CN113842950A - Application method of metal oxide and metal organic framework composite material in photocatalytic degradation of antibiotics - Google Patents
Application method of metal oxide and metal organic framework composite material in photocatalytic degradation of antibiotics Download PDFInfo
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- CN113842950A CN113842950A CN202110957598.3A CN202110957598A CN113842950A CN 113842950 A CN113842950 A CN 113842950A CN 202110957598 A CN202110957598 A CN 202110957598A CN 113842950 A CN113842950 A CN 113842950A
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- metal oxide
- organic framework
- antibiotics
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- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 74
- 239000000463 material Substances 0.000 title claims abstract description 72
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 68
- 239000003242 anti bacterial agent Substances 0.000 title claims abstract description 39
- 229940088710 antibiotic agent Drugs 0.000 title claims abstract description 39
- 238000013033 photocatalytic degradation reaction Methods 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000012924 metal-organic framework composite Substances 0.000 title claims abstract description 21
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 230000001699 photocatalysis Effects 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000002131 composite material Substances 0.000 claims abstract description 17
- 238000011065 in-situ storage Methods 0.000 claims abstract description 16
- 230000015556 catabolic process Effects 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 238000006731 degradation reaction Methods 0.000 claims abstract description 13
- 239000012702 metal oxide precursor Substances 0.000 claims abstract description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 27
- 239000013110 organic ligand Substances 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 230000003115 biocidal effect Effects 0.000 claims description 14
- 229910021645 metal ion Inorganic materials 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 6
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 229940079593 drug Drugs 0.000 claims description 6
- 239000003814 drug Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000001509 sodium citrate Substances 0.000 claims description 6
- 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 6
- 239000011701 zinc Substances 0.000 claims description 6
- 238000005286 illumination Methods 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 239000000395 magnesium oxide Substances 0.000 claims description 5
- 238000007146 photocatalysis Methods 0.000 claims description 5
- 238000013032 photocatalytic reaction Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- -1 iron ions Chemical class 0.000 claims description 4
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 3
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 3
- QPBGNSFASPVGTP-UHFFFAOYSA-N 2-bromoterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(Br)=C1 QPBGNSFASPVGTP-UHFFFAOYSA-N 0.000 claims description 3
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 3
- BQRBAXFOPZRMCU-UHFFFAOYSA-N 5-chloro-1h-imidazole Chemical compound ClC1=CN=CN1 BQRBAXFOPZRMCU-UHFFFAOYSA-N 0.000 claims description 3
- 239000013148 Cu-BTC MOF Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 238000000498 ball milling Methods 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- 239000000969 carrier Substances 0.000 claims description 3
- 239000001530 fumaric acid Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000003446 ligand Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 229910001451 bismuth ion Inorganic materials 0.000 claims 1
- 229910001429 cobalt ion Inorganic materials 0.000 claims 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims 1
- 229910001431 copper ion Inorganic materials 0.000 claims 1
- 229910001425 magnesium ion Inorganic materials 0.000 claims 1
- 229910001453 nickel ion Inorganic materials 0.000 claims 1
- 239000004065 semiconductor Substances 0.000 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000010865 sewage Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 37
- 238000001179 sorption measurement Methods 0.000 description 8
- 239000011787 zinc oxide Substances 0.000 description 7
- 229910000480 nickel oxide Inorganic materials 0.000 description 6
- 239000004098 Tetracycline Substances 0.000 description 5
- 229960002180 tetracycline Drugs 0.000 description 5
- 229930101283 tetracycline Natural products 0.000 description 5
- 235000019364 tetracycline Nutrition 0.000 description 5
- 150000003522 tetracyclines Chemical class 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 3
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 3
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 2
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 239000013132 MOF-5 Substances 0.000 description 1
- 229930182555 Penicillin Natural products 0.000 description 1
- 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 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 230000001133 acceleration Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052729 chemical element Inorganic materials 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
- 229960005091 chloramphenicol Drugs 0.000 description 1
- 229960003405 ciprofloxacin Drugs 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000010840 domestic wastewater Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229940049954 penicillin Drugs 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229940063650 terramycin Drugs 0.000 description 1
- 229940072172 tetracycline antibiotic Drugs 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
- B01J31/1625—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups
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- B01J35/39—
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- B01J35/394—
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- B01J35/61—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
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- 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
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/40—Organic compounds containing sulfur
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- 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
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Abstract
The invention relates to an application method of a metal oxide and metal organic framework composite material in photocatalytic degradation of antibiotics, and belongs to the field of composite material synthesis and environmental management. The application method of the metal oxide and metal organic framework composite material in photocatalytic degradation of antibiotics is that firstly a petal-shaped metal oxide precursor is prepared, and then the metal organic framework material is prepared in situ on the metal oxide through chemical reaction. The invention brings the advantages of environmental protection, no pollution, high efficiency, low energy consumption, wide application range and the like when the photocatalytic technology is used for treating antibiotics in water body environment, is used for realizing high-efficiency degradation of the antibiotics in wastewater of sewage treatment plants and agriculture and animal husbandry, is beneficial to treating the environment, and simultaneously solves the problem that a semiconductor catalyst cannot enrich a substrate due to the porous characteristic and the high specific surface area characteristic of the metal organic framework material, so that the semiconductor catalyst can adsorb and enrich the antibiotics in the environment, and the photocatalytic degradation efficiency is enhanced.
