CN112138721A - MOF material loaded with ferroferric oxide and application thereof - Google Patents
MOF material loaded with ferroferric oxide and application thereof Download PDFInfo
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- CN112138721A CN112138721A CN202011001214.2A CN202011001214A CN112138721A CN 112138721 A CN112138721 A CN 112138721A CN 202011001214 A CN202011001214 A CN 202011001214A CN 112138721 A CN112138721 A CN 112138721A
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- rhodamine
- mof material
- mof
- water
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 239000000463 material Substances 0.000 title claims abstract description 54
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims abstract description 11
- 239000000725 suspension Substances 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 117
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 68
- 229910001868 water Inorganic materials 0.000 claims description 67
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 65
- 238000006243 chemical reaction Methods 0.000 claims description 60
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 49
- 239000000047 product Substances 0.000 claims description 38
- 239000002351 wastewater Substances 0.000 claims description 27
- 239000000843 powder Substances 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 18
- 238000007885 magnetic separation Methods 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 17
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 12
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 12
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 230000000593 degrading effect Effects 0.000 claims description 7
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 7
- 239000011790 ferrous sulphate Substances 0.000 claims description 7
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- 230000010355 oscillation Effects 0.000 claims description 2
- 238000003672 processing method Methods 0.000 claims 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical group [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 2
- 238000009388 chemical precipitation Methods 0.000 abstract 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 105
- 229940043267 rhodamine b Drugs 0.000 description 103
- 239000000975 dye Substances 0.000 description 88
- 239000003054 catalyst Substances 0.000 description 64
- 239000012621 metal-organic framework Substances 0.000 description 33
- 230000000694 effects Effects 0.000 description 27
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 21
- 230000035484 reaction time Effects 0.000 description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 20
- 238000002474 experimental method Methods 0.000 description 17
- 229910021642 ultra pure water Inorganic materials 0.000 description 17
- 239000012498 ultrapure water Substances 0.000 description 17
- 239000000203 mixture Substances 0.000 description 14
- 238000002835 absorbance Methods 0.000 description 13
- 238000011160 research Methods 0.000 description 12
- 238000001291 vacuum drying Methods 0.000 description 12
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 10
- 238000004042 decolorization Methods 0.000 description 10
- 230000005291 magnetic effect Effects 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 238000000967 suction filtration Methods 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000012528 membrane Substances 0.000 description 9
- 238000002604 ultrasonography Methods 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 239000011258 core-shell material Substances 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- 239000010842 industrial wastewater Substances 0.000 description 3
- 230000005408 paramagnetism Effects 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229910007566 Zn-MOF Inorganic materials 0.000 description 2
- 239000012921 cobalt-based metal-organic framework Substances 0.000 description 2
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000010977 jade Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 2
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
- 230000003278 mimic effect Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 230000005298 paramagnetic effect Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000004729 solvothermal method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 239000012917 MOF crystal Substances 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 238000011111 UV-scan method Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 238000012863 analytical testing Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000009990 desizing Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- JBFYUZGYRGXSFL-UHFFFAOYSA-N imidazolide Chemical compound C1=C[N-]C=N1 JBFYUZGYRGXSFL-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 230000026045 iodination Effects 0.000 description 1
- 238000006192 iodination reaction Methods 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000012924 metal-organic framework composite Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
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- 229920001778 nylon Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000013260 porous coordination network Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000010405 reoxidation reaction Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000013094 zinc-based metal-organic framework Substances 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- B01J35/33—
-
- 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
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
-
- 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
- C02F2101/38—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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
Abstract
The invention discloses a MOF material loaded with ferroferric oxide and application thereof. Fe is prepared by chemical precipitation method by using water-soluble ferric salt and ferrous salt3O4Powdering and then dispersing to obtain Fe3O4Mixing the suspension with a trimesic acid solution, heating to 65-75 ℃, uniformly mixing, adding a copper acetate solution, and continuing to react; and carrying out post-treatment to obtain the MOF material loaded with ferroferric oxide. The MOF material loaded with ferroferric oxide in some examples of the invention has good catalytic performance, can well catalyze the Fenton oxidation reaction, improve the utilization rate of hydroxyl free radicals (HO.), and better degrade organic pollutants, in particular dye organic pollutants. Hair brushThe MOF material loaded with ferroferric oxide in some examples has better catalytic capability in a wider pH range and is wider in application range.
Description
Technical Field
The invention relates to an MOF material and application thereof, in particular to an MOF material loaded with ferroferric oxide and application thereof in wastewater decolorization.
Background
The amount of dye consumed and produced by the dye industry worldwide is about 80000 tons per year, with the amount of dye used in the commercial dye industry being about 10000 tons, according to incomplete data statistics.
The dye industrial wastewater is generally wastewater discharged in the production process of manufacturing dyes and pigments by using benzene, toluene, naphthalene and the like as raw materials, producing an intermediate through nitration and iodination, and performing a plurality of reaction stages such as diazotization, coupling, vulcanization and the like by using the intermediate[3]. The dye industrial wastewater mainly comes from wastewater generated in the refining process of textile products such as desizing, scouring, bleaching, mercerizing, dyeing, printing, finishing and the like. In each step of the process, a large amount of water is required, and generally, the amount of water consumed for producing 1kg of product is 200-500L. It is understood that 15 to 20 percent of the wastewater generated by each process is directly discharged without treatment. Such waste water generally contains dyes, auxiliaries and multiple pastes, and is especially common in the wash water of toning, printing rollers and printing screens.
