CN108993548A - A kind of visible light responsive photocatalyst and application thereof, preparation method and application method - Google Patents
A kind of visible light responsive photocatalyst and application thereof, preparation method and application method Download PDFInfo
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- CN108993548A CN108993548A CN201810797202.1A CN201810797202A CN108993548A CN 108993548 A CN108993548 A CN 108993548A CN 201810797202 A CN201810797202 A CN 201810797202A CN 108993548 A CN108993548 A CN 108993548A
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- solution
- bismuth
- catalyst
- visible light
- organic matter
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- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000011941 photocatalyst Substances 0.000 title abstract description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 86
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 50
- 230000015556 catabolic process Effects 0.000 claims abstract description 50
- 238000006731 degradation reaction Methods 0.000 claims abstract description 50
- 239000005416 organic matter Substances 0.000 claims abstract description 48
- 238000003756 stirring Methods 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- OZKCXDPUSFUPRJ-UHFFFAOYSA-N oxobismuth;hydrobromide Chemical compound Br.[Bi]=O OZKCXDPUSFUPRJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 230000001699 photocatalysis Effects 0.000 claims abstract description 22
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 21
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- -1 bismuth salt compound Chemical class 0.000 claims abstract description 16
- 238000007146 photocatalysis Methods 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 10
- 230000007935 neutral effect Effects 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 8
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 49
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 39
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 32
- 239000000975 dye Substances 0.000 claims description 27
- 230000003115 biocidal effect Effects 0.000 claims description 26
- 230000000694 effects Effects 0.000 claims description 25
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 20
- 235000019441 ethanol Nutrition 0.000 claims description 19
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 18
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 10
- 229940043267 rhodamine b Drugs 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 9
- 239000001000 anthraquinone dye Substances 0.000 claims description 9
- 239000000987 azo dye Substances 0.000 claims description 9
- GSDSWSVVBLHKDQ-UHFFFAOYSA-N 9-fluoro-3-methyl-10-(4-methylpiperazin-1-yl)-7-oxo-2,3-dihydro-7H-[1,4]oxazino[2,3,4-ij]quinoline-6-carboxylic acid Chemical compound FC1=CC(C(C(C(O)=O)=C2)=O)=C3N2C(C)COC3=C1N1CCN(C)CC1 GSDSWSVVBLHKDQ-UHFFFAOYSA-N 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 229960001699 ofloxacin Drugs 0.000 claims description 8
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- 230000001476 alcoholic effect Effects 0.000 claims description 6
- 235000011187 glycerol Nutrition 0.000 claims description 6
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 6
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 6
- SGHZXLIDFTYFHQ-UHFFFAOYSA-L Brilliant Blue Chemical compound [Na+].[Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C(=CC=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 SGHZXLIDFTYFHQ-UHFFFAOYSA-L 0.000 claims description 5
- 229930186147 Cephalosporin Natural products 0.000 claims description 5
- 241000233855 Orchidaceae Species 0.000 claims description 5
- 229930182555 Penicillin Natural products 0.000 claims description 5
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 claims description 5
- FHNINJWBTRXEBC-UHFFFAOYSA-N Sudan III Chemical compound OC1=CC=C2C=CC=CC2=C1N=NC(C=C1)=CC=C1N=NC1=CC=CC=C1 FHNINJWBTRXEBC-UHFFFAOYSA-N 0.000 claims description 5
- KIPLYOUQVMMOHB-MXWBXKMOSA-L [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O Chemical compound [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O KIPLYOUQVMMOHB-MXWBXKMOSA-L 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 229940124587 cephalosporin Drugs 0.000 claims description 5
- 150000001780 cephalosporins Chemical class 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229940049954 penicillin Drugs 0.000 claims description 5
- 229940063650 terramycin Drugs 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- POJOORKDYOPQLS-UHFFFAOYSA-L barium(2+) 5-chloro-2-[(2-hydroxynaphthalen-1-yl)diazenyl]-4-methylbenzenesulfonate Chemical compound [Ba+2].C1=C(Cl)C(C)=CC(N=NC=2C3=CC=CC=C3C=CC=2O)=C1S([O-])(=O)=O.C1=C(Cl)C(C)=CC(N=NC=2C3=CC=CC=C3C=CC=2O)=C1S([O-])(=O)=O POJOORKDYOPQLS-UHFFFAOYSA-L 0.000 claims description 4
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 4
- 229940012189 methyl orange Drugs 0.000 claims description 4
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 claims description 4
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- 229910001451 bismuth ion Inorganic materials 0.000 claims description 3
- 229910000380 bismuth sulfate Inorganic materials 0.000 claims description 3
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 2
- 230000000593 degrading effect Effects 0.000 claims 3
- JNRLEMMIVRBKJE-UHFFFAOYSA-N 4,4'-Methylenebis(N,N-dimethylaniline) Chemical compound C1=CC(N(C)C)=CC=C1CC1=CC=C(N(C)C)C=C1 JNRLEMMIVRBKJE-UHFFFAOYSA-N 0.000 claims 1
- 241001062009 Indigofera Species 0.000 claims 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims 1
- 150000004056 anthraquinones Chemical class 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 65
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 14
- BDJYZEWQEALFKK-UHFFFAOYSA-N bismuth;hydrate Chemical compound O.[Bi] BDJYZEWQEALFKK-UHFFFAOYSA-N 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000011534 incubation Methods 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- FOQHYNYNHYNUIN-UHFFFAOYSA-N [O].[Br] Chemical compound [O].[Br] FOQHYNYNHYNUIN-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001621 bismuth Chemical class 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- PNZDZRMOBIIQTC-UHFFFAOYSA-N ethanamine;hydron;bromide Chemical compound Br.CCN PNZDZRMOBIIQTC-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000001603 reducing effect Effects 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
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UIOFUWFRIANQPC-JKIFEVAISA-N Floxacillin Chemical compound N([C@@H]1C(N2[C@H](C(C)(C)S[C@@H]21)C(O)=O)=O)C(=O)C1=C(C)ON=C1C1=C(F)C=CC=C1Cl UIOFUWFRIANQPC-JKIFEVAISA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229960004273 floxacillin Drugs 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 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
- B01J27/06—Halogens; Compounds thereof
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses a kind of visible light-responded photochemical catalysts, to hydrogenate bismuth deposit bismuth oxybromide, molecular formula H-Bi BiOBr, for the organic matter in Photocatalytic Activity for Degradation water body.The preparation method of catalyst, comprising steps of 1, take Organic Alcohol as solvent；2, organic alcohol solvent is added in bismuth salt compound and bromide compound, mixes and is sufficiently stirred；3, neutral solution is added after stirring to clarify solution and a certain amount of reducing agent is added, is fitted into reaction kettle after stirring, carries out isothermal reaction；4, it is cooled to room temperature and is centrifuged and is repeatedly washed with water and ethanol solution, collect powder after dry；5, it calcines under an atmosphere of hydrogen, obtains hydrogenation bismuth deposit bismuth oxybromide.The hydrogenation bismuth deposit bismuth oxybromide photocatalyst that the method for the present invention obtains is environmentally friendly, material source is extensive, cheap, method is controllable and easy to operate, can be produced in batches, the photocatalysis performance with good degradation of organic substances.
Description
Technical field
The present invention relates to catalysis material technical fields, more specifically to a kind of hydrogenation bismuth deposit bismuth oxybromide (H-
Bi@BiOBr) visible light-responded organic matter degradation photochemical catalyst preparation and application.
Background technique
It is well known that the organic matter especially dyestuff and antibiotic pollutant in water body seriously affect Water quality, destroy
Environment threatens human health.Although traditional biological treatment can handle Organic substance in water well, due to microorganism
Specificity, to increase processing cost.In addition to this, biological treatment process is longer, safeguards more difficult.Compared to biological treatment
Method, photocatalysis oxidation technique are thoroughly received significant attention because of its environment-protection low-consumption, processing.But due to semiconductor catalyst quantum
Low efficiency, recycling rate of waterused is limited and is difficult to the problems such as recycling and is difficult to meet actual needs.For semiconductor light-catalyst, by
In biggish forbidden bandwidth make it low to the utilization rate of sunlight and its practical application in another huge challenge.
Now, more and more photochemical catalysts are used in photocatalysis degradation organic contaminant.Such as: titanium dioxide, two
Molybdenum sulfide, graphite phase carbon nitride, bismuth tungstate, pucherite etc..However, since bismuth oxybromide (BiOBr) has unique stratiform knot
Structure is conducive to electron-transport, and suitable forbidden bandwidth has wider light abstraction width, and has simple production process, cheap, nothing
The advantages that malicious.Nevertheless, traditional BiOBr still shows lower organic matter degradation ability.
Summary of the invention
It is an object of that present invention to provide a kind of visible light-responded organic matter degradation photochemical catalyst and its synthetic method, purposes and
Biodegrading process.
To achieve the goals above, the technical solution of the present invention is as follows:
A kind of visible light-responded organic matter degradation photochemical catalyst of the present invention, catalyst are hydrogenation bismuth deposit bismuth oxybromide, point
Minor H-Bi@BiOBr.Structure is the flower ball-shaped microballoon with bismuth simple substance and Lacking oxygen.
Catalyst provided by the invention, for the dyestuff or antibiotic organic matter under visible light in catalytic degradation water body.Institute
Stating dyestuff is anthraquinone dyes or azo dyes, and the antibiotic is Ofloxacin, terramycin, cephalosporin or penicillin.
Wherein anthraquinone dyes are reactive brilliant blue, reactive brilliant red, Disperse Blue 2BLN, RSN vat blue, the gorgeous orchid RAW, rhodamine B of faintly acid
It is methyl orange, methylene blue, tonyred etc. Deng, azo dyes.
The present invention provides a kind of preparation methods of visible light-responded degradation of organic substances photochemical catalyst, include the following steps:
S1, at room temperature using ethylene glycol, diethylene glycol, triethylene glycol, isopropanol or glycerine as solvent；
S2, the alcoholic solvent is added in bismuth salt compound and bromide compound, mixes and is sufficiently stirred；The bismuth salt chemical combination
Object is five nitric hydrate bismuths, bismuth sulfate or bismuth ion complex compound；The bromide compound is sodium bromide, potassium bromide, CTAB or 2-
Ethylamine hydrobromide；
S3, it stirs to clarify and neutral solution is added after solution stirs 20~80min, add reducing agent solution, stirring 3~
It is fitted into after 10min in the autoclave that pressure is 1~2Mpa, carries out 120~180 DEG C of isothermal reactions；
S4, it is cooled to room temperature and is centrifuged and is washed with water and ethanol solution, collect powder after dry at 50~80 DEG C
End；
S5,2~6h is calcined under 100~300 DEG C, 320~380mL/min atmosphere of hydrogen, obtain hydrogenation bismuth deposit bromine oxygen
Change bismuth.
Wherein, in step s3, the neutral solution is the monohydric alcohols such as methanol, ethyl alcohol, isopropanol, the tert-butyl alcohol, octanol；Institute
Stating reducing agent solution is hydrazine hydrate, thiocarbamide, sodium citrate, ascorbic acid or sodium borohydride solution.
The present invention provides a kind of preparation methods of visible light-responded organic matter degradation photochemical catalyst, specifically include following step
It is rapid:
S1, at room temperature using 20~40ml ethylene glycol, diethylene glycol, triethylene glycol, isopropanol or glycerine as solvent；
S2, the alcoholic solvent is added in 0.1~0.5g bismuth salt compound and 0.01~0.3g bromide compound, mixes and fills
Divide stirring 5~30min；
S3,40~80mL neutral solution, 20~80min of stirring is added after stirring to clarify solution, adds 0.1~4mL also
Former agent solution stirs 3~10min, is packed into autoclave after acquired solution stirring, carry out 120~180 DEG C of isothermal reaction 10h with
On；
S4, it is cooled to room temperature and is centrifuged and is washed 4~8 times with water and ethanol solution, after 50~80 DEG C dry, receive
Collect powder；
S5,2~6h is calcined under 100~300 DEG C, 320~380mL/min atmosphere of hydrogen, obtain hydrogenation bismuth deposit bromine oxygen
Change bismuth.
Wherein, when isothermal reaction described in step S3, it is 60% that the volume for filling solution, which accounts for the ratio of autoclave liner volume,
~90%, the reaction time be 10~for 24 hours.
The present invention provides a kind of using the method for dyestuff or antibiotic in above-mentioned catalyst degradation water, including following
Step: photochemical catalyst H-Bi@BiOBr being added into dyestuff or antibiotic organic solution, and maintains room temperature, is carrying out photocatalysis
Before, no light stirs 30min, then filters out catalyst after stirring 40~150min under visible light photograph.
Content of organics is 5~50mg/L in organic solution in above-mentioned reaction, the additional amount of catalyst meets 5~
30mg.The dyestuff be anthraquinone dyes or azo dyes, the antibiotic be Ofloxacin, terramycin, cephalosporin or
Penicillin.Wherein anthraquinone dyes be reactive brilliant blue, reactive brilliant red, Disperse Blue 2BLN, RSN vat blue, the gorgeous orchid RAW of faintly acid,
Rhodamine B etc., azo dyes are methyl orange, methylene blue, tonyred etc..
The present invention has the advantage that
Photochemical catalyst of the invention is H-Bi@BiOBr, and not only there is photochemical catalyst of the invention good visible light light to urge
Change degradation of organic substances performance, and possesses higher quantum efficiency.Under visible light, H-Bi@BiOBr can be incited somebody to action within a hour
Concentration is that the rhodamine B of 10mg/L is degradable, and degradation efficiency is 1.2 times of Bi@BiOBr, is 2.5 times of traditional BiOBr.
Not only there is significant organic matter degradation effect, quantum efficiency also with higher under visible light.In Environmental pollution and control
Field has broad application prospects, and strong theoretical basis is provided for the type catalyst.
Detailed description of the invention
Fig. 1 is the XRD diffraction pattern of 1 catalyst of embodiment.
Fig. 2 is the scanning electron microscope (SEM) photograph of 1 catalyst of embodiment.
Fig. 3 is the UV-vis abosrption spectrogram of 1 catalyst of embodiment.
Fig. 4 is that the forbidden bandwidth of 1 catalyst of embodiment estimates spectrogram.
Fig. 5 is the current versus time curve figure of 1 catalyst of embodiment.
Fig. 6 is the AC impedance figure of 1 catalyst of embodiment.
Fig. 7 is the photocatalytic degradation of dye organic matter effect picture of 4~7 catalyst of embodiment.
Fig. 8 is the photocatalytic degradation of dye organic matter effect picture of Examples 1 to 4,7 catalyst.
Fig. 9 is the photocatalytic degradation antibiotic organic matter effect picture of 4~7 catalyst of embodiment.
Figure 10 is the photocatalytic degradation antibiotic organic matter effect picture of Examples 1 to 4,7 catalyst.
Specific embodiment
The present invention it is a kind of hydrogenation bismuth deposit bismuth oxybromide efficient visible light response organic matter degradation photochemical catalyst preparation and
Application method belongs to catalysis material technical field.This method comprises the following steps: bismuth salt and bromide are dissolved in alcoholic solution
In；Neutral solution is added and reducing agent solution is added；Carry out hydro-thermal reaction；With water and ethanol washing and it is centrifugated；It is dry
After obtain solid powder；Hydrogen calcining is passed through in tube furnace；It is cooled to room temperature and obtains product.To dyestuff or antibiotic organic matter
Above-mentioned catalyst is added in solution, no light stirs evenly, then stirs under visible light photograph, and catalyst is filtered out after the completion of degradation.
The hydrogenation bismuth deposit bismuth oxybromide photocatalyst that the method for the present invention obtains is environmentally friendly, material source is extensive, cheap, method
It is controllable and easy to operate, can be produced in batches, have good Visible Light Induced Photocatalytic organic matter photocatalysis performance.
Below with reference to the attached drawing in the embodiment of the present invention, come technical solution in the embodiment of the present invention make it is clear,
Complete statement.Embodiments described below is only a part of the invention, is not whole embodiments.This field
Technical staff's above content according to the present invention is made some nonessential improvement and is all belonged to the scope of protection of the present invention.
It is an object of the present invention to provide a kind of visible light-responded organic matter degradation photochemical catalysts, provide described in a kind of prepare
The method of photochemical catalyst, while a kind of biodegrading process of visible light-responded organic matter degradation photochemical catalyst being provided.
Using 20~40mL ethylene glycol, diethylene glycol, triethylene glycol, isopropanol or glycerine as solvent, room in the present invention
It is reacted under temperature.The alcohol includes but is not limited to ethylene glycol, diethylene glycol, triethylene glycol, isopropanol or glycerine.
The alcoholic solution is added in 0.1~0.5g bismuth salt compound and 0.01~0.3g bromide compound, is mixed and abundant
Stirring, mixing time are 5~30min.The bismuth-containing compound includes but is not limited to five nitric hydrate bismuths, bismuth sulfate or bismuth ion
Complex compound；The bromine-containing compound includes but is not limited to sodium bromide, potassium bromide, CTAB or 2- ethylamine hydrobromide.
40~80mL neutral solution is added after above-mentioned solution is stirred to clarify solution in the present invention, and 0.1~4mL is added
Reducing solution, acquired solution are packed into autoclave after stirring 3~10min, carry out 120~180 DEG C of isothermal reactions 10~
24h.The neutral solution includes but is not limited to the monohydric alcohols such as methanol, ethyl alcohol, isopropanol, the tert-butyl alcohol or octanol.The reproducibility
Solution is hydrazine hydrate, thiocarbamide, sodium citrate, ascorbic acid or sodium borohydride solution.Product, which is cooled to room temperature, to be centrifuged
And washed 4 times~8 times with water and ethanol solution, powder is collected after dry at 50~80 DEG C.Wherein, when synthetic reaction, solution is filled
Volume account for autoclave liner volume ratio be 60%~90%；Reaction time be 10~for 24 hours.
2~6h is calcined under 100~300 DEG C, 320~380mL/min atmosphere of hydrogen, obtains final products H-Bi@
BiOBr。
The above-mentioned photochemical catalyst of 5~30mg is added in the present invention into 5~50mg/L dyestuff or antibiotic organic solution, and
Room temperature is maintained, before carrying out photocatalysis, no light stirs 30min, then filters out and urge after 40~150min of stirring under visible light photograph
Agent.
Compared with existing photocatalysis technology, the present invention is had the advantage that
(1) the H-Bi@BiOBr catalysis material that the present invention obtains not only there is good Photocatalytic Activity for Degradation to have
Machine physical performance, and possess higher quantum efficiency.Under visible light, sieve that can be 10mg/L by concentration within a hour
Red bright B is degradable, and degradation efficiency is 1.2 times of Bi@BiOBr, is 2.5 times of traditional BiOBr.Have under visible light aobvious
The organic matter degradation effect of work.It has broad application prospects in Environmental pollution and control field.
(2) preparation method of H-Bi@BiOBr catalysis material is environmentally protective, easy to operate, cheap, sets to special
Low for requiring, controllability is strong, has certain practicability.
Embodiment 1
Five nitric hydrate bismuth of 0.24g and 0.102g sodium bromide are added in 10mL ethylene glycol solution, 20min is sufficiently stirred
25mL aqueous isopropanol is added after to clear solution, 1mL thiourea solution is added after stirring 30min in mixed solution, after stirring 5min
It is packed into 1~2Mpa autoclave, carries out 160 DEG C of incubation water heating reaction 12h.Product is cooled to room temperature to be centrifuged and be used in combination
Water and ethanol solution are washed 6 times, collect powder after dry in 60 DEG C.4h is calcined under 200 DEG C, 360mL/min atmosphere of hydrogen, is obtained
Final products H-Bi@BiOBr.
Fig. 1 is the H-Bi@BiOBr photochemical catalyst XRD diffracting spectrum that the present embodiment obtains, through comparing with PDF standard card
It learns, the BiOBr obtained for tetragonal phase.
Fig. 2 is the H-Bi@BiOBr photochemical catalyst scanning electron microscope (SEM) photograph that the present embodiment obtains, and being obtained is what piece was polymerized
Diameter is about 1.5 μm of bouquets.
Fig. 3 is the H-Bi@BiOBr photochemical catalyst UV-vis absorption spectrum that the present embodiment obtains, and is inhaled compared to pure phase BiOBr
Side red shift is received, is obviously improved in visible-range internal absorbance, there is stronger light abstraction width.
Fig. 4 is the forbidden bandwidth estimation map for the H-Bi@BiOBr photochemical catalyst that the present embodiment obtains, the band of resulting materials
Gap relative narrower accelerates electron-transport speed, to promote photocatalytic activity.
Fig. 5 is the H-Bi@BiOBr photochemical catalyst photocurrent-time curve figure that the present embodiment obtains, compared to pure phase
BiOBr presents stronger photoelectric current, illustrates to have efficiently separated light induced electron and hole.
Fig. 6 is that the H-Bi@BiOBr photochemical catalyst AC impedance figure that the present embodiment obtains shows compared to pure phase BiOBr
Lesser resistance, at the same illustrate it is for the recombination rate of photo-generated carrier low, it is preferable to promote charge conversion and efficiently separate.
Embodiment 2
Five nitric hydrate bismuth of 0.24g and 0.102g sodium bromide are added in 10mL ethylene glycol solution, 20min is sufficiently stirred
25mL aqueous isopropanol is added after to clear solution, mixed solution stirs the thiourea solution of addition 1mL after 30min, stirs 5min
It is packed into 1~2Mpa autoclave afterwards, carries out 160 DEG C of incubation water heating reaction 12h.Product, which is cooled to room temperature, to be centrifuged simultaneously
It is washed 6 times with water and ethanol solution, collects powder after dry in 60 DEG C.4h is calcined under 250 DEG C, 360mL/min atmosphere of hydrogen, is obtained
To final products H-Bi@BiOBr.
Embodiment 3
Five nitric hydrate bismuth of 0.24g and 0.102g sodium bromide are added in 10mL ethylene glycol solution, 20min is sufficiently stirred
25mL aqueous isopropanol is added after to clear solution, mixed solution stirs the thiourea solution of addition 1mL after 30min, stirs 5min
It is packed into 1~2Mpa autoclave afterwards, carries out 160 DEG C of incubation water heating reaction 12h.Product, which is cooled to room temperature, to be centrifuged simultaneously
It is washed 6 times with water and ethanol solution, collects powder after dry in 60 DEG C.4h is calcined under 150 DEG C, 360mL/min atmosphere of hydrogen, is obtained
To final products H-Bi@BiOBr.
Embodiment 4
Five nitric hydrate bismuth of 0.24g and 0.102g sodium bromide are added in 10mL ethylene glycol solution, 20min is sufficiently stirred
25mL aqueous isopropanol is added after to clear solution, mixed solution is added 1.0mL thiourea solution after stirring 30min, stirs 5min
It is packed into 1~2Mpa autoclave afterwards, carries out 160 DEG C of incubation water heating reaction 12h.Product, which is cooled to room temperature, to be centrifuged simultaneously
It is washed 6 times with water and ethanol solution, collects powder after dry in 60 DEG C.Obtain final products Bi@BiOBr.
Embodiment 5
Five nitric hydrate bismuth of 0.24g and 0.102g sodium bromide are added in 10mL ethylene glycol solution, 20min is sufficiently stirred
25mL aqueous isopropanol is added after to clear solution, mixed solution is added 0.5mL thiourea solution after stirring 30min, stirs 5min
It is packed into 1~2Mpa autoclave afterwards, carries out 160 DEG C of incubation water heating reaction 12h.Product, which is cooled to room temperature, to be centrifuged simultaneously
It is washed 6 times with water and ethanol solution, collects powder after dry in 60 DEG C.Obtain final products Bi@BiOBr.
Embodiment 6
Five nitric hydrate bismuth of 0.24g and 0.102g sodium bromide are added in 10mL ethylene glycol solution, 20min is sufficiently stirred
25mL aqueous isopropanol is added after to clear solution, 2mL thiourea solution is added after stirring 30min in mixed solution, after stirring 5min
It is packed into 1~2Mpa autoclave, carries out 160 DEG C of incubation water heating reaction 12h.Product is cooled to room temperature to be centrifuged and be used in combination
Water and ethanol solution are washed 6 times, collect powder after dry in 60 DEG C.Obtain final products Bi@BiOBr.
Embodiment 7
Five nitric hydrate bismuth of 0.24g and 0.102g sodium bromide are added in 10mL ethylene glycol solution, 20min is sufficiently stirred
25mL aqueous isopropanol is added after to clear solution, mixed solution is packed into 1~2Mpa autoclave after stirring 30min, carries out
160 DEG C of incubation water heatings react 12h.Product, which is cooled to room temperature, to be centrifuged and is washed 6 times with water and ethanol solution, dry in 60 DEG C
Powder is collected after dry.Obtain final products BiOBr.
The test of photocatalysis dyestuff organic matter degradation is carried out for Examples 1 to 7 sample.
All photocatalysis experiments are at room temperature that visible light executes with 300W xenon lamp band 420nm cut out tab.Light is urged
Change degradation of dye organic matter process: the rhodamine B solution of 0.01g catalyst and 50mL being added in glass photocatalytic reactor
(solution concentration 10mg/L), and recirculated water is passed through to maintain room temperature.Before carrying out photocatalysis, no light stirring 30min, then
Visible light extracts 4ml solution out according to lower every 10min or 20min.It is further filtered with 0.22 μm of filter, and in ultraviolet specrophotometer
Absorbance is measured under specific absorption wavelength, for indicating palliating degradation degree.Photocatalysis rhodamine B is carried out for Examples 1 to 7 sample
Organic matter degradation test.
Fig. 7 illustrates 2 hours photocatalytic degradation of dye organic matter effects of 4~7 catalyst of embodiment.It is obvious that implementing
4 catalyst of example shows optimal photocatalytic degradation of organic matter effect, and the degradation rate of rhodamine B reaches 98.2% after 2 hours.It is real
Applying 5 catalyst of example is 93.0%, and 6 catalyst of embodiment is 95.5%, and 7 catalyst of untreated embodiment is 52.2%.
Fig. 8 illustrates Examples 1 to 4,1 hour photocatalytic degradation of organic matter effect of 7 catalyst.It is obvious that 1 catalyst of embodiment is aobvious
Optimal photocatalytic degradation of organic matter effect is shown, the degradation rate of rhodamine B reaches 99.5% after 1 hour.2 catalyst of embodiment
It is 96.5%, 3 catalyst of embodiment is 89.6%, and 4 catalyst of embodiment is 80.5%, and untreated embodiment 7 is catalyzed
Agent is 29.2%.To find out, H-Bi@BiOBr photochemical catalyst of the invention possesses brilliant photocatalytic degradation of organic matter effect.
The test of photocatalysis antibiotic organic matter degradation is carried out for Examples 1 to 7 sample.
All photocatalysis experiments are at room temperature that visible light executes with 300W xenon lamp band 420nm cut out tab.Light is urged
Change degradation antibiotic organic matter process: 0.01g catalyst being added in glass photocatalytic reactor and the Ofloxacin of 50mL is molten
Liquid (solution concentration 10mg/L), and recirculated water is passed through to maintain room temperature.Before carrying out photocatalysis, no light stirs 30min, then
Every 30min extracts 4ml solution out under visible light photograph.It is further filtered with 0.22 μm of filter, and specific in ultraviolet specrophotometer
Absorbance is measured under absorbing wavelength, for indicating palliating degradation degree.Carrying out photocatalytic-oxidation Flucloxacillin for Examples 1 to 7 sample has
The degradation test of machine object.
Fig. 9 illustrates 4 hours photocatalytic degradation antibiotic organic matter effects of 4~7 catalyst of embodiment.It is obvious that real
It applies 4 catalyst of example and shows optimal photocatalytic degradation of organic matter effect, the degradation rate of Ofloxacin reaches after 4 hours
77.5%.5 catalyst of embodiment is 61.4%, and 6 catalyst of embodiment is 71.2%, and 7 catalyst of untreated embodiment
It is 32.2%.Figure 10 illustrates Examples 1 to 4,3 hours photocatalytic degradation of organic matter effects of 7 catalyst.It is obvious that implementing
1 catalyst of example shows optimal photocatalytic degradation of organic matter effect, and the degradation rate of Ofloxacin reaches 81.9% after 3 hours.
2 catalyst of embodiment is 76.9%, and 3 catalyst of embodiment is 71.9%, and 4 catalyst of embodiment is 64.8%, and unprocessed
7 catalyst of embodiment be 25.3%.To find out, H-Bi@BiOBr photochemical catalyst of the invention possesses brilliant photocatalysis drop
Solve organic matter effect.
Catalyst provided by the invention, for the dyestuff or antibiotic organic matter under visible light in catalytic degradation water body.Needle
To different dyes and antibiotic, there are different degradation effects；It is prominent for anthraquinone dyes or azo dyes effect.Particular for
Anthraquinone dyes or the first such as gorgeous orchid RAW, the rhodamine B of reactive brilliant blue, reactive brilliant red, Disperse Blue 2BLN, RSN vat blue, faintly acid
The antibiosis such as azo dyes or Ofloxacin, terramycin, cephalosporin, penicillin such as base orange, methylene blue, tonyred are known as aobvious
The organic matter degradation effect of work.Since length is limited, whole organic matters and its test data can not be enumerated, the present invention only offer portion
Separating tests data support beneficial effects of the present invention.And the present invention can not also enumerate the specific organic matter for all having degradation effect,
It will be appreciated by those skilled in the art that, protection scope of the present invention should include all catalyst of the present invention according to claim
There is the organic matter of degradation effect；And the dyestuff or antibiotic for utilizing catalyst degradation of the present invention invalid, it is not protected in the present invention
In range, inventor does not determine specifically dyestuff or antibiotic without degradation effect at present.
In order to preferably carry out organic matter degradation light-catalyzed reaction using BiOBr, present invention employs bismuth deposits and low temperature
The method of hydrogen calcining, is successfully prepared the BiOBr microballoon of the flower ball-shaped with bismuth with elementary and a large amount of Lacking oxygens.For dyestuff and
The performance of good photocatalytic degradation of organic matter is presented in antibiotic organic wastewater, catalyst.Due to the deposition of bismuth simple substance, at it
While carrying out transmitting electronic action, SPR effect can more absorb visible light, enhance visible light utilization efficiency.Due to hydrogen
The reducing property of gas, hydrogenation process can make nano grain surface confusion to remove oxygen atom.This is that a kind of easy method is gone
Manufacture Lacking oxygen and the amount for controlling Lacking oxygen.Meanwhile 3D micro-sphere structure possesses a high specific surface area, this material presents Zhuo
Adsorption capacity more, so that under visible light, there is good organic matter degradation effect.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art within the technical scope of the present disclosure, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (14)
1. a kind of visible light-responded organic matter degradation photochemical catalyst, which is characterized in that catalyst is hydrogenation bismuth deposit bismuth oxybromide,
Molecular formula is H-Bi@BiOBr.
2. photochemical catalyst according to claim 1, which is characterized in that in the flower ball-shaped microballoon knot with bismuth simple substance and Lacking oxygen
Structure.
3. a kind of purposes of catalyst, which is characterized in that for the dyestuff or antibiotic organic matter in water body of degrading under visible light.
4. the purposes of catalyst according to claim 3, which is characterized in that the dyestuff is that anthraquinone dyes or azo contaminate
Material, the antibiotic are Ofloxacin, terramycin, cephalosporin or penicillin.
5. the purposes of catalyst according to claim 4, which is characterized in that the anthraquinone dyes are reactive brilliant blue, activity
The gorgeous orchid RAW of bright red, Disperse Blue 2BLN, RSN vat blue, faintly acid or rhodamine B, the azo dyes are methyl orange, methylene
Base indigo plant or tonyred.
