CN113120944A - Preparation method of spinel type transition metal oxide and application of spinel type transition metal oxide in degrading antibiotics - Google Patents
Preparation method of spinel type transition metal oxide and application of spinel type transition metal oxide in degrading antibiotics Download PDFInfo
- Publication number
- CN113120944A CN113120944A CN202010024839.4A CN202010024839A CN113120944A CN 113120944 A CN113120944 A CN 113120944A CN 202010024839 A CN202010024839 A CN 202010024839A CN 113120944 A CN113120944 A CN 113120944A
- Authority
- CN
- China
- Prior art keywords
- transition metal
- oxide
- metal oxide
- degradation
- microwave
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910000314 transition metal oxide Inorganic materials 0.000 title claims abstract description 28
- 239000003242 anti bacterial agent Substances 0.000 title claims abstract description 20
- 229940088710 antibiotic agent Drugs 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 230000000593 degrading effect Effects 0.000 title abstract description 10
- 229910052596 spinel Inorganic materials 0.000 title description 5
- 239000011029 spinel Substances 0.000 title description 5
- 230000015556 catabolic process Effects 0.000 claims abstract description 61
- 238000006731 degradation reaction Methods 0.000 claims abstract description 61
- 239000011701 zinc Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 24
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 23
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 9
- 239000001099 ammonium carbonate Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- -1 salt compound Chemical class 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 229910052723 transition metal Inorganic materials 0.000 claims description 7
- 150000003624 transition metals Chemical class 0.000 claims description 7
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 6
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 235000017281 sodium acetate Nutrition 0.000 claims description 6
- 239000012265 solid product Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- 239000012286 potassium permanganate Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 150000005846 sugar alcohols Polymers 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-N iron;hydrochloride Chemical compound Cl.[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-N 0.000 claims description 2
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 2
- 239000002019 doping agent Substances 0.000 claims 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 claims 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 abstract description 38
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 abstract description 35
- 229910000428 cobalt oxide Inorganic materials 0.000 abstract description 18
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 abstract description 18
- 230000006698 induction Effects 0.000 abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 3
- 239000004098 Tetracycline Substances 0.000 description 29
- 229960002180 tetracycline Drugs 0.000 description 29
- 235000019364 tetracycline Nutrition 0.000 description 29
- 229930101283 tetracycline Natural products 0.000 description 29
- 150000003522 tetracyclines Chemical class 0.000 description 29
- 230000000694 effects Effects 0.000 description 20
- 235000013980 iron oxide Nutrition 0.000 description 20
- 238000006467 substitution reaction Methods 0.000 description 19
- 239000011572 manganese Substances 0.000 description 17
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 15
- 238000002441 X-ray diffraction Methods 0.000 description 14
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 230000003115 biocidal effect Effects 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- 238000005119 centrifugation Methods 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- ULGZDMOVFRHVEP-RWJQBGPGSA-N Erythromycin Chemical compound O([C@@H]1[C@@H](C)C(=O)O[C@@H]([C@@]([C@H](O)[C@@H](C)C(=O)[C@H](C)C[C@@](C)(O)[C@H](O[C@H]2[C@@H]([C@H](C[C@@H](C)O2)N(C)C)O)[C@H]1C)(C)O)CC)[C@H]1C[C@@](C)(OC)[C@@H](O)[C@H](C)O1 ULGZDMOVFRHVEP-RWJQBGPGSA-N 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 4
- 229960003022 amoxicillin Drugs 0.000 description 4
- LSQZJLSUYDQPKJ-NJBDSQKTSA-N amoxicillin Chemical compound C1([C@@H](N)C(=O)N[C@H]2[C@H]3SC([C@@H](N3C2=O)C(O)=O)(C)C)=CC=C(O)C=C1 LSQZJLSUYDQPKJ-NJBDSQKTSA-N 0.000 description 4
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229940079593 drug Drugs 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 4
- 150000002823 nitrates Chemical class 0.000 description 4
- LSQZJLSUYDQPKJ-UHFFFAOYSA-N p-Hydroxyampicillin Natural products O=C1N2C(C(O)=O)C(C)(C)SC2C1NC(=O)C(N)C1=CC=C(O)C=C1 LSQZJLSUYDQPKJ-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- BDKLKNJTMLIAFE-UHFFFAOYSA-N 2-(3-fluorophenyl)-1,3-oxazole-4-carbaldehyde Chemical compound FC1=CC=CC(C=2OC=C(C=O)N=2)=C1 BDKLKNJTMLIAFE-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 150000003840 hydrochlorides Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000004626 scanning electron microscopy Methods 0.000 description 3
- 229940087562 sodium acetate trihydrate Drugs 0.000 description 3
- 239000012798 spherical particle Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004100 Oxytetracycline Substances 0.000 description 2
- 239000004182 Tylosin Substances 0.000 description 2
- 229930194936 Tylosin Natural products 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 229960003276 erythromycin Drugs 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- YVKBMQONWVQBGH-UHFFFAOYSA-N manganese zinc Chemical compound [Mn][Zn][Mn][Zn] YVKBMQONWVQBGH-UHFFFAOYSA-N 0.000 description 2
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229960000625 oxytetracycline Drugs 0.000 description 2
