photocatalyst ultrasonic disperse synthesized of 0.05g steps (3) is weighed to 50mL In water, the organic acid or organic amine that add 5-20mL purge 5min as hole sacrifice agent, nitrogen；Using 300W xenon lamp as Light source, while ultraviolet light and extreme ultraviolet light of the wavelength less than 420nm are filtered out using optical filter, carry out visible light catalytic decomposition water Hydrogen production reaction, hydrogen growing amount is detected using gas chromatograph.
- 2. a kind of preparation method of graphene-based bimetallic sulfide nano composite photo-catalyst according to claim 1, Characterized in that, in step (2), complexing agent 0-0.6mg monohydrate potassium, 0-0.8mg DEXTROSE ANHYDROUS, 0- are added 1mg polyvinylpyrrolidone and 0-0.6mg cetyl trimethylammonium bromide, and then influence the structure of bimetallic sulfide Size and oriented growth.
- 3. a kind of preparation method of graphene-based bimetallic sulfide nano composite photo-catalyst according to claim 1, Characterized in that, in step (2), the metal salt presoma pink salt compound of metal sulfide is tin ash, stannous oxide Or the one or more in butter of tin；Cadmium salt compound is cadmium sulfate, caddy, cadmium carbonate, cadmium oxide, cadmium nitrate or acetic acid One or more in cadmium；Molybdenum salt compound be ammonium molybdate, bismuth molybdate, ammonium heptamolybdate, potassium molybdate or sodium molybdate in one kind or It is a variety of；Nickel salt compound is the one or more in nickel chloride, nickel nitrate, nickel acetate, ammonium nickel sulfate or nickel sulfamic acid；Zinc salt Compound is the one or more in zinc oxide, zinc sulfate, zinc acetate or zinc nitrate.
- 4. a kind of preparation method of graphene-based bimetallic sulfide nano composite photo-catalyst according to claim 3, Characterized in that, in step (2), the metal salt presoma cadmium salt compound of bimetallic sulfide and mole of pink salt compound Than for 6~1:3；The mol ratio of molybdenum salt compound and cadmium salt compound is 0.01~0.3:1；Nickel salt compound, zinc salt compound Mol ratio with cadmium salt compound is 0.05~1:1:4.
- 5. a kind of preparation method of graphene-based bimetallic sulfide nano composite photo-catalyst according to claim 1, Characterized in that, in step (4), choose organic acid or organic amine as hole sacrifice agent, wherein, organic acid can for lactic acid, Any one in malic acid or citric acid, and organic amine can be any in diethanol amine, n-propanolamine or triethanolamine It is a kind of；And the addition of hole sacrifice agent and the volume range of water are 0.1~0.5:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710508676.5A CN107349937B (en) | 2017-06-28 | 2017-06-28 | Preparation method of graphene-based bimetallic sulfide nano composite photocatalyst |
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| CN108069390A (en) * | 2017-12-11 | 2018-05-25 | 河南师范大学 | The method that zinc sulphide photochemical catalyst photocatalysis lactic acid aqueous solution prepares hydrogen |
| CN108288693A (en) * | 2017-12-22 | 2018-07-17 | 天津师范大学 | A kind of anode material of lithium-ion battery zinc-tin bimetallic sulfide and the preparation method and application thereof |
| CN108686681A (en) * | 2018-05-14 | 2018-10-23 | 南昌航空大学 | A kind of graphene/ZnS-MoS with visible light catalysis activity2Nano Solid Solution photochemical catalyst |
| CN109659544A (en) * | 2018-12-24 | 2019-04-19 | 肇庆市华师大光电产业研究院 | A kind of lithium/anode material of lithium-ion battery preparation method of graphene coated bimetallic sulfide |
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| CN108288693A (en) * | 2017-12-22 | 2018-07-17 | 天津师范大学 | A kind of anode material of lithium-ion battery zinc-tin bimetallic sulfide and the preparation method and application thereof |
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