CN106622318A - Layered composite photocatalyst using bimetallic nanoparticles as heterojunctions and preparation method thereof - Google Patents
Layered composite photocatalyst using bimetallic nanoparticles as heterojunctions and preparation method thereof Download PDFInfo
- Publication number
- CN106622318A CN106622318A CN201610980539.7A CN201610980539A CN106622318A CN 106622318 A CN106622318 A CN 106622318A CN 201610980539 A CN201610980539 A CN 201610980539A CN 106622318 A CN106622318 A CN 106622318A
- Authority
- CN
- China
- Prior art keywords
- nano particles
- bimetal nano
- hetero
- activity component
- bimetal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 79
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 54
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910001868 water Inorganic materials 0.000 claims abstract description 27
- 230000000694 effects Effects 0.000 claims abstract description 24
- 230000001699 photocatalysis Effects 0.000 claims abstract description 24
- 229910009819 Ti3C2 Inorganic materials 0.000 claims abstract description 18
- 239000011347 resin Substances 0.000 claims abstract description 9
- 229920005989 resin Polymers 0.000 claims abstract description 9
- 229920000557 Nafion® Polymers 0.000 claims abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 49
- 239000003054 catalyst Substances 0.000 claims description 38
- 239000000243 solution Substances 0.000 claims description 24
- 239000010936 titanium Substances 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 239000011230 binding agent Substances 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 229910003081 TiO2−x Inorganic materials 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 229920000609 methyl cellulose Polymers 0.000 claims description 8
- 239000001923 methylcellulose Substances 0.000 claims description 8
- 238000004064 recycling Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 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 description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 239000003381 stabilizer Substances 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 4
- 229920003169 water-soluble polymer Polymers 0.000 claims description 4
- 239000011258 core-shell material Substances 0.000 claims description 3
- 239000008246 gaseous mixture Substances 0.000 claims description 3
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229940084030 carboxymethylcellulose calcium Drugs 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims 2
- 239000010931 gold Substances 0.000 claims 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 229920002521 macromolecule Polymers 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- 238000007146 photocatalysis Methods 0.000 abstract description 16
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract description 2
- 239000000853 adhesive Substances 0.000 abstract 3
- 230000001070 adhesive effect Effects 0.000 abstract 3
- 238000013329 compounding Methods 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 29
- 239000000463 material Substances 0.000 description 24
- 238000004519 manufacturing process Methods 0.000 description 18
- 238000000354 decomposition reaction Methods 0.000 description 14
- 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
- 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
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 9
- 239000013207 UiO-66 Substances 0.000 description 8
- 238000000034 method 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
- 150000001875 compounds Chemical class 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000003643 water by type Substances 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
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 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
- 238000005119 centrifugation Methods 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
- 229910001961 silver nitrate Inorganic materials 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
- 238000005516 engineering process Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000002082 metal nanoparticle Substances 0.000 description 3
- 238000002156 mixing 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
- 230000009467 reduction Effects 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
- 235000007164 Oryza sativa Nutrition 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
- 238000003421 catalytic decomposition reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 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
- 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
- 238000001027 hydrothermal synthesis Methods 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
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 235000009566 rice Nutrition 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
- 238000001291 vacuum drying Methods 0.000 description 2
- -1 wherein Chemical compound 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
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 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
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 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
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 239000004567 concrete Substances 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
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005868 electrolysis reaction 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
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 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
- 239000003921 oil Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 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
- 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
- 238000004062 sedimentation Methods 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
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical class [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 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
- 239000007787 solid Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 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
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012546 transfer 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a layered composite photocatalyst using bimetallic nanoparticles as heterojunctions. The composite photocatalyst consists of a photocatalysis active component and bimetallic nanoparticles, wherein the bimetallic nanoparticles are uniformly distributed on the photocatalysis active component through an adhesive; the photocatalysis active component is Ti3C2 with a layered structure or an oxidizing product TiO2-xCx, and the adhesive is 0.1-5wt% Nafion perfluorination resin solution, preferably 0.5wt%; the weight percentage of bimetallic nanoparticles and photocatalysis active component is 0.01 to 10.0%; the weight percentage of adhesive and photocatalysis active component is 0.01 to 5.0%. Compared with the prior art, the composite photocatalyst has the advantages that the visible light is more effectively utilized, and the compounding of photo-induced electrons and cavities is inhibited; when the composite photocatalyst is used for photocatalyzing to decompose water to produce hydrogen, the activity is high, and the stability is good.
Description
Technical field
The present invention relates to field, particularly a kind of lamellar composite photochemical catalyst with bimetal nano particles as hetero-junctions and
Its preparation method.