- IWVCMVBTMGNXQD-PXOLEDIWSA-N oxytetracycline Chemical compound C1=CC=C2[C@](O)(C)[C@H]3[C@H](O)[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O IWVCMVBTMGNXQD-PXOLEDIWSA-N 0.000 description 2
- 235000019366 oxytetracycline Nutrition 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 229960002135 sulfadimidine Drugs 0.000 description 2
- ASWVTGNCAZCNNR-UHFFFAOYSA-N sulfamethazine Chemical compound CC1=CC(C)=NC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 ASWVTGNCAZCNNR-UHFFFAOYSA-N 0.000 description 2
- IWVCMVBTMGNXQD-UHFFFAOYSA-N terramycin dehydrate Natural products C1=CC=C2C(O)(C)C3C(O)C4C(N(C)C)C(O)=C(C(N)=O)C(=O)C4(O)C(O)=C3C(=O)C2=C1O IWVCMVBTMGNXQD-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229960004059 tylosin Drugs 0.000 description 2
- WBPYTXDJUQJLPQ-VMXQISHHSA-N tylosin Chemical compound O([C@@H]1[C@@H](C)O[C@H]([C@@H]([C@H]1N(C)C)O)O[C@@H]1[C@@H](C)[C@H](O)CC(=O)O[C@@H]([C@H](/C=C(\C)/C=C/C(=O)[C@H](C)C[C@@H]1CC=O)CO[C@H]1[C@@H]([C@H](OC)[C@H](O)[C@@H](C)O1)OC)CC)[C@H]1C[C@@](C)(O)[C@@H](O)[C@H](C)O1 WBPYTXDJUQJLPQ-VMXQISHHSA-N 0.000 description 2
- 235000019375 tylosin Nutrition 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- VGVIKVCCUATMNG-UHFFFAOYSA-N 1,2,4-trichloro-5-phenylbenzene Chemical group C1=C(Cl)C(Cl)=CC(Cl)=C1C1=CC=CC=C1 VGVIKVCCUATMNG-UHFFFAOYSA-N 0.000 description 1
- IUYHQGMDSZOPDZ-UHFFFAOYSA-N 2,3,4-trichlorobiphenyl Chemical group ClC1=C(Cl)C(Cl)=CC=C1C1=CC=CC=C1 IUYHQGMDSZOPDZ-UHFFFAOYSA-N 0.000 description 1
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 1
- QCQCHGYLTSGIGX-GHXANHINSA-N 4-[[(3ar,5ar,5br,7ar,9s,11ar,11br,13as)-5a,5b,8,8,11a-pentamethyl-3a-[(5-methylpyridine-3-carbonyl)amino]-2-oxo-1-propan-2-yl-4,5,6,7,7a,9,10,11,11b,12,13,13a-dodecahydro-3h-cyclopenta[a]chrysen-9-yl]oxy]-2,2-dimethyl-4-oxobutanoic acid Chemical compound N([C@@]12CC[C@@]3(C)[C@]4(C)CC[C@H]5C(C)(C)[C@@H](OC(=O)CC(C)(C)C(O)=O)CC[C@]5(C)[C@H]4CC[C@@H]3C1=C(C(C2)=O)C(C)C)C(=O)C1=CN=CC(C)=C1 QCQCHGYLTSGIGX-GHXANHINSA-N 0.000 description 1
- 229910002706 AlOOH Inorganic materials 0.000 description 1
- 208000035143 Bacterial infection Diseases 0.000 description 1
- 229910016523 CuKa Inorganic materials 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 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
- PJSFRIWCGOHTNF-UHFFFAOYSA-N Sulphormetoxin Chemical compound COC1=NC=NC(NS(=O)(=O)C=2C=CC(N)=CC=2)=C1OC PJSFRIWCGOHTNF-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- SWCIQHXIXUMHKA-UHFFFAOYSA-N aluminum;trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SWCIQHXIXUMHKA-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000001775 anti-pathogenic effect Effects 0.000 description 1
- 208000022362 bacterial infectious disease Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229960002588 cefradine Drugs 0.000 description 1
- RDLPVSKMFDYCOR-UEKVPHQBSA-N cephradine Chemical compound C1([C@@H](N)C(=O)N[C@H]2[C@@H]3N(C2=O)C(=C(CS3)C)C(O)=O)=CCC=CC1 RDLPVSKMFDYCOR-UEKVPHQBSA-N 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 1
- MSNWSDPPULHLDL-UHFFFAOYSA-K ferric hydroxide Chemical compound [OH-].[OH-].[OH-].[Fe+3] MSNWSDPPULHLDL-UHFFFAOYSA-K 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 229940049954 penicillin Drugs 0.000 description 1
- 150000003071 polychlorinated biphenyls Chemical group 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- SEEPANYCNGTZFQ-UHFFFAOYSA-N sulfadiazine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CC=N1 SEEPANYCNGTZFQ-UHFFFAOYSA-N 0.000 description 1
- 229960004306 sulfadiazine Drugs 0.000 description 1
- 229960004673 sulfadoxine Drugs 0.000 description 1
- JNMRHUJNCSQMMB-UHFFFAOYSA-N sulfathiazole Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CS1 JNMRHUJNCSQMMB-UHFFFAOYSA-N 0.000 description 1
- 229960001544 sulfathiazole Drugs 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G1/00—Methods of preparing compounds of metals not covered by subclasses C01B, C01C, C01D, or C01F, in general
- C01G1/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/08—Ferroso-ferric oxide [Fe3O4]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/302—Treatment of water, waste water, or sewage by irradiation with microwaves
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Compounds Of Iron (AREA)
Abstract
The invention relates to a preparation method of spinel-type transition metal oxide and application thereof in degrading antibiotics, wherein cobalt oxide is prepared by a hydrothermal-calcination method, iron oxide and manganese oxide are directly synthesized by the hydrothermal method, and zinc and aluminum are respectively doped to prepare the spinel-type transition metal oxide, the transition metal oxide degrades the antibiotics under microwave induction, and the degradation amount of the antibiotics can reach more than 40 mg/g.
Description
Technical Field
The invention relates to a preparation method of spinel-type transition metal oxide and application of the spinel-type transition metal oxide in degrading antibiotics, belonging to the field of material chemistry.
Background
In recent years, persistent organic pollutants in water have attracted a great deal of social attention, particularly antibiotic pollution. Antibiotics, a commonly used drug for the treatment of bacterial infections, refer to a class of substances produced by bacteria, molds, or other microbial metabolic processes that have anti-pathogenic or other activities. The antibiotic pollution in the water body of the east China is serious, the discharge density is more than 6 times of that of the water body of the west China, the antibiotic pollution in the water body of the Beijing city is the most serious, and the tetracycline is the highest in content. At present, most of antibiotics taken into the body cannot be completely absorbed, and more than 85 percent of antibiotics are discharged out of the body in the form of original forms or metabolites and pass through sewage or directly enter the environment.
