CN106622318B - It is a kind of using bimetal nano particles as lamellar composite photochemical catalyst of hetero-junctions and preparation method thereof - Google Patents
It is a kind of using bimetal nano particles as lamellar composite photochemical catalyst of hetero-junctions and preparation method thereof Download PDFInfo
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- CN106622318B CN106622318B CN201610980539.7A CN201610980539A CN106622318B CN 106622318 B CN106622318 B CN 106622318B CN 201610980539 A CN201610980539 A CN 201610980539A CN 106622318 B CN106622318 B CN 106622318B
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- 239000002105 nanoparticle Substances 0.000 title claims abstract description 75
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 239000003054 catalyst Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 54
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 54
- 239000011941 photocatalyst Substances 0.000 claims abstract description 53
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 51
- 230000000694 effects Effects 0.000 claims abstract description 28
- 230000001699 photocatalysis Effects 0.000 claims abstract description 21
- 239000010936 titanium Substances 0.000 claims abstract description 19
- 239000011230 binding agent Substances 0.000 claims abstract description 15
- 229910003081 TiO2−x Inorganic materials 0.000 claims abstract description 10
- 230000003647 oxidation Effects 0.000 claims abstract description 10
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 10
- 239000011347 resin Substances 0.000 claims abstract description 9
- 229920005989 resin Polymers 0.000 claims abstract description 9
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920000557 Nafion® Polymers 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 229910001868 water Inorganic materials 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 25
- 229910009819 Ti3C2 Inorganic materials 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
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- 229910017053 inorganic salt Inorganic materials 0.000 claims description 4
- 239000002082 metal nanoparticle Substances 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- 229920003169 water-soluble polymer Polymers 0.000 claims description 4
- 235000007164 Oryza sativa Nutrition 0.000 claims description 3
- 239000011258 core-shell material Substances 0.000 claims description 3
- 239000008246 gaseous mixture Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 235000009566 rice Nutrition 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- ZVUZTTDXWACDHD-UHFFFAOYSA-N gold(3+);trinitrate Chemical compound [Au+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O ZVUZTTDXWACDHD-UHFFFAOYSA-N 0.000 claims 1
- 229920002521 macromolecule Polymers 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- 238000000354 decomposition reaction Methods 0.000 abstract description 15
- 238000007146 photocatalysis Methods 0.000 abstract description 12
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 29
- 239000000463 material Substances 0.000 description 22
- 238000004519 manufacturing process Methods 0.000 description 18
- 239000000047 product Substances 0.000 description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000004065 semiconductor Substances 0.000 description 11
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 10
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 9
- 239000013207 UiO-66 Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000011787 zinc oxide Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052793 cadmium Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- SFOQXWSZZPWNCL-UHFFFAOYSA-K bismuth;phosphate Chemical compound [Bi+3].[O-]P([O-])([O-])=O SFOQXWSZZPWNCL-UHFFFAOYSA-K 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 229910021389 graphene Inorganic materials 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 229910001961 silver nitrate Inorganic materials 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- QGUBTCKXCHGNIU-UHFFFAOYSA-N [BiH2][Sr] Chemical compound [BiH2][Sr] QGUBTCKXCHGNIU-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 150000001661 cadmium Chemical class 0.000 description 2
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
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- 239000003245 coal Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- 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
- B01J27/20—Carbon compounds
-
- 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
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- 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 kind of using bimetal nano particles as the lamellar composite photochemical catalyst of hetero-junctions, the composite photo-catalyst is formed by photocatalytic activity component and by the bimetal nano particles that binder is evenly distributed in photocatalyst activity component, and the photocatalyst activity group is divided into the titanium carbide Ti of layer structure3C2Or its oxidation product TiO2‑xCxThe binder is the Nafion perfluorinated resin solution of 0.1-5wt.%, it is preferred that 0.5wt.%, the weight percent of the bimetal nano particles and photocatalyst activity component is 0.01-10.0%, and the weight percent of binder and photocatalyst activity component is 0.01-5.0%.Compared with prior art, composite photo-catalyst of the invention more effectively using visible light and can inhibit the compound of light induced electron and hole, thus composite photo-catalyst of the present invention is applied to that photocatalysis Decomposition aquatic products hydrogen activity is high, stability is good.
Description
Technical field
The present invention relates to field, it is especially a kind of using bimetal nano particles as the lamellar composite photochemical catalyst of hetero-junctions and
Preparation method.
