CN115532285B - Biochar-loaded magnetic ZIF-67 derivative material and application thereof in degradation of ciprofloxacin in water - Google Patents
Biochar-loaded magnetic ZIF-67 derivative material and application thereof in degradation of ciprofloxacin in water Download PDFInfo
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- CN115532285B CN115532285B CN202211107714.3A CN202211107714A CN115532285B CN 115532285 B CN115532285 B CN 115532285B CN 202211107714 A CN202211107714 A CN 202211107714A CN 115532285 B CN115532285 B CN 115532285B
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- cip
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- conc
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- 239000000463 material Substances 0.000 title claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 230000005291 magnetic effect Effects 0.000 title claims abstract description 25
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 title abstract description 164
- 229960003405 ciprofloxacin Drugs 0.000 title abstract description 82
- 238000006731 degradation reaction Methods 0.000 title abstract description 58
- 230000015556 catabolic process Effects 0.000 title abstract description 57
- 235000017060 Arachis glabrata Nutrition 0.000 claims abstract description 26
- 235000010777 Arachis hypogaea Nutrition 0.000 claims abstract description 26
- 235000018262 Arachis monticola Nutrition 0.000 claims abstract description 26
- 235000020232 peanut Nutrition 0.000 claims abstract description 26
- 230000000593 degrading effect Effects 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 9
- 241001553178 Arachis glabrata Species 0.000 claims abstract 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 49
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 238000002360 preparation method Methods 0.000 claims description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 239000008399 tap water Substances 0.000 claims description 4
- 235000020679 tap water Nutrition 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims 1
- 239000012467 final product Substances 0.000 claims 1
- 239000000356 contaminant Substances 0.000 abstract description 7
- 238000000197 pyrolysis Methods 0.000 abstract description 7
- 239000003242 anti bacterial agent Substances 0.000 abstract description 6
- 229940088710 antibiotic agent Drugs 0.000 abstract description 6
- 230000002349 favourable effect Effects 0.000 abstract description 5
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000975 dye Substances 0.000 abstract description 4
- 239000003446 ligand Substances 0.000 abstract description 4
- 150000002989 phenols Chemical class 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000005389 magnetism Effects 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical class [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 description 64
- 239000003054 catalyst Substances 0.000 description 35
- 244000105624 Arachis hypogaea Species 0.000 description 22
- 239000000243 solution Substances 0.000 description 22
- 230000000694 effects Effects 0.000 description 20
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 17
- 238000001994 activation Methods 0.000 description 16
- 238000002474 experimental method Methods 0.000 description 16
- 230000004913 activation Effects 0.000 description 15
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Natural products OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 13
- 230000001965 increasing effect Effects 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 150000003254 radicals Chemical class 0.000 description 11
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 10
- 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 10
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 10
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 10
- 229960000907 methylthioninium chloride Drugs 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 9
- 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 9
- 229960004989 tetracycline hydrochloride Drugs 0.000 description 9
- 238000004435 EPR spectroscopy Methods 0.000 description 8
- 239000012621 metal-organic framework Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 7
- 239000002131 composite material Substances 0.000 description 7
- 239000004021 humic acid Substances 0.000 description 7
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
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- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
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- 238000012512 characterization method Methods 0.000 description 5
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- 238000001228 spectrum Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000027756 respiratory electron transport chain Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- -1 Sulfate radical Chemical class 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- 229910020647 Co-O Inorganic materials 0.000 description 2
- 229910020704 Co—O Inorganic materials 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 2
- 229910021386 carbon form Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000005087 graphitization Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000002516 radical scavenger Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- NQTSTBMCCAVWOS-UHFFFAOYSA-N 1-dimethoxyphosphoryl-3-phenoxypropan-2-one Chemical compound COP(=O)(OC)CC(=O)COC1=CC=CC=C1 NQTSTBMCCAVWOS-UHFFFAOYSA-N 0.000 description 1
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 1
- 229910014033 C-OH Inorganic materials 0.000 description 1
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 1
- 229910014570 C—OH Inorganic materials 0.000 description 1
- 238000003775 Density Functional Theory Methods 0.000 description 1
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 240000001549 Ipomoea eriocarpa Species 0.000 description 1
- 235000005146 Ipomoea eriocarpa Nutrition 0.000 description 1
- 239000013206 MIL-53 Substances 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000004098 Tetracycline Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 1
- MBLBDJOUHNCFQT-LXGUWJNJSA-N aldehydo-N-acetyl-D-glucosamine Chemical compound CC(=O)N[C@@H](C=O)[C@@H](O)[C@H](O)[C@H](O)CO MBLBDJOUHNCFQT-LXGUWJNJSA-N 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- AAMATCKFMHVIDO-UHFFFAOYSA-N azane;1h-pyrrole Chemical compound N.C=1C=CNC=1 AAMATCKFMHVIDO-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000006652 catabolic pathway Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 239000012921 cobalt-based metal-organic framework Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
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- 238000002003 electron diffraction Methods 0.000 description 1
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- 231100000584 environmental toxicity Toxicity 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
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- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- 229960001180 norfloxacin Drugs 0.000 description 1
- OGJPXUAPXNRGGI-UHFFFAOYSA-N norfloxacin Chemical compound C1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNCC1 OGJPXUAPXNRGGI-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 125000005385 peroxodisulfate group Chemical group 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical compound [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000003306 quinoline derived antiinfective agent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001105 regulatory effect 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
- 229940043267 rhodamine b Drugs 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 230000007281 self degradation Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229960002180 tetracycline Drugs 0.000 description 1
- 229930101283 tetracycline Natural products 0.000 description 1
- 235000019364 tetracycline Nutrition 0.000 description 1
- 150000003522 tetracyclines Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000000101 transmission high energy electron diffraction Methods 0.000 description 1
- 238000001106 transmission high energy electron diffraction data Methods 0.000 description 1
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
-
- B01J35/33—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
-
- 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
- C02F1/722—Oxidation by peroxides
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
Abstract
The invention belongs to the field of environmental protection and water treatment, and particularly relates to a method for degrading ciprofloxacin in water, in particular to a peanut shell biochar loaded magnetic ZIF-67 derivative material and application thereof in degrading ciprofloxacin. The invention prepares the peanut shell biochar-loaded magnetic ZIF-67 derivative material (BC/CoNC) through simple in-situ growth and pyrolysis strategies, has good magnetism, is favorable for separation, and N derived from dimethyl imidazole ligand is uniformly distributed on the material. With the material, the degradation efficiency of CIP within 30min is 95.9%, and the TOC removal efficiency is 42.0%. The pH application range is wide, and the CIP degradation rate exceeds 84% in a wide range of 3-11. It has also been verified that the material is effective for the treatment of a wide variety of contaminants, including antibiotics (CIP, TC), phenols (BPA) and dyes (MB), with good versatility.