Background technology
At present because the environmental problem that the deposit of traditional fossil energy is limited and is brought using them is increasingly projected, people
Be badly in need of finding new alternative energy source.Hydrogen Energy is due to its high efficiency and spatter property and attention.Various countries scientist competitively develops
The Related products such as the product related to Hydrogen Energy, Ni-MH battery, hydrogen cell automobile just move towards society, hydrogen economy from laboratory
At hand.
Traditional hydrogen manufacturing mode mainly produces hydrogen by the cracking of coal, oil, natural gas；Or by electrolysis water system
Obtain hydrogen；Substantial amounts of fossil fuel is consumed during due to preparing in hydrogen, and causes Regional Environmental Pollution and the whole world
Warm, so the hydrogen manufacturing approach for developing green cleaning becomes one of target of hydrogen energy source exploitation.Solar energy and water are the earth
Upper two kinds of important recyclability resources, it is the hydrogen manufacturing approach for most cleaning that hydrogen is prepared using decomposing water with solar energy, always
The dream of human development Hydrogen Energy.Therefore, the research of novel photocatalyst is following developing direction.
China Patent Publication No. CN102641741A discloses a kind of compound as shell by dyskaryosis structure of cadmium metal
Photochemical catalyst and preparation method.The composite photocatalyst with cadmium metal as core, semiconductor heterostructure zinc oxide and cadmium sulfide
For shell, in 50%-90%, molar ratio shared by zinc oxide is 5% to the shared molar ratio of cadmium metal, mol ratio shared by cadmium sulfide
Example is 5%-45%；Semiconductor heterostructure zinc oxide and cadmium sulfide are shell, refer to that zinc oxide is inlayed in surface for cadmium sulfide
The shell of grain, the thickness of cadmium sulfide shell is 5-50nm, and Zinc oxide particles size is 3-50nm；Its preparation method will contain cadmium ion forerunner
Body dissolves in deionized water, under the conditions of being subsequently adding zinc powder ultrasound and magnetic agitation, cadmium ion displacement metallic zinc；After washing,
Sulfuration saline solution vulcanizing treatment is added, or hydrogen sulfide gas vulcanizing treatment is used after drying, it is to be with cadmium metal to obtain product
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, it has higher hydrogen-producing speed.
China Patent Publication No. CN103316693A disclose a kind of photochemical catalyst Cd/CdS containing cocatalyst Cd and
Its preparation.The photochemical catalyst is by 3CdSO4·8H2O and Na2S2O3·5H2O is dissolved in distilled water, and stirring, ultrasound make its abundant
Dispersion, then react 10-25h under the xenon lamp of 350-500W；Then in the microwave ingle 5-25min of 500-800W, centrifugation is washed
Solids of sedimentation is washed, is dried, grinding obtains photochemical catalyst Cd/CdS, it is applied in Photocatalyzed Hydrogen Production reaction.
China Patent Publication No. CN101623644A discloses a kind of composite hollow ball CdS-TiO2Preparation and urge 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
Secondary employing hydro-thermal method, two step infusion processes, sol-gal process is obtained on carbon core and is enclosed with cadmium sulfide and TiO successively2Core shell structure
C-CdS-TiO2Composite, then obtains composite hollow ball CdS-TiO in Muffle furnace in 400 DEG C of roasting 2h2Photochemical catalyst,
The catalyst is by CdS and TiO2It is compound, widen TiO2Spectral response range, uses it 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 is increased considerably, and hydrogen-producing speed is significantly improved.
China Patent Publication No. CN101623645 A discloses a kind of p-n junction hollow ball NiO-CdS nano composite materials
Prepare and the application in photocatalytic hydrogen production by water decomposition.The preparation method of the nano composite material is by Ni (NO3)2·6H2O makees
For nickel source and Cd (NO3)2·4H2Used as cadmium source, using hydro-thermal method synthetic method, four step infusion processes are by n-NiO semiconductors and p-CdS for O
Semiconductors coupling, prepares a kind of p-n junction hollow ball NiO-CdS composite nano materials, as solar visible light catalysis
The photochemical catalyst of hydrogen production by water decomposition, accelerates the transfer 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-catalysts
Preparation method, the preparation method of the composite semiconductor light-catalyst is by ammonium salt, cadmium salt, thiocarbamide and deionized water hybrid reaction
Afterwards, Jing is filtered, washed, roasting and grinding obtain CdS pressed powders；Again by cobalt salt, ammoniacal liquor and deionized water hybrid reaction, then add
Enter tri- pressed powders of CdS, agitated, ultrasonic disperse, vacuum distillation, heat treatment, washing, filtration, roasting and grinding obtain p-
CoO/n-CdS composite semiconductor light-catalysts, the composite semiconductor light-catalyst can be used for photocatalysis degradation organic contaminant, light
The hydrogen manufacturing of catalytic decomposition water and manufacture solar cell.
