CN113262824B - Preparation of composite photocatalyst and application of composite photocatalyst in VOCs purification - Google Patents
Preparation of composite photocatalyst and application of composite photocatalyst in VOCs purification Download PDFInfo
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- CN113262824B CN113262824B CN202110461222.3A CN202110461222A CN113262824B CN 113262824 B CN113262824 B CN 113262824B CN 202110461222 A CN202110461222 A CN 202110461222A CN 113262824 B CN113262824 B CN 113262824B
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 59
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000000746 purification Methods 0.000 title claims abstract description 7
- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 174
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 26
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 26
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 24
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 14
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 14
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 230000003197 catalytic effect Effects 0.000 claims abstract description 6
- 239000013110 organic ligand Substances 0.000 claims abstract description 5
- 239000004094 surface-active agent Substances 0.000 claims abstract description 5
- -1 PVP modified nano titanium dioxide Chemical class 0.000 claims abstract description 4
- 230000015556 catabolic process Effects 0.000 claims abstract description 4
- 238000006731 degradation reaction Methods 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract 2
- 239000002184 metal Substances 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 70
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 239000002244 precipitate Substances 0.000 claims description 39
- 238000003756 stirring Methods 0.000 claims description 39
- 239000000725 suspension Substances 0.000 claims description 39
- 239000008367 deionised water Substances 0.000 claims description 36
- 229910021641 deionized water Inorganic materials 0.000 claims description 36
- 238000005406 washing Methods 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 25
- 238000005303 weighing Methods 0.000 claims description 22
- 239000000047 product Substances 0.000 claims description 21
- 239000006185 dispersion Substances 0.000 claims description 20
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 16
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 230000001376 precipitating effect Effects 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 238000001556 precipitation Methods 0.000 claims description 12
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 11
- XKMAKWPZGDBONG-UHFFFAOYSA-N [Co].[Cd] Chemical compound [Co].[Cd] XKMAKWPZGDBONG-UHFFFAOYSA-N 0.000 claims description 11
- 239000006104 solid solution Substances 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 8
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 8
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 8
- 229940005605 valeric acid Drugs 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 6
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 claims description 4
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 229910001868 water Inorganic materials 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- 150000004677 hydrates Chemical class 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 18
- 239000012621 metal-organic framework Substances 0.000 abstract description 11
- 230000001699 photocatalysis Effects 0.000 abstract description 11
- 230000003647 oxidation Effects 0.000 abstract description 8
- 238000007254 oxidation reaction Methods 0.000 abstract description 8
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 3
- 238000003933 environmental pollution control Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 239000004793 Polystyrene Substances 0.000 abstract 1
- 238000005530 etching Methods 0.000 abstract 1
- 239000004005 microsphere Substances 0.000 abstract 1
- 238000005580 one pot reaction Methods 0.000 abstract 1
- 229920002223 polystyrene Polymers 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 abstract 1
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 abstract 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000007789 gas Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 231100000331 toxic Toxicity 0.000 description 4
- 230000002588 toxic effect Effects 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000004887 air purification Methods 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000004065 semiconductor Substances 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
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000498 cooling water Substances 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
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- JBFYUZGYRGXSFL-UHFFFAOYSA-N imidazolide Chemical compound C1=C[N-]C=N1 JBFYUZGYRGXSFL-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 239000013309 porous organic framework Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/007—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by irradiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B01J35/23—
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- B01J35/39—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/80—Type of catalytic reaction
- B01D2255/802—Photocatalytic
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
- B01D2257/7027—Aromatic hydrocarbons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
Abstract
The invention provides a preparation method of a composite photocatalyst and application of the composite photocatalyst in VOCs purification, belonging to the technical field of environmental pollution control, wherein commercial nano titanium dioxide is used as a catalytic main body, polyvinylpyrrolidone is used as a surfactant, methanol is used as a solvent, zinc nitrate/cobalt nitrate is used as a metal salt, 2-methylimidazole is used as an organic ligand, polystyrene nano microspheres are used as an etching template, a porous metal organic framework ZIF-8 is prepared by a one-pot method and used as a carrier, PVP modified nano titanium dioxide is highly and uniformly dispersed on the composite photocatalyst on the metal organic framework, the adsorption performance of the photocatalyst on VOCs in the photocatalytic degradation process is enhanced, the photocatalytic oxidation performance on typical VOCs is remarkably enhanced, and the problems of poor adsorption performance and low degradation efficiency of the traditional titanium dioxide photocatalyst are solved.
Description
Technical Field
The invention relates to the technical field of environmental pollution control, in particular to the technical field of catalytic oxidation purification, and specifically relates to preparation of a composite photocatalyst and application of the composite photocatalyst in purification of VOCs.
Background
Is volatile such asOrganic Substances (VOCs) are important gaseous pollutants, not only comprise a plurality of toxic and harmful substances, but also form important precursors of organic aerosol, PM2.5 and ozone, and greatly affect the environmental quality and the human health. The photocatalytic oxidation can degrade toxic and harmful substances into harmless CO under the condition of illumination2And H2O, has the characteristics of mild reaction conditions, low cost, high mineralization rate, wide application range, less secondary pollution and the like, and has important research significance for saving energy, reducing emission, reducing the generation of toxic particles and improving the living environment practically.
Commercial titanium dioxide (P25) is the most representative photocatalytic material and has been widely used in the fields of indoor air purification, industrial organic waste gas treatment, and the like. However, P25 has the characteristics of wide band gap and high photogenerated electron-hole recombination rate, which reduces the utilization rate of the P25 to sunlight; in addition, the P25 has a low specific surface area, so that it cannot effectively adsorb low-concentration VOCs pollutants in actual atmosphere, and significantly affects the efficiency of photocatalytic oxidation, which greatly limits the further application of P25 in practice, and therefore, the development of P25 composite materials with high specific surface area and high adsorption capacity is the key to solve these problems.
The Metal Organic Framework (MOF) material is a porous material with high specific surface area and semiconductor properties, is widely applied to gas adsorption and separation, and particularly is a zeolite imidazolate framework material (ZIF-8) consisting of Zn (II), Co (II) ions and imidazole ligands, and has excellent adsorption performance on VOCs gases. The zinc oxide nano cluster not only can be used as a VOCs adsorption site, but also can be used as a catalytic oxidation active site of VOCs. The MOFs material and the P25 are organically compounded, so that the specific surface area of the P25 photocatalyst can be effectively increased, the semiconductor property of the MOF material can improve the separation efficiency of P25 photo-generated electrons and holes, and the in-situ adsorption enrichment, mass transfer and high-efficiency degradation performance of typical VOCs on the P25 composite photocatalyst are promoted. Therefore, the MOFs material and the P25 are organically compounded for purifying typical toxic VOCs, so that the organic composite material has unique innovation and important application prospect in the field of air purification, and although the small pore size of the MOFs provides a larger specific surface area, the mass transfer resistance is increased, the diffusion speed of substances is reduced, and the catalytic efficiency is influenced.
Disclosure of Invention
Aiming at the problems, the invention provides a preparation method of a composite photocatalyst and application of the composite photocatalyst in VOCs purification.
The purpose of the invention is realized by adopting the following technical scheme:
a preparation method of a composite photocatalyst comprises the following steps:
s1, respectively weighing polyvinylpyrrolidone, azodicyano valeric acid and styrene, mixing, adding an ethanol water solution, fully stirring uniformly, heating to boil within 30min, carrying out reflux reaction for 12-36h under the stirring condition, cooling, carrying out centrifugal separation on precipitate, washing the precipitate with methanol and/or deionized water, and then dispersing in methanol to obtain a suspension A, wherein the precipitation dispersion ratio is (3-4) mg/ml;
s2, weighing polyvinylpyrrolidone, completely dissolving the polyvinylpyrrolidone in methanol at a dissolving concentration of 1-5 wt.%, adding a nano photocatalyst, stirring and reacting for 1-60min, centrifugally separating precipitates, washing the precipitates with methanol and/or deionized water, drying, and dispersing in the suspension A to obtain a suspension B, wherein the precipitation dispersion ratio is (1-10) mg/ml;
wherein the nano photocatalyst comprises nano titanium dioxide, and the mass ratio of the polyvinylpyrrolidone to the nano photocatalyst is (1-100): 1;
s3, dissolving the alcohol-soluble salt of zinc and/or cobalt in methanol to obtain a solution A, wherein the dissolving concentration is 0.01-1 mol/L; dissolving an organic ligand in methanol to obtain a solution B, wherein the dissolving concentration is 0.01-1 mol/L; adding the suspension B into the solution A, fully stirring and mixing, adding the solution B, standing for 1-96h at 15-160 ℃, centrifugally separating and precipitating, washing the precipitate with methanol, N-dimethylformamide, tetrahydrofuran and deionized water in sequence, and drying to obtain the composite photocatalyst;
wherein the mixing volume ratio of the suspension B to the solution A to the solution B is 1: (1-100): (1-100).
Preferably, in step S1, the volume ratio of ethanol to water in the ethanol aqueous solution is (1-2): 1, the mass ratio of the polyvinylpyrrolidone to the azodicyano valeric acid, the styrene to the ethanol aqueous solution is (0.7-0.8): (0.1-0.2): 1: (20-25).
Preferably, the alcohol-soluble salt is one or more of zinc nitrate, zinc sulfate, cobalt nitrate, cobalt sulfate, cobalt chloride and hydrates thereof; the organic ligand is one or more of 2-methylimidazole, 1, 4-terephthalic acid and 2, 5-dihydroxy terephthalic acid.
Preferably, the nano titanium dioxide is reduction-treated titanium dioxide, and the preparation method of the reduction-treated titanium dioxide comprises the following steps:
respectively weighing sodium borohydride and nano titanium dioxide according to the weight ratio of (1-2): 4, after fully and uniformly mixing, heating to 200-300 ℃ in protective atmosphere or vacuum, carrying out heat preservation reaction for 20-60min, cooling, washing and drying the product, and grinding and crushing to obtain the catalyst.
Preferably, the nano-scale photocatalyst also comprises a sulfide solid solution of cadmium cobalt bimetal.
Preferably, the preparation method of the sulfide solid solution of the cadmium-cobalt bimetal comprises the following steps:
s1, respectively weighing 2-methylimidazole and surfactant, dissolving in deionized water, wherein the dissolving concentrations of the 2-methylimidazole and the surfactant in the deionized water are 0.1-1mol/L and 5-10mmol/L respectively to obtain a solution C, adding Co2+And Cd2+Fully stirring and dissolving the soluble salt to obtain a solution D, continuously stirring and reacting for 1-6h, centrifugally separating and precipitating, washing the precipitate with deionized water and methanol in sequence, and drying to obtain a product A;
s2, dispersing the product A in deionized water, wherein the dispersion ratio is (1-10) mg/ml, adding thioacetamide, fully stirring until the thioacetamide is dissolved to obtain a solution E, transferring the solution E into a reaction kettle with a polytetrafluoroethylene lining, heating to 86-92 ℃ at the temperature rise rate of not less than 10 ℃/min, carrying out heat preservation reaction for 12-16min, cooling, carrying out centrifugal separation on the precipitate, washing the precipitate with methanol and deionized water in sequence, drying, and grinding and crushing to obtain the cadmium-cobalt bimetallic sulfide solid solution;
wherein the mass ratio of the product A to the thioacetamide is (1.5-2): 1.
preferably, in step s1, Co in the solution D2+And Cd2+The ratio of the amounts of the substances (1-3): 1, Co2+And Cd2+The sum of the concentrations of (A) and (B) is 0.1-1 mol/L.
Preferably, the preparation method further comprises step S4, specifically:
transferring the product prepared after drying in the step S3 into a vacuum furnace for activation heat treatment, heating to 225 ℃ at a heating rate of 5 ℃/min under a vacuum condition, preserving heat for 40min, naturally cooling, dispersing the product of the activation heat treatment in methanol at a dispersion ratio of (3-5) mg/ml to obtain a suspension C, weighing 1, 10-phenanthroline, dissolving in the methanol at a dissolution concentration of (0.5-1) mg/ml to obtain a solution F, dropwise adding the solution F into the suspension C under a stirring condition, stirring and reacting at 50-60 ℃ for 2-3h after dropwise adding, centrifugally separating and precipitating, washing the precipitate with methanol and deionized water in sequence, and drying to obtain the product;
wherein the mixing volume ratio of the solution F to the suspension C is 1: (2-3).
Another object of the present application is to provide a composite photocatalyst prepared by the aforementioned preparation method.
The application further aims to provide an application of the composite photocatalyst, and the composite photocatalyst is particularly used for catalyzing, degrading and purifying volatile organic compounds.
The invention has the beneficial effects that:
(1) according to the invention, a porous metal organic framework ZIF-8 is used as a carrier, nanometer titanium dioxide modified by PVP is highly and uniformly dispersed on the metal organic framework ZIF-8, so that the composite photocatalyst with large specific surface area and high dispersion degree is prepared, the adsorption performance of the photocatalyst on VOCs in a photocatalytic degradation process is enhanced, the photocatalytic oxidation performance on typical VOCs is obviously enhanced, and the problems of poor adsorption performance and low degradation efficiency of the traditional photocatalyst are solved;
(2) the ZIF-8 metal organic framework material has small pore diameter within a micropore range, and the small pore diameter provides larger specific surface area, but has the problems of large mass transfer resistance and low diffusion rate.
(3) According to the method, titanium dioxide is partially reduced through sodium borohydride, oxygen vacancies are generated on the surface of nano titanium dioxide, and are easily converted into surface hydroxyl groups, so that organic pollutants can be adsorbed more quickly, the conversion of a catalyst from chemisorption oxygen to active oxygen is promoted, and the catalytic oxidation effect is improved; according to the method, the cadmium-cobalt bimetallic sulfide solid solution is compounded with titanium dioxide, so that the visible light photocatalytic activity of the titanium dioxide is greatly improved, the strong electronic coupling between ZIF-8 and the cadmium-cobalt bimetallic sulfide is realized, and the high-activity atomic-level dispersed reduced titanium sites in the ZIF-8 are combined to generate high photocatalytic performance, and meanwhile, the ZIF-8 serving as a dispersion body is a high-performance carrier and an accelerant of a nanostructure photocatalyst, so that the photocatalytic activity of cadmium sulfide can be improved; the application also uses 1, 10-phenanthroline with strong electron donating capability as ligand molecules for coordination doping, and utilizes the proper molecular size of a phenanthrene condensed ring structure and the electron donating characteristic thereof to induce generation of a charge transfer effect, reduce the photogenerated electron-hole recombination rate and improve the photocatalytic performance.
Drawings
The invention is further illustrated by means of the attached drawings, but the embodiments in the drawings do not constitute any limitation to the invention, and for a person skilled in the art, other drawings can be obtained on the basis of the following drawings without inventive effort.
FIG. 1 is a TEM image of the composite photocatalyst described in example 1;
FIG. 2 is a graph of the adsorption isotherm of the composite photocatalyst and P25 on acetone as described in example 1.
Detailed Description
The invention is further described with reference to the following examples.
Example 1
A preparation method of the composite photocatalyst comprises the following steps:
s1, weighing 2.0g of polyvinylpyrrolidone, 0.6g of azodicyano valeric acid and 3.0g of styrene respectively, mixing, adding 25ml of ethanol water solution with the volume ratio of 2:1, fully and uniformly stirring, heating to boil within 30min, refluxing and reacting for 24h under the stirring condition, cooling, centrifugally separating and precipitating, washing the precipitate with methanol and/or deionized water, and then dispersing in methanol to obtain a suspension A, wherein the precipitation dispersion ratio is 3 mg/ml;
s2, weighing 2.0g of polyvinylpyrrolidone, completely dissolving the polyvinylpyrrolidone in 40ml of methanol, adding 0.5g of nano titanium dioxide (P25), stirring for reacting for 20min, centrifugally separating precipitates, washing the precipitates with methanol and/or deionized water, drying, and dispersing in the suspension A to obtain a suspension B, wherein the dispersion ratio of the precipitates is 4 mg/ml;
s3, dissolving zinc nitrate and/or cobalt nitrate in methanol to obtain a solution A, wherein the dissolving concentration is 0.1 mol/L; dissolving 2-methylimidazole in methanol to obtain a solution B, wherein the dissolving concentration is 0.1 mol/L; adding the suspension B into the solution A, fully stirring and mixing, and then adding the solution B, wherein the mixing volume ratio of the suspension B to the solution A to the solution B is 1: 50: and 50, standing at normal temperature for 24 hours, centrifugally separating and precipitating, washing the precipitate with methanol, N-dimethylformamide, tetrahydrofuran and deionized water in sequence, and drying to obtain the composite photocatalyst.
FIG. 1 is a TEM image of the composite photocatalyst prepared in this example. It can be seen from the TEM images that the P25 nanoparticles have no significant agglomeration, which indicates that the P25 nanoparticles are successfully dispersed on the porous organic framework.
Acetone is used as an adsorbate, and a nitrogen adsorption apparatus (BELSORP-max) is adopted to test the adsorption capacity of the composite photocatalyst to the acetone, wherein the adsorption temperature is (30 ℃). Fig. 2 is an adsorption isotherm of the composite photocatalyst prepared in this embodiment and P25 on acetone, and it can be seen from this that, under the same relative pressure condition, the adsorption performance of the composite photocatalyst prepared in this embodiment on acetone is always higher than that of P25, and when the relative pressure is 1, the adsorption value of P25 on acetone is 100mg/g, and the adsorption value of the composite photocatalyst on acetone is 253.9mg/g, which is significantly improved compared with that of P25 on acetone (100.3mg/g), so that compounding ZIF-8 and P25 not only can effectively increase the adsorption performance on acetone, but also can increase the photocatalytic oxidation performance of the composite photocatalyst on acetone.
Example 2
A preparation method of the composite photocatalyst comprises the following steps:
s1, weighing 2.0g of polyvinylpyrrolidone, 0.6g of azodicyano valeric acid and 3.0g of styrene respectively, mixing, adding 25ml of ethanol water solution with the volume ratio of 2:1, fully and uniformly stirring, heating to boil within 30min, refluxing and reacting for 24h under the stirring condition, cooling, centrifugally separating and precipitating, washing the precipitate with methanol and/or deionized water, and then dispersing in methanol to obtain a suspension A, wherein the precipitation dispersion ratio is 3 mg/ml;
s2, weighing 2.0g of polyvinylpyrrolidone, completely dissolving the polyvinylpyrrolidone in 40ml of methanol, adding 0.5g of reduced titanium dioxide, stirring for reacting for 20min, centrifugally separating precipitates, washing the precipitates with methanol and/or deionized water, drying, and dispersing in the suspension A to obtain a suspension B, wherein the dispersion ratio of the precipitates is 4 mg/ml;
s3, dissolving zinc nitrate and/or cobalt nitrate in methanol to obtain a solution A, wherein the dissolving concentration is 0.1 mol/L; dissolving 2-methylimidazole in methanol to obtain a solution B, wherein the dissolving concentration is 0.1 mol/L; adding the suspension B into the solution A, fully stirring and mixing, and then adding the solution B, wherein the mixing volume ratio of the suspension B to the solution A to the solution B is 1: 50: 50, standing at normal temperature for 24 hours, centrifugally separating and precipitating, washing the precipitate with methanol, N-dimethylformamide, tetrahydrofuran and deionized water in sequence, and drying to obtain the composite photocatalyst;
the preparation method of the titanium dioxide subjected to reduction treatment comprises the following steps:
respectively weighing sodium borohydride and nano titanium dioxide (P25) according to the weight ratio of 1: 2, after fully and uniformly mixing, heating to 250 ℃ in protective atmosphere or vacuum, preserving heat for reaction for 40min, cooling, washing and drying the product, and grinding and crushing to obtain the catalyst.
Example 3
A preparation method of the composite photocatalyst comprises the following steps:
s1, weighing 2.0g of polyvinylpyrrolidone, 0.6g of azodicyano valeric acid and 3.0g of styrene respectively, mixing, adding 25ml of ethanol water solution with the volume ratio of 2:1, fully and uniformly stirring, heating to boil within 30min, refluxing and reacting for 24h under the stirring condition, cooling, centrifugally separating and precipitating, washing the precipitate with methanol and/or deionized water, and then dispersing in methanol to obtain a suspension A, wherein the precipitation dispersion ratio is 3 mg/ml;
s2, weighing 2.0g of polyvinylpyrrolidone, completely dissolving the polyvinylpyrrolidone in 40ml of methanol, adding 0.5g of reduced titanium dioxide and 0.14g of cadmium-cobalt bimetallic sulfide solid solution, stirring and reacting for 20min, centrifugally separating and precipitating, washing and drying the precipitate with methanol and/or deionized water, and re-dispersing in the suspension A to obtain a suspension B, wherein the precipitation dispersion ratio is 4 mg/ml;
s3, dissolving zinc nitrate and/or cobalt nitrate in methanol to obtain a solution A, wherein the dissolving concentration is 0.1 mol/L; dissolving 2-methylimidazole in methanol to obtain a solution B, wherein the dissolving concentration is 0.1 mol/L; adding the suspension B into the solution A, fully stirring and mixing, and then adding the solution B, wherein the mixing volume ratio of the suspension B to the solution A to the solution B is 1: 50: 50, standing at normal temperature for 24 hours, centrifugally separating and precipitating, washing the precipitate with methanol, N-dimethylformamide, tetrahydrofuran and deionized water in sequence, and drying to obtain the composite photocatalyst;
the preparation method of the titanium dioxide subjected to reduction treatment comprises the following steps:
respectively weighing sodium borohydride and nano titanium dioxide (P25) according to the weight ratio of 1: 2, after fully and uniformly mixing, heating to 250 ℃ under protective atmosphere or vacuum, preserving heat for reaction for 40min, cooling, washing and drying a product, and grinding and crushing to obtain the catalyst;
the preparation method of the cadmium-cobalt bimetallic sulfide solid solution comprises the following steps:
s1, minuteRespectively weighing 2-methylimidazole and polyvinylpyrrolidone, dissolving in deionized water to obtain solutions with the concentration of 0.1mol/L and 8mmol/L, adding Co2+And Cd2+Is prepared into Co2+And Cd2+The concentration of the solution is 0.3mol/L and 0.1mol/L respectively, the solution D is obtained after fully stirring and dissolving, the stirring reaction is continued for 4 hours, the centrifugal separation and precipitation are carried out, the precipitation is washed by deionized water and methanol in sequence, and the product A is obtained after drying;
s2, dispersing the product A in deionized water at a dispersion ratio of 5mg/ml, and adding thioacetamide, wherein the mass ratio of the product A to the thioacetamide is 1.6: 1, fully stirring until the solution is dissolved to obtain a solution E, transferring the solution E into a reaction kettle with a polytetrafluoroethylene lining, heating to 90 ℃ at the heating rate of 20 ℃/min, carrying out heat preservation reaction for 15min, cooling, carrying out centrifugal separation and precipitation, washing the precipitate with methanol and deionized water in sequence, drying, and grinding and crushing to obtain the cadmium-cobalt bimetallic sulfide solid solution.
Example 4
A preparation method of the composite photocatalyst comprises the following steps:
s1, weighing 2.0g of polyvinylpyrrolidone, 0.6g of azodicyano valeric acid and 3.0g of styrene respectively, mixing, adding 25ml of ethanol water solution with the volume ratio of 2:1, fully and uniformly stirring, heating to boil within 30min, refluxing and reacting for 24h under the stirring condition, cooling, centrifugally separating and precipitating, washing the precipitate with methanol and/or deionized water, and then dispersing in methanol to obtain a suspension A, wherein the precipitation dispersion ratio is 3 mg/ml;
s2, weighing 2.0g of polyvinylpyrrolidone, completely dissolving the polyvinylpyrrolidone in 40ml of methanol, adding 0.5g of nano titanium dioxide (P25), stirring for reacting for 20min, centrifugally separating precipitates, washing the precipitates with methanol and/or deionized water, drying, and dispersing in the suspension A to obtain a suspension B, wherein the dispersion ratio of the precipitates is 4 mg/ml;
s3, dissolving zinc nitrate and/or cobalt nitrate in methanol to obtain a solution A, wherein the dissolving concentration is 0.1 mol/L; dissolving 2-methylimidazole in methanol to obtain a solution B, wherein the dissolving concentration is 0.1 mol/L; adding the suspension B into the solution A, fully stirring and mixing, and then adding the solution B, wherein the mixing volume ratio of the suspension B to the solution A to the solution B is 1: 50: 50, standing for 24 hours at normal temperature, centrifugally separating and precipitating, washing the precipitate with methanol, N-dimethylformamide, tetrahydrofuran and deionized water in sequence, and drying;
s4, transferring the product obtained after drying in the step S3 into a vacuum furnace for activation heat treatment, heating to 225 ℃ at a heating rate of 5 ℃/min under a vacuum condition, preserving heat for 40min, naturally cooling, dispersing the product of the activation heat treatment in methanol at a dispersion ratio of 3mg/ml to obtain a suspension C, weighing 1, 10-phenanthroline, dissolving in methanol at a dissolution concentration of 0.7mg/ml to obtain a solution F, dropwise adding the solution F into the suspension C under a stirring condition, wherein the mixing volume ratio of the solution F to the suspension C is 1: and 2, stirring and reacting for 2 hours at the temperature of 50-60 ℃ after the dropwise addition is finished, centrifugally separating and precipitating, washing the precipitate with methanol and deionized water in sequence, and drying to obtain the composite photocatalyst.
Photocatalytic Performance test
The test is carried out in a closed glass reactor with the internal volume of 100ml, quartz glass is arranged at the top of the reactor, a gas inlet, a gas outlet, a gas sampling port and a temperature sensor are arranged, cooling water is circulated by a circulating water pump to enable the photocatalytic reaction to be carried out under the normal temperature condition, so that the influence of the thermal effect on the experimental result is eliminated, and a 300W xenon lamp is used for simulating a sunlight source.