Description
Technical Field
The invention belongs to the field of environmental protection and water treatment, and particularly relates to a method for degrading ciprofloxacin in water, in particular to a peanut shell biochar loaded magnetic ZIF-67 derivative material and application thereof in degrading ciprofloxacin.
Background
Antibiotics are a new contaminant and have attracted considerable international attention [1.2 ]]. Ciprofloxacin (CIP) is a fluoroquinolone antibiotic. However, since humans and animals do not fully absorb CIP ingested into the body, most of them will enter the environment with excreta, thereby posing a threat to the environment and human health [1.2 ]]. Sulfate radical (SO) generation based on activated Peroxymonosulfate (PMS) 4 ·- ) Is widely applied to water treatment, SO 4 ·- Is Gao Yu OH, previous studies also indicate SO 4 ·- The pH range of (4.5)]. Therefore, the advanced oxidation technology based on PMS has good application potential in the aspect of treating antibiotics in water.
Biochar and metal organic framework Materials (MOFs) are commonly reported to activate PMS to degrade organic contaminants in water [6.7]. Biochar is a carbonaceous material with catalytic function, and has rich raw material sources, simple preparation process and low cost [7 ]]. A variety of biomass-derived biochar are used for persulfate activation, such as shrimp shell biochar, soybean straw biochar, and straw biochar [8-10 ]]. In addition, many researchers have been working on improvements in biochar to further increase its application capacity, and the strategies for improvement have been to dope N or transition metals (Co, fe, etc.) and to support metal oxides, etc. [7.11.12 ]]. For example, coO-N/BC, coFe 2 O 4 @BC and Fe 3 O 4 BC Material [12-14 ]]. MOFs are novel materials composed of metal centers coordinated with organic ligands [15 ]]. Both single MOFs and derived materials of MOFs can be used for PMS activation. For example, lin et al [16 ]]Activating PMS by using ZIF-67 to degrade rhodamine B in water; li et al [17 ]]Preparation of MOFs-derived Co 3 O 4 -La 2 O 2 CO 3 the/C material activates PMS to degrade phenylphosphonic acid. However, studies have shown that poor separation properties and susceptibility to agglomeration of MOFs and their derived materials are an obstacle in practical use [6.18]. To solve these problems, materials such as graphene oxide, porous spherical substrates, and ion exchange resins have been reported as carriers for MOFs. In the choice of carrier, biochar, which is low cost and has PMS activating ability, may be an ideal choice. For example, TONG et al [18 ]]Activated peroxodisulfate is used for degrading norfloxacin by using biochar loaded magnetic MIL-53 (Fe) derivative material, so that good degradation effect is obtained. ZIF-67 is a typical cobalt-based MOFs synthesized by the reaction of cobalt ions with dimethylimidazole. On the one hand, it has been reported that Co 2+ Exhibits excellent performance in PMS activation [16 ]]. On the other hand, the ZIF-67 can be calcined in an inert atmosphere to obtain the magnetic ZIF-67 derivative material, which is beneficial to separation. In addition, the dimethylimidazole ligand contains nitrogen element, and nitrogen doping can be realized by a calcination mode without adding an additional nitrogen source, and previous researches have shown that nitrogen species play an important role in the activation of PMS. Based on these conditions, it is speculated that the biochar-supported magnetic ZIF-67-derived composite can be obtained using biomass-supported ZIF-67 followed by one calcination in an inert atmosphere.
Reference is made to:
[1]N.Roy,S.A.Alex,N.Chandrasekaran,A.Mukherjee,K.Kannabiran,A comprehensive update on antibiotics as an emerging water pollutant and their removal using nano-structured photocatalysts,Journal of Environmental Chemical Engineering,9(2021)104796.
[2]T.L.Nguyen,T.H.Pham,N.M.Viet,P.Q.Thang,R.Rajagopal,R.Sathya,S.H.Jung,T.Kim,Improved photodegradation of antibiotics pollutants in wastewaters by advanced oxidation process based on Ni-doped TiO 2 ,CHEMOSPHERE,302(2022)134837.
[3]J.Luo,S.Bo,Y.Qin,Q.An,Z.Xiao,S.Zhai,Transforming goat manure into surface-loaded cobalt/biochar as PMS activator for highly efficient ciprofloxacin degradation,CHEM.ENG.J., 395(2020)125063.
[4]F.Xie,W.Zhu,P.Lin,J.Zhang,Z.Hao,J.Zhang,T.Huang,A bimetallic(Co/Fe)modified nickel foam(NF)anode as the peroxymonosulfate(PMS)activator:Characteristics and mechanism,SEP.PURIF.TECHNOL.,296(2022)121429.
[5]S.Shao,X.Li,Z.Gong,B.Fan,J.Hu,J.Peng,K.Lu,S.Gao,A new insight into the mechanism in Fe 3 O 4 @CuO/PMS system with low oxidant dosage,CHEM.ENG.J.,438(2022) 135474.
[6]Z.Xiong,Y.Jiang,Z.Wu,G.Yao,B.Lai,Synthesis strategies and emerging mechanisms of metal-organic frameworks for sulfate radical-based advanced oxidation process:A review, CHEM.ENG.J.,421(2021)127863.
[7]G.Song,F.Qin,J.Yu,L.Tang,Y.Pang,C.Zhang,J.Wang,L.Deng,Tailoring biochar for persulfate-based environmental catalysis:Impact of biomass feedstocks,J.HAZARD.MATER., 424(2022)127663.