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.The method be by mol ratio be 1:It is molten that 1 inorganic cadmium source or inorganic zinc source and sulphur powder are added to tetrahydrofuran
In liquid, ultrasonic disperse；Molar content and sulphur powder identical sodium borohydride are weighed again, in being added to tetrahydrofuran solution, ultrasound point
Dissipate；The solution for obtaining is added drop-wise to and is added in the solution that tetrahydrofuran solution is constituted by inorganic cadmium source and sulphur powder, ultrasonic reaction；Institute
The product for obtaining absolute ethyl alcohol centrifugation；Vacuum drying, obtains final yellow product and is that cadmium sulfide is hollow to be received
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, the 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%):
(0.001%-98%) ratio, reacted successively, centrifugation, distillation water washing, ultrasonic disperse, centrifugation, ultrasound at
The processes such as reason, vacuum distillation, drying, roasting, natural cooling and grinding, obtain porous nano p-CuS/n-CdS composite semiconductors
Photochemical catalyst, it 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 composited 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
Compare, hydrogen-producing speed is significantly improved.
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 of graphene oxide GO,
BiPO4With monoclinic form or hexagonal structure, GO is partially reduced in preparation process, with the graphene oxide RGO shapes for reducing
Formula is present；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 preparation method of bismuthino strontium magnetic photocatalyst and its
Bismuthino strontium magnetic photocatalyst.The magnetic photocatalyst is with neopelex with bismuth nitrate and strontium ferrite as raw material
Dispersant, first prepares the presoma of bismuthino strontium magnetic photocatalyst, then Jing 55-65 DEG C drying, 500-600 DEG C of roasting 3-5h obtain bismuth
Base strontium magnetic photocatalyst, it is used in the fields such as degradable organic pollutant, photocatalytic hydrogen production by water decomposition and solar cell.
Although above-mentioned these photochemical catalysts belong to composite photocatalyst, but these photochemical catalysts 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 poisonous to human body
Evil effect, it is a large amount of using the pollution for easily causing soil, water body environment.
Therefore, from avoiding causing the angle of environmental pollution, present invention employs the titanium carbide Ti of layer structure3C2Or
Its oxidation product TiO2-xCxAs photocatalyst activity component and bimetal nano particles one kind is have developed with bimetal nano
Particle is the lamellar composite photochemical catalyst of hetero-junctions.
The content of the invention
The invention aims to provide a kind of lamellar composite photochemical catalyst with bimetal nano particles as hetero-junctions and
Its preparation method, bimetallic is obtained by any two kinds of metal nanoparticles in Pd, Au, Ag by the mutual modulation of electronic structure
Nano-particle, then it is uniformly compound to catalysis material stratiform titanium carbide or its oxidation product surface can be realized using visible
Light carries out the purpose of light-catalyzed reaction.
To reach above-mentioned purpose, the present invention is implemented according to technical scheme below：One kind is with bimetal nano particles
The lamellar composite photochemical catalyst of hetero-junctions, the composite photo-catalyst is uniformly distributed by photocatalytic activity component and by binding agent
Bimetal nano particles composition in photocatalyst activity component, the photocatalyst activity component is the carbonization of layer structure
Titanium Ti3C2Or its oxidation product TiO2-xCx, the binding agent is the Nafion perfluorinated resin solution of 0.1-5wt.%, preferably
0.5wt.%, the percentage by weight of the bimetal nano particles and photocatalyst activity component is 0.01-10.0%, binding agent
It is 0.01-5.0% with the percentage by weight of photocatalyst activity component.
Further, the titanium carbide Ti3C2Or its oxidation product TiO2-xCxThe thickness of monolithic layer is 1- in layer structure
400nm, preferred 1-100nm.
Preferably, the bimetal nano particles are Pd-Ag nano-particles, Pd-Au nano-particles and Au-Ag nanoparticles
At least one in son, being shaped as bimetal nano particles is spherical, granular, the one kind in 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.
Prepare the concrete grammar of the lamellar composite photochemical catalyst with bimetal nano particles as hetero-junctions, including following step
Suddenly：
Step one, described water soluble polymer stabilizer is dissolved in deionized water, after being sufficiently stirred for dissolving, then is divided
The water-soluble metal inorganic salt solution of 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, adjustment pH value be 6-9 and be sufficiently mixed it is uniform after, recycling is refluxed dress
Put and reduce 1-2h with the gaseous mixture of the hydrogen and argon gas that hydrogen is 1% under the conditions of being kept for 80 DEG C, then in 40 DEG C of water bath with thermostatic control
If still aging 4-24h in pot, the solution containing bimetal nano particles is obtained；
Step 2, described photocatalyst activity component and binding agent be added to step one obtains containing bimetal nano
In the solution of particle, wherein, bimetal nano particles and photocatalyst activity component in the solution containing bimetal nano particles
Percentage by weight is 0.01-10.0%, and binding agent is 0.01-5.0% with the percentage by weight of photocatalyst activity component, is carried out
Ultrasonic disperse 10-60min, after photocatalyst activity component and binding agent is sufficiently mixed uniformly, is then carried out at 60-120 DEG C
Vacuum drying 8-48h, you can obtain the lamellar composite photochemical catalyst with bimetal nano particles as hetero-junctions.