The existing antibiotic treatment technologies at home and abroad mainly comprise a conventional method (flocculation, filtration and the like), an adsorption method, a biodegradation method, a chemical oxidation method and the like. The chemical oxidation method mainly comprises chlorination, Fenton, ozone, photocatalysis and electrochemical oxidation, and is a chemical treatment technology. Although the water-soluble characteristics of the antibiotics can be utilized to achieve good degradation effects on various antibiotics, the antibiotics are not removed selectively, and the use cost and the energy consumption are high. Studies found that penicillin was completely degraded within 2h by chlorination treatment technique and amoxicillin and cefradine were completely degraded within 1min (Navalon S, 2008). By fenton's technique, sulfamethazine is totally removed within 2min, but the toxicity of the resulting product is increased and amoxicillin can be removed within 1min in combination with photocatalysis (Elmolla E, 2009). By using the ozone catalytic oxidation technology, 90% of amoxicillin can be removed after 4min, and 18% of amoxicillin can be mineralized after 20min (Andreozzi R, 2005); the combination of H2O2 can accelerate the degradation of antibiotics, ozone can degrade 97% of erythromycin and tylosin in wastewater within 10min, and erythromycin and tylosin can be completely degraded within 20min (Lin A Y C, 2009). 0.4mg/mg-1 ozone can 100% remove oxytetracycline in 10mg/L-1 simulated water, 1.2mg/mg-1 can remove oxytetracycline in waste mother liquor with the concentration of 92% being 702mg/L-1, and the generation of drug-resistant bacteria and drug-resistant genes in the subsequent biological treatment process can be reduced (Liu M, 2017). Under the photocatalysis technology, 66% of antibiotics can be degraded under the condition that the pH value is 6.0 (Molinari R, 2006); sulfadoxine, sulfathiazole were able to be totally degraded after 30min under UV lamp and 200mg/L-1TiO2, 80% of sulfadiazine was removed and 90% of sulfamethazine was removed (Calza P, 2004). Therefore, it is of great significance to develop new efficient degradation technology for antibiotic contamination.
The microwave is an electromagnetic wave having a frequency of 300MHz to 300GHz (wavelength of 1m to 1 mm). The application of microwave technology to environmental pollution treatment is a new research field which is emerging in recent years, and is favored by researchers due to the characteristics of rapidness, high efficiency, no secondary pollution and the like. Microwaves belong to non-ionizing radiation waves and act mainly by exciting molecular translation. The microwave action does not alter or break the chemical bonds of the molecules, but the molecules can vibrate or rotate by absorbing microwave energy under the action of the microwaves. The microwave energy interacts with the polar part in the substance to be absorbed, and the converted energy enables part of surface sites to be rapidly heated to form a 'hot spot effect', so that the oxidation activity of the material is improved, and the oxidative decomposition of organic pollutants is further enhanced (Zhang L, 2011). At present, the microwave technology is widely applied to the field of organic matters which are difficult to degrade in the treatment environment. Abramovith R A et al (Zhang L, 2011; Sun H J, 2015) utilize microwave technology to treat organic pollutants such as polychlorinated biphenyl and the like in soil, and obtain good effect. The Xitao Liu and the Gang Yu (Lu A H, 2004) utilize microwave-assisted activated carbon to adsorb and degrade 2,4, 5-trichlorobiphenyl in soil, and test results show that the degradation rate of the trichlorobiphenyl can reach 100 percent, and dioxin is not generated. Rural areas and the like (Guan H T, 2015; cheng tao, 2008) adopt activated carbon as a catalyst, microwave irradiation is used for treating high-concentration dioctyl phthalate production wastewater, and the removal rate of COD reaches 86.3%. Therefore, the microwave technology can be widely applied as an efficient antibiotic treatment technology.
Disclosure of Invention
The invention provides a preparation method of spinel-type transition metal oxide, and the spinel-type transition metal oxide is used for degrading antibiotics. Cobalt oxide is prepared by a hydrothermal-calcination method, iron oxide and manganese oxide are directly synthesized by the hydrothermal method, zinc and aluminum are respectively doped to prepare spinel-type transition metal oxide, the transition metal oxide degrades antibiotics under microwave induction, and the degradation amount of the antibiotics can reach more than 40mg/g, so that the invention is completed.
Accordingly, the present invention provides, in a first aspect, a process for preparing a spinel-type transition metal oxide, the process comprising the steps of:
and 3, carrying out reaction in the reactor to obtain a solid product, and optionally carrying out post-treatment.
In the step 1, the transition metal comprises cobalt, iron and manganese, and the doping metal comprises zinc and aluminum; precursors of the transition metal oxide are salt compounds, such as hydrochlorides of cobalt and iron, preferably hydrated hydrochlorides, and manganates, such as potassium permanganate; precursors of the doping metal are nitrates, such as zinc nitrate, preferably hydrated nitrates, and hydrochlorides, such as aluminum chloride.
In the step 2, the solvent is water, alcohol or a hydroalcoholic solution, and the alcohol is monohydric alcohol or polyhydric alcohol, preferably ethylene glycol; after the raw materials are dissolved in the solvent, optionally stirring, and preferably adding salt substances into the mixture; the salt is preferably ammonium salt, more preferably ammonium carbonate or ammonium bicarbonate, and sodium acetate can also be used.
In step 3, the reaction is carried out in a high-pressure device, preferably a stainless steel high-pressure reactor, and the reaction is heated at the temperature of 120-; the post-treatment includes washing, drying and calcining.
The oxide prepared by the method can be used for degrading antibiotics, and the degradation amount can reach more than 40 mg/g.