Description
Technical Field
The invention relates to the technical field of composite material synthesis and environmental management, in particular to an application method of a metal oxide and metal organic framework composite material in photocatalytic degradation of antibiotics.
Background
With the further industrialization and the acceleration of urbanization, a large amount of industrial wastewater and urban wastewater contain a large amount of pollutants such as heavy metal ions, dyes, medicines and the like. The antibiotics are used as the most widely applied medicines, and due to the fact that the antibiotics exist in a large amount in a water body environment due to overuse, the enrichment of the antibiotics in the water body has biological toxicity on microorganisms in the water body environment, so that the water body ecological environment is damaged and gradually worsened, meanwhile, the occurrence of drug resistance genes can be caused after the antibiotics are placed in the water body environment for a long time, the public health and health crisis is caused, unexpected consequences are brought, if the antibiotics are not timely treated in a proper mode, and an irreversible situation can be formed in the past for a long time.
The traditional antibiotic treatment technology in the water environment, such as physical adsorption, chemical oxidation, biomembrane and the like, is difficult to efficiently degrade the antibiotic in the water, the photocatalysis technology has the advantages of greenness, no pollution, high efficiency, low energy consumption, wide application range and the like, is widely concerned by people, but the traditional semiconductor photocatalyst, such as titanium dioxide(TiO2) Cadmium sulfide (CdS), zinc oxide (ZnO), zirconium dioxide (ZrO)2) And tin oxide (SnO), which is faced with the problems of low photocatalytic degradation efficiency, no substrate enrichment capacity, poor stability in water environment, and the like, and these problems are often difficult to overcome in practical use, so that an application method of a metal oxide and metal organic framework composite material in photocatalytic degradation of antibiotics is urgently needed to solve the problems.
Disclosure of Invention
The invention aims to provide an application method of a metal oxide and metal organic framework composite material in photocatalytic degradation of antibiotics, and aims to solve the problems that the technologies such as physical adsorption, chemical oxidation and biomembrane and the like in the background technology are difficult to efficiently degrade the antibiotics in water, and for a traditional semiconductor photocatalyst, the traditional semiconductor photocatalyst has low photocatalytic degradation efficiency, no substrate enrichment capacity and poor stability in a water environment.
In order to achieve the purpose, the invention provides the following technical scheme: the application method of the metal oxide and metal organic framework composite material in photocatalytic degradation of antibiotics is that firstly, a petal-shaped metal oxide precursor is prepared, and then the metal organic framework material is prepared in situ on the metal oxide through a chemical reaction; and performing high-efficiency catalytic degradation on the antibiotics in the water body under the room temperature condition through visible light irradiation.
The method specifically comprises the following steps:
step one, preparing raw materials: metal ions, sodium citrate, sodium hydroxide, organic ligands and solvents.
Step two, adding raw materials: metal ions, sodium citrate and sodium hydroxide are placed inside the container.