Preferably, water soluble polymer stabilizer is methylcellulose, carboxymethylcellulose calcium, polyethylene in the step one
At least one in pyrrolidones and polyacrylamide.
Preferably, the water-soluble metal inorganic salts of two kinds of metals that bimetal nano particles contain are two in the step one
Plant nitrate, acetate or the chloride of metal.
Compared with the existing composite photo-catalyst for photocatalysis Decomposition aquatic products hydrogen, due to Pd, Au and Ag nano-particle
Local surface plasma resonance effect can affect its luminous flux and conduction electronics, on the surface of metallic particles, conduct electronics
Jing light irradiations generate the high energy electron that chemical reaction is participated in compared with multipotency, and 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 so as to which photoelectric properties produce qualitative change, using bimetal nano particles as photochemical catalyst hetero-junctions
With surface plasmon resonance effect and interface Schottky effect, can more effectively using visible ray and suppress light induced electron and
Compound, the raising photocatalysis efficiency in hole, then it is uniformly compound to catalysis material stratiform titanium carbide or oxidation product surface
Can realize carrying out light-catalyzed reaction using visible ray, the raw material that the present invention is used is environmentally friendly material, obtained multiple
Closing light catalyst is applied to photocatalysis Decomposition aquatic products hydrogen activity height, good stability.
Description of the drawings
Fig. 1 is stratiform Ti3C2The SEM photograph of material.
Fig. 2 is stratiform Ti3C2The TEM photos 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 stratiform Ti with Pd-Ag bimetal nano particles as hetero-junctions3C2The TEM of the monolithic layer of composite photo-catalyst
Photo.
Fig. 6 (a) is stratiform Ti with Pd-Ag bimetal nano particles as hetero-junctions3C2The monolithic layer of composite photo-catalyst
EDX spectrograms (a), Fig. 6 (b) are stratiform Ti with Pd-Ag bimetal nano particles as hetero-junctions3C2The monolithic of composite photo-catalyst
The STEM photos of layer.
Specific embodiment
With reference to specific embodiment, the invention will be further described, illustrative examples and explanation that here is invented
It is for explaining the present invention but not as a limitation of the invention.
Embodiment 1
Weigh 15mg methylcellulose to be dissolved in 40mL deionized waters, after being sufficiently stirred for dissolving, then be separately added into containing for 2mL
Pd for 2mg/mL palladium nitrate aqueous solution and 3mL containing Au for 2.4mg/mL aqueous solution of chloraurate, adjustment pH value is to 7.5, Jing
After being sufficiently mixed uniformly, recycling is refluxed device and keeps mixing with the hydrogen and argon gas that hydrogen is 1% under the conditions of 80 DEG C
After closing gas reduction 1h, then the still aging 4h in 40 DEG C of thermostat water bath, obtain molten containing the bimetallic nano-particles of Pd-Au
Liquid；
In the solution containing bimetal nano particles for obtaining, 500mg stratiforms Ti are added3C2With the 0.5wt.% perfluors of 2mL
Sulfonate resin solution, carries out ultrasonic disperse 30min so as to after being sufficiently mixed uniformly, is then maintained at 80 DEG C and is vacuum dried
24h, is obtained stratiform Ti with Pd-Au bimetal nano particles as hetero-junctions3C2Composite photo-catalyst A.
Embodiment 2
Weigh 10mg methylcellulose to be dissolved in 40mL deionized waters, after being sufficiently stirred for dissolving, then be separately added into containing for 1mL
Pd for 2mg/mL palladium nitrate aqueous solution and 4mL containing Ag for 2mg/mL silver nitrate aqueous solution, adjustment pH value fill to 7.5, Jing
Point be well mixed after, recycling is refluxed device and keeps mixed with the hydrogen and argon gas that hydrogen is 1% under the conditions of 80 DEG C
After closing gas reduction 1h, then the still aging 4h in 40 DEG C of thermostat water bath, obtain molten containing the bimetallic nano-particles of Pd-Ag
Liquid；
In the solution containing bimetal nano particles for obtaining, 500mg stratiforms Ti are added3C2With the 0.5wt.% perfluors of 2mL
Sulfonate resin solution, carries out ultrasonic disperse 30min so as to after being sufficiently mixed uniformly, is then maintained at 80 DEG C and is vacuum dried
24h, is obtained stratiform Ti with Pd-Ag bimetal nano particles as hetero-junctions3C2Composite photo-catalyst B.