Drawings
Fig. 1 shows an XRD pattern of zinc-doped cobalt oxide prepared in example 1;
FIG. 2 shows the XRD pattern of the aluminum-doped cobalt oxide prepared in example 2;
fig. 3 shows an XRD pattern of zinc-doped iron oxide prepared in example 3;
FIG. 4 shows an XRD pattern of aluminum-doped iron oxide prepared in example 4;
FIG. 5 shows the XRD pattern of the new doped manganese oxide prepared in example 5;
FIG. 6 shows an XRD pattern of aluminum-doped manganese oxide prepared in example 6;
FIG. 7 shows the effect of microwave-induced degradation of tetracycline by zinc-doped cobalt oxide prepared in example 1;
FIG. 8 shows the effect of microwave-induced degradation of tetracycline by aluminum-doped cobalt oxide prepared in example 2;
FIG. 9 shows the effect of microwave-induced degradation of tetracycline by zinc-doped iron oxide prepared in example 3;
FIG. 10 shows the effect of microwave-induced degradation of tetracycline by aluminum-doped iron oxide obtained in example 4;
FIG. 11 shows the effect of microwave-induced degradation of tetracycline by the novel doped oxides of manganese prepared in example 5;
fig. 12 shows the effect of removing tetracycline by microwave-induced degradation of aluminum-doped manganese oxide prepared in example 6.
FIG. 13 shows an SEM image of Zn-doped Co oxide prepared in example 1, where Co is present3O4(a),Zn0.2Co2.8O4(b),Zn0.4Co2.6O4(c),Zn0.6Co2.4O4(d),Zn0.8Co2.2O4(e),Zn1Co2O4(f)。
Detailed Description
The features and advantages of the present invention will become more apparent and appreciated from the following detailed description of the invention.
The word "exemplary" is used exclusively herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
According to the invention, a spinel-type transition metal oxide, a preparation method thereof and application thereof in the aspect of antibiotic degradation are provided.
The preparation method of the spinel-type transition metal oxide provided by the invention comprises the following steps:
The transition metals include cobalt, iron, and manganese.
For the transition metal, the oxide precursor thereof is a respective salt compound, for example, cobalt, iron hydrochloride, i.e., cobalt chloride, iron chloride, preferably, respective hydrated hydrochloride, and a manganate salt, such as potassium permanganate.
The doped metals include zinc and aluminum.
For the doping metal, the oxide precursor is a respective salt compound, preferably a nitrate salt, such as zinc nitrate, preferably a respective hydrated nitrate salt, such as zinc nitrate hexahydrate and aluminum nitrate nonahydrate, and a hydrochloride salt, such as aluminum chloride.
And 2, dissolving the raw materials in a solvent to prepare a solution.
The solvent is capable of dissolving the above-mentioned raw materials, for example, water or alcohol, or a hydroalcoholic solution may be used, and the alcohol may be a monohydric alcohol such as methanol, ethanol, butanol, etc., or a polyhydric alcohol such as a dihydric alcohol, preferably ethylene glycol and propylene glycol, more preferably ethylene glycol, or a polyhydric alcohol such as glycerin.
In the preparation of the iron oxide, it is preferable to use a glycol solvent, and the iron oxide is first dissolved in glycol, so that Fe can be effectively prevented3+And (3) hydrolyzing and stirring to uniformly disperse the mixture.
According to a preferred embodiment of the present invention, after dissolving the above raw materials in the solvent, optionally stirring, preferably a salt-like substance, preferably an ammonium salt, more preferably ammonium carbonate or ammonium bicarbonate, and also preferably sodium acetate, such as sodium acetate trihydrate, is added to the mixture, and then stirring is continued.
When preparing the iron oxide, sodium acetate trihydrate is added into the mixture at 50 ℃ to promote the formation of ferric hydroxide gel, and finally the spinel-structured iron oxide is directly synthesized under the hydrothermal condition.
In the case of cobalt oxide preparation, ammonium bicarbonate is preferably used to control morphology. Firstly, carbonate particles are formed by ammonium bicarbonate under hydrothermal conditions, and carbonate clusters are formed after self-assembly to finally form carbonate spheres. Then the carbonate is changed into oxide by calcining.
And 3, carrying out reaction in the reactor to obtain a solid product, and optionally carrying out post-treatment.
According to the present invention, the above stirred solution may be reacted in situ to obtain a fixed product, but is preferably transferred to a high pressure apparatus, preferably a stainless steel autoclave reactor, and heated at high temperature, for example at 120-.
The post-treatment includes washing, drying and calcining.
The washing is preferably a centrifugal washing, 5 times, wherein 3 times with deionized water and 2 times with ethanol.
Drying may be carried out at ambient temperature, preferably at 60 ℃, more preferably in an oven, for example overnight.
The calcination the dried product is calcined at 350 c for 2 hours using a dry gas, preferably air in a furnace.
The product is obtained and can be ground to a powder. The prepared metal oxide can degrade antibiotics under microwave induction, and the degradation amount can reach more than 40 mg/g.
The spinel-type transition metal oxide, the preparation method thereof and the application thereof in the aspect of antibiotic degradation have the following advantages or beneficial effects:
1) and synthesize a series of Zn2+And Al3+Respective isomorphism substituting for M2+(M: Co, Fe, Mn) and M3+Three kinds of spinel-structured transition metal oxides of (M: Co, Fe, Mn). Wherein, the cobalt oxide is successfully prepared by adopting a hydrothermal-calcining method, and the hydrothermal method is adoptedThe method directly synthesizes iron oxide and manganese oxide.
2)、Zn2+And Al3+Respectively successfully doped to M3O4In the crystal lattice of (M: Co, Fe, Mn), neither the crystal system nor the space group is changed. For Co3O4,Zn2+The doping of (A) is not changed in morphology, and is spherical particles with diameters of about 6-7 mu m, Al3+The doping of (a) causes the morphology to become cubic block-shaped particles with side lengths of 7-9 μm. For Fe3O4,Al3+The doping of (A) is not changed in shape, and is spherical particles with the diameter of about 400nm, Zn2+The doping of (2) reduces the diameter to around 100 nm. For Mn3O4,Zn2+The doping of (A) does not change the appearance, and all are octahedral particles with uniform size.
3) And the influence of components and morphology on the microwave-induced oxidative degradation performance is researched by regulating and controlling the spinel oxide structure, and the relation between the components and the microwave-induced degradation mechanism is disclosed.