Background technique
At present since the deposit of traditional fossil energy is limited and more and more prominent, the people using their bring environmental problems
Be badly in need of finding new alternative energy source.Hydrogen Energy is had attracted much attention due to its high efficiency and spatter property.Scientists from all over the world competitively develop
Product relevant to Hydrogen Energy, nickel-metal hydride battery, the Related products such as hydrogen cell automobile just move towards society, hydrogen economy from laboratory
At hand.
Traditional hydrogen manufacturing mode is mainly the cracking generation hydrogen for passing through coal, petroleum, natural gas；Or pass through electrolysis water system
Obtain hydrogen；Due to consuming a large amount of fossil fuel during prepared by hydrogen, and cause Regional Environmental Pollution and the whole world
Warm, so developing the clean hydrogen manufacturing approach of green becomes one of the target of hydrogen energy source exploitation.Solar energy and water are the earth
Upper two kinds of important reproducibility resources, it is most clean hydrogen manufacturing approach that hydrogen is prepared using decomposing water with solar energy, is always
The dream of human development Hydrogen Energy.Therefore, the research of novel photocatalyst is following developing direction.
It using cadmium metal is dyskaryosis structure as the compound of shell that China Patent Publication No. CN102641741A, which is disclosed a kind of,
Photochemical catalyst and preparation method.The composite photocatalyst is using cadmium metal as core, semiconductor heterostructure zinc oxide and cadmium sulfide
For shell, the shared molar ratio of cadmium metal is in 50%-90%, and molar ratio shared by zinc oxide is 5%, molar ratio shared by cadmium sulfide
Example is 5%-45%；Semiconductor heterostructure zinc oxide and cadmium sulfide are shell, refer to that surface is that cadmium sulfide inlays zinc oxide
The shell of grain, cadmium sulfide shell with a thickness of 5-50nm, Zinc oxide particles size is 3-50nm；Preparation method will contain cadmium ion forerunner
Body dissolves in deionized water, is then added under the conditions of zinc powder ultrasound and magnetic agitation, and cadmium ion replaces metallic zinc；After washing,
Vulcanization saline solution vulcanizing treatment is added, or uses hydrogen sulfide gas vulcanizing treatment after drying, obtaining product is to be with cadmium metal
Core, semiconductor heterostructure zinc oxide and cadmium sulfide are the composite photocatalyst of shell.The composite photocatalyst is urged for light
Change hydrogen production by water decomposition, hydrogen-producing speed with higher.
China Patent Publication No. CN103316693A disclose a kind of Cd containing cocatalyst photochemical catalyst Cd/CdS and
It is prepared.The photochemical catalyst is by 3CdSO4·8H2O and Na2S2O3·5H2O is dissolved in distilled water, and stirring, ultrasound make it sufficiently
Dispersion, then 10-25h is reacted under the xenon lamp of 350-500W；Then in the microwave ingle 5-25min of 500-800W, centrifugation is washed
Solid precipitating is washed, is dried, grinding obtains photochemical catalyst Cd/CdS, applies in Photocatalyzed Hydrogen Production reaction.
China Patent Publication No. CN101623644A discloses a kind of composite hollow ball CdS-TiO2Preparation and urged in light
Change the application in hydrogen production by water decomposition.The photochemical catalyst preparation method utilizes Cd (NO3)2·4H2O is cadmium source and TiCl4For titanium source according to
It is secondary use hydro-thermal method, two step infusion processes, sol-gal process be made carbon core on be successively enclosed with cadmium sulfide and TiO2Core-shell structure
C-CdS-TiO2Then composite material obtains composite hollow ball CdS-TiO in 400 DEG C of roasting 2h in Muffle furnace2Photochemical catalyst,
The catalyst is by CdS and TiO2It is compound, widen TiO2Spectral response range is used for solar visible light catalytic decomposition water
In the reaction of hydrogen manufacturing, with TiO2Photochemical catalyst is compared, and the solar energy efficiency of light energy utilization increases considerably, and hydrogen-producing speed significantly improves.