[8]C.Liu,L.Chen,D.Ding,T.Cai,From rice straw to magnetically recoverable nitrogen doped biochar:Efficient activation of peroxymonosulfate for the degradation of metolachlor,Applied Catalysis B:Environmental,254(2019)312-320.
[9]J.Yu,L.Tang,Y.Pang,G.Zeng,H.Feng,J.Zou,J.Wang,C.Feng,X.Zhu,X.Ouyang,J.Tan,Hierarchical porous biochar from shrimp shell for persulfate activation:A two-electron transfer path and key impact factors,Applied Catalysis B:Environmental,260(2020)118160.
[10]R.Duan,S.Ma,S.Xu,B.Wang,M.He,G.Li,H.Fu,P.Zhao,Soybean straw biochar activating peroxydisulfate to simultaneously eliminate tetracycline and tetracycline resistance bacteria:Insights on the mechanism,WATER RES.,218(2022)118489.
[11]Y.Zhu,S.Ji,W.Liang,C.Li,Y.Nie,J.Dong,W.Shi,S.Ai,A low-cost and eco-friendly powder catalyst:Iron and copper nanoparticles supported on biochar/geopolymer for activating potassium peroxymonosulfate to degrade naphthalene in water and soil,CHEMOSPHERE,303(2022)135185.
[12]H.Luo,C.Ni,C.Zhang,W.Wang,Y.Yang,W.Xiong,M.Cheng,C.Zhou,Y.Zhou,S.Tian,Q.Lin,G.Fang,Z.Zeng,G.Zeng,Lignocellulosic biomass derived N-doped and CoO-loaded carbocatalyst used as highly efficient peroxymonosulfate activator for ciprofloxacin degradation,J.COLLOID INTERF.SCI.,610(2022)221-233.
[13]Z.Zhi,D.Wu,F.Meng,Y.Yin,B.Song,Y.Zhao,M.Song,Facile synthesis of CoFe 2 O 4 @BC activated peroxymonosulfate for p-nitrochlorobenzene degradation:Matrix effect and toxicity evaluation,SCI.TOTAL ENVIRON.,828(2022)154275.
[14]X.Cui,S.Zhang,Y.Geng,J.Zhen,J.Zhan,C.Cao,S.Ni,Synergistic catalysis by Fe 3 O 4 -biochar/peroxymonosulfate system for the removal of bisphenol a,SEP.PURIF. TECHNOL.,276(2021)119351.
[15]Y.Shi,L.Wang,S.Dong,X.Miao,M.Zhang,K.Sun,Y.Zhang,Z.Cao,J.Sun,Wool-ball-like BiOBr@ZnFe-MOF composites for degradation organic pollutant under visible-light:Synthesis,performance,characterization and mechanism,OPT.MATER.,131(2022)112580.
[16]T.Nguyen,V.Thai,C.Chen,C.P.Huang,R.Doong,L.Chen,C.Dong,N-doping modified zeolitic imidazole Framework-67(ZIF-67)for enhanced peroxymonosulfate activation to remove ciprofloxacin from aqueous solution,SEP.PURIF.TECHNOL.,288(2022)120719.
[17]Y.Li,L.Liu,W.Li,Y.Lan,C.Chen,Simultaneously rapid degradation of phenylphosphonic acid and efficient adsorption of released phosphate in the system of peroxymonosulfate(PMS)and Co 3 O 4 -La 2 O 2 CO 3 /C derived from MOFs,Journal of Environmental Chemical Engineering,9(2021)106332.
[18]J.Tong,L.Chen,J.Cao,Z.Yang,W.Xiong,M.Jia,Y.Xiang,H.Peng,Biochar supported magnetic MIL-53-Fe derivatives as an efficient catalyst for peroxydisulfate activation towards antibiotics degradation,SEP.PURIF.TECHNOL.,294(2022)121064.
disclosure of Invention
According to the invention, ZIF-67 grows on peanut shells in a simple in-situ growth mode, and the peanut shell biochar loaded magnetic ZIF-67 derivative material (BC/CoNC) is prepared by one-step pyrolysis in an inert atmosphere.
The invention provides a preparation method of a biochar-supported magnetic ZIF-67 derivative material, which is characterized by comprising the steps of preparing a material from Co (NO 3 ) 2 ·6H 2 O is dissolved in methanol to form solution A, and then peanut shell powder is added and stirred vigorously; dissolving 2-MIM in methanol to form solution B, rapidly pouring the solution B into the solution A, stirring for at least 20h, washing with methanol, vacuum drying at 50-70deg.C overnight, heating to 700-900deg.C in nitrogen atmosphere, and maintaining for 1-3 h.
Preferably Co (NO 3 ) 2 ·6H 2 The molar ratio of O to 2-MIM is 4:16; the dosage of peanut shell powder is Co (NO) 3 ) 2 ·6H 2 0.5-4.0 times of the mass of O.
Specifically, heating to 750-850 ℃ in nitrogen atmosphere and keeping for 2 hours.
The invention also provides the biochar-loaded magnetic ZIF-67 derivative material obtained by the preparation method.
The invention further provides the application of the biochar-supported magnetic ZIF-67 derivative material in degrading antibiotics (such as CIP, TC), phenols (such as BPA) or dyes (such as MB), preferably in degrading CIP in water.
The invention provides a method for degrading CIP in water, which comprises the following steps:
dispersing the biochar-supported magnetic ZIF-67 derivative material according to claim 4 in a solution containing CIP, and then adding PMS to the solution for reaction.
Optionally, after the reaction is completed, the obtained sample is filtered by a filter membrane and then added into methanol to terminate the reaction, and specifically the CIP-containing solution is from tap water or lake water or river water.
Preferably, the pH of the reaction system is adjusted to 3-11, preferably 5-9.
Preferably, the addition amount of the biochar-supported magnetic ZIF-67 derivative material is 0.1-0.4g/L, preferably 0.2-0.3g/L; the PMS concentration is 0.25 to 3mM, preferably 0.5 to 2mM, more preferably 0.75 to 1.25mM.
For the concentration of CIP in the solution, it is preferably controlled to be within 30mg/L, preferably within 25mg/L, for example 5-25mg/L.