6. a kind of preparation method of visible light-responded organic matter degradation photochemical catalyst, which comprises the steps of:
S1, at room temperature using ethylene glycol, diethylene glycol, triethylene glycol, isopropanol or glycerine as solvent；
S2, the alcoholic solvent is added in bismuth salt compound and bromide compound, mixes and is sufficiently stirred；The bismuth salt compound is
Five nitric hydrate bismuths, bismuth sulfate or bismuth ion complex compound；The bromide compound is sodium bromide, potassium bromide, CTAB or 2- ethamine
Hydrobromate；
S3, it stirs to clarify and neutral solution is added after solution stirs 20~80min, add reducing agent solution, stirring 3~
It is fitted into after 10min in the autoclave that pressure is 1~2Mpa, carries out 120~180 DEG C of isothermal reactions；
S4, it is cooled to room temperature and is centrifuged and is washed with water and ethanol solution, collect powder after dry at 50~80 DEG C；
S5,2~6h is calcined under 100~300 DEG C, 320~380mL/min atmosphere of hydrogen, obtain hydrogenation bismuth deposit bismuth oxybromide.
7. the preparation method of visible light-responded organic matter degradation photochemical catalyst according to claim 6, which is characterized in that step
In S3, the neutral solution is methanol, ethyl alcohol, isopropanol, the tert-butyl alcohol or octanol.
8. the preparation method of visible light-responded organic matter degradation photochemical catalyst according to claim 6, which is characterized in that step
In S3, the reducing agent solution is hydrazine hydrate, thiocarbamide, sodium citrate, ascorbic acid or sodium borohydride solution.
9. according to the preparation method of any visible light-responded organic matter degradation photochemical catalyst of claim 6~8, feature exists
In, comprising the following steps:
S1, at room temperature using 20~40ml ethylene glycol, diethylene glycol, triethylene glycol, isopropanol or glycerine as solvent；
S2, the alcoholic solvent is added in 0.1~0.5g bismuth salt compound and 0.01~0.3g bromide compound, mixes and sufficiently stirs
Mix 5~30min；
S3,40~80mL neutral solution, 20~80min of stirring is added after stirring to clarify solution, adds 0.1~4mL reducing agent
Solution stirs 3~10min, is packed into autoclave after acquired solution stirring, carries out 120~180 DEG C of isothermal reaction 10h or more；
S4, it is cooled to room temperature and is centrifuged and is washed 4~8 times with water and ethanol solution, after 50~80 DEG C dry, collect powder
End；
S5,2~6h is calcined under 100~300 DEG C, 320~380mL/min atmosphere of hydrogen, obtain hydrogenation bismuth deposit bismuth oxybromide.
10. the preparation method of visible light-responded organic matter degradation photochemical catalyst according to claim 9, which is characterized in that step
When isothermal reaction described in rapid S3, it is 60%~90% that the volume for filling solution, which accounts for the ratio of autoclave liner volume, the reaction time
For 10~for 24 hours.
11. a kind of use the method for dyestuff or antibiotic in above-mentioned catalyst degradation water, which is characterized in that dyestuff or resist
Photochemical catalyst H-Bi BiOBr is added in raw element organic solution, and maintains room temperature, before carrying out photocatalysis, stirs 30min, then
Catalyst is filtered out after stirring 40~150min under visible light photograph.
12. the method for dyestuff or antibiotic in water of degrading according to claim 11, which is characterized in that have in organic solution
Machine object content is 5~50mg/L, and the additional amount of catalyst meets 5~30mg.
13. the method for dyestuff or antibiotic in water of degrading according to claim 11, which is characterized in that the dyestuff is anthraquinone
Class dyestuff or azo dyes, the antibiotic are Ofloxacin, terramycin, cephalosporin or penicillin.
14. the method for dyestuff or antibiotic in the 3 degradation water according to claim 1, which is characterized in that the anthraquinone dyes
For reactive brilliant blue, reactive brilliant red, Disperse Blue 2BLN, RSN vat blue, the gorgeous orchid RAW of faintly acid or rhodamine B, the azo dye
Material is methyl orange, methylene blue or tonyred.
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| CN114345320A (en) * | 2021-11-19 | 2022-04-15 | 绍兴道普新材料科技有限公司 | Hydrogenated BiXOnMaterial, preparation method and application thereof |
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| CN113942977B (en) * | 2021-11-25 | 2023-12-15 | 哈尔滨工业大学水资源国家工程研究中心有限公司 | Method and device for preparing chlorine by anthraquinone photocatalytic oxidation |
| CN116251608A (en) * | 2022-10-31 | 2023-06-13 | 长春理工大学 | ZnO/Bi/BiOBr photocatalyst capable of efficiently degrading organic dye and simultaneously producing hydrogen and preparation method thereof |
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