Embodiment 3
Weigh 20mg methylcellulose to be dissolved in 40mL deionized waters, after being sufficiently stirred for dissolving, then be separately added into containing for 4mL
Au for 2.4mg/mL aqueous solution of chloraurate and 5mL containing Ag for 2mg/mL silver nitrate aqueous solution, adjustment pH value is to 7.5, Jing
After being sufficiently mixed uniformly, recycling is refluxed device and keeps mixing with the hydrogen and argon gas that hydrogen is 1% under the conditions of 80 DEG C
After closing gas reductase 12 h, then the still aging 4h in 40 DEG C of thermostat water bath, obtain molten containing the bimetallic nano-particles of Au-Ag
Liquid；
In the solution containing bimetal nano particles for obtaining, 500mg stratiforms Ti are added3C2With the 0.5wt.% perfluors of 2mL
Sulfonate resin solution, carries out ultrasonic disperse 30min so as to after being sufficiently mixed uniformly, is then maintained at 80 DEG C and is vacuum dried
24h, is obtained stratiform Ti with Au-Ag bimetal nano particles as hetero-junctions3C2Composite photo-catalyst C.
Embodiment 4
Weigh 20mg methylcellulose to be dissolved in 40mL deionized waters, after being sufficiently stirred for dissolving, then be separately added into containing for 5mL
Pd for 2mg/mL palladium nitrate aqueous solution and 4mL containing Au for 2.4mg/mL aqueous solution of chloraurate, adjustment pH value is to 7.5, Jing
After being sufficiently mixed uniformly, recycling is refluxed device and keeps mixing with the hydrogen and argon gas that hydrogen is 1% under the conditions of 80 DEG C
After closing gas reductase 12 h, then the still aging 4h in 40 DEG C of thermostat water bath, obtain molten containing the bimetallic nano-particles of Pd-Au
Liquid；
In the solution containing bimetal nano particles for obtaining, 500mg stratiforms TiO are added2-xCxWith the 0.5wt.% of 2mL
Perfluor sulfoacid resin solution, carries out ultrasonic disperse 30min so as to which after being sufficiently mixed uniformly, being then maintained at 80 DEG C carries out vacuum
24h is dried, stratiform TiO with Pd-Au bimetal nano particles as hetero-junctions is obtained2-xCxComposite photo-catalyst D.
Embodiment 5
Weigh 20mg methylcellulose to be dissolved in 40mL deionized waters, after being sufficiently stirred for dissolving, then be separately added into containing for 4mL
Au for 2.4mg/mL aqueous solution of chloraurate and 5mL containing Ag for 2mg/mL silver nitrate aqueous solution, adjustment pH value is to 7.5, Jing
After being sufficiently mixed uniformly, recycling is refluxed under the conditions of being kept for 80 DEG C in device with the hydrogen and argon gas that hydrogen is 1%
After gaseous mixture reductase 12 h, then the still aging 4h in 40 DEG C of thermostat water baths, obtain molten containing the bimetallic nano-particles of Au-Ag
Liquid；
In the solution containing bimetal nano particles for obtaining, 500mg stratiforms TiO are added2-xCxWith the 0.5wt.% of 2mL
Perfluor sulfoacid resin solution, carries out ultrasonic disperse 30min so as to which after being sufficiently mixed uniformly, being then maintained at 80 DEG C carries out vacuum
24h is dried, stratiform TiO with Au-Ag bimetal nano particles as hetero-junctions is obtained2-xCxComposite photo-catalyst E.