Further preferably, the reaction temperature is 20-40 ℃, preferably 25-35 ℃.
The peanut shell biochar loaded magnetic ZIF-67 derivative material prepared by the invention has good magnetism, is favorable for material separation, and is derived from dimethyl imidazole ligand in uniform distribution on the material. The invention deeply researches the CIP removal efficiency in the BC/CoNC/PMS system, considers different degradation conditions, explores degradation mechanisms by utilizing free radical quenching experiments, electron spin resonance (EPR) and the like, and focuses on non-free radical oxidation paths in the system except for the free radical oxidation paths pointed out by the previous researches on ZIF-67-derived carbon composite materials. The obtained material can also realize the high-efficiency degradation of tetracycline, bisphenol A and methylene blue. Peanut shell, a cheap, clean and renewable biomass [24], therefore the invention has great practical value.
Drawings
FIG. 1 is a schematic diagram of the synthesis of BC/CoNC.
FIG. 2 is an SEM image of ZIF-67, PS/ZIF-67 and BC/CoNC (a, b and c, respectively); a BC/CoNC energy spectrum (d); TEM image of BC/CoNC (e); SAED patterns of BC/CoNC (f).
FIG. 3 is XRD pattern (a, b), FTIR pattern (c), raman analysis of BC, coNC and BC/CoNC (d), N of BC/CoNC 2 Adsorption and desorption curves (e), VSM characterization of BC/CoNC (f).
FIG. 4 shows XPS spectra of BC/CoNC: c1s (a), N1 s (b), O1s (C), co 2p (d).
FIG. 5 shows the effect of catalytic performance (a), mass ratio of BC to Co/NC on CIP degradation (b). Catalyst 0 (representing the amount of catalyst dosed in the experiment, the same applies hereinafter) =0.2 g/L, PMS0 (initial PMS concentration in solution, the same applies hereinafter) =1 mM, ph=5.7 (unadjusted).
FIG. 6 shows the effects (d) of the amount (a) of 1.0-BC/CoNC, the amount (b) of PMS, pH (c), reaction temperature, and CIP concentration (e). Catalyst 0=0.2 g/L, pms0=1 mm, ph=5.7 (unadjusted).
FIG. 7 is Na 2 SO 4 (a)、NaNO 3 (b)、NaCl(c)、NaHCO 3 (d) Humic Acid (HA) (e), CIP removal efficiency in actual water matrix (f). Catalyst 0=0.2 g/L, pms0=1 mm, ph=5.7 (unadjusted).
FIG. 8 shows the effect (a) of the radical scavenger. EPR spectroscopy using DMPO to capture SO 4 ·– And OH (b), capturing O using DMPO 2 ·– (c) Capturing using TEMP 1 O 2 (d) A. The invention relates to a method for producing a fibre-reinforced plastic composite Catalyst 0=0.2 g/L, pms0=1 mm, ph=5.7 (unadjusted).
FIG. 9 shows XPS spectra of BC/CoNC before and after use: co 2p (a), N1 s (b).
FIG. 10 shows a possible catalytic mechanism in a 1.0-BC/CoNC/PMS system.
FIG. 11 shows the TOC removal rates (b) for different contaminants for the versatility test (a). CIP (CIP) 0 ＝TC 0 ＝BPA 0 ＝MB 0 =20 mg/L catalyst 0=0.2 g/L, pms0=1 mm, ph=5.7 (unadjusted).
FIG. 12 is an EIS diagram of a sample.
FIG. 13 is an XPS full spectrum of BC/CoNC.
FIG. 14 shows the degradation efficiency of CIP by 1.0-BC/CoNC catalysts prepared at different pyrolysis temperatures. Catalyst 0=0.2 g/L, pms0=1 mm, ph=5.7 (unadjusted).
FIG. 15 shows the TOC removal efficiency of PMS at various doses. Catalyst 0=0.2 g/L, ph=5.7 (unadjusted).
FIG. 16 is a 1.0-BC/CoNC reusability. Catalyst 0=0.2 g/L, pms0=1 mm, ph=5.7 (unadjusted).
Detailed Description
The invention will be further illustrated by the following specific examples in order to provide a better understanding of the invention, but without limiting the invention thereto.
Materials used in the following examples include: cobalt nitrate hexahydrate (Co (NO) 3 ) 2 ·6H 2 O), 2-methylimidazole (2-MIM), potassium hydrogen Persulfate (PMS), 5-dimethyl-1-pyrrole-N-oxide (DMPO), 2, 6-Tetramethylpiperidine (TEMP), p-benzoquinone (p-BQ), bisphenol A (BPA), tetracycline hydrochloride (TC) and Methylene Blue (MB) were purchased from Shanghai microphone Lin ShenghuaCiprofloxacin (CIP) was purchased from synfebrile bioscience, inc, furfuryl alcohol (FFA), humic Acid (HA) was purchased from aladine, methanol, t-butanol, sodium chloride (NaCl), sodium bicarbonate, sodium nitrate, sodium hydroxide (NaOH) and hydrochloric acid (HCl) were purchased from the company of the midbody chemical reagent, inc. All chemicals were at least analytically pure, peanut shells were purchased from a farm in Henan, china, and the laboratory water was ultrapure water.
Example one, synthesis of catalyst
Preparation of ZIF-67 and CoNC
ZIF-67 was prepared according to the previously reported method with appropriate modifications. Co (NO) 3 ) 2 ·6H 2 O and 2-MIM were dissolved in methanol at a molar ratio of 4:16 to form solutions A and B, respectively, and then solution B was quickly poured into solution A, after stirring at room temperature for 24h, the material was collected and washed multiple times with methanol and dried overnight at 60℃under vacuum. The ZIF-67 was heated to 800℃under a nitrogen atmosphere and maintained for 2 hours to produce a magnetic ZIF-67 derivative material (CoNC).