Firstly, 2ml of deionized water is dropped into the bottom of the reactor, then a quartz reactor (30mm multiplied by 20mm) filled with 50mg of composite photocatalyst is placed at the bottom of the reactor, and pure O is introduced2(2atm) to remove the air in the device, injecting 3 μ L of toluene/formaldehyde solution into the reactor with a micro-injector, placing the reactor in the dark for 30min to establish adsorption-desorption equilibrium between the sample and toluene/formaldehyde, then turning on the xenon lamp to perform photocatalytic degradation reaction, taking 500 μ L of reacted gas sample out of the sampling port with a glass syringe at regular time intervals to perform quantitative analysis, and performing a blank experiment without composite photocatalyst under the same conditions to eliminate the photolysis from degrading toluene/formaldehydeThe initial concentration of toluene and formaldehyde is 0.8mg/L and 0.16mg/L, and the test results are shown in the following table.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (9)
1. A preparation method of the composite photocatalyst is characterized by comprising the following steps:
s1, respectively weighing polyvinylpyrrolidone, azodicyano valeric acid and styrene, mixing, adding an ethanol water solution, fully stirring uniformly, heating to boil within 30min, carrying out reflux reaction for 12-36h under the stirring condition, cooling, carrying out centrifugal separation on precipitate, washing the precipitate with methanol and/or deionized water, and then dispersing in methanol to obtain a suspension A, wherein the precipitation dispersion ratio is (3-4) mg/ml;
s2, weighing polyvinylpyrrolidone, completely dissolving the polyvinylpyrrolidone in methanol at a dissolving concentration of 1-5 wt.%, adding a nano photocatalyst, stirring and reacting for 1-60min, centrifugally separating precipitates, washing the precipitates with methanol and/or deionized water, drying, and dispersing in the suspension A to obtain a suspension B, wherein the precipitation dispersion ratio is (1-10) mg/ml;
wherein the nano photocatalyst comprises nano titanium dioxide, and the mass ratio of the polyvinylpyrrolidone to the nano photocatalyst is (1-100): 1;
s3, dissolving the alcohol-soluble salt of zinc and/or cobalt in methanol to obtain a solution A, wherein the dissolving concentration is 0.01-1 mol/L; dissolving an organic ligand in methanol to obtain a solution B, wherein the dissolving concentration is 0.01-1 mol/L; adding the suspension B into the solution A, fully stirring and mixing, adding the solution B, standing for 1-96h at 15-160 ℃, centrifugally separating and precipitating, washing the precipitate with methanol, N-dimethylformamide, tetrahydrofuran and deionized water in sequence, and drying;
wherein the mixing volume ratio of the suspension B to the solution A to the solution B is 1: (1-100): (1-100);
s4, transferring the product obtained after drying in the step S3 into a vacuum furnace for activation heat treatment, heating to 225 ℃ at a heating rate of 5 ℃/min under a vacuum condition, preserving heat for 40min, naturally cooling, dispersing the product of the activation heat treatment in methanol at a dispersion ratio of (3-5) mg/ml to obtain a suspension C, weighing 1, 10-phenanthroline, dissolving in the methanol at a dissolution concentration of (0.5-1) mg/ml to obtain a solution F, dropwise adding the solution F into the suspension C under a stirring condition, stirring and reacting at 50-60 ℃ for 2-3h after dropwise adding, centrifugally separating the precipitate, washing the precipitate with methanol and deionized water in sequence, and drying to obtain the product;
wherein the mixing volume ratio of the solution F to the suspension C is 1: (2-3).
2. The method for preparing a composite photocatalyst as claimed in claim 1, wherein in step S1, the volume ratio of ethanol to water in the ethanol aqueous solution is (1-2): 1, the mass ratio of the polyvinylpyrrolidone to the azodicyano valeric acid, the styrene to the ethanol aqueous solution is (0.7-0.8): (0.1-0.2): 1: (20-25).
3. The method for preparing the composite photocatalyst as claimed in claim 1, wherein the alcohol-soluble salt is one or more of zinc nitrate, zinc sulfate, cobalt nitrate, cobalt sulfate, cobalt chloride and hydrates thereof; the organic ligand is one or more of 2-methylimidazole, 1, 4-terephthalic acid and 2, 5-dihydroxy terephthalic acid.
4. The method for preparing a composite photocatalyst as claimed in claim 1, wherein the nano titanium dioxide is reduction-treated titanium dioxide, and the preparation method of the reduction-treated titanium dioxide comprises:
respectively weighing sodium borohydride and nano titanium dioxide according to the weight ratio of (1-2): 4, after fully and uniformly mixing, heating to 200-300 ℃ in protective atmosphere or vacuum, carrying out heat preservation reaction for 20-60min, cooling, washing and drying the product, and grinding and crushing to obtain the catalyst.
5. The method for preparing a composite photocatalyst as claimed in claim 1, wherein the nano-scale photocatalyst further comprises a sulfide solid solution of a cadmium-cobalt bimetallic metal.
6. The method for preparing a composite photocatalyst as claimed in claim 5, wherein the method for preparing a solid solution of a sulfide of a cadmium-cobalt bimetal comprises the following steps:
s1, respectively weighing 2-methylimidazole and surfactant, dissolving in deionized water, wherein the dissolving concentrations of the 2-methylimidazole and the surfactant in the deionized water are 0.1-1mol/L and 5-10mmol/L respectively to obtain a solution C, adding Co2+And Cd2+Fully stirring and dissolving the soluble salt to obtain a solution D, continuously stirring and reacting for 1-6h, centrifugally separating and precipitating, washing the precipitate with deionized water and methanol in sequence, and drying to obtain a product A;
s2, dispersing the product A in deionized water, wherein the dispersion ratio is (1-10) mg/ml, adding thioacetamide, fully stirring until the thioacetamide is dissolved to obtain a solution E, transferring the solution E into a reaction kettle with a polytetrafluoroethylene lining, heating to 86-92 ℃ at the temperature rise rate of not less than 10 ℃/min, carrying out heat preservation reaction for 12-16min, cooling, carrying out centrifugal separation on the precipitate, washing the precipitate with methanol and deionized water in sequence, drying, and grinding and crushing to obtain the cadmium-cobalt bimetallic sulfide solid solution;
wherein the mass ratio of the product A to the thioacetamide is (1.5-2): 1.
7. the method for preparing a composite photocatalyst as claimed in claim 6, wherein the Co in the solution D in the step s12+And Cd2+The ratio of the amounts of the substances (1-3): 1, Co2+And Cd2+The sum of the concentrations of (A) and (B) is 0.1-1 mol/L.
8. A composite photocatalyst produced by the production method according to any one of claims 1 to 7.
9. The use of the composite photocatalyst as claimed in claim 8, for catalytic degradation and purification of volatile organic compounds.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106881155A (en) * | 2016-12-29 | 2017-06-23 | 广州凯耀资产管理有限公司 | A kind of Au/TiO2/ metal organic framework composite photo-catalyst and preparation method and application |
| CN107629076A (en) * | 2017-09-13 | 2018-01-26 | 华南理工大学 | A kind of ordered big hole metal organic frame monocrystalline and preparation method thereof |
| CN108855220A (en) * | 2018-07-02 | 2018-11-23 | 肇庆市华师大光电产业研究院 | A kind of titania additive ZIF and its preparation method and application |
| CN109331883A (en) * | 2018-11-26 | 2019-02-15 | 中南大学 | A kind of CdS/ metal organic frame composite photocatalyst material and its preparation method and application |
| CN109499620A (en) * | 2018-12-10 | 2019-03-22 | 怀化学院 | TiO2The preparation method of/ZIF-8 composite photo-catalyst |
| CN111203188A (en) * | 2020-01-17 | 2020-05-29 | 广东工业大学 | MOFs adsorbent for selectively adsorbing esters as well as preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB201706805D0 (en) * | 2017-04-28 | 2017-06-14 | Cambridge Entpr Ltd | Composite metal organic framework materials, processes for their manufacture and uses thereof |
-
2021
- 2021-04-27 CN CN202110461222.3A patent/CN113262824B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106881155A (en) * | 2016-12-29 | 2017-06-23 | 广州凯耀资产管理有限公司 | A kind of Au/TiO2/ metal organic framework composite photo-catalyst and preparation method and application |
| CN107629076A (en) * | 2017-09-13 | 2018-01-26 | 华南理工大学 | A kind of ordered big hole metal organic frame monocrystalline and preparation method thereof |
| CN108855220A (en) * | 2018-07-02 | 2018-11-23 | 肇庆市华师大光电产业研究院 | A kind of titania additive ZIF and its preparation method and application |
| CN109331883A (en) * | 2018-11-26 | 2019-02-15 | 中南大学 | A kind of CdS/ metal organic frame composite photocatalyst material and its preparation method and application |
| CN109499620A (en) * | 2018-12-10 | 2019-03-22 | 怀化学院 | TiO2The preparation method of/ZIF-8 composite photo-catalyst |
| CN111203188A (en) * | 2020-01-17 | 2020-05-29 | 广东工业大学 | MOFs adsorbent for selectively adsorbing esters as well as preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 二氧化钛/金属有机骨架复合材料的制备及其应用;车广波等;《吉林师范大学学报(自然科学版)》;20200510;第41卷(第02期);429-450 * |
| 金属有机框架孔径调控进展;原野等;《化工学报》;20201231(第02期);12-28 * |
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