4) Microwave induced Co3O4、Fe3O4The degradation amount of the degradable tetracycline can reach 47.7mg/g and 47.8mg/g respectively, and Zn is2+Has no influence on the microwave induced degradation effect, and Al3+The microwave degradation rate is reduced, and the balance time is prolonged. Microwave induced Mn3O4The degradation amount of degrading tetracycline can reach 42.81mg/g, Zn2+Reducing degradation rate, reducing degradation amount, prolonging balance time, and adding Al3+Has no influence on the microwave induced degradation effect.
Examples
Examples and information relating to the drugs and instruments used in the comparative examples are listed below:
experimental materials
The structure of the transition metal oxide was characterized by an X-ray diffraction analyzer (XRD), from Bruker, model TC-FY-II, with CuKa radiation at 40kV and 100mA, step-by-step scanning at 8 deg./min, step size 0.02 deg.. And performing Rietveld structure refinement on the transition metal oxide by utilizing Topas software, refining the crystal structure and calculating the structural parameters of the crystal structure.
ExamplesExample 1:preparation of cobalt oxide and zinc-doped cobalt oxide
Weighing 6 parts of cobalt chloride hexahydrate and zinc nitrate hexahydrate by an analytical balance according to corresponding stoichiometric ratio, wherein the total substance amount of the cobalt chloride hexahydrate and the zinc nitrate hexahydrate in each part is 3.0mmol, the zinc nitrate hexahydrate comprises 0, 0.2mmol, 0.4mmol, 0.6mmol, 0.80mmol and 1.0mmol respectively, and the balance is cobalt chloride hexahydrate;
the above raw materials were dissolved in a mixed solution of 30mL of ethylene glycol and 10mL of deionized water, and stirred for 30 minutes. Then 30mmol ammonium bicarbonate was added to the mixture and dissolved for 30 minutes with stirring.
The solution was then transferred to a stainless steel autoclave reactor and heated in an oven at 180 ℃ for 24 hours. The resulting solid product was washed 5 times by centrifugation, 3 times by centrifugation with deionized water, 2 times by centrifugation with ethanol, and then dried overnight in an oven at 60 ℃.
Finally, the dried product was calcined at 350 ℃ for 2 hours using air in a furnace and ground to a powder to give the (zinc doped) cobalt oxide ZnxCo(3-x)O4(x is more than or equal to 0 and less than or equal to 1), wherein x is 0, 0.2, 0.4, 0.6, 0.8 and 1.0 respectively, namely Zn2+Isomorphism substitution of Co occupying tetrahedral voids2+Substitution ratios are 0%, 20%, 40%, 60%, 80%, 100%.
The XRD results are shown in FIG. 1, and it can be seen from FIG. 1 that (Zn-doped) cobalt oxide ZnxCo(3-x)O4In accordance with the standard diffractogram of cobaltosic oxide (JCPDS: 42-1476). The space group of cobaltosic oxide is as follows: fd-3m, standard cell parameters are:Z=8。
through Rietveld structure refinement calculation, the space group of the synthesized cobaltosic oxide is not changed,and after the structure is refined RexpIs 1.687, RwpIs 2.140, RpIs 1.687. When Co is present2+Is covered with Zn2+After all the substitutions, the space group is not changed,and after the structure is refined RexpIs 1.589, RwpIs 2.236, RpIs 1.733. With Zn2+Does not change the space group of the synthesized cobalt oxide due to Zn2+Has an ionic radius greater than that of Co2+And thus the cell parameters gradually increase.
Example 2:preparation of cobalt oxide and aluminum-doped cobalt oxide
Example 1 was repeated, with the difference that zinc nitrate hexahydrate was replaced by aluminium nitrate nonahydrate, giving an (aluminium-doped) cobalt oxide Co(3-x)AlxO4(x is more than or equal to 0 and less than or equal to 2), wherein x is 0, 0.5, 0.9, 1.3, 1.7 and 2.0 respectively, namely Al3+Substitution of isomorphs for Co occupying octahedral voids3+Substitution ratios are 0%, 20%, 40%, 60%, 80%, 100%.
The XRD results are shown in FIG. 2, and it can be seen from FIG. 1 that (aluminum-doped) cobalt oxide Co(3-x)AlxO4In accordance with the standard diffraction pattern of cobaltosic oxide (JCPDS: 42-1476). The space group of cobaltosic oxide is as follows: fd-3m, standard cell parameters are:Z=8。
when Co is present3+Is covered with Al3+After all the substitutions, the space group is not changed,and after the structure is refined RexpIs 1.508, RwpIs 3.751, RpIs 2.394. With Zn2+Gradually increasing of (2), emptying of synthesized cobalt oxideThe cell population is unchanged, but the cell parameters are gradually increased.
Example 3:preparation of iron oxides and zinc-doped iron oxides
Weighing 6 parts of ferric chloride hexahydrate and zinc nitrate hexahydrate in a corresponding stoichiometric ratio by using an analytical balance, wherein the total amount of substances is 2.4mmol, the zinc nitrate hexahydrate comprises 0, 0.16mmol, 0.32mmol, 0.48mmol, 0.64mmol and 0.8mmol respectively, and the balance is cobalt chloride hexahydrate;
the above raw materials were dissolved in 40mL of ethylene glycol and stirred for 30 minutes. Then 30mmol of sodium acetate trihydrate was added to the mixture and stirred at 50 ℃ for 30 minutes;
the solution was then transferred to a stainless steel autoclave reactor and heated in an oven at 180 ℃ for 12 hours. The resulting solid product was washed 5 times by centrifugation, 3 times by centrifugation with deionized water, 2 times by centrifugation with ethanol, and then dried overnight in an oven at 60 ℃.
Finally, the prepared sample was ground to a powder to obtain the (zinc doped) iron oxide ZnxFe(3-x)O4(x is more than or equal to 0 and less than or equal to 1), wherein x is 0, 0.2, 0.4, 0.6, 0.8 and 1.0 respectively, namely Zn2+Substitution of class homologies for Fe occupying octahedral voids2+Substitution ratios are 0%, 20%, 40%, 60%, 80%, 100%.