Step three, reaction of raw materials: preparing a stirrer, and stirring at room temperature or under hydrothermal conditions to react to form petal-shaped metal oxides;
step four, forming material preparation: carrying out reaction on the obtained metal oxide in the presence of an organic ligand in a hydrothermal, microwave, ball milling or ultrasonic mode, and growing a metal organic framework material on the surface of the petal-shaped metal oxide in situ; thereby obtaining the composite material with photocatalytic performance.
Step five, the method for preparing the material comprises the following steps: the obtained metal oxide and metal organic framework composite material is placed in water, and the antibiotic in the water can be catalytically degraded under the condition of illumination.
Further, the metal ions can be zinc, cobalt, nickel, iron, copper, titanium, bismuth, magnesium and aluminum ions, the organic ligands can be carboxylic acid ligands and imidazole organic ligands, and the metal oxide surface in-situ growth metal organic framework material can be NiO @ ZIF-8, CoO @ ZIF-67, NiO @ BIT-11, CuO @ HKUST-1, ZnO @ ZIF-8, HKUST-1, ZnO @ ZIF-62, ZnO @ ZIF-4, ZnO @ MOF-5, TiO @ MOF-5, or a mixture thereof2@MIL-125、MgO@MOF-74(Mg)、ZnO@MOF-74(Zn)。
Further, the organic ligand includes: terephthalic acid, trimesic acid, aminoterephthalic acid, fumaric acid, 4-biphenyldicarboxylic acid, 2-bromoterephthalic acid and 2, 5-dihydroxyterephthalic acid, wherein the imidazole organic ligand can be imidazole, dimethylimidazole, benzimidazole and 4-chloroimidazole.
Furthermore, metal oxide metal ions are used as metal sites, and are coordinated and combined with the metal sites through organic ligands, so that metal organic framework materials grow in situ on the surfaces of the metal oxides to form composite materials combined with the metal oxides and the metal organic frameworks, the composite materials combined with the metal oxides and the metal organic frameworks have high specific surface area and regular pore channel characteristics, the high specific surface area provides more reaction sites for photocatalytic reaction, heterojunction formed by the metal oxides and the metal organic frameworks contributes to separation of photon-generated carriers, the photocatalytic performance of the materials is remarkably enhanced, and the composite materials combined with the metal oxides and the metal organic frameworks have high specific surface area and regular pore channel characteristics.
Further, the metal oxide @ metal organic framework material has high photocatalytic degradation efficiency on antibiotics in water, wherein the antibiotic drugs comprise: the metal oxide @ metal organic framework material has excellent photocatalytic performance, and the structure, the appearance and the catalytic performance of the catalyst are almost unchanged before and after photocatalysis.
Further, the room temperature can be 18-28 ℃, and the heating temperature for heating and stirring can be 25-150 ℃.
Further, the stirring time can be 0-180 min.
Compared with the prior art, the invention has the beneficial effects that:
1. the photocatalytic technology is used for treating antibiotics in the water body environment, has the advantages of environmental friendliness, no pollution, high efficiency, low energy consumption, wide application range and the like, is used for sewage treatment plants, and realizes high-efficiency degradation of antibiotics in domestic wastewater, industrial wastewater and agricultural and animal husbandry wastewater, so that various environmental problems caused by antibiotic enrichment in the water body are solved, the environment is favorably treated, and the environment is kept in a healthy state;
2. the metal oxide and the metal organic framework material which is porous and has uniformly dispersed active sites are combined in situ to be applied to the antibiotic drugs in the environment of high-efficiency photocatalytic degradation, the forbidden bandwidth of most of metal oxides is matched with the forbidden bandwidth required in the photocatalytic reaction process, the energy level structure and the forbidden bandwidth of the material are optimized by combining the metal oxide and the metal organic framework material, the problem that part of single semiconductor catalysts are low in catalytic performance is solved, the single semiconductor catalysts show more excellent photocatalytic performance, and meanwhile, the problem that the semiconductor catalysts cannot enrich substrates is solved by the porous characteristic and the high specific surface area characteristic of the metal organic framework material, so that the single semiconductor catalysts can adsorb and enrich antibiotics in the environment, and the efficiency of photocatalytic degradation of the antibiotics is improved.