Embodiment 6
Weigh 20mg methylcellulose to be dissolved in 40mL deionized waters, after being sufficiently stirred for dissolving, then be separately added into containing for 5mL
Pd for 2mg/mL palladium nitrate aqueous solution and 5mL containing Ag for 2mg/mL silver nitrate aqueous solution, adjustment pH value fill to 7.5, Jing
Point be well mixed after, recycling is refluxed device and keeps mixed with the hydrogen and argon gas that hydrogen is 1% under the conditions of 80 DEG C
After closing gas reductase 12 h, then the still aging 4h in 40 DEG C of thermostat water bath, obtain molten containing the bimetallic nano-particles of Pd-Ag
Liquid；
In the solution containing bimetal nano particles for obtaining, 500mg stratiforms TiO are added2-xCxWith the 0.5wt.% of 2mL
Perfluor sulfoacid resin solution, carries out ultrasonic disperse 30min so as to which after being sufficiently mixed uniformly, being then maintained at 80 DEG C carries out vacuum
24h is dried, stratiform TiO with Pd-Ag bimetal nano particles as hetero-junctions is obtained2-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 its layer structure the thickness of monolithic layer 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, and the thickness of monolithic layer is less than 100nm in its layer structure；
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
Penetrate and obtain stratiform Ti3C2The XRD spectra of material, as shown in figure 3, stratiform Ti3C2Material is shown as in X-ray diffraction spectrogram
Ti3C2Spectral peak；
Take obtained stratiform Ti with Pd-Ag bimetal nano particles as hetero-junctions in above-described embodiment 2 or 63C2Complex light
The monolithic layer of catalyst, obtains the stratiform with Pd-Ag bimetal nano particles as hetero-junctions under high power transmission electron microscope
Ti3C2The TEM photos 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 with Pd-Ag bimetal nano particles as hetero-junctions
Stratiform Ti3C2Can 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 stratiform Ti with Pd-Ag bimetal nano particles as hetero-junctions3C2Complex light is urged
EDX spectrograms 6 (a) and STEM photos 6 (b) of the monolithic layer of agent, enters line and sweeps by the region 1 to rectangle inframe in Fig. 6 (b)
Energy spectrum analysis is retouched, the spectrogram for drawing is Fig. 6 (a), knowable in Fig. 6 (a), the hetero-junctions for obtaining is that the nano-particle of Pd and Ag is tied
Structure.
Composite photo-catalyst prepared by embodiment 1-6 is used for photocatalysis Decomposition aquatic products hydrogen, and reaction condition is as follows：
The composite photo-catalyst prepared by above-described embodiment 1-6 is taken respectively to be respectively put in different quartzy bottles, is added
The distilled water of 300mL, adds 4g vulcanized sodium and is dissolved in wherein as photocatalysis sacrifice agent with 2g sodium sulfites, tests the light for using
Source is 500W xenon lamp simulated solar irradiations, and light intensity is 100mWcm-2, needing first to be passed through nitrogen before reaction carries out purging 30min, then,
Start photocatalysis successive reaction 48h, collect produced gas, measure its volume and constituted with gas chromatographic analysis gas, it is real
Apply a composite photo-catalyst hydrogen output for 1-6 preparations and be shown in Table 1：
The Photocatalyzed Hydrogen Production reaction result of table 1
As can be known from Table 1, precious metals pd, Au and Ag are mutually combined after reduction and obtain bimetal nano in embodiment 1-6
Particle nano-particle, it loads to respectively stratiform Ti as hetero-junctions3C2Or stratiform TiO2-xCxThe complex light obtained on material is urged
Agent has the effect of photocatalysis Decomposition aquatic products hydrogen.
Technical scheme is not limited to the restriction of above-mentioned specific embodiment, and every technology according to the present invention scheme is done
The technology deformation for going out, each falls within protection scope of the present invention.
Claims (6)
1. a kind of lamellar composite photochemical catalyst with bimetal nano particles as 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 binding agent
Composition, the photocatalyst activity component is the titanium carbide Ti of layer structure3C2Or its oxidation product TiO2-xCx, the binding agent
For the weight of the Nafion perfluorinated resin solution of 0.1-5wt.%, the bimetal nano particles and photocatalyst activity component
Percentage is 0.01-10.0%, and binding agent is 0.01-5.0% with the percentage by weight of photocatalyst activity component.
2. the lamellar composite photochemical catalyst with bimetal nano particles as hetero-junctions according to claim 1, its feature exists
In：The titanium carbide Ti3C2Or its oxidation product TiO2-xCxThe thickness of monolithic layer is 1-400nm in layer structure.
3. the lamellar composite photochemical catalyst with bimetal nano particles as hetero-junctions according to claim 1, its feature exists
In：The bimetal nano particles are at least in Pd-Ag nano-particles, Pd-Au nano-particles and Au-Ag nano-particles
Kind, being shaped as bimetal nano particles is spherical, granular, the one kind in vermiform and core-shell structure copolymer shape, the bimetal nano particles
Size be 1-50nm.
4. a kind of lamellar composite photochemical catalyst system with bimetal nano particles as hetero-junctions as described in claim 1-3 is arbitrary
Preparation Method, it is characterised in that comprise the following steps：
Step one, described water soluble polymer stabilizer is dissolved in deionized water, after being sufficiently stirred for dissolving, then is separately added into
The water-soluble metal inorganic salt solution of two kinds of metals that above-mentioned bimetal nano particles contain, wherein, macromolecule stabilizer：Metal
Inorganic salts weight ratio is (1-10):1, adjustment pH value be 6-9 and be sufficiently mixed it is uniform after, recycling is refluxed device and keeps 80
1-2h is reduced with the gaseous mixture of the hydrogen and argon gas that hydrogen is 1% under the conditions of DEG C, then is stood in 40 DEG C of thermostat water bath
If ageing 4-24h, obtains the solution containing bimetal nano particles；
Step 2, described photocatalyst activity component and binding agent be added to step one 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 binding agent is 0.01-5.0% with the percentage by weight of photocatalyst activity component, carries out ultrasound
Dispersion 10-60min, after photocatalyst activity component and binding agent is sufficiently mixed uniformly, then carries out vacuum at 60-120 DEG C
It is dried 8-48h, you can obtain the lamellar composite photochemical catalyst with bimetal nano particles as hetero-junctions.