The XRD results are shown in FIG. 3, and it can be seen from FIG. 3 that (Zn-doped) iron oxide ZnxFe(3-x)O4In accordance with the standard diffraction pattern (JCPDS: 19-629). The space group of ferroferric oxide is as follows: fd-3m, standard cell parameters are:Z=8。
through Rietveld structure refinement calculation, the space group of the synthesized ferroferric oxide is not changed,and after the structure is refined RexpIs 3.644, RwpIs 9.905, RpIs 7.444. When Fe2+Is covered with Zn2+After all the substitutions, the space group is not changed,and after the structure is refined RexpIs 8.276, RwpIs 10.557, RpIs 8.240. Among other iron oxides, with Zn2+The space group of the synthesized iron oxide is not changed, but the unit cell parameter is increased.
Example 4:preparation of iron oxide and aluminum-doped cobalt oxide
Example 3 was repeated, with the difference that crystalline aluminum chloride was used instead of zinc nitrate hexahydrate, giving the (aluminum-doped) iron oxide Fe(3-x)AlxO4(x is more than or equal to 0 and less than or equal to 1), wherein x is 0, 0.1, 0.2, 0.3, 0.4 and 0.5 respectively, namely Al3+Isomorphism substitution of Fe occupying tetrahedral (or octahedral) voids3+The substitution ratios are 0%, 10%, 20%, 30%, 40%, 50%.
The XRD results are shown in FIG. 4, and Fe can be seen from FIG. 4(3-x)AlxO4In accordance with the standard diffractogram of ferroferric oxide (JCPDS: 19-629). The space group of ferroferric oxide is as follows: fd-3m, standard cell parameters are:Z=8。
when Fe3+Is covered with Al3+After all the substitutions, the space group is not changed,and after the structure is refined RexpIs 3.158, RwpIs 8.296, RpIs 6.407. Among other iron oxides, with Al3+The space group of the synthesized iron oxide is not changed, but the unit cell parameter is reduced.
Example 5:preparation of manganese oxide and zinc-doped manganese oxide
Potassium permanganate and zinc nitrate hexahydrate are weighed according to the corresponding stoichiometric ratio by an analytical balance, the total amount of substances is 2.4mmol, wherein the zinc nitrate hexahydrate comprises 0, 0.48mmol, 0.56mmol, 0.64mmol, 0.72mmol and 0.8mmol respectively, and the balance is potassium permanganate;
the above starting material was dissolved in 20mL of deionized water and stirred for 30 minutes. Then adding 5mmol ethanol into the mixture and stirring to dissolve for 30 minutes;
the solution was then transferred to a stainless steel autoclave reactor and heated in an oven at 180 ℃ for 12 hours. The resulting solid product was washed 3 times by centrifugation with deionized water and then dried in an oven at 60 ℃ overnight.
Finally, the prepared sample is ground into powder to obtain the (zinc doped) manganese oxide ZnxMn(3-x)O4(x is more than or equal to 0.6 and less than or equal to 1), wherein x is respectively 0.6, 0.7, 0.8, 0.9 and 1.0, namely Zn2+Substitution of isomorphs for Mn occupying octahedral voids2+The substitution ratios are 60%, 70%, 80%, 90%, 100%.
The XRD results are shown in FIG. 5, and it can be seen from FIG. 5 that (Zn-doped) manganese oxide ZnxMn(3-x)O4In accordance with the standard diffractogram (JCPDS: 24-734). The manganous manganic oxide is a tetragonal system, and the space group is as follows: i41/amd, standard cell parameters:Z=4。
through Rietveld structure refinement calculation, the space group of the synthesized ferroferric oxide is not changed,and after the structure is refined RexpIs 17.001, RwpIs 20.813, RpIs 13.936. When Mn is present2+Is covered with Zn2+After all the substitutions, the space group is not changed,and after the structure is refined RexpIs 14.506, RwpIs 19.655, RpIs 15.747. Among other oxides of manganeseWith Zn2+The space group of the synthesized manganese oxide is not changed but the unit cell parameter is reduced.
Example 6:preparation of manganese oxide and zinc-doped manganese oxide
Example 5 was repeated, with the difference that crystalline aluminum chloride was used instead of zinc nitrate hexahydrate, to give the (aluminum-doped) manganese oxide Mn(3-x)AlxO4(x is more than or equal to 0.5 and less than or equal to 0.9), wherein x is respectively 0.5, 0.6, 0.7, 0.8 and 0.9, namely Al3+Substitution of isomorphs for Mn occupying octahedral voids3+The substitution ratios are 50%, 60%, 70%, 80%, 90%.
The XRD results are shown in FIG. 6, and it can be seen from FIG. 6 that Mn is(3-x)AlxO4In accordance with the standard diffractogram of manganomanganic oxide (JCPDS: 24-734). The space group of the manganous manganic oxide is as follows: i41/amd, standard cell parameters:Z=4。
when Mn is present3+Is covered with Al3+After all the substitutions, the space group is not changed,but due to the influence of AlOOH impurities, R is obtained after the structure is refinedexpIs 14.945, RwpIs 27.483, RpIs 20.945. Among other oxides of manganese, with Al3+The space group of the synthesized manganese oxide is not changed but the unit cell parameter is reduced.
Examples of the experiments
Microwave absorption characteristics
A network analyzer is adopted to represent the microwave absorption characteristic of the transition metal oxide, the manufacturer is Agilent, the model is N5244A, the dielectric loss and the magnetic loss are calculated, the microwave loss mechanism of the transition metal oxide is discussed by representing and calculating the spin magnetic moment, and the relationship between the spin magnetic moment and the microwave absorption performance and the microwave induced degradation is further disclosed.
Microwave induced degradation
The microwave oven device is adopted to explore the effect of the transition metal oxide on the tetracycline microwave-induced degradation. An ultraviolet-visible spectrophotometer is adopted to represent the effect of degrading tetracycline by three transition metal oxides, a manufacturer is Beijing Sundapu apparatus technology company Limited, the model is TU-1901, the spectral bandwidth is 2nm, the response time is 0.2s, the wavelength range is 500nm-700nm, the interval is 1nm in the scanning speed, and the absorbance display range is 0.2-0.8.