2. Preparation of peanut Shell/ZIF-67 and BC/CoNC
A schematic diagram of the synthesis of BC/CoNC is shown in FIG. 1. The preparation of peanut shell/ZIF-67 is the same as ZIF-67 except that peanut shell powder with a certain mass ratio is added into solution A and stirred vigorously for 2 hours. A series of composite materials with different peanut shell mass ratios are called x-peanut shell/ZIF-67, wherein x=0.5, 1.0,2.0,4.0, and x represents peanut shell and Co (NO) 3 ) 2 ·6H 2 Mass ratio of O. And then calcining peanut shells/ZIF-67 with different proportions at high temperature for 2h (respectively carrying out three temperatures of 700, 800 and 900 ℃) in nitrogen atmosphere to obtain the biochar-loaded magnetic ZIF-67 derivative material with different proportions, which is named (0.5,1.0,2.0,4.0) -BC/CoNC.
Example two characterization of catalyst
1. Characterization method
X-ray diffraction (XRD) patterns and Fourier Transform Infrared (FTIR) spectra were performed on Rigaku D/max 2500 and Braker Alpha instruments, respectively. Morphology was examined by scanning electron microscopy (SEM, ZEISS Sigma 300) and transmission electron microscopy (HR-TEM, JEM 2100F). The surface defect status of the samples was measured by Raman analysis (Thermo Scientific DXR xi Micro-Raman). Electrochemical Impedance Spectroscopy (EIS) was obtained using an electrochemical workstation (760E, shanghai morning glory). The magnetic properties of the samples were analyzed using a Vibrating Sample Magnetometer (VSM). Specific surface area and pore size information of the sample was obtained using a specific surface area and pore size analyzer (Micrometrics TriStar II 3020). X-ray photoelectron spectroscopy (XPS) was determined from Thermo Scientific EscaLab 250Xi and corrected using the c1s= 284.80eV binding energy standard. The concentration of active species and ions in the solution was measured using an electron paramagnetic resonance spectrometer (EPR, JES-X310) and an inductively coupled plasma mass spectrometer (ICPMS, agilent 8900), respectively. In addition, CIP, TC and MB concentrations were determined using an ultraviolet spectrophotometer at λ=276 nm, λ=357 nm and λ=660 nm, respectively, and BPA concentrations were determined by high performance liquid chromatography (methanol and water as mobile phases).
2. Characterization results of the catalyst
In the experiments, BC/CoNC materials with different proportions are discussed, and 1.0-BC/CoNC is the best, so that the 1.0-BC/CoNC materials (and peanut hulls and Co (NO) 3 )2·6H 2 The mass ratio of O is 1:1). The morphology of the prepared catalyst was observed by SEM. SEM image of ZIF-67 shows that it is a typical rhombohedral shape (a in FIG. 2). SEM image (b in FIG. 2) of the synthesized peanut shell/ZIF-67 (PS/ZIF-67) showed that the peanut shell was successfully loaded with ZIF-67, and ZIF-67 was uniformly and densely distributed on the peanut shell. SEM image of BC/CoNC as shown in FIG. 2 c, ZIF-67 derived CoNC was uniformly distributed over BC with no significant agglomeration. In addition, the cenc still maintains the rhombohedral shape with slightly concave interior, exhibiting a porous structure, which may expose more active sites, thereby improving the degradation efficiency of CIP. EDS results (d in FIG. 2) revealed that C, N, O and Co were uniformly distributed over BC/CoNC, N being derived from the ligand ZIF-67 (2-MIM).
Further observations of BC/CoNC by TEM, ZIF-67 derived CoNC presented polygonal shapes, consistent with SEM images. As shown in fig. 2 e, lattice spacings of 0.353 and 0.201nm correspond to the (002) and (111) crystal planes of C and Co, respectively. In addition, two diffraction rings of electron diffraction (SAED) also correspond to the above two crystal planes (f in fig. 2), respectively. SEM and TEM results show that BC/CoNC materials are successfully prepared by high temperature calcination.
XRD patterns of ZIF-67 and peanut shell/ZIF-67 (PS/ZIF-67) are shown in FIG. 3 a, with peaks at 2θ=7.5, 10.6, 12.9 and 18.3℃corresponding to the (011), (002), (112) and (222) crystal planes of ZIF-67, consistent with previous reports indicating successful synthesis of ZIF-67. The peaks at 2θ=44.2, 51.5 and 75.8 ° for BC/cotc correspond to the (111), (200) and (220) crystal planes (JCPDS No. 15-0806) of Co, respectively (b in fig. 3). Indicating that the crystal structure of ZIF-67 produces metallic Co after high temperature calcination under an inert atmosphere. Further, the peak of 2θ=26.3° corresponds to the (0 00 2) crystal plane [19] of the graphitic carbon. XRD results indicate successful BC/CoNC synthesis.
The positions of 758, 1140 and 1453cm can be clearly seen on the infrared spectrogram of ZIF-67 -1 Absorption peak at (c in FIG. 3). Peanut shell/ZIF-67 (PS/ZIF-67) had the same peaks at these points, indicating successful composite preparation. 3445 cm -1 The nearby peaks are the stretching vibration peaks of the hydroxyl groups, PC and BC/CoNC at 1060 and 1389cm -1 The peaks at these are caused by vibrations of C-O and C-O-H, respectively. In addition, BC/CoNC is at 567 and 661cm -1 The peak at this point is caused by Co-O bond vibration.
BC. The Raman spectra of CoNC and BC/CoNC are shown in FIG. 3 d, 1350cm -1 Where D band represents sp 3 Disordered carbon form, 1580cm -1 The G band at this point represents sp 2 Graphitized carbon forms. Integrated strength ratio of D band to G band (I D /I G ) Is commonly used to indicate the degree of graphitization. BC. I of CoNC and BC/CoNC D /I G The values were 0.96, 0.95 and 0.91, respectively. Indicating that more graphitic carbon is present in the three samples, with the highest graphitization degree of BC/cotc, more favorable for PMS activation. In addition, fig. 12 is an Electrochemical Impedance (EIS) spectrum of BC, cotc, and BC/cotc, with the minimum arc radius size of the electrodes of BC/cotc, indicating small resistance to surface charge transfer, more favorable to electron transfer.
BC/CoNC N 2 Adsorption-desorption isotherms are shown in fig. 3e, wherein the inset is the pore size distribution plot. The adsorption-desorption isotherms are typical type iv isotherms, indicating that the material is mesoporous in structure. The specific surface area, pore volume and pore diameter of BC/CoNC were 219.06m respectively 2 /g、0.23cm 3 /g and 4.79nm. In addition, as shown in FIG. 3f, the saturation magnetization of BC/CoNC is 14.57emu/g, which can be easily separated in solution by an additional magnetic field, and good magnetic separation performance will facilitate recovery of materials.
XPS test and analysis were performed on the prepared material. From the XPS plot (FIG. 13), it can be seen that BC/CoNC contains C, N, O and Co elements, which are consistent with the previous EDS results. In the XPS spectrum of C1s (a in fig. 4) there are peaks at 284.8, 285.1, 286.4 and 289.5eV respectively, C-C, C-OH, C-O and c=o respectively. The XPS spectrum of N1 s is shown in FIG. 4 b, with peaks at binding energies 398.5, 399.5, 400.9 and 401.8eV attributed to pyridine nitrogen, co-N, pyrrole nitrogen and graphite nitrogen, respectively. The presence of N has been shown to favor PMS activation, which may either enhance some additional active sites or accelerate electron transfer, thereby enhancing the catalytic properties of the material. The XPS spectrum of O1s for C in FIG. 4, peaks at 530.06, 531.58 and 533.33eV are attributed to Co-O, OH and C-O functionalities. For the XPS profile of Co 2p, in combination with previous reports, the peaks at 779.8 and 794.9eV correspond to Co 0 Peaks at 781.2 and 796.9eV are attributed to Co 2+ 。
Example three, catalytic experiments
1. Catalytic experimental method
All experiments were performed in 150mL Erlenmeyer flasks. 0.02g of catalyst was dispersed in 100mL of 20mg/L CIP solution and placed in a constant temperature shaker at 25 ℃. A quantity of PMS was then added to the solution to initiate the reaction and samples were taken at fixed time points. The sample was filtered through a 0.22 μm pore size filter and then added to an equal volume of methanol to terminate the reaction, and the sample was analyzed by ultraviolet spectrophotometry.
The influence of peanut shells, different pyrolysis temperatures, catalyst and PMS addition amounts, initial pH value (pH value of a solution is regulated by 0.1M HCl or 0.1M NaOH solution), environmental temperature, coexisting materials and actual water base on CIP degradation effect is studied; the degradation efficiency of the catalyst on different organic pollutants is discussed, and active species in the system are identified through a quenching experiment and an EPR experiment. Meanwhile, in the recycling experiment, the used materials were collected, washed with water and dried, and then subjected to the next cycle. Except for the pH experiments, all experiments were not performed with any pH adjustment, and all experiments were repeated.
2. Catalytic performance
The PMS activation capacity of the catalyst was evaluated by degradation of CIP. The catalytic performance of the catalyst is shown in fig. 5 a, and the degradation capability of PMS alone to CIP is limited, which confirms that the self-degradation capability of PMS is poor. When BC/CoNC is used alone, 31.57% CIP can be adsorbed, which indicates that the prepared catalyst has better CIP adsorption capacity. Compared with BC/PMS, PS/ZIF-67/PMS and CoNC/PMS systems, the BC/CoNC/PMS system has the highest degradation efficiency on CIP. The CIP degradation efficiency is close to 90% in 10min and is as high as 95.9% in 30min in a BC/CoNC/PMS system by adopting 1.0-BC/CoNC. The results indicate that the introduction of BC favors the distribution of the cenc, providing more active sites. Meanwhile, BC/CoNC has a relatively high graphitic carbon content, and the presence of graphitic carbon is reported to facilitate electron transfer, thereby promoting PMS activation. Table 1 lists the PMS activation effects of the different catalysts, in contrast to BC/CoNC which exhibits good PMS activation performance.
The degradation efficiency of CIP by 1.0-BC/CoNC catalysts prepared at different pyrolysis temperatures is compared, as shown in FIG. 14, when the pyrolysis temperature is 800 ℃, the degradation efficiency of CIP is highest.
By way of comparison, four different mass composite ratios of x-BC/CoNC materials were prepared, with b in FIG. 5 being the CIP degradation efficiencies of (0.5, 1, 2, 4) -BC/CoNC for the different composite ratios, with 1.0-C/CoNC exhibiting the best performance. When the amount of BC is small, BC is insufficient to disperse connc, part of active sites may be covered due to agglomeration; when the BC content is large, it is again possible to cover some of the active sites of the connc.
TABLE 1 comparison of different catalysts to activate PMS to degrade CIP
The documents mentioned above are each as follows:
[1]B.He,L.Song,Z.Zhao,W.Liu,Y.Zhou,J.Shang,X.Cheng,CuFe 2 O 4 /CuO magnetic nano-composite activates PMS to remove ciprofloxacin:Ecotoxicity and DFT calculation,CHEM.ENG.J.,446(2022)137183.
[2]M.Pu,D.Ye,J.Wan,B.Xu,W.Sun,W.Li,Zinc-based metal–organic framework nanofibers membrane ZIF-65/PAN as efficient peroxymonosulfate activator to degrade aqueous ciprofloxacin,SEP.PURIF.TECHNOL.,299(2022)121716.
[3]H.Pourzamani,E.Jafari,M.Salehirozveh,H.Mohammadi,M.Rostami,N.Menglizadeh,Degradation of ciprofloxacin in aqueous solution by activating the proxymonosulfate using graphene based on CoFe 2 O 4 ,DESALIN WATER TREAT,167(2019)156-169.
[4]L.Qin,H.Ye,C.Lai,S.Liu,X.Zhou,F.Qin,D.Ma,B.Long,Y.Sun,L.Tang,M.Yan,W.Chen,W.Chen,L.Xiang,Citrate-regulated synthesis of hydrotalcite-like compounds as peroxymonosulfate activator-Investigation of oxygen vacancies and degradation pathways by combining DFT,Applied Catalysis B:Environmental,317(2022)121704.
[5]Z.Yang,X.Li,Y.Huang,Y.Chen,A.Wang,Y.Wang,C.Li,Z.Hu,K.Yan,Facile synthesis of cobalt-iron layered double hydroxides nanosheets for direct activation of peroxymonosulfate(PMS)during degradation of fluoroquinolones antibiotics,J.CLEAN.PROD.,310(2021)127584.
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[7]H.Luo,C.Ni,C.Zhang,W.Wang,Y.Yang,W.Xiong,M.Cheng,C.Zhou,Y.Zhou,S.Tian,Q.Lin,G.Fang,Z.Zeng,G.Zeng,Lignocellulosic biomass derived N-doped and CoO-loaded carbocatalyst used as highly efficient peroxymonosulfate activator for ciprofloxacin degradation,J.COLLOID INTERF.SCI.,610(2022)221-233。
3. influence of various experimental parameters
1) Influence of the addition of BC/CoNC and PMS
The addition of 1.0-BC/CoNC and PMS directly affects the CIP removal effect and time. As shown in fig. 6 a, the CIP removal rate gradually increased with increasing addition of BC/cotc, and the CIP degradation efficiency was 93.7% at 10min when the addition was 0.3 g/L. The increase of the catalyst dosage promotes the decomposition of PMS, generates more free radicals and accelerates the removal of CIP. After the reaction time exceeded 20min, the addition amount was 0.2g/L and the CIP degradation effect was close to 0.3g/L, with the following experiment using 0.2g/L considering the best effect achieved with the least amount.
Likewise, increasing the PMS concentration favors the improvement of the degradation effect of CIP in water (fig. 6 b), increasing the degradation efficiency from 79.3% to 95.9% when the PMS concentration is increased from 0.25 to 1 mM. When the PMS concentration was further increased to 2mM, the degradation efficiency of CIP was not significantly increased, but the TOC removal rate in the solution was increased by 27.4% (FIG. 15). PMS as sulfate radical (SO 4 ·- ) The source of the CIP is increased, the total amount of the generated active species is correspondingly increased, and the CIP removal and the mineralization rate improvement are facilitated.
2) Influence of initial pH
As shown in FIG. 6 c, the 1.0-BC/CoNC/PMS system is effective in degrading CIP in the pH range of 3-11, and the degradation rate is over 90% especially at pH 5-9. The CIP removal effect was 85.6% and 84.3% in acidic ph=3 and alkaline ph=11 environments, respectively
3) Influence of temperature
As shown in fig. 6 d, CIP degradation efficiency increases with increasing temperature, and at a temperature of 35 ℃, CIP removal rate reaches 97.4%, revealing the endothermic nature of the PMS activation process. The higher the temperature, the more energy is supplied to the reactant molecules, which promotes activation of PMS, and the release rate of radicals increases, thereby increasing the reaction rate.
4) Effects of CIP concentration
As shown in fig. 6 e, the degradation effect was evaluated when CIP concentration was varied from 5 to 30 mg/L. The 1.0-BC/CoNC/PMS system can effectively degrade the CIP of 5-20mg/L within 30 minutes, and the degradation efficiency of the CIP is over 95 percent. As the concentration increased to 30mg/L, the degradation rate slowed down. This suggests that as the concentration of CIP increases to higher levels, degradation intermediates compete with CIP for active sites and actives, thereby impeding degradation efficiency.
5) Influence of coexisting substances
In practice there are a variety of substances in water, including a variety of inorganic ions and natural organics. Figure 7 shows the effect of four inorganic anions and Humic Acid (HA) on contaminant degradation. SO (SO) 4 2- The effect of the presence of (a) is not great, and the CIP removal rate is stabilized at about 95% (a in FIG. 7); low concentration of NO 3 - Hardly affect the removal of contaminants, but 20mM NO 3 - The presence reduced CIP removal by 9.29%, the slight effect may be a higher concentration of NO 3 - Consume a part of SO 4 ·- And OH (b in FIG. 7); cl - Has certain inhibiting effect on degradation of pollutants. When Cl is added - At a concentration of 5mM, the CIP degradation efficiency was reduced by 11.5% at 30 min. Continue to increase Cl - At a concentration of 20mM, the early reaction rate was slightly reduced, but CIP removal was almost the same at 30 min. This may occur due to a higher concentration of Cl - Other active products, such as Cl.and Cl, are formed by a series of reactions 2 -· (formulae (5) - (7)) which are an order of magnitude with OH in terms of degradation rate constant, thereby compensating for SO to some extent 4 ·- And loss of OH. HCO (hydrogen chloride) 3 - Has a significant impeding effect on the degradation of CIP. The presence of HA HAs little effect on the degradation of CIP (e in fig. 7).
In a real water environment, a plurality of substances possibly coexist, so the CIP degradation condition of the system in tap water and lake water is tested (f in FIG. 7). The results show that the CIP removal efficiency in the two water matrixes is over 90 percent, and the catalyst has good anti-interference capability.
Example four, catalytic mechanism
Methanol (MeOH) as SO 4 ·- And OH scavengers, t-butanol (TBA), p-benzoquinone (p-BQ) and furfuryl alcohol (FFA) as OH, O, respectively 2 ·- And 1 O 2 is a scavenger of (a). As shown in fig. 8 a, meOH has a significant inhibitory effect on CIP degradation. However, after the equal amount of TBA is added, the inhibition effect is not obvious, and the degradation rate is reduced by 11.19% in 30 min. The MeOH inhibition was significantly stronger than TBA, indicating that compared to OH, SO 4 ·- Play a more important role in the degradation of CIP. The presence of p-BQ also inhibits the degradation of CIP, proving that O is generated in the system 2 ·- . The degradation inhibition effect of FFA on CIP is maximum, and the degradation rate is reduced by more than 60% at 30min, which reveals 1 O 2 Is of great importance. In addition, EPR experiments were performed, as shown in the figure, it is evident that DMPO-SO 4 ·- 、DMPO-·OH、DMPO-O 2 ·- And TEMP- 1 O 2 The presence of (b) - (d) in FIG. 8) further confirms the production of SO in the system 4 ·- 、·OH、O 2 ·- And 1 O 2 。
the change in the valence of the surface element of the catalyst before and after use was investigated using XPS (fig. 9). As shown in fig. 9 a. After use, the new peaks at 785.7 and 801.5eV are attributed to Co 3+ ，Co 0 The proportion in the catalyst was reduced from 56.7% to 42.9%, co 2+ The ratio of (2) increases. This indicates that a redox reaction occurred during the reaction. In addition, as shown in fig. 9 b, the ratio of pyridine N to graphite N decreases after the reaction, indicating that pyridine N and graphite N also participate in the activation of PMS.