China Patent Publication No. CN101623645 A discloses a kind of p-n junction hollow sphere NiO-CdS nanocomposite
Preparation and the application in photocatalytic hydrogen production by water decomposition.The preparation method of the nanocomposite is by Ni (NO3)2·6H2O makees
For nickel source and Cd (NO3)2·4H2O is as cadmium source, and using hydro-thermal synthetic method, four step infusion processes are by n-NiO semiconductor and p-CdS
Semiconductors coupling prepares a kind of p-n junction hollow sphere NiO-CdS composite nano materials, is catalyzed as solar visible light
The photochemical catalyst of hydrogen production by water decomposition accelerates the delivery rate of light induced electron, and hydrogen manufacturing yield is greatly improved.
China Patent Publication No. CN101767021 A discloses a kind of p-CoO/n-CdS composite semiconductor light-catalyst
Preparation method, the preparation method of the composite semiconductor light-catalyst are by ammonium salt, cadmium salt, thiocarbamide and deionized water hybrid reaction
Afterwards, it is filtered, washed, roasted and grinding obtains CdS solid powder；Again by cobalt salt, ammonium hydroxide and deionized water hybrid reaction, then plus
Enter CdS solid powder three times, agitated, ultrasonic disperse, vacuum distillation, heat treatment, washing, filtering, roasting and grinding obtain p-
CoO/n-CdS composite semiconductor light-catalyst, the composite semiconductor light-catalyst can be used for photocatalysis degradation organic contaminant, light
Water hydrogen manufacturing and manufacture solar battery is catalytically decomposed.
China Patent Publication No. CN102107904 A discloses a kind of non-template method and prepares that cadmium sulfide, zinc sulphide are hollow to be received
The method of rice square.This method is that inorganic cadmium source that molar ratio is 1:1 or inorganic zinc source and sulphur powder are added to tetrahydrofuran is molten
In liquid, ultrasonic disperse；Molar content sodium borohydride identical with sulphur powder is weighed again, is added in tetrahydrofuran solution, ultrasound point
It dissipates；Obtained solution is added drop-wise to be added in the solution that tetrahydrofuran solution forms by inorganic cadmium source and sulphur powder, ultrasonic reaction；Institute
Obtained reaction product is centrifugated with dehydrated alcohol；Vacuum drying, obtaining final yellow product, to be that cadmium sulfide is hollow receive
Rice square, it is hollow nanostructured to be conducive in photocatalysis Decomposition poisonous and harmful substances and photocatalytic hydrogen production by water decomposition reaction
Improve its photocatalysis performance.
China Patent Publication No. CN102489318 A discloses a kind of porous nano p-CuS/n-CdS composite semiconductor light
The preparation method of catalyst, this method is according to mantoquita, cadmium salt, sulfur-containing compound, sublimable compound template and deionized water
Mass percent be (0.001%-75%): (0.00001%-90%): (0.001%-85%): (0.001%-75%):
The ratio of (0.001%-98%), it is successively reacted, centrifuge separation, distillation water washing, ultrasonic disperse, centrifuge separation, ultrasound at
The processes such as reason, vacuum distillation, drying, roasting, natural cooling and grinding, obtain porous nano p-CuS/n-CdS composite semiconductor
Photochemical catalyst is applied to photocatalytic hydrogen production by water decomposition, photocatalysis degradation organic contaminant.
China Patent Publication No. CN103316714 A discloses a kind of photocatalytic hydrogen production by water decomposition catalyst and its preparation
Method.Photocatalytic hydrogen production by water decomposition catalyst CdS/UiO-66 or CdS/UiO-66 (NH2) it is by UiO-66 or UiO-66
(NH2) be combined with CdS, wherein the CdS and UiO-66 or UiO-66 (NH2) mass ratio be 100:1-100,
CdS/UiO-66 and CdS/UiO-66 (NH2) two kinds of In-situ reaction photochemical catalysts have very high hydrogen-producing speed, with simple CdS
It compares, hydrogen-producing speed significantly improves.
China Patent Publication No. CN103386317 A discloses a kind of bismuth phosphate combined oxidation graphene photo-catalyst
BiPO4/ RGO and its preparation method and application.The photochemical catalyst is bismuth phosphate BiPO4With the composite material of graphene oxide GO,
BiPO4With monoclinic form or hexagonal structure, GO is partially reduced during the preparation process, with the graphene oxide RGO shape of reduction
Formula exists；GO and BiPO4Theoretical Mass percentage be 0.5~10:100, the bismuth phosphate combined oxidation graphene photo-catalyst
BiPO4/ RGO is applied to photolysis water hydrogen.
China Patent Publication No. CN103447024 A disclose a kind of bismuthino strontium magnetic photocatalyst preparation method and its
Bismuthino strontium magnetic photocatalyst.The magnetic photocatalyst is with neopelex using bismuth nitrate and strontium ferrite as raw material
Dispersing agent first prepares the presoma of bismuthino strontium magnetic photocatalyst, then obtains bismuth through 55-65 DEG C of drying, 500-600 DEG C of roasting 3-5h
Base strontium magnetic photocatalyst, is used in the fields such as degradable organic pollutant, photocatalytic hydrogen production by water decomposition and solar battery.
Although these above-mentioned photochemical catalysts belong to composite photocatalyst, but these photochemical catalysts are respectively with traditional material
The composite photo-catalyst prepared based on material cadmium sulfide, bismuth phosphate or bismuth nitrate, wherein cadmium element and bismuth element are toxic to human body
Evil effect, it is a large amount of to use the pollution for be easy to causeing soil, water body environment.
Therefore, from the angle for avoiding environmental pollution, present invention employs the titanium carbide Ti of layer structure3C2Or
Its oxidation product TiO2-xCxOne kind is had developed as photocatalyst activity component and bimetal nano particles with bimetal nano
Particle is the lamellar composite photochemical catalyst of hetero-junctions.
Summary of the invention
The invention aims to provide it is a kind of using bimetal nano particles as the lamellar composite photochemical catalyst of hetero-junctions and
Any two kinds of metal nanoparticles in Pd, Au, Ag are obtained bimetallic by the mutual modulation of electronic structure by preparation method
Nanoparticle, then it is uniformly combined to catalysis material stratiform titanium carbide or its oxidation product surface and may be implemented using visible
The purpose of light progress light-catalyzed reaction.
In order to achieve the above objectives, the present invention is implemented according to following technical scheme: one kind is with bimetal nano particles
The lamellar composite photochemical catalyst of hetero-junctions, the composite photo-catalyst are uniformly distributed by photocatalytic activity component and by binder
Bimetal nano particles composition in photocatalyst activity component, the photocatalyst activity group are divided into the carbonization of layer structure
Titanium Ti3C2Or its oxidation product TiO2-xCx, the binder is the Nafion perfluorinated resin solution of 0.1-5wt.%, preferably
The weight percent of 0.5wt.%, the bimetal nano particles and photocatalyst activity component is 0.01-10.0%, binder
Weight percent with photocatalyst activity component is 0.01-5.0%.
Further, the titanium carbide Ti3C2Or its oxidation product TiO2-xCxMonolithic layer with a thickness of 1- in layer structure
400nm, preferably 1-100nm.
Preferably, the bimetal nano particles are Pd-Ag nanoparticle, Pd-Au nanoparticle and Au-Ag nanoparticle
At least one of son, the shape of bimetal nano particles are one of spherical, granular, vermiform and core-shell structure copolymer shape, this pair
The size of metal nanoparticle is 1-50nm, and preferred size size is in 1-20nm.
Preparation is using bimetal nano particles as the specific method of the lamellar composite photochemical catalyst of hetero-junctions, including following step
It is rapid:
Step 1: the water soluble polymer stabilizer is dissolved in deionized water, after dissolution is sufficiently stirred, then divide
The water-soluble metal inorganic salt solution for two kinds of metals that above-mentioned bimetal nano particles contain is not added, wherein stabilizing polymer
Agent: metal inorganic salt weight ratio is (1-10): 1, after adjustment pH value is 6-9 and is sufficiently mixed uniformly, recycle return stirring dress
The gaseous mixture for setting the hydrogen and argon gas that are 1% with hydrogen under the conditions of being kept for 80 DEG C restores 1-2h, then in 40 DEG C of water bath with thermostatic control
If still aging 4-24h in pot, obtains the solution containing bimetal nano particles；
Step 2: by the photocatalyst activity component and binder be added to that step 1 obtains containing bimetal nano
In the solution of particle, wherein bimetal nano particles and photocatalyst activity component in the solution containing bimetal nano particles
Weight percent is 0.01-10.0%, and the weight percent of binder and photocatalyst activity component is 0.01-5.0%, is carried out
Ultrasonic disperse 10-60min after being sufficiently mixed photocatalyst activity component and binder uniformly, is then carried out at 60-120 DEG C
It is dried in vacuo 8-48h, the lamellar composite photochemical catalyst using bimetal nano particles as hetero-junctions can be obtained.
Preferably, water soluble polymer stabilizer is methylcellulose, carboxymethyl cellulose, polyethylene in the step 1
At least one of pyrrolidones and polyacrylamide.
Preferably, the water-soluble metal inorganic salts for two kinds of metals that bimetal nano particles contain in the step 1 are two
Nitrate, acetate or the chloride of kind metal.
With it is existing for the composite photo-catalyst of photocatalysis Decomposition aquatic products hydrogen compared with, due to Pd, Au and Ag nanoparticle
Local surface plasma resonance effect can influence its luminous flux and conduction electronics, on the surface of metallic particles, conduct electronics
The high energy electron that chemical reaction is participated in compared with multipotency is produced through light irradiation, the property of bimetal nano particles is not original performance
The simple superposition of " 1+1 " formula, but possess new functional characteristic, any two kinds of metal nanoparticles in Pd, Au, Ag are passed through
The mutual modulation of electronic structure makes its photoelectric properties generate qualitative change, uses bimetal nano particles as photochemical catalyst hetero-junctions
With surface plasmon resonance effect and interface Schottky effect, can more effectively using visible light and inhibit light induced electron and
Compound, the raising photocatalysis efficiency in hole, then it is uniformly combined to catalysis material stratiform titanium carbide or oxidation product surface
It may be implemented to carry out light-catalyzed reaction using visible light, the raw material that the present invention uses is environmentally friendly material, obtained multiple
It is good that light combination catalyst is applied to photocatalysis Decomposition aquatic products hydrogen activity height, stability.
Detailed description of the invention
Fig. 1 is stratiform Ti3C2The SEM photograph of material.
Fig. 2 is stratiform Ti3C2The TEM photo of material monolithic layer.
Fig. 3 is stratiform Ti3C2The XRD spectra of material.
Fig. 4 is stratiform TiO2-xCxThe SEM photograph of material.
Fig. 5 is using Pd-Ag bimetal nano particles as the stratiform Ti of hetero-junctions3C2The TEM of the monolithic layer of composite photo-catalyst
Photo.
Fig. 6 (a) is using Pd-Ag bimetal nano particles as the stratiform Ti of hetero-junctions3C2The monolithic layer of composite photo-catalyst
EDX spectrogram (a), Fig. 6 (b) are using Pd-Ag bimetal nano particles as the stratiform Ti of hetero-junctions3C2The monolithic of composite photo-catalyst
The STEM photo of layer.
Specific embodiment
The invention will be further described combined with specific embodiments below, in the illustrative examples and explanation of the invention
For explaining the present invention, but it is not as a limitation of the invention.
Embodiment 1
It weighs 15mg methylcellulose to be dissolved in 40mL deionized water, after dissolution is sufficiently stirred, then is separately added into containing for 2mL
The aqueous solution of chloraurate for being 2.4mg/mL containing Au of palladium nitrate aqueous solution and 3mL that Pd is 2mg/mL, adjustment pH value to 7.5, warp
After being sufficiently mixed uniformly, under the conditions of recycling return stirring device to be kept for 80 DEG C with hydrogen be 1% hydrogen and argon gas it is mixed
After closing gas reduction 1h, then the still aging 4h in 40 DEG C of thermostat water bath, obtain the molten of the bimetallic nanoparticle containing Pd-Au
Liquid；
In the obtained solution containing bimetal nano particles, 500mg stratiform Ti is added3C2With the 0.5wt.% perfluor of 2mL
Sulfonate resin solution carries out ultrasonic disperse 30min, after mixing them thoroughly uniformly, is then maintained at 80 DEG C and is dried in vacuo
For 24 hours, it can be obtained using Pd-Au bimetal nano particles as the stratiform Ti of hetero-junctions3C2Composite photo-catalyst A.
Embodiment 2
It weighs 10mg methylcellulose to be dissolved in 40mL deionized water, after dissolution is sufficiently stirred, then is separately added into containing for 1mL
The silver nitrate aqueous solution for being 2mg/mL containing Ag of palladium nitrate aqueous solution and 4mL that Pd is 2mg/mL adjusts pH value to 7.5, through filling
Point after mixing, under the conditions of recycling return stirring device to be kept for 80 DEG C with hydrogen be 1% hydrogen and argon gas it is mixed
After closing gas reduction 1h, then the still aging 4h in 40 DEG C of thermostat water bath, obtain the molten of the bimetallic nanoparticle containing Pd-Ag
Liquid；
In the obtained solution containing bimetal nano particles, 500mg stratiform Ti is added3C2With the 0.5wt.% perfluor of 2mL
Sulfonate resin solution carries out ultrasonic disperse 30min, after mixing them thoroughly uniformly, is then maintained at 80 DEG C and is dried in vacuo
For 24 hours, it can be obtained using Pd-Ag bimetal nano particles as the stratiform Ti of hetero-junctions3C2Composite photo-catalyst B.
Embodiment 3
It weighs 20mg methylcellulose to be dissolved in 40mL deionized water, after dissolution is sufficiently stirred, then is separately added into containing for 4mL
The silver nitrate aqueous solution for being 2mg/mL containing Ag of aqueous solution of chloraurate and 5mL that Au is 2.4mg/mL, adjustment pH value to 7.5, warp
After being sufficiently mixed uniformly, under the conditions of recycling return stirring device to be kept for 80 DEG C with hydrogen be 1% hydrogen and argon gas it is mixed
After closing gas reductase 12 h, then the still aging 4h in 40 DEG C of thermostat water bath, obtain the molten of the bimetallic nanoparticle containing Au-Ag
Liquid；
In the obtained solution containing bimetal nano particles, 500mg stratiform Ti is added3C2With the 0.5wt.% perfluor of 2mL
Sulfonate resin solution carries out ultrasonic disperse 30min, after mixing them thoroughly uniformly, is then maintained at 80 DEG C and is dried in vacuo
For 24 hours, it can be obtained using Au-Ag bimetal nano particles as the stratiform Ti of hetero-junctions3C2Composite photo-catalyst C.
Embodiment 4
It weighs 20mg methylcellulose to be dissolved in 40mL deionized water, after dissolution is sufficiently stirred, then is separately added into containing for 5mL
The aqueous solution of chloraurate for being 2.4mg/mL containing Au of palladium nitrate aqueous solution and 4mL that Pd is 2mg/mL, adjustment pH value to 7.5, warp
After being sufficiently mixed uniformly, under the conditions of recycling return stirring device to be kept for 80 DEG C with hydrogen be 1% hydrogen and argon gas it is mixed
After closing gas reductase 12 h, then the still aging 4h in 40 DEG C of thermostat water bath, obtain the molten of the bimetallic nanoparticle containing Pd-Au
Liquid；
In the obtained solution containing bimetal nano particles, 500mg stratiform TiO is added2-xCxWith the 0.5wt.% of 2mL
Perfluor sulfoacid resin solution carries out ultrasonic disperse 30min, after mixing them thoroughly uniformly, is then maintained at 80 DEG C of progress vacuum
Drying for 24 hours, can be obtained using Pd-Au bimetal nano particles as the stratiform TiO of hetero-junctions2-xCxComposite photo-catalyst D.
Embodiment 5
It weighs 20mg methylcellulose to be dissolved in 40mL deionized water, after dissolution is sufficiently stirred, then is separately added into containing for 4mL
The silver nitrate aqueous solution for being 2mg/mL containing Ag of aqueous solution of chloraurate and 5mL that Au is 2.4mg/mL, adjustment pH value to 7.5, warp
After being sufficiently mixed uniformly, the hydrogen and argon gas that are 1% with hydrogen under the conditions of being kept for 80 DEG C in return stirring device are recycled
After gaseous mixture reductase 12 h, then the still aging 4h in 40 DEG C of thermostat water baths, obtain the molten of the bimetallic nanoparticle containing Au-Ag
Liquid；
In the obtained solution containing bimetal nano particles, 500mg stratiform TiO is added2-xCxWith the 0.5wt.% of 2mL
Perfluor sulfoacid resin solution carries out ultrasonic disperse 30min, after mixing them thoroughly uniformly, is then maintained at 80 DEG C of progress vacuum
Drying for 24 hours, can be obtained using Au-Ag bimetal nano particles as the stratiform TiO of hetero-junctions2-xCxComposite photo-catalyst E.
Embodiment 6
It weighs 20mg methylcellulose to be dissolved in 40mL deionized water, after dissolution is sufficiently stirred, then is separately added into containing for 5mL
The silver nitrate aqueous solution for being 2mg/mL containing Ag of palladium nitrate aqueous solution and 5mL that Pd is 2mg/mL adjusts pH value to 7.5, through filling
Point after mixing, under the conditions of recycling return stirring device to be kept for 80 DEG C with hydrogen be 1% hydrogen and argon gas it is mixed
After closing gas reductase 12 h, then the still aging 4h in 40 DEG C of thermostat water bath, obtain the molten of the bimetallic nanoparticle containing Pd-Ag
Liquid；
In the obtained solution containing bimetal nano particles, 500mg stratiform TiO is added2-xCxWith the 0.5wt.% of 2mL
Perfluor sulfoacid resin solution carries out ultrasonic disperse 30min, after mixing them thoroughly uniformly, is then maintained at 80 DEG C of progress vacuum
Drying for 24 hours, can be obtained using Pd-Ag bimetal nano particles as the stratiform TiO of hetero-junctions2-xCxComposite photo-catalyst F.
Test experience:
Take Ti3C2Material obtains Ti under high power Scanning Electron microscope3C2The SEM photograph of material, as shown in Figure 1, Ti3C2
Material is shown as layer structure under high power Scanning Electron microscope, in layer structure monolithic layer with a thickness of be less than 100nm,
Take TiO2-xCxMaterial obtains TiO under high power Scanning Electron microscope2-xCxThe SEM photograph of material, as shown in figure 4, TiO2-xCx
Material is shown as layer structure under high power Scanning Electron microscope, in layer structure monolithic layer with a thickness of be less than 100nm；
Take stratiform Ti3C2The monolithic layer of material obtains stratiform Ti under high power transmission electron microscope3C2The TEM of the monolithic layer of material shines
Piece, as shown in Fig. 2, stratiform Ti3C2The monolithic layer of material is shown as flaky texture；By stratiform Ti3C2Material spreads out under X-ray
It penetrates to obtain stratiform Ti3C2The XRD spectra of material, as shown in figure 3, stratiform Ti3C2Material is shown as in X-ray diffraction spectrogram
Ti3C2Spectral peak；
It takes obtained using Pd-Ag bimetal nano particles as the stratiform Ti of hetero-junctions in above-described embodiment 2 or 63C2Complex light
The monolithic layer of catalyst is obtained under high power transmission electron microscope using Pd-Ag bimetal nano particles as the stratiform of hetero-junctions
Ti3C2The TEM photo of the monolithic layer of composite photo-catalyst, as shown in figure 5, Pd-Ag bimetal nano particles are in high power transmitted electron
Be shown as the granular or vermiform less than 50nm under microscope, and stratiform using Pd-Ag bimetal nano particles as hetero-junctions
Stratiform Ti3C2It can be clearly seen that Pd-Ag bimetal nano particles hetero-junctions is uniform in the monolithic layer of composite photo-catalyst
It is distributed in Ti3C2On thin slice；It is illustrated in figure 6 the stratiform Ti using Pd-Ag bimetal nano particles as hetero-junctions3C2Complex light is urged
The EDX spectrogram 6 (a) and STEM photo 6 (b) of the monolithic layer of agent are swept by carrying out line to the region 1 in rectangle frame in Fig. 6 (b)
Energy spectrum analysis is retouched, the spectrogram obtained is Fig. 6 (a), it is found that obtained hetero-junctions is the nanoparticle knot of Pd and Ag from Fig. 6 (a)
Structure.
The embodiment 1-6 composite photo-catalyst prepared is used for photocatalysis Decomposition aquatic products hydrogen, reaction condition is as follows:
It takes composite photo-catalyst prepared by above-described embodiment 1-6 to be respectively put into different quartzy bottles respectively, is added
The distilled water of 300mL, adds 4g vulcanized sodium and 2g sodium sulfite is dissolved in wherein as photocatalysis sacrifice agent, tests the light used
Source is 500W xenon lamp simulated solar irradiation, light intensity 100mWcm-2, it needs first to be passed through nitrogen before reaction and carries out purging 30min, then,
Start photocatalysis successive reaction 48h, collect caused by gas, measure its volume and use gas chromatographic analysis gas composition, reality
It applies a composite photo-catalyst hydrogen output for 1-6 preparation and is shown in Table 1:
1 Photocatalyzed Hydrogen Production reaction result of table
As can be known from Table 1, precious metals pd, Au and Ag obtain bimetal nano after being combined with each other reduction in embodiment 1-6
Particle nanoparticle loads to stratiform Ti as hetero-junctions respectively3C2Or stratiform TiO2-xCxThe complex light obtained on material is urged
Agent has the effect of photocatalysis Decomposition aquatic products hydrogen.
The limitation that technical solution of the present invention is not limited to the above specific embodiments, it is all to do according to the technique and scheme of the present invention
Technology deformation out, falls within the scope of protection of the present invention.
Claims (5)
1. a kind of using bimetal nano particles as the lamellar composite photochemical catalyst of hetero-junctions, it is characterised in that: the composite photocatalyst
Agent is evenly distributed on the bimetal nano particles in photocatalyst activity component by photocatalytic activity component and by binder
Composition, the photocatalyst activity group are divided into the titanium carbide Ti of layer structure3C2Or its oxidation product TiO2-xCx, the binder
For the Nafion perfluorinated resin solution of 0.1-5 wt.%, the bimetal nano particles are Pd-Ag nanoparticle, Pd-Au receives
At least one of rice corpuscles and Au-Ag nanoparticle, the shapes of bimetal nano particles be spherical, granular, vermiform with
And one of core-shell structure copolymer shape, the size of the bimetal nano particles are 1-50 nm；The bimetal nano particles and light
The weight percent of catalyst activity component is 0.01-10.0%, and binder and the weight percent of photocatalyst activity component are
0.01-5.0%。
2. according to claim 1 using bimetal nano particles as the lamellar composite photochemical catalyst of hetero-junctions, feature exists
In: the titanium carbide Ti3C2Or its oxidation product TiO2-xCxMonolithic layer with a thickness of 1-400nm in layer structure.
3. it is a kind of as described in claim 1-2 is any using bimetal nano particles as the lamellar composite photochemical catalyst system of hetero-junctions
Preparation Method, which comprises the following steps:
Step 1: water soluble polymer stabilizer is dissolved in deionized water, after dissolution is sufficiently stirred, then it is separately added into above-mentioned double
The water-soluble metal inorganic salt solution for two kinds of metals that metal nanoparticle contains, wherein macromolecule stabilizer: metal inorganic salt
Weight ratio is (1-10): 1, after adjustment pH value is 6-9 and is sufficiently mixed uniformly, return stirring device is recycled to keep 80 DEG C of conditions
The gaseous mixture of the lower hydrogen and argon gas for being 1% with hydrogen restores 1-2h, then the still aging 4-24 in 40 DEG C of thermostat water bath
H obtains the solution containing bimetal nano particles；
Step 2: by the photocatalyst activity component and binder be added to that step 1 obtains containing bimetal nano particles
Solution in, wherein the weight of bimetal nano particles and photocatalyst activity component in the solution containing bimetal nano particles
Percentage is 0.01-10.0%, and the weight percent of binder and photocatalyst activity component is 0.01-5.0%, carries out ultrasound point
10-60 min is dissipated, after being sufficiently mixed photocatalyst activity component and binder uniformly, then in 60-120 DEG C of progress vacuum
Dry 8-48 h, can be obtained the lamellar composite photochemical catalyst using bimetal nano particles as hetero-junctions.
4. it is according to claim 3 using bimetal nano particles as the lamellar composite photochemical catalyst preparation method of hetero-junctions,
It is characterized by: water soluble polymer stabilizer is methylcellulose, carboxymethyl cellulose, polyvinyl pyrrole in the step 1
At least one of alkanone and polyacrylamide.
5. it is according to claim 3 using bimetal nano particles as the lamellar composite photochemical catalyst preparation method of hetero-junctions,
It is characterized by: the water-soluble metal inorganic salts for two kinds of metals that bimetal nano particles contain in the step 1 are two kinds of gold
Nitrate, acetate or the chloride of category.
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| JP2016524534A (en) * | 2013-06-17 | 2016-08-18 | ヒンドゥスタン・ペトロリアム・コーポレーション・リミテッド | NATAO3: LA2O3 catalyst with cocatalyst composition for photocatalytic reduction of carbon dioxide |
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