Zn obtained in example 1xCo(3-x)O4The removal effect of microwave-induced degradation of tetracycline is shown in fig. 7. As can be seen from FIG. 7, Co3O4The physical adsorption value of the zinc oxide to tetracycline is 2.2mg/g at 30min, and Zn is combinedxCo(3-x)O4The appearance of the adsorbent has no obvious change, and the physical adsorption quantity is basically kept consistent. Compared with single microwave induced degradation of tetracycline, the degradation amount is 36.8mg/g at 30 min. After adding ZnxCo(3-x)O4Then, the degradation rate is obviously accelerated, the degradation balance can be achieved within 15min, and the degradation amount can reach 47.7 mg/g. With Zn2+The content is increased, the degradation rate and the degradation amount are basically kept consistent.
Co obtained in example 2(3-x)AlxO4The removal effect of microwave-induced degradation of tetracycline is shown in fig. 8. As can be seen from FIG. 8, Co3O4The physical adsorption value of the tetracycline at 30min is 2.2 mg/g. The same comparison shows that the degradation amount of tetracycline induced by microwave alone is 36.8mg/g at 30 min. After adding Co(3-x)AlxO4After, compare Co3O4The degradation rate is obviously slowed down, the degradation balance can be achieved only after 20min, but the degradation amount is basically kept consistent. With Al3+The content is increased, the degradation rate is obviously slowed down, and the degradation amount at 15min is also lower, which indicates that Co3+Plays an obvious role in the process of degrading tetracycline by microwave induction.
Zn obtained in example 3xFe(3-x)O4The removal effect of microwave-induced degradation of tetracycline is shown in fig. 9. As can be seen from the view in figure 9,Fe3O4the physical adsorption value of the zinc oxide to tetracycline is 4.4mg/g at 30min, and Zn is combinedxFe(3-x)O4The appearance of the oxide has no obvious change, and the physical adsorption quantity is basically kept consistent. Compared with single microwave induced degradation of tetracycline, the degradation amount is 35.96mg/g at 30 min. After adding ZnxFe(3-x)O4Then, the degradation rate is obviously accelerated, the degradation balance can be achieved within 20min, and the degradation amount can reach 47.8 mg/g.
Fe obtained in example 4(3-x)AlxO4The removal effect of microwave-induced degradation of tetracycline is shown in fig. 10. As can be seen from FIG. 10, after addition of Fe(3-x)AlxO4After, phase ratio of Fe3O4The degradation rate is obviously slowed down, the degradation balance can be achieved only within 30min, and the degradation amount is also reduced.
Zn obtained in example 5xMn(3-x)O4The removal effect of microwave-induced degradation of tetracycline is shown in fig. 11. As can be seen from FIG. 11, Mn3O4The physical adsorption value of the zinc oxide to tetracycline is 2.38mg/g at 30min, and Zn is combinedxMn(3-x)O4The appearance of the adsorbent has no obvious change, and the physical adsorption quantity is basically kept consistent. Compared with single microwave induced degradation of tetracycline, the degradation amount is 35.81mg/g at 30 min. After adding Mn3O4After the oxide catalyst is used, the degradation rate is obviously accelerated, and the maximum degradation amount, namely 42.81mg/g, can be reached within 30 min.
Mn obtained in example 6(3-x)AlxO4The removal effect of microwave-induced degradation of tetracycline is shown in fig. 12. As can be seen from FIG. 12, Mn is added(3-x)AlxO4Then, the degradation rate is obviously accelerated, and the maximum degradation amount of the product can reach 42.81mg/g within 30 min.
SEM testing and analysis
The morphology of the transition metal oxide was characterized by Scanning Electron Microscopy (SEM), with the manufacturer being JEOL, model JSM-IT300, a scanning voltage of 20kV, and a magnification of 5000.
Obtained in example 1ZnxCo(3-x)O4The sample was analyzed for morphology, and its SEM is shown in FIG. 13. FIG. 13 results show that different Zn2+The appearance of the sample with the doping proportion is not obviously changed, and the sample is spherical particles with uniform size, the diameter is about 6-7 mu m, and the sample is assembled by small blocky particles with different side lengths of 400-900 nm. On one hand, the contact area with the tetracycline is increased, the tetracycline is favorably adsorbed, and the rate of degrading the tetracycline by microwave induction is increased; on the other hand, with Zn2+The content is increased, the appearance is not obviously changed, and the interference of other factors can be eliminated.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. A method for preparing a spinel-type transition metal oxide, comprising the steps of:
step 1, preparing a precursor compound of transition metal and doped metal;
step 2, dissolving the raw materials in a solvent to prepare a solution;
and 3, carrying out reaction in the reactor to obtain a solid product, and optionally carrying out post-treatment.
2. The method of claim 1, wherein in step 1, the transition metal comprises cobalt, iron, and manganese, and the dopant metal comprises zinc and aluminum.
3. The method according to claim 1, wherein in step 1, the precursor of the transition metal oxide is a salt compound, such as cobalt, iron hydrochloride, preferably hydrate hydrochloride, and manganate, such as potassium permanganate.
4. The method according to claim 1, characterized in that in step 1, the precursor of the doping metal is a nitrate, such as zinc nitrate, preferably a hydrated nitrate, and a hydrochloride, such as aluminum chloride.
5. The process according to any one of claims 1 to 4, wherein in step 2, the solvent is water, an alcohol or a hydroalcoholic solution, and the alcohol is a monohydric or polyhydric alcohol, preferably ethylene glycol.
6. The method according to any one of claims 1 to 5, wherein in step 2, after the raw material is dissolved in the solvent, optionally with stirring, the mixture is preferably added with a salt.
7. A method according to claim 6, wherein the salt is preferably an ammonium salt, more preferably ammonium carbonate or ammonium bicarbonate, and sodium acetate may also be used.
8. Process according to one of claims 1 to 7, characterized in that in step 3 the reaction is carried out in a high-pressure apparatus, preferably a stainless steel autoclave reactor, and is heated at 120-.
9. The method according to one of claims 1 to 8, characterized in that in step 3, the post-treatment comprises washing, drying and calcination.