In combination with the above analysis and some previous reports, the 1.0-BC/CoNC/PMS system involved free radical and non-free radical pathways in degrading CIP. Co in catalyst 0 Can react with PMS to generate SO 4 ·- Simultaneous oxidation to Co 2+ 。Co 2+ Then the PMS is activated to generate SO 4 ·- And OH at the same timeFurther oxidation to Co 3+ . Here, co formed during the reaction 3+ And then reacts with PMS to receive electrons and reduce the electrons into Co 2+ . In addition, co 0 Also with Co 3+ Reacting Co 3+ Accelerating the conversion to Co 2+ (12). Co (Co) 0 /Co 2+ /Co 3+ The conversion between the two components promotes the activation of PMS and keeps the efficient CIP degradation performance of the system. Pyridine nitrogen and graphite nitrogen in the catalyst also participate in PMS activation, so that electron transfer between the catalyst and PMS is accelerated, and PMS activation capacity on BC/CoNC is enhanced. Part of SO generated by the reaction 4 ·- Can be combined with H 2 O reacts to form OH.
Furthermore, self-decomposition generation of PMS 1 O 2 The c=o group in the catalyst can activate PMS production 1 O 2 ，O 2 ·- And OH/OH - Interactions between them will also occur 1 O 2 。
The mechanism of degradation of CIP by PMS activated by 0-BC/CoNC is shown in FIG. 10. Radical and non-radical mediated oxidation processes promote decomposition of CIP to 1 O 2 Is the dominant non-radical process.
Example six, reusability and ubiquity
The 1.0-BC/CoNC material has good magnetism, is favorable for being separated from solution and is convenient for repeated use. FIG. 16 shows the re-use performance of BC/CoNC. The CIP degradation efficiency at 30min is 84.2% at the second use and 87.8% at the first use. After 30min after the fourth cycle, the degradation efficiency of CIP was also 70.3%, and when the reaction time was prolonged to 60min, the degradation rate exceeded 80%, and the concentration of leached Co ions in the solution was 0.63mg/L as determined by ICP-MS. Degradation efficiency in recycling may be due to loss of active ingredient during recovery and use and coverage of part of the active site by CIP or its intermediates. In addition, SEM images, XPS full spectrum and FTIR spectrum before and after the use were compared, and the used 1.0-BC/CoNC was not significantly changed, indicating that the catalyst structure was relatively stable
The 1.0-BC/CoNC/PMS system exhibited excellent performance in the degradation of CIP, and to examine the versatility of the 1.0-BC/CoNC/PMS system, the removal ability of different types of organic compounds (TC, BPA and MB) in the system was studied (FIG. 11). In less than 10 minutes, BPA and MB are completely removed, and the degradation efficiency of TC is also over 96 percent. In addition, at 30min, TOC removal rates for TC, BPA and MB contaminants were 45.7%, 54.8% and 58.1%, respectively. The results show that the 1.0-BC/CoNC/PMS system can be effectively applied to the treatment of various pollutants, including antibiotics, phenols and dyes, and has better universality.
In conclusion, the peanut shell biochar-loaded magnetic ZIF-67 derivative material (1.0-BC/CoNC) is successfully prepared by pyrolysis in an inert atmosphere. Successful synthesis of the catalyst is confirmed by characterization means such as XRD, SEM, TEM and XPS. In particular, in the 1.0-BC/CoNC/PMS system, the degradation efficiency of CIP within 30min is 95.9%, and the TOC removal rate is 42.0%. In the pH range of 3-11, CIP degradation efficiency is over 84%. Meanwhile, the influence conditions of experimental parameters such as the consumption of the catalyst and PMS, the reaction temperature, coexisting materials and the like are studied, and the CIP removal rate exceeds 90% in a real water matrix (tap water and lake water), so that the catalyst has good anti-interference capability. The degradation mechanism was investigated by quenching experiments, EPR experiments and XPS analysis to 1 O 2 The dominant non-radical degradation pathway is the primary cause of CIP degradation, SO 4 ·- (OH) and O 2 ·- Plays an auxiliary role in the degradation process. In addition, it is verified that the 1.0-BC/CoNC/PMS system can be effectively applied to treatment of various pollutants, including antibiotics (CIP, TC), phenols (BPA) and dyes (MB), and has better universality.
Claims (3)
1. A method for degrading CIP in water by using biochar-loaded magnetic ZIF-67 derivative material is characterized in that,
dispersing biochar-loaded magnetic ZIF-67 derivative materials in a CIP-containing solution, and then adding PMS into the solution for reaction; filtering the obtained sample by a filter membrane, and adding methanol to terminate the reaction;
wherein the addition amount of the biochar-loaded magnetic ZIF-67 derivative material is 0.2-0.3g/L; PMS concentration is 0.75 to 1.25mM; the pH value of the reaction system is adjusted to 5-9; the reaction temperature is 25-35 ℃; CIP is controlled within 25mg/L of the concentration of the solution;
the preparation method of the biochar-supported magnetic ZIF-67 derivative material comprises the following steps:
from Co (NO) 3 ) 2 ·6H 2 O is dissolved in methanol to form solution A, and then peanut shell powder is added and stirred vigorously; dissolving 2-MIM in methanol to form solution B, then rapidly pouring the solution B into the solution A, stirring for at least 20h, washing with methanol, vacuum drying at 50-70deg.C overnight, heating to 800 deg.C in nitrogen atmosphere, and maintaining for 2h to obtain the final product;
wherein the dosage of peanut shell powder is Co (NO) 3 ) 2 ·6H 2 1.0 times of the mass of O; co (NO) 3 ) 2 ·6H 2 The molar ratio of O to 2-MIM was 4:16.
2. The method of claim 1, wherein the concentration of CIP in the solution is controlled to be 5-25mg/L.
3. The method of claim 2, wherein the CIP-containing solution is derived from tap water or lake water or river water.
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