5. the lamellar composite photochemical catalyst preparation method with bimetal nano particles as hetero-junctions according to claim 4,
It is characterized in that：Water soluble polymer stabilizer is methylcellulose, carboxymethylcellulose calcium, polyvinyl pyrrole in the step one
At least one in alkanone and polyacrylamide.
6. the lamellar composite photochemical catalyst preparation method with bimetal nano particles as hetero-junctions according to claim 4,
It is characterized in that：The water-soluble metal inorganic salts of two kinds of metals that bimetal nano particles contain are two kinds of gold in the step one
The nitrate of category, acetate or chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610980539.7A CN106622318B (en) | 2016-11-08 | 2016-11-08 | It is a kind of using bimetal nano particles as lamellar composite photochemical catalyst of hetero-junctions and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610980539.7A CN106622318B (en) | 2016-11-08 | 2016-11-08 | It is a kind of using bimetal nano particles as lamellar composite photochemical catalyst of hetero-junctions and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106622318A true CN106622318A (en) | 2017-05-10 |
| CN106622318B CN106622318B (en) | 2019-04-02 |
Family
ID=58806125
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610980539.7A Expired - Fee Related CN106622318B (en) | 2016-11-08 | 2016-11-08 | It is a kind of using bimetal nano particles as lamellar composite photochemical catalyst of hetero-junctions and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106622318B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109752411A (en) * | 2017-11-07 | 2019-05-14 | 国家纳米科学中心 | A kind of composite air-sensitive material and its preparation method and application |
| CN110038606A (en) * | 2019-05-20 | 2019-07-23 | 西南石油大学 | A kind of preparation method and its usage of the modified bismuthino photochemical catalyst of titanium carbide for nitrogen conversion ammonification under visible light |
| CN110721689A (en) * | 2019-11-12 | 2020-01-24 | 江苏师范大学 | Porous spherical NiO/TiO2Heterostructure nano material and preparation method thereof |
| CN111330610A (en) * | 2020-04-10 | 2020-06-26 | 合肥工业大学 | Silver nanoflower/Ti3C2TxPreparation method and application of composite material |
| CN111632614A (en) * | 2020-05-11 | 2020-09-08 | 湖北臻润环境科技股份有限公司 | Three-dimensional petal-shaped NiAl-LDH/Ti3C2Composite photocatalyst and preparation method and application thereof |
| CN112795937A (en) * | 2020-12-24 | 2021-05-14 | 郑州大学 | Composite material for photoelectrochemical water decomposition, preparation method and application thereof, and electrode |
| CN113145152A (en) * | 2021-02-01 | 2021-07-23 | 重庆工商大学 | Visible light catalysis one-pot multidirectional chemoselectivity N-alkylation method |
| US12033809B2 (en) | 2019-08-05 | 2024-07-09 | Murata Manufacturing Co., Ltd. | Conductive material, conductive film, electrochemical capacitor, conductive material production method, and conductive film production method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104492431A (en) * | 2014-12-10 | 2015-04-08 | 青岛农业大学 | Preparation method of Au-Pd/TiO2 NBs photocatalyst |
| 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 |
-
2016
- 2016-11-08 CN CN201610980539.7A patent/CN106622318B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104492431A (en) * | 2014-12-10 | 2015-04-08 | 青岛农业大学 | Preparation method of Au-Pd/TiO2 NBs photocatalyst |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109752411A (en) * | 2017-11-07 | 2019-05-14 | 国家纳米科学中心 | A kind of composite air-sensitive material and its preparation method and application |
| CN109752411B (en) * | 2017-11-07 | 2021-09-17 | 国家纳米科学中心 | Composite gas-sensitive material and preparation method and application thereof |
| CN110038606A (en) * | 2019-05-20 | 2019-07-23 | 西南石油大学 | A kind of preparation method and its usage of the modified bismuthino photochemical catalyst of titanium carbide for nitrogen conversion ammonification under visible light |
| US12033809B2 (en) | 2019-08-05 | 2024-07-09 | Murata Manufacturing Co., Ltd. | Conductive material, conductive film, electrochemical capacitor, conductive material production method, and conductive film production method |
| CN110721689A (en) * | 2019-11-12 | 2020-01-24 | 江苏师范大学 | Porous spherical NiO/TiO2Heterostructure nano material and preparation method thereof |