10. Use of the oxide obtained according to the process of one of claims 1 to 9 for the degradation of antibiotics in amounts up to 40mg/g or more.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010024839.4A CN113120944A (en) | 2020-01-10 | 2020-01-10 | Preparation method of spinel type transition metal oxide and application of spinel type transition metal oxide in degrading antibiotics |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010024839.4A CN113120944A (en) | 2020-01-10 | 2020-01-10 | Preparation method of spinel type transition metal oxide and application of spinel type transition metal oxide in degrading antibiotics |
Publications (1)
Publication Number | Publication Date |
---|---|
CN113120944A true CN113120944A (en) | 2021-07-16 |
Family
ID=76771539
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010024839.4A Pending CN113120944A (en) | 2020-01-10 | 2020-01-10 | Preparation method of spinel type transition metal oxide and application of spinel type transition metal oxide in degrading antibiotics |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113120944A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113877599A (en) * | 2021-09-27 | 2022-01-04 | 中国地质大学(武汉) | Cobalt-manganese spinel material and preparation method and application thereof |
-
2020
- 2020-01-10 CN CN202010024839.4A patent/CN113120944A/en active Pending
Non-Patent Citations (4)
Title |
---|
JUN LIU ET AL.: ""Facile synthesis of stoichiometric zinc ferrite nanocrystal clusters with superparamagnetism and high magnetization"", 《MATERIALS RESEARCH BULLETIN》 * |
XIN LIU ET AL.: ""Structural, Magnetic, and Thermodynamic Evolutions of Zn-Doped Fe3O4 Nanoparticles Synthesized Using a One-Step Solvothermal Method"", 《THE JOURNAL OF PHYSICAL CHEMISTRY C》 * |
YIXIONG PANG ET AL.: ""Combined microwave-induced and photocatalytic oxidation using zinc ferrite catalyst for efficient degradation of tetracycline hydrochloride in aqueous solution"", 《JOURNAL OF THE TAIWAN INSTITUTE OF CHEMICAL ENGINEERS》 * |
幸雪冰: ""两种典型结构氧化锰矿物的微波吸收及对抗生素的微波降解研究"", 《中国优秀博硕士学位论文全文数据库(硕士)工程科技Ⅰ辑》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113877599A (en) * | 2021-09-27 | 2022-01-04 | 中国地质大学(武汉) | Cobalt-manganese spinel material and preparation method and application thereof |
CN113877599B (en) * | 2021-09-27 | 2024-02-09 | 中国地质大学(武汉) | Cobalt manganese spinel material and preparation method and application thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Huo et al. | Citric acid assisted solvothermal synthesis of BiFeO3 microspheres with high visible-light photocatalytic activity | |
Ren et al. | A Fenton-like method using ZnO doped MIL-88A for degradation of methylene blue dyes | |
CN114534759A (en) | Monoatomic cobalt-supported tubular carbon nitride catalyst and preparation method and application thereof | |
Xie et al. | Non-radical activation of peroxymonosulfate with oxygen vacancy-rich amorphous MnOX for removing sulfamethoxazole in water | |
CN111821982B (en) | Graphene oxide-cerium oxide-ferric oxide composite material, synthetic method and application thereof in catalytic degradability | |
CN111617731A (en) | Method for treating antibiotics in water body by coupling magnetic nano material with persulfate | |
CN109364924B (en) | Magnetic nano ozone catalyst CoFe2O4And preparation method and application thereof | |
CN114870882B (en) | Catalyst for oxidizing and degrading antibiotic wastewater based on microwave rapid activation of peroxyacetic acid and preparation and application methods thereof | |
CN112705242B (en) | Porous carbon nitride composite material modified by metal bismuth nanoparticles, preparation method thereof and application of porous carbon nitride composite material in removal of antibiotics in water | |
CN113120944A (en) | Preparation method of spinel type transition metal oxide and application of spinel type transition metal oxide in degrading antibiotics | |
Wang et al. | Highly efficient degradation of rhodamine B by α-MnO2 nanorods | |
CN111545211B (en) | Graphene oxide-lanthanum oxide-cobalt hydroxide composite material, and synthesis method and application thereof | |
Zhang et al. | Confined catalytic with yolk-shell nanoreactor boosting the efficient removal of antibiotic by low temperature plasma-catalytic degradation: Reaction kinetics and mechanisms | |
CN115350711B (en) | Preparation method of ammonium polythiomolybdate/manganese ferrite persulfate catalyst | |
CN114177911B (en) | Carbon-supported multi-metal oxide catalyst and preparation method and application thereof | |
CN115228476A (en) | Metal-loaded lignin carbon material and preparation method and application thereof | |
Prakash et al. | Wastewater Treatment: The Emergence of Cobalt Ferrite and Its Composites in Sulfate Radical-Based Advanced Oxidation Processes | |
CN113244929B (en) | Iron bismuth oxide Bi 2 Fe 4 O 9 Preparation method and application in organic wastewater treatment | |
CN111569890B (en) | Graphene oxide-terbium oxide-ferric oxide composite material, synthetic method and application thereof in catalytic degradation | |
Ivanova-Kolcheva et al. | Catalytic activation of PMS by Co3O4 modified g-C3N4 for oxidative degradation of the azo dye Acid Orange 7 in aqueous solutions | |
CN108816214B (en) | Bi with full solar spectral response2O2.75/BiO2-xComposite photocatalyst and preparation method and application thereof | |
Mohammadzadeh Kakhki et al. | Efficient photodegradation of tetracycline with BaCO3@ BaCa (CO3) 2 modified perlite-incorporated chitosan heterostructure under visible light | |
CN115845856B (en) | Nanocomposite prepared by ultraviolet light assistance and preparation method thereof | |
Qin et al. | Rapid one-pot microwave-hydrothermal synthesis of OMS-2 and full-solar-spectrum photocatalytic performance for high phenol concentration | |
CN115814837B (en) | Hollow flower-ball-shaped Z-shaped heterojunction BCN/Bi 2 O 2 [BO 2 (OH)]Photocatalyst |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210716 |
|
RJ01 | Rejection of invention patent application after publication |