3. The invention clearly explains the mechanism of the composite material combining the metal oxide and the metal organic framework material for degrading the antibiotic in the environment, and simultaneously performs example tests, so that the material shows higher photocatalytic antibiotic degradation efficiency;
4. the method can realize the economic, green and efficient photocatalytic degradation of antibiotics in the environment and the treatment of the problem of antibiotic pollution in the environment, and has the advantages that the material has more excellent photocatalytic efficiency compared with a single system due to the heterojunction structure formed by the metal organic framework and the metal oxide and the characteristics of high specific surface area and multiple reaction sites of the metal organic framework material, and the high-efficiency degradation of various antibiotics in different working environments can be ensured due to the diversity of the selection of the metal oxide and the metal organic framework material.
Drawings
FIG. 1 is a schematic view showing the flow state of the photocatalytic degradation of antibiotics in water by using a metal oxide and metal organic framework composite material;
FIG. 2 is a scanning electron microscope image of ZnO @ ZIF-8 prepared by the following example, which shows that a metal organic framework material can be successfully grown in situ on the surface of a metal oxide to prepare a composite material combining the metal oxide and the metal organic framework material, wherein a circle mark is an enlarged region of an enlarged schematic diagram;
FIG. 3 is a nitrogen adsorption and desorption curve of ZnO @ ZIF-8 prepared in the example, and it can be seen from FIG. 3 that the composite material formed by combining the metal oxide and the metal organic framework material in the example has high specific surface area and regular pore channel characteristics, and the specific surface area of ZnO @ ZIF-8 is improved by nearly 6-7 times compared with ZnO without a pore channel structure, and is 320m2 g-1；
FIG. 4 is a graph of saturated adsorption capacity and adsorption rate of ZnO @ ZIF-8 prepared in the example to tetracycline in water, and the saturated adsorption capacity of ZnO @ ZIF-8 to tetracycline is 140.9mg g through an adsorption model and the adsorption rate graph-1The catalyst can reach 2-3 times of the same kind of catalyst.
Fig. 5 is a graph of the degradation efficiency of the ZnO @ ZIF-8 photocatalytic degradation tetracycline antibiotics prepared in the examples, and it can be seen from fig. 5 that a single ZnO shows poor photocatalytic activity, and the degradation efficiency of TC is 48% after irradiation for 90min, while for ZIF-8, TC is hardly degraded under visible light irradiation. ZnO @ ZIF-8 showed superior photocatalytic performance compared to ZnO and ZIF-8. When the visible light illumination time is 50 minutes, the degradation rate of ZnO @ ZIF-8 to tetracycline reaches 91%.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1-5, the present invention provides an embodiment: the application method of the metal oxide and metal organic framework composite material in photocatalytic degradation of antibiotics is that firstly, a petal-shaped metal oxide precursor is prepared, and then the metal organic framework material is prepared in situ on the metal oxide through chemical reaction;
the method specifically comprises the following steps:
step one, preparing raw materials: metal ions, sodium citrate and sodium hydroxide, wherein the metal oxide refers to a binary compound consisting of oxygen and another metal chemical element, the metal ions can be zinc, cobalt, nickel, iron, copper, titanium, bismuth, magnesium and aluminum ions, and the prepared metal oxide can be zinc oxide (ZnO), copper oxide (CuO), nickel oxide (NiO), magnesium oxide (MgO), cobalt oxide (CoO) and titanium oxide (TiO)2),
Step two, adding raw materials: placing metal ions, sodium citrate and sodium hydroxide inside a container; adding the raw materials into a container in batches, and then adding a certain amount of solvent, wherein the solvent can be water, ethanol, acetone or methanol.
Step three, reaction of raw materials: a stirrer is prepared, and then stirred at room temperature or under hydrothermal conditions to react, thereby forming petal-shaped metal oxides.
Step four, forming material preparation: carrying out reaction on the obtained metal oxide in the presence of an organic ligand in a hydrothermal, microwave, ball milling or ultrasonic mode, and growing a metal organic framework material on the surface of the petal-shaped metal oxide in situ; thereby obtaining the composite material with photocatalytic performance.
Step five, the method for preparing the material comprises the following steps: the obtained metal oxide and metal organic framework composite material is placed in water, and the antibiotic in the water can be catalytically degraded under the condition of illumination.