| CN111330610A (en) * | 2020-04-10 | 2020-06-26 | 合肥工业大学 | Silver nanoflower/Ti3C2TxPreparation method and application of composite material |
| CN111632614A (en) * | 2020-05-11 | 2020-09-08 | 湖北臻润环境科技股份有限公司 | Three-dimensional petal-shaped NiAl-LDH/Ti3C2Composite photocatalyst and preparation method and application thereof |
| CN112795937A (en) * | 2020-12-24 | 2021-05-14 | 郑州大学 | Composite material for photoelectrochemical water decomposition, preparation method and application thereof, and electrode |
| CN113145152A (en) * | 2021-02-01 | 2021-07-23 | 重庆工商大学 | Visible light catalysis one-pot multidirectional chemoselectivity N-alkylation method |
| CN113145152B (en) * | 2021-02-01 | 2022-05-27 | 重庆工商大学 | Visible light catalysis one-pot multidirectional chemoselectivity N-alkylation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106622318B (en) | 2019-04-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106622318B (en) | It is a kind of using bimetal nano particles as lamellar composite photochemical catalyst of hetero-junctions and preparation method thereof | |
| US20220042184A1 (en) | Preparation Method and Application of Non-noble Metal Single Atom Catalyst | |
| Wang et al. | In situ surface engineering of ultrafine Ni 2 P nanoparticles on cadmium sulfide for robust hydrogen evolution | |
| CN106622322B (en) | It is a kind of using bimetal nano particles as two-dimensional nano piece composite photo-catalyst of hetero-junctions and preparation method thereof | |
| Wang et al. | Monoclinic β-AgVO3 coupled with CdS formed a 1D/1D p–n heterojunction for efficient photocatalytic hydrogen evolution | |
| CN105950140B (en) | It is a kind of to prepare Ag:ZnIn2S4The method of luminescent quantum dot and photochemical catalyst | |
| CN111729675B (en) | ZIF-67-DERIVED Co 3 S 4 And ZnIn 2 S 4 Preparation method and application of formed composite photocatalyst | |
| Zou et al. | Synthesis of CdS/CoP hollow nanocages with improved photocatalytic water splitting performance for hydrogen evolution | |
| CN109201102B (en) | Z-type heterojunction M-C3N4Preparation method of CdS composite photocatalyst | |
| CN107376944B (en) | Application of transition metal sulfide loaded Mn-Cd-S solid solution in aspect of photocatalytic hydrogen production | |
| CN105214656A (en) | Gold nano cluster-golden nanometer particle-titanium dioxide composite photocatalyst and application | |
| CN114588888B (en) | Photocatalyst, and preparation method and application thereof | |
| CN107433203B (en) | Z-Scheme composite system, preparation method and application | |
| CN105195144A (en) | Method for synthetizing Au/ZnO bar-shaped heterojunction photocatalyst | |
| CN113209989A (en) | Zinc cadmium sulfide nanorod and nickel nanorod heterojunction photocatalyst, preparation method thereof, hydrogen production system and hydrogen production method | |
| CN110280281B (en) | Preparation method of zinc ferrite/black phosphorus microsphere compound and application of zinc ferrite/black phosphorus microsphere compound in photocatalysis field | |
| CN109821562B (en) | MoP-Zn3In2S6Preparation method of composite nano material | |
| CN111359652A (en) | Carbon nitride-based nickel-gold bimetallic supported catalyst and preparation method thereof | |
| CN107537501A (en) | A kind of hierarchical Z nO/CuO composites and preparation method thereof | |
| CN107537520B (en) | Bismuth oxybromide-copper oxide nano composite photocatalyst and preparation method thereof | |
| CN109772394B (en) | Phosphorus-doped carbon/cuprous oxide composite catalyst and preparation method and application thereof | |
| Guo et al. | In situ self-assembly of mesoporous Zn-Cd-Mo-S quaternary metal sulfides with double heterojunction synergistic charge transfer for boosting photocatalytic hydrogen production | |
| Wang et al. | Hollow rod-shaped Cu-In-Zn-S@ ZnCo2O4@ In2O3 tandem heterojunction for efficient visible light-induced photocatalytic hydrogen production | |
| Jiang et al. | Ag 3 VO 4/gC 3 N 4/diatomite ternary compound reduces Cr (vi) ion in aqueous solution effectively under visible light | |
| Cai et al. | Z-type heterojunction of Cu2O-modified layered BiOI composites with superior photocatalytic performance for CO2 reduction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190402 Termination date: 20191108 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |