CN115228510A - Conjugated polyvinyl chloride/zinc ferrite composite photocatalyst and preparation method and application thereof - Google Patents
Conjugated polyvinyl chloride/zinc ferrite composite photocatalyst and preparation method and application thereof Download PDFInfo
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- CN115228510A CN115228510A CN202210788911.XA CN202210788911A CN115228510A CN 115228510 A CN115228510 A CN 115228510A CN 202210788911 A CN202210788911 A CN 202210788911A CN 115228510 A CN115228510 A CN 115228510A
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- polyvinyl chloride
- znfe
- zinc ferrite
- composite photocatalyst
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- 239000004800 polyvinyl chloride Substances 0.000 title claims abstract description 97
- 229920000915 polyvinyl chloride Polymers 0.000 title claims abstract description 91
- 239000002131 composite material Substances 0.000 title claims abstract description 80
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 74
- 229910001308 Zinc ferrite Inorganic materials 0.000 title claims abstract description 58
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical compound O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000000498 ball milling Methods 0.000 claims abstract description 55
- 239000002245 particle Substances 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 20
- 239000004094 surface-active agent Substances 0.000 claims abstract description 20
- 238000002386 leaching Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 10
- 150000002500 ions Chemical class 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 7
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 8
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 235000021355 Stearic acid Nutrition 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 239000008117 stearic acid Substances 0.000 claims description 5
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 3
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 3
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims 1
- 230000010355 oscillation Effects 0.000 claims 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 24
- 230000008569 process Effects 0.000 abstract description 18
- 239000000463 material Substances 0.000 abstract description 17
- 238000005054 agglomeration Methods 0.000 abstract description 12
- 230000002776 aggregation Effects 0.000 abstract description 12
- 230000009467 reduction Effects 0.000 abstract description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 3
- 238000009854 hydrometallurgy Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000011701 zinc Substances 0.000 abstract description 3
- 229910052725 zinc Inorganic materials 0.000 abstract description 3
- 238000002203 pretreatment Methods 0.000 abstract description 2
- 239000010865 sewage Substances 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000002699 waste material Substances 0.000 description 8
- 238000002835 absorbance Methods 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 230000006798 recombination Effects 0.000 description 5
- 238000005215 recombination Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 238000000137 annealing Methods 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000013032 photocatalytic reaction Methods 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- 241001460678 Napo <wasp> Species 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- VBBRYJMZLIYUJQ-UHFFFAOYSA-N cyclopropanone Chemical compound O=C1CC1 VBBRYJMZLIYUJQ-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000009837 dry grinding Methods 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 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 description 2
- 229940012189 methyl orange Drugs 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- PDWBGRKARJFJGI-UHFFFAOYSA-N 2-phenylcyclohexa-2,4-dien-1-one Chemical compound O=C1CC=CC=C1C1=CC=CC=C1 PDWBGRKARJFJGI-UHFFFAOYSA-N 0.000 description 1
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- 239000004099 Chlortetracycline Substances 0.000 description 1
- FVIGODVHAVLZOO-UHFFFAOYSA-N Dixanthogen Chemical compound CCOC(=S)SSC(=S)OCC FVIGODVHAVLZOO-UHFFFAOYSA-N 0.000 description 1
- 239000004100 Oxytetracycline Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229960005091 chloramphenicol Drugs 0.000 description 1
- WIIZWVCIJKGZOK-RKDXNWHRSA-N chloramphenicol Chemical compound ClC(Cl)C(=O)N[C@H](CO)[C@H](O)C1=CC=C([N+]([O-])=O)C=C1 WIIZWVCIJKGZOK-RKDXNWHRSA-N 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- CYDMQBQPVICBEU-UHFFFAOYSA-N chlorotetracycline Natural products C1=CC(Cl)=C2C(O)(C)C3CC4C(N(C)C)C(O)=C(C(N)=O)C(=O)C4(O)C(O)=C3C(=O)C2=C1O CYDMQBQPVICBEU-UHFFFAOYSA-N 0.000 description 1
- 229960004475 chlortetracycline Drugs 0.000 description 1
- 235000019365 chlortetracycline Nutrition 0.000 description 1
- CYDMQBQPVICBEU-XRNKAMNCSA-N chlortetracycline Chemical compound C1=CC(Cl)=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O CYDMQBQPVICBEU-XRNKAMNCSA-N 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
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- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- CEQFOVLGLXCDCX-WUKNDPDISA-N methyl red Chemical compound C1=CC(N(C)C)=CC=C1\N=N\C1=CC=CC=C1C(O)=O CEQFOVLGLXCDCX-WUKNDPDISA-N 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229960000625 oxytetracycline Drugs 0.000 description 1
- 235000019366 oxytetracycline Nutrition 0.000 description 1
- IWVCMVBTMGNXQD-PXOLEDIWSA-N oxytetracycline Chemical compound C1=CC=C2[C@](O)(C)[C@H]3[C@H](O)[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O IWVCMVBTMGNXQD-PXOLEDIWSA-N 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 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 description 1
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- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- IWVCMVBTMGNXQD-UHFFFAOYSA-N terramycin dehydrate Natural products C1=CC=C2C(O)(C)C3C(O)C4C(N(C)C)C(O)=C(C(N)=O)C(=O)C4(O)C(O)=C3C(=O)C2=C1O IWVCMVBTMGNXQD-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229960004989 tetracycline hydrochloride Drugs 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
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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
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- B01J35/39—
-
- B01J35/40—
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
-
- 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
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
- C02F1/705—Reduction by metals
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- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/62—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2
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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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
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- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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- 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
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- 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
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- 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
Abstract
The invention provides a preparation method and application of a conjugated polyvinyl chloride/zinc ferrite composite photocatalyst. The zinc ferrite photocatalyst is prepared by taking zinc ferrite leaching residues generated in the traditional zinc hydrometallurgy process as raw materials and carrying out pretreatment methods of concentrated acid leaching, water washing and alcohol washing. The method comprises the steps of adopting a wet ball milling method, adjusting the particle size of zinc ferrite, adding a surfactant to solve the problem of material agglomeration in the ball milling process, then compounding zinc ferrite particles with polyvinyl chloride to obtain a polyvinyl chloride/zinc ferrite composite material, and finally carrying out heat treatment to obtain the conjugated polyvinyl chloride/zinc ferrite composite photocatalyst. The conjugated polyvinyl chloride/zinc ferrite composite photocatalyst can be used for photocatalytic degradation of organic pollutants in water or photocatalytic reduction of heavy metal ions, and compared with single-phase zinc ferrite, the photocatalytic performance is improved by 3-4 times. The composite photocatalyst prepared by the invention has the advantages of wide material source, low cost and excellent photocatalytic performance, and can be used for sewage treatment.
Description
Technical Field
The invention belongs to the field of photocatalytic materials, and particularly relates to a conjugated polyvinyl chloride/zinc ferrite composite photocatalyst as well as a preparation method and application thereof.
Background
With the rapid development of the industry, a large amount of organic matters and heavy metal ions are discharged into a water body, which causes a serious problem of environmental pollution. Among various sewage treatment technologies, the semiconductor photocatalytic oxidation or reduction technology is a low-cost, green and efficient technology. However, most of the photocatalysts have complex preparation methods and high cost, and the preparation of a wide-source photocatalyst with excellent performance and capability of realizing large-scale use is urgent.
The roasting process of the traditional zinc hydrometallurgy can generate a large amount of zinc ferrite, and the zinc ferrite is difficult to leach through conventional low acid, so that serious valuable metal resources are generatedIs wasted and puts stress on the environment. Zinc ferrite is a common photocatalytic semiconductor material, has the characteristics of stability, low price, wide material source and the like, and is widely used for photocatalytic degradation of pollutants. ZnFe in leaching slag of zinc hydrometallurgy 2 O 4 The pollutants in the water are recycled and used for photocatalytic degradation, and the purpose of treating wastes with processes of wastes against one another can be achieved. However, znFe 2 O 4 The fast recombination of the photo-generated electrons and holes and the short lifetime of the carriers lead to extremely low photocatalytic performance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a conjugated polyvinyl chloride/zinc ferrite composite photocatalyst, a preparation method and application thereof, and aims to solve the problem of single-phase ZnFe 2 O 4 Photo-generated electron (e) - ) And a cavity (h) + ) The problem of low photocatalytic performance caused by serious recombination and the problem of organic pollutants and heavy metal ion pollution in water.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention relates to a conjugated polyvinyl chloride/zinc ferrite composite photocatalyst, which comprises zinc ferrite particles and conjugated polyvinyl chloride coated on the surfaces of the zinc ferrite particles, wherein the mass fraction of the conjugated polyvinyl chloride in the composite photocatalyst A is 1-8%.
The inventor finds that the composite photocatalyst A has the optimal performance by controlling the mass fraction of the conjugated polyvinyl chloride in the range, and if the addition amount of the conjugated polyvinyl chloride is too large, znFe is caused 2 O 4 The composite photocatalyst is bonded together, so that a serious agglomeration phenomenon is caused, and the performance of the composite photocatalyst is influenced.
The invention provides a conjugated polyvinyl chloride/zinc ferrite composite photocatalyst, which is prepared by modifying ZnFe with conjugated polyvinyl chloride (CPVC) 2 O 4 The CPVC has an energy band structure similar to a semiconductor structure, a conjugated structure of the CPVC has higher absorption to visible light and has good electron transmission,for ZnFe 2 O 4 After the catalyst is modified, the photoresponse range is expanded to a visible light region, and CPVC and ZnFe are utilized simultaneously 2 O 4 The energy level difference of (2) improves the separation efficiency of the photo-generated electron-hole pairs. Under the irradiation of visible light, CPVC/ZnFe 2 O 4 The composite photocatalyst absorbs visible light to generate electron hole pairs, and electrons are transited from a valence band to a conduction band; simultaneously loaded on ZnFe 2 O 4 Electrons on the highest occupied orbital (HOMO) of CPVC of the surface are excited to the lowest unoccupied orbital (LUMO). The composite structure realizes the ZnFe 2 O 4 Mainly adopts photo-generated electron distribution, and mainly adopts hole distribution on the CPVC, so that the effective separation of photo-generated electron-hole pairs is promoted, the recombination rate of photo-generated carriers is reduced, and the photocatalytic activity is improved.
In a preferred embodiment, in the composite photocatalyst a, the mass fraction of the conjugated polyvinyl chloride is 3 to 5%, and is preferably 4%.
In a preferred embodiment, the zinc ferrite particles have a particle size of 500 to 1000nm, preferably 500 to 600nm.
The particle size is controlled within the above range, so that the performance of the final composite photocatalyst a is optimal, and if the particle size is too large, the specific surface area of the material is too small, which affects the absorption of the material on visible light, and further causes the photocatalytic performance to be low. When the particle size is too small, agglomeration is easily generated in the CPVC coating process, and the photocatalysis performance is also influenced.
The invention relates to a preparation method of a conjugated polyvinyl chloride/zinc ferrite composite photocatalyst, which comprises the steps of adding zinc ferrite leaching residues into an acid solution, and soaking to obtain ZnFe 2 O 4 Then ZnFe is mixed 2 O 4 Performing wet ball milling, and adding a surfactant during the wet ball milling to obtain ZnFe 2 O 4 Particles, then ZnFe 2 O 4 Placing the particles in a solution containing polyvinyl chloride (PVC), and reacting to obtain PVC/ZnFe 2 O 4 And (3) carrying out heat treatment on the composite material to obtain the composite photocatalyst A.
In a preferred scheme, zinc ferrite leaching residue is added into an acid solution, stirred and soaked for 10-60 min at the rotating speed of 400-800 rpm,then washing for 3-5 times by adopting a centrifugal mode, washing for 2-3 times by adopting ethanol, and drying to obtain ZnFe 2 O 4 。
Further preferably, the acid solution is selected from the group consisting of HCl solution, HNO 3 Solution, H 2 SO 4 At least one of solutions of H in acid solution + The concentration of (B) is 4 to 12mol/L.
In a preferable scheme, the rotation speed of the wet ball milling is 200-400 rpm, and the time of the wet ball milling is 2-8 h.
In the invention, ball milling has certain influence on the performance of the final composite photocatalyst A, and ZnFe can not be crushed due to too short ball milling time and too low ball milling rotating speed 2 O 4 Of ZnFe 2 O 4 Without a significant reduction in particle size. Too long ball milling time and too high ball milling speed can cause over-milling phenomenon, influence the crystallinity of the material, generate agglomeration phenomenon and seriously consume energy.
In a preferred embodiment, the ball milling medium for wet ball milling is absolute ethyl alcohol or water.
In a preferred scheme, the addition amount of the surfactant is ZnFe 2 O 4 5 to 20 percent of the mass.
In the invention, the surfactant with the mass can effectively reduce the agglomeration effect in the ball milling process by adding the surfactant with the mass, and too much surfactant which cannot play a role in reducing the agglomeration effect in the ball milling process can influence ZnFe 2 O 4 Direct contact with the ball milling beads results in a reduction in the ball milling effect.
Preferably, the surfactant is selected from the group consisting of cetyltrimethylammonium bromide (CTAB), stearic Acid (SA), polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), sodium Dodecyl Sulfonate (SDS), and sodium hexametaphosphate (NaPO) 3 ) 6 At least one of (a).
In a preferred embodiment, polyvinyl chloride (PVC) is dissolved in an organic solvent selected from the group consisting of N, N-Dimethylformamide (DMF), dimethylsulphoxide (DMSO), and cyclopropanone (C) to obtain a solution containing polyvinyl chloride (PVC) 3 H 4 O)、Tetrahydrofuran (THF) and dichloroethane (C) 2 H 4 Cl 2 ) At least one of (a).
In a preferred embodiment, znFe is used 2 O 4 The particles are put into solution containing polyvinyl chloride (PVC), stirred and reacted for 1 to 4 hours, ultrasonically oscillated for 30 to 120min and then dried to obtain PVC/ZnFe 2 O 4 A composite material.
In the preferred scheme, the addition amount of the PVC is ZnFe 2 O 4 1 to 8%, preferably 3 to 5% of the mass of the particles.
In actual operation, the PVC material can be one of waste PVC pipes, PVC plates, PVC films, various PVC plastic products and commercial PVC powder.
Preferably, the temperature of the heat treatment is 150-300 ℃, and the time of the heat treatment is 2-3 h.
PVC is subjected to a heat treatment annealing process to remove hydrogen chloride molecules to form CPVC/ZnFe with saturated double bonds 2 O 4 A composite photocatalyst of a compound light source and a compound light source,
the invention relates to a conjugated polyvinyl chloride/zinc ferrite composite photocatalyst, wherein the composite photocatalyst B consists of conjugated polyvinyl chloride and zinc ferrite particles modified on the surface of the conjugated polyvinyl chloride, the particle size of the conjugated polyvinyl chloride is 1-2 mu m, the particle size of the zinc ferrite particles is less than 1 mu m, and the mass fraction of the conjugated polyvinyl chloride in the composite photocatalyst B is 30-90%.
The inventors have found that when conjugated polyvinyl chloride is used as the core material and zinc ferrite particles are used for modification, the modification is caused by ZnFe 2 O 4 The size is smaller, so that the mass ratio of the conjugated polyvinyl chloride to the zinc ferrite particles is more or less, and the zinc ferrite particles can be modified on the surface of the conjugated polyvinyl chloride.
In a preferred embodiment, the zinc ferrite particles have a particle size of 500 to 1000nm, preferably 500 to 600nm.
The invention relates to a preparation method of a conjugated polyvinyl chloride/zinc ferrite composite photocatalyst, which comprises the steps of adding zinc ferrite leaching residues into an acid solution, and soaking to obtain ZnFe 2 O 4 Then ZnFe is mixed 2 O 4 Carrying out wet ball milling, and adding a surfactant during the wet ball milling to obtain ZnFe 2 O 4 The particles are mixed with ZnFe according to the designed proportion 2 O 4 Carrying out dry ball milling on the particles and the polyvinyl chloride to obtain PVC/ZnFe 2 O 4 And (4) carrying out heat treatment on the composite material to obtain the composite photocatalyst B.
Preferably, the zinc ferrite leaching residue is added into an acid solution, stirred and soaked for 10-60 min at the rotating speed of 400-800 rpm, then washed for 3-5 times by adopting a centrifugal mode, washed for 2-3 times by adopting ethanol and dried to obtain ZnFe 2 O 4 。
Further preferably, the acid solution is selected from the group consisting of HCl solution, HNO 3 Solution, H 2 SO 4 At least one of a solution of H in said acid solution + The concentration of (b) is 4 to 12mol/L.
In a preferable scheme, the rotation speed of the wet ball milling is 200-400 rpm, and the time of the wet ball milling is 2-8 h.
In the invention, the ball milling has certain influence on the performance of the final composite photocatalyst B, and ZnFe can not be crushed due to too short ball milling time and too low ball milling rotating speed 2 O 4 Of (b) ZnFe 2 O 4 Without a significant reduction in particle size. Too long ball milling time and too high ball milling speed can cause over-milling phenomenon, influence the crystallinity of the material, generate agglomeration phenomenon and seriously consume energy.
In a preferred embodiment, the ball milling medium for wet ball milling is absolute ethyl alcohol or water.
In a preferred scheme, the addition amount of the surfactant is ZnFe 2 O 4 5 to 20 percent of the mass.
In the invention, the surfactant with the mass can effectively reduce the agglomeration effect in the ball milling process, and too much surfactant which cannot play a role in reducing the agglomeration effect in the ball milling process can influence ZnFe 2 O 4 Direct contact with the ball milling beads results in a reduction in the ball milling effect.
In a preferred embodiment, the surfactant isSelected from cetyl trimethylammonium bromide (CTAB), stearic Acid (SA), polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), sodium Dodecyl Sulfonate (SDS) and sodium hexametaphosphate (NaPO) 3 ) 6 At least one of (a).
In a preferred embodiment, polyvinyl chloride (PVC) is dissolved in an organic solvent selected from the group consisting of N, N-Dimethylformamide (DMF), dimethylsulphoxide (DMSO), and cyclopropanone (C) to obtain a solution containing polyvinyl chloride (PVC) 3 H 4 O), tetrahydrofuran (THF) and dichloroethane (C) 2 H 4 Cl 2 ) At least one of (1).
In a preferable scheme, the rotating speed of the dry ball milling is 200-400 rpm, and the time of the dry ball milling is 2-6 h.
In the actual operation process, the PVC material can be one of waste PVC pipes, PVC plates, PVC films, various PVC plastic products and commercial PVC powder.
Preferably, the temperature of the heat treatment is 150-300 ℃, and the time of the heat treatment is 2-3 h.
PVC is subjected to a heat treatment annealing process to remove hydrogen chloride molecules to form CPVC/ZnFe with saturated double bonds 2 O 4 A composite photocatalyst of a compound light source and a compound light source,
the invention also provides a conjugated polyvinyl chloride/zinc ferrite composite photocatalyst, and the composite photocatalyst A or the composite photocatalyst B is used for photocatalytic degradation of organic pollutants or heavy metal ions in water.
In the actual operation process, the CPVC/ZnFe is mixed 2 O 4 The composite photocatalyst is put into a proper amount of organic solution/solution containing heavy metal ions, and the organic pollutants in the solution are oxidized or the heavy metal ions in the solution are reduced under the irradiation and the stirring of a light source.
Wherein the light source can be one of sunlight, xenon lamp, fluorescent lamp, LED lamp, halogen tungsten lamp and mercury lamp, and the power of the light source is 100-150 mW/cm 2 . The stirring speed is 200-500 rpm, and the reaction time is 2-4 h.
The organic pollutants comprise tetracycline hydrochloride, chloramphenicol, oxytetracycline, chlortetracycline, and ciprofloxacinStar, methylene blue, methyl orange, methyl red and rhodamine B. The heavy metal ions comprise Cu 2+ 、 Pb 2+ 、Cd 2+ And Cr 6+ The concentration of the organic solution or the solution containing heavy metal ions is 1 mol/L-100 mol/L, and the pH value of the solution is kept acidic.
Principles and advantages
The main component of the zinc ferrite leaching residue is ZnFe 2 O 4 、ZnO、CaSO 4 ·2H 2 O and a trace amount of Fe 3 O 4 . For the impurity removal process, it depends on the spinel phase ZnFe 2 O 4 Has stable structure, and is insoluble in concentrated acid, znO and Fe 3 O 4 Reaction with concentrated acid, caSO 4 ·2H 2 O is dissolved in concentrated acid. The water washing and the ethanol washing can remove water-soluble impurities and are easy to dry.
ZnFe prepared by the process 2 O 4 The particle size is too large and the specific surface area is small, resulting in single-phase ZnFe 2 O 4 The photocatalytic performance is low, and the photocatalytic performance is low, it is not easy to form a composite structure with CPVC. Thus, znFe is reduced by wet ball milling 2 O 4 The specific surface area is increased. After ball milling for a certain time, znFe 2 O 4 The nanometer particles have obviously reduced particle size, large surface atom proportion, large specific surface area and large surface energy and are in an unstable energy state, so that fine particles tend to aggregate together and are easy to aggregate to form secondary particles, and the particle size is enlarged again. Therefore, a certain amount of surfactant is added, and a layer of molecular film is formed to prevent the particles from contacting with each other by utilizing the adsorption effect of the surfactant on a solid-liquid interface, so that the agglomeration is reduced.
PVC is general plastic, and the decomposition temperature is lower, and when receiving high temperature, when taking off a hydrogen chloride molecule on PVC molecular chain, can form an unsaturated double bond, and this double bond can activate adjacent chlorine atom and nearby hydrogen atom to combine again, removes with the form of hydrogen chloride finally, forms conjugated polyvinyl chloride (CPVC). CPVC has an energy band structure similar to that of a semiconductor structure, has a conjugated structure with high absorption of visible light, andhas good electron transmission property and can modify ZnFe 2 O 4 Catalyst for extending photoresponse range to visible region while using CPVC and ZnFe 2 O 4 The energy level difference of the photo-generated electron-hole pairs is improved. ZnFe is obtained by calculation through Tauc plots method 2 O 4 And the forbidden band widths of CPVC are 1.71eV and 1.88eV, respectively. ZnFe measured by M-S curve 2 O 4 The potential of the conduction band of the CPVC is 0.01V, and the lowest empty orbit of the CPVC is-0.29V. Thus, znFe 2 O 4 The valence band potential of (1.72V) and the highest occupied track of CPVC is 1.59V. Under the irradiation of visible light, CPVC/ZnFe 2 O 4 The composite photocatalyst absorbs visible light to generate electron hole pairs, and electrons are transited from a valence band to a conduction band; simultaneously loaded on ZnFe 2 O 4 Electrons on the highest occupied orbital (HOMO) of CPVC at the surface are excited to the lowest unoccupied orbital (LUMO), and the transfer of electrons and holes is shown in fig. 7. The composite structure realizes the ZnFe 2 O 4 Mainly adopts photon-generated electron distribution, and mainly adopts hole distribution on the CPVC, so that the effective separation of photon-generated electron-hole pairs is promoted, the recombination rate of photon-generated carriers is reduced, and the photocatalytic activity is improved.
For CPVC/ZnFe 2 O 4 The composite material adopts a reaction mechanism of photocatalytic degradation of organic pollutants, taking methyl orange as an example:
ZnFe 2 O 4 +hv→ZnFe 2 O 4 (e - +h + ) (1)
CPVC+hv→CPVC(e - +h + ) (2)
ZnFe 2 O 4 (h + )+CPVC→ZnFe 2 O 4 +CPVC(h + ) (3)
ZnFe 2 O 4 (h + )/CPVC(h + )+H 2 O→ZnFe 2 O 4 /CPVC+H + +·OH (4)
·OH/h + +MO→CO 2 +H 2 O (5)
for CPVC/ZnFe 2 O 4 Composite material, photocatalytic reductionThe reaction mechanism of heavy metal ions is simpler, and Cr is used 6 + For example, the following steps are carried out:
CPVC(e - )+ZnFe 2 O 4 →CPVC+ZnFe 2 O 4 (e - ) (6)
compared with the prior art, the technical scheme of the invention has the following beneficial effects:
(1) The raw material used in the invention is zinc ferrite leaching residue, and the material source is wide. The pretreatment method is simple and reliable, and high-efficiency ZnFe is prepared 2 O 4 A photocatalyst. Compared with the treatment method for recovering the zinc ferrite leaching residue by pyrogenic reduction or hot acid leaching decomposition, which is mostly adopted at present, the method greatly reduces the energy consumption and does not cause secondary pollution;
(2) The wet ball milling process used in the invention improves ZnFe 2 O 4 The specific surface area of the nano-particle reduces the particle size, and the problem of serious agglomeration of nano-particles in the ball milling process is solved by adding the surfactant;
(3) PVC is widely applied in actual life, and waste PVC materials (PVC pipes, PVC plates, PVC films and various PVC plastic products) can be used for replacing commercial nano PVC powder, so that the preparation cost of the materials is further reduced;
(4) CPVC/ZnFe prepared by the invention 2 O 4 The composite material has excellent photocatalytic performance compared with single-phase ZnFe 2 O 4 The photocatalytic degradation rate is improved by 3 to 4 times. Solve the problem of ZnFe 2 O 4 The general problem of low photocatalytic performance caused by serious recombination of photon-generated carriers;
(5) The method provided by the invention realizes preparation of the efficient composite photocatalyst by taking industrial leaching residues and waste PVC materials as raw materials, and the efficient composite photocatalyst is used for treating pollutants in water, so that the effect of treating wastes with processes of wastes against one another is achieved.
Drawings
FIG. 1 shows ZnFe prepared in example 1 of the present invention 2 O 4 And CPVC/ZnFe prepared in example 2 2 O 4 XRD pattern of the composite photocatalyst;
FIG. 2 (a) shows ZnFe prepared in example 1 of the present invention 2 O 4 SEM picture of (1); (b, c) CPVC/ZnFe prepared in example 2 2 O 4 -4% and CPVC/ZnFe 2 O 4 -SEM image of 5%; (d) CPVC/ZnFe 2 O 4 EDS spectrum of 4%.
FIG. 3 (a) is ZnFe prepared in example 1 of the present invention 2 O 4 The forbidden band width of the capacitor; (b) forbidden bandwidth of CPVC prepared in example 2.
FIG. 4 shows CPVC/ZnFe in different ratios in example 3 of the present invention 2 O 4 Degradation curve of photocatalytic reduction Cr (VI).
FIG. 5 (a) is an SEM image of CPVC in example 4 of the present invention; (b) ZnFe prepared by dry grinding method 2 O 4 SEM image of/CPVC composite photocatalyst; (c) ZnFe 2 O 4 EDS energy spectrogram of the/CPVC composite photocatalyst.
FIG. 6 shows ZnFe in example 4 of the present invention 2 O 4 Absorbance curve for MB degradation process (left panel); znFe 2 O 4 Absorbance curve of CPVC versus MB degradation (right panel).
FIG. 7CPVC/ZnFe 2 O 4 The transfer diagram of electrons and holes of the composite photocatalyst.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples. It is to be understood that the specific embodiments described herein are merely illustrative of the invention and are not limiting of the invention.
Example 1:
ZnFe 2 O 4 and (3) preparing the photocatalyst.
ZnFe provided in this example 2 O 4 The preparation method of (2) firstly prepares concentrated hydrochloric acid with different concentrations: 12 Hydrochloric acid solution of mol/L, 8mol/L and 4 mol/L.
10g of zinc ferrite leaching residue is taken and placed in 100ml of concentrated acid solution (8 mol/L), the stirring speed is 600 rpm, and the stirring time is 30min. Washing for 3-5 times by adopting a centrifugal modeWashing with ethanol for 2-3 times, and drying at 100 deg.C to obtain ZnFe 2 O 4 A photocatalyst.
Mixing 10g ZnFe 2 O 4 Placing in a planetary ball mill, adding 200g ZrO 2 Ball milling beads, taking a proper amount of ethanol as a medium and 1g of CTAB as a surfactant, ball milling for 2-6 h at the rotating speed of 300rpm, and drying at 60 ℃. Ball milling of ZnFe for 2h, 4h and 6h 2 O 4 The particle diameters of (a) are 669nm, 564nm and 813nm, respectively. FIG. 1 shows ZnFe prepared by the above process 2 O 4 XRD pattern of (1), znFe can be seen 2 O 4 Good crystallinity, completely matched with standard PDF card, and residual diffraction peak of the material is trace SiO 2 And (4) the following steps. FIG. 2 (a) shows ZnFe 2 O 4 Is composed of irregular block-shaped structures with non-uniform sizes. FIG. 3 (a) is ZnFe calculated by the Tauc plots method 2 O 4 The forbidden band width of (c).
In which ZnFe is ball milled for 4h 2 O 4 The particle size is minimum, the specific surface area is maximum, and the single-phase photocatalysis performance is optimal.
Example 2:
preparing the conjugated polyvinyl chloride/zinc ferrite composite photocatalyst.
10mg, 20mg, 30mg, 40mg and 50mg of PVC were dissolved in 20ml of tetrahydrofuran, and 1g of the above ZnFe ball-milled for 4 hours was added 2 O 4 Stirring and reacting for 3h at the rotating speed of 700rpm, ultrasonically oscillating for 40min, and drying for 10h at the temperature of 60 ℃ to prepare PVC/ZnFe 2 O 4 A material. Mixing PVC/ZnFe 2 O 4 Annealing at 150 ℃ for 120min to obtain CPVC/ZnFe 2 O 4 Composite photocatalyst marked as CPVC/ZnFe 2 O 4 -1％、CPVC/ZnFe 2 O 4 -2％、CPVC/ZnFe 2 O 4 -3％、 CPVC/ZnFe 2 O 4 -4% and CPVC/ZnFe 2 O 4 -5%. FIG. 1 shows CPVC/ZnFe 2 O 4 XRD pattern of 4% vs. ZnFe in single phase 2 O 4 Exhibits a relatively weak and broad diffraction peak in the range of 20 to 30 DEG, is caused by CPVC, and is characterized in that the surface CPVC is almost amorphousAnd (5) performing characterization. FIG. 2 (b) shows CPVC/ZnFe 2 O 4 SEM image of 4%, the right amount of CPVC can be in ZnFe 2 O 4 The surface is uniformly distributed. FIG. 2 (c) CPVC/ZnFe 2 O 4 SEM of-5% shows that excess CPVC would result in ZnFe 2 O 4 The composite photocatalyst is bonded together, so that a serious agglomeration phenomenon is caused, and the performance of the composite photocatalyst is influenced. FIG. 2 (d) shows CPVC/ZnFe 2 O 4 EDS spectrum at 4%, presence of elements C and Cl further verifies presence of CPVC. As a control, a proper amount of PVC is taken to anneal for 120min at 150 ℃, and the single-phase CPVC is obtained.
10mg of CPVC is dissolved in 1ml of DMF solvent, a CPVC film is prepared by adopting a spin coating method, and the flat band potential of the CPVC is measured to be-0.09V and the conduction band potential is measured to be-0.29V by using a three-electrode system. The energy gap of the CPVC calculated by the Tauc plots method is 1.88eV, as shown in fig. 3 (b). ZnFe is prepared by adopting the method 2 O 4 Film, CPVC and ZnFe obtained by calculation 2 O 4 The conduction band potential, valence band potential and forbidden band width of the heterojunction are shown in the abstract diagram, and a typical type-II heterojunction can be formed.
Example 3:
CPVC/ZnFe with different proportions 2 O 4 And (3) carrying out photocatalytic reduction on Cr (VI).
CPVC/ZnFe provided by the embodiment 2 O 4 The photocatalyst is used for reducing Cr (VI) in the water body, and CPVC/ZnFe with different proportions prepared in example 2 is adopted 2 O 4 As photocatalyst, potassium dichromate solution is used as target reducing substance.
Preparation K 2 Cr 2 O 4 Solution 4.079ml of standard potassium dichromate was dissolved in 1L of ionized water to obtain a Cr (vi) solution with a concentration of 20mg/L, and the solution pH =3 was adjusted. Respectively taking 40mg of CPVC/ZnFe 2 O 4 -1％、CPVC/ZnFe 2 O 4 -2％、CPVC/ZnFe 2 O 4 -3％、CPVC/ZnFe 2 O 4 -4% and CPVC/ZnFe 2 O 4 Putting 5 percent of the solution in 50ml of 20mg/L Cr (VI) solution, stirring the solution for 30min in a dark state to realize the adsorption and desorption balance of the composite photocatalyst on the solution, wherein the concentration of the solution is 100mW/cm 2 Xenon lamp illuminationThen, the photocatalytic reaction is carried out. Carrying out photocatalytic reaction for 120min, taking 3ml of supernatant every 20min, centrifuging, measuring the absorbance of the solution at the maximum wavelength (350 nm), and further calculating the reduction rate. As a result, as shown in FIG. 4, as the ratio of CPVC was increased from 1% to 5%, the reduction rates of Cr (VI) were 17.59%, 25.12%, 37.078%, 47.079%, 72.154% and 68.713%, respectively. CPVC/ZnFe 2 O 4 4% showed the highest photocatalytic performance.
Example 4:
ZnFe is prepared by adopting dry ball milling method 2 O 4 /CPVC composite photocatalyst.
In this example, znFe was modified on the CPVC surface by dry grinding 2 O 4 Taking 1g of PVC and 2g of ZnFe 2 O4, 60g of ZrO added 2 Ball milling beads, ball milling for 4 hours at the rotating speed of 300rpm, and preparing ZnFe 2 O 4 PVC powder. ZnFe 2 O 4 PVC annealing at 150 deg.C for 120min, and heating rate of 5 deg.C/min to obtain ZnFe 2 O 4 /CPVC composite photocatalyst. The size of PVC is 1-2 μm, and the spherical structure is shown in FIG. 5 (a). ZnFe of smaller size 2 O 4 Ball-milling to modify the surface of CPVC, as shown in FIG. 5 (b). The EDS spectrum of FIG. 5 (c) further demonstrates ZnFe 2 O 4 Presence at the CPVC surface.
Preparing 20mg/L MB solution, adjusting the pH of the solution to be =3, and adding 40mg of ZnFe 2 O 4 The CPVC composite photocatalyst is stirred for 30min in a dark state, and the photocatalytic reaction is carried out for 4h. In the reaction process, samples are taken every 30min to test the absorbance, and then the degradation rate is calculated. Shown as the left diagram of FIG. 6 is single-phase ZnFe 2 O 4 The absorbance curve when MB is degraded by photocatalysis, and the right graph of figure 6 is ZnFe 2 O 4 Absorbance curve of CPVC composite photocatalysis to MB degradation. ZnFe 2 O 4 The photocatalytic activity of the/CPVC is obviously superior to that of single-phase ZnFe 2 O 4 The degradation rate for MB increased from 22.5% to 60.67%.
Claims (10)
1. A conjugated polyvinyl chloride/zinc ferrite composite photocatalyst is characterized in that: the composite photocatalyst A consists of zinc ferrite particles and conjugated polyvinyl chloride coated on the surfaces of the zinc ferrite particles, and the mass fraction of the conjugated polyvinyl chloride in the composite photocatalyst A is 1-8%.
2. The conjugated polyvinyl chloride/zinc ferrite composite photocatalyst as claimed in claim 1, wherein: in the composite photocatalyst A, the mass fraction of the conjugated polyvinyl chloride is 3-5%, and the particle size of the zinc ferrite particles is 500-1000 nm.
3. The preparation method of the conjugated polyvinyl chloride/zinc ferrite composite photocatalyst as claimed in claim 1 or 2, wherein: adding the zinc ferrite leaching residue into an acid solution, and soaking to obtain ZnFe 2 O 4 Then ZnFe is mixed 2 O 4 Carrying out wet ball milling, and adding a surfactant during the wet ball milling to obtain ZnFe 2 O 4 Particles, then ZnFe 2 O 4 The particles are put into solution containing polyvinyl chloride for reaction to obtain PVC/ZnFe 2 O 4 And (3) carrying out heat treatment on the composite material to obtain the composite photocatalyst A.
4. The preparation method of the conjugated polyvinyl chloride/zinc ferrite composite photocatalyst according to claim 3, wherein the preparation method comprises the following steps: adding zinc ferrite leaching residue into acid solution, stirring and soaking for 10-60 min at the rotating speed of 400-800 rpm, then adopting a centrifugal mode to wash for 3-5 times, washing for 2-3 times by using ethanol, and drying to obtain ZnFe 2 O 4 (ii) a The acid solution is selected from HCl solution and HNO 3 Solution, H 2 SO 4 At least one of a solution of H in said acid solution + The concentration of (b) is 4 to 12mol/L.
5. The preparation method of the conjugated polyvinyl chloride/zinc ferrite composite photocatalyst according to claim 3, wherein the preparation method comprises the following steps: the rotation speed of the wet ball milling is 200-400 rpm, and the time of the wet ball milling is 2-8 h; the ball milling medium of the wet ball milling is anhydrousEthanol or water; the addition amount of the surfactant is ZnFe 2 O 4 5-20% of the mass; the surfactant is at least one selected from cetyl trimethyl ammonium bromide, stearic acid, polyvinyl alcohol, polyvinylpyrrolidone, sodium dodecyl sulfate and sodium hexametaphosphate.
6. The preparation method of the conjugated polyvinyl chloride/zinc ferrite composite photocatalyst according to claim 3, wherein the preparation method comprises the following steps: znFe is mixed with water 2 O 4 The particles are put into solution containing polyvinyl chloride, firstly react for 1 to 4 hours under stirring, then are subjected to ultrasonic oscillation for 30 to 120min, and then are dried to obtain PVC/ZnFe 2 O 4 A composite material; the addition amount of the polyvinyl chloride is ZnFe 2 O 4 1 to 8 percent of the mass of the particles.
7. The method for preparing the conjugated polyvinyl chloride/zinc ferrite composite photocatalyst as claimed in claim 3, wherein the method comprises the following steps: the temperature of the heat treatment is 150-300 ℃, and the time of the heat treatment is 2-3 h.
8. A conjugated polyvinyl chloride/zinc ferrite composite photocatalyst is characterized in that: the composite photocatalyst B is composed of conjugated polyvinyl chloride and zinc ferrite particles modified on the surface of the conjugated polyvinyl chloride, the particle size of the conjugated polyvinyl chloride is 1-2 mu m, the particle size of the zinc ferrite particles is less than 1 mu m, and the mass fraction of the conjugated polyvinyl chloride in the composite photocatalyst B is 30-90%.
9. The method for preparing the conjugated polyvinyl chloride/zinc ferrite composite photocatalyst according to claim 8, wherein the method comprises the following steps: adding the zinc ferrite leaching residue into an acid solution, and soaking to obtain ZnFe 2 O 4 Then ZnFe is mixed 2 O 4 Carrying out wet ball milling, and adding a surfactant during the wet ball milling to obtain ZnFe 2 O 4 Particles are then prepared according to the designed proportion 2 O 4 Carrying out dry ball milling on the particles and the polyvinyl chloride to obtain PVC/ZnFe 2 O 4 And (3) carrying out heat treatment on the composite material to obtain the composite photocatalyst B.
10. The application of the conjugated polyvinyl chloride/zinc ferrite composite photocatalyst is characterized in that: the composite photocatalyst A as claimed in claim 1 or 2 or the composite photocatalyst B as claimed in claim 8 is used for photocatalytic degradation of organic pollutants or heavy metal ions in a water body.
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| CN115688430A (en) * | 2022-11-01 | 2023-02-03 | 烟台大学 | Method for obtaining desorption behavior of hydrogen atoms on surface of material based on COMSOL software |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1370619A (en) * | 2001-12-03 | 2002-09-25 | 山东中科纳米技术有限公司 | Prepn of loaded nano TiO2 photocatalyst |
| CN103623870A (en) * | 2013-12-11 | 2014-03-12 | 河北科技大学 | Method for preparing silver phosphate/polyvinyl chloride-based conjugated-polyene visible-light catalyst |
| CN105038996A (en) * | 2015-07-24 | 2015-11-11 | 河南工程学院 | Nanofiber composite membrane reactor |
| CN108101114A (en) * | 2017-12-21 | 2018-06-01 | 湖南大学 | A kind of nanometer ferrite composite material of bivalve layer structure and preparation method thereof |
| CN108940291A (en) * | 2018-07-06 | 2018-12-07 | 武汉霖泉环保科技有限公司 | A kind of preparation method and applications of zinc ferrite magnetic photocatalyst |
| CN109908915A (en) * | 2019-04-02 | 2019-06-21 | 扬州大学 | A kind of magnetic photocatalyst and preparation method thereof handling hexavalent chromium wastewater |
| KR20200099858A (en) * | 2019-02-15 | 2020-08-25 | 영남대학교 산학협력단 | Synthetic method of zinc iron oxide on graphene and its photocatalytic activity under sunlight irradation |
| CN111977696A (en) * | 2020-08-13 | 2020-11-24 | 吉林化工学院 | Preparation method and application of pomegranate-shaped magnetic visible light heterogeneous Fenton catalyst material |
| CN114604957A (en) * | 2022-03-17 | 2022-06-10 | 中南大学 | Method for treating organic dye and heavy metal ions in water body |
-
2022
- 2022-07-06 CN CN202210788911.XA patent/CN115228510B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1370619A (en) * | 2001-12-03 | 2002-09-25 | 山东中科纳米技术有限公司 | Prepn of loaded nano TiO2 photocatalyst |
| CN103623870A (en) * | 2013-12-11 | 2014-03-12 | 河北科技大学 | Method for preparing silver phosphate/polyvinyl chloride-based conjugated-polyene visible-light catalyst |
| CN105038996A (en) * | 2015-07-24 | 2015-11-11 | 河南工程学院 | Nanofiber composite membrane reactor |
| CN108101114A (en) * | 2017-12-21 | 2018-06-01 | 湖南大学 | A kind of nanometer ferrite composite material of bivalve layer structure and preparation method thereof |
| CN108940291A (en) * | 2018-07-06 | 2018-12-07 | 武汉霖泉环保科技有限公司 | A kind of preparation method and applications of zinc ferrite magnetic photocatalyst |
| KR20200099858A (en) * | 2019-02-15 | 2020-08-25 | 영남대학교 산학협력단 | Synthetic method of zinc iron oxide on graphene and its photocatalytic activity under sunlight irradation |
| CN109908915A (en) * | 2019-04-02 | 2019-06-21 | 扬州大学 | A kind of magnetic photocatalyst and preparation method thereof handling hexavalent chromium wastewater |
| CN111977696A (en) * | 2020-08-13 | 2020-11-24 | 吉林化工学院 | Preparation method and application of pomegranate-shaped magnetic visible light heterogeneous Fenton catalyst material |
| CN114604957A (en) * | 2022-03-17 | 2022-06-10 | 中南大学 | Method for treating organic dye and heavy metal ions in water body |
Non-Patent Citations (3)
| Title |
|---|
| YUANHANG ZHANG ET AL.: "Modification of ZnFe2O4 by conjugated polyvinyl chloride derivative for more efficient photocatalytic reduction of Cr(VI)", 《JOURNAL OF MOLECULAR STRUCTURE》, vol. 1242, pages 142 * |
| 冉方等: "ZnFe2O4/聚苯胺复合材料的制备及光催化性能", 《浙江师范大学学报（自然科学版）》, vol. 40, no. 01, pages 64 - 70 * |
| 高海霞等: "纳米ZnO/共轭聚合物复合材料光催化降解苯胺的研究", 《水处理技术》, no. 09, pages 39 - 42 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115688430A (en) * | 2022-11-01 | 2023-02-03 | 烟台大学 | Method for obtaining desorption behavior of hydrogen atoms on surface of material based on COMSOL software |
| CN115688430B (en) * | 2022-11-01 | 2024-01-30 | 烟台大学 | Method for obtaining desorption behavior of hydrogen atoms on material surface based on COMSOL software |
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