The metal ions can be Zn ions, the metal oxide surface in-situ growth metal organic framework material can be ZnO @ ZIF-8, the ZIF-8 has high hydrophobicity and excellent chemical stability and thermal stability, the organic ligands can be carboxylic acid ligands and imidazole organic ligands, the metal oxide surface in-situ growth metal organic framework material can be NiO @ ZIF-8, CoO @ ZIF-67, NiO @ BIT-11, CuO @ HKUST-1, ZnO @ ZIF-8, HKUST-1, ZnO @ ZIF-62, ZnO @ ZIF-4, ZnO MOF-5, TiO @ ZIF-62, ZnO @ ZIF-42@MIL-125、MgO@MOF-74(Mg)、ZnO@MOF-74(Zn)。
The organic ligands include: terephthalic acid, trimesic acid, aminoterephthalic acid, fumaric acid, 4-biphenyldicarboxylic acid, 2-bromoterephthalic acid and 2, 5-dihydroxyterephthalic acid, wherein the imidazole organic ligand can be imidazole, dimethylimidazole, benzimidazole and 4-chloroimidazole.
The metal oxide metal ions are used as metal sites, and the organic ligand and the metal sites are coordinated and combined, so that the metal organic framework material grows in situ on the surface of the metal oxide to form the composite material combined with the metal oxide and the metal organic framework, the composite material combined with the metal oxide and the metal organic framework material has the characteristics of high specific surface area and regular pore channels, the high specific surface area provides more reaction sites for photocatalytic reaction, a heterojunction formed by the metal oxide and the metal organic framework material is helpful for separating photon-generated carriers, and the photocatalytic performance of the material is remarkably enhanced.
The metal oxide @ metal organic framework material has high photocatalytic degradation efficiency on antibiotics in water, wherein the antibiotic drugs comprise: ciprofloxacin, chloramphenicol, terramycin, penicillin, metal oxide @ metal organic framework material has excellent photocatalysis propertyThe structure, the morphology and the catalytic performance of the catalyst are almost unchanged before and after photocatalysis, ZnO @ ZIF-8 has high photocatalytic degradation efficiency on antibiotics in a water body, meanwhile, the change of the photocatalytic efficiency of the catalyst is small after 3 times of circulation, high photocatalytic activity is still maintained, subsequent degradation is facilitated, the duration is longer, the catalyst is beneficial to long-time use, the composite material formed by combining the metal oxide and the metal organic framework material has the characteristics of high specific surface area and regular pore channel, and the specific surface area of the ZnO @ ZIF-8 is improved by nearly 6-7 times compared with ZnO with a pore-free structure and is 320m2 g-1The high specific surface area provides more reaction sites for photocatalytic reaction, and the photocatalytic performance of the material is obviously enhanced, so that the effect of the material in actual use is obviously improved, and the photocatalytic performance of the material is favorably improved.
ZnO @ ZIF-8 has excellent photocatalytic performance, and when the illumination time is 50 minutes, the degradation rate of ZnO @ ZIF-8 to tetracycline reaches 91%, so that the degradation efficiency is greatly improved, the treatment efficiency is higher, and the tetracycline is more easily subjected to degradation treatment.
The room temperature can be 18-28 ℃, the heating temperature for heating and stirring can be 25-150 ℃, the design is convenient for selecting proper temperature, and the requirement is lower under the room temperature condition, so that the process is simpler in the preparation process, excessive adjustment is not needed, the reaction condition is milder, the realization condition is facilitated, the reaction is facilitated, and the subsequent production is more convenient.
The stirring time can be 0-150 min, so that the reaction is more sufficient, and meanwhile, the reverse time fault tolerance rate is high, so that the preparation is easier during the subsequent large-scale production, various conditions are easy to achieve, and the production is facilitated.
The above examples are only preferred embodiments of the present invention, and it should be noted that it is obvious to those skilled in the art that several modifications, such as changes of the metal oxide species, the metal organic framework species, the composite material system of the metal oxide and the metal organic framework material synthesized by other methods, and the application to different antibiotic species, can be made without departing from the principle of the present invention, and these modifications should be considered as the protection scope of the present invention.
Claims (7)
1. The application method of the metal oxide and metal organic framework composite material in photocatalytic degradation of antibiotics is characterized by comprising the following steps: the application method of the metal oxide and metal organic framework composite material in photocatalytic degradation of antibiotics comprises the steps of firstly preparing a petal-shaped metal oxide precursor, then preparing a metal organic framework material on the metal oxide in situ, and performing efficient catalytic degradation on the antibiotics in a water body under the room temperature condition through visible light irradiation;
the method specifically comprises the following steps:
step one, preparing raw materials: metal ions, sodium citrate, sodium hydroxide, an organic ligand and a solvent;
step two, adding raw materials: placing metal ions, sodium citrate and sodium hydroxide inside a container;
step three, reaction of raw materials: preparing a stirrer, and stirring at room temperature or under hydrothermal conditions to react to form petal-shaped metal oxides;
step four, forming material preparation: carrying out reaction on the obtained metal oxide in the presence of an organic ligand in a hydrothermal, microwave, ball milling or ultrasonic mode, and growing a metal organic framework material on the surface of the petal-shaped metal oxide in situ; thereby obtaining the composite material with photocatalytic performance;
step five, the method for preparing the material comprises the following steps: the obtained metal oxide and metal organic framework composite material is placed in water, and the antibiotic in the water can be catalytically degraded under the condition of illumination.
2. The application method of the metal oxide and metal organic framework composite material in photocatalytic degradation of antibiotics according to claim 1 is characterized in that: the metal ions in the first step, the second step, the third step, the fourth step and the fifth step can be zinc ions, cobalt ions, nickel ions, iron ions, copper ions, titanium ions, bismuth ions, magnesium ions and aluminum ionsThe organic ligand can be carboxylic acid ligand and imidazole organic ligand, wherein the metal oxide surface in-situ growth metal organic framework material can be NiO @ ZIF-8, CoO @ ZIF-67, NiO @ BIT-11, CuO @ HKUST-1, ZnO @ ZIF-8, HKUST-1, ZnO @ ZIF-62, ZnO @ ZIF-4, ZnO @ MOF-5, TiO @ ZIF-622@MIL-125、MgO@MOF-74(Mg)、ZnO@MOF-74(Zn)。
3. The application method of the metal oxide and metal organic framework composite material in photocatalytic degradation of antibiotics according to claim 2 is characterized in that: the organic ligand includes: terephthalic acid, trimesic acid, aminoterephthalic acid, fumaric acid, 4-biphenyldicarboxylic acid, 2-bromoterephthalic acid and 2, 5-dihydroxyterephthalic acid, wherein the imidazole organic ligand can be imidazole, dimethylimidazole, benzimidazole and 4-chloroimidazole.
4. The application method of the metal oxide and metal organic framework composite material in photocatalytic degradation of antibiotics according to claim 1 is characterized in that: the metal oxide metal ions are used as metal sites, and the organic ligand and the metal sites are coordinated and combined, so that the metal organic framework material grows in situ on the surface of the metal oxide to form the composite material combined with the metal oxide and the metal organic framework, the composite material combined with the metal oxide and the metal organic framework material has the characteristics of high specific surface area and regular pore channels, the high specific surface area provides more reaction sites for photocatalytic reaction, and a heterojunction formed by the metal oxide and the metal organic framework material is helpful for separating photon-generated carriers, so that the photocatalytic performance of the material is remarkably enhanced.
5. The application method of the metal oxide and metal organic framework composite material in photocatalytic degradation of antibiotics according to claim 1 is characterized in that: the metal oxide @ metal organic framework material has high photocatalytic degradation efficiency on antibiotics in a water body, wherein the antibiotic drugs comprise: the metal oxide @ metal organic framework material has excellent photocatalytic performance, and the structure, the appearance and the catalytic performance of the catalyst are almost unchanged before and after photocatalysis.
6. The application method of the metal oxide and metal organic framework composite material in photocatalytic degradation of antibiotics according to claim 1 is characterized in that: the room temperature can be 18-28 ℃, and the heating temperature for heating and stirring can be 25-150 ℃.
7. The application method of the metal oxide and metal organic framework composite material in photocatalytic degradation of antibiotics according to claim 1 is characterized in that: the stirring time can be 0-180 min.
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