The use of a large amount of dye obviously increases the discharge amount of untreated dye wastewater, and extremely bad influences are generated on the surrounding water quality and environment, wherein the chromaticity problem caused by the dye wastewater is particularly obvious, and the extremely large chromaticity can be generated by mixing a very small amount of dye into the water, so that the intuitive chromaticity problem brings extremely bad influences to surrounding residents.
Besides, the serious harm of the dye wastewater to the environment is mainly as follows:
(1) the dye wastewater can absorb or reflect sunlight, so that the sunlight cannot enter a water body, and the growth and development of plants needing photosynthesis in the water body are seriously hindered;
(2) heavy metal ions contained in part of dye wastewater enter a water body to destroy an ecosystem of a community in water, and the propagation of a food chain endangers the health of microorganisms, fishes and human beings, so that serious adverse effects are generated;
(3) when part of the dye wastewater flows through the ground surface, the dye wastewater pollutes the underground water through the infiltration effect, thereby threatening the life health of human beings;
(4) the dye wastewater is discharged into the polluted water body, and the dissolved oxygen is consumed, so that the reoxidation capability of the polluted water body is weakened to the greatest extent, and the self-purification of the water body is not facilitated.
When small Organic molecules are used as ligands and freely assembled with central atoms, compounds with periodic network structures are formed, and the compounds are Metal-Organic frameworks (MOFs). MOF materials typically include one-dimensional (1D) chain compounds, two-dimensional network compounds (2D), and three-dimensional (3D) framework compounds. MOF materials can be generally classified into IRMOF (metal-organic framework network), ZIF (imidazolate framework like zeolite), MIL (levamil framework material), and PCN (pore-channel framework material).
Metal Organic Framework (MOF) materials are mainly composed of two materials, which are a higher valent metal ion and a multidentate organic ligand. The synthesis methods of MOF materials are more commonly used as follows:
(1) a solvothermal method: heating the raw material mixture in the presence of water or an organic solvent by using a lining glass test tube with polytetrafluoroethylene;
(2) liquid phase diffusion method: soaking and sealing by using a protonation solution to generate an MOF crystal structure;
(3) other methods are as follows: for example, stirring synthesis, solid phase synthesis, ultrasonic method, etc.
Most MOF materials have the excellent characteristics of large specific surface area, stable and variable pore channels and the like, and are widely applied to the aspects of hot problems of medicine, industry, nonlinear optical activity, magnetism, environmental treatment and the like.
The Fenton oxidation method has multiple advantages of high efficiency, good removal rate and the like in the treatment of dye wastewater, and is widely applied to the treatment of dye wastewater. The removal rate of the traditional homogeneous Fenton to the dye wastewater can reach 60% -70%, but the traditional homogeneous Fenton reaction has the following steps: insufficient utilization of hydroxyl radical (HO. cndot.), narrow available pH range, Fe2+Residual secondary pollution to the environment and the like. Therefore, the research on stable homogeneous and easily separated catalyst is the hot spot of the current Fenton catalyst research.
CN107029671A discloses modified Fe3O4The preparation method and the application of the @ MOF composite material comprise the steps of preparing superparamagnetic ferroferric oxide nanoparticles by a solvothermal method, adopting a layer-by-layer self-assembly method, taking superparamagnetic ferroferric oxide as a core, and depositing metal central ions and organic ligands on the surface of the superparamagnetic ferroferric oxide to synthesize MOF in situ to obtain Fe3O4@ MOF composite, and for Fe3O4Carrying out surface mercapto modification on the @ MOF composite material to obtain modified Fe3O4@ MOF composite of the modified Fe3O4The @ MOF composite material can be used for adsorbing heavy metal mercury ions in industrial wastewater.
CN109126721A discloses a magnetic metal organic framework nano material with a three-layer core-shell structure, a preparation method and application thereof. The method firstly adopts Fe3O4@SiO2The particles are subjected to hydroxylation modification to obtain nano Fe3O4@SiO2the-OH particles are subjected to surface amination modification to obtain the nano Fe3O4@SiO2-NH2The particles are then connected with Zn-MOF to finally obtain the magnetic metal organic framework nano material Fe with a three-layer core-shell structure3O4@SiO2@ Zn-MOF. The magnetic metal organic framework nano material with the three-layer core-shell structure can be used for adsorbing organic dyes in water, has good adsorption effect on Congo red and methylene blue, and has 5 strips at pHThe removal rate of Congo red under the workpiece reaches 100%, the removal rate of methylene blue reaches more than 75% under the condition that pH is 7, the adsorbing material can be easily recovered through an external magnetic field, and the material can be effectively reused.
CN103337327A discloses heterogeneous Fe3O4the/Co metal organic framework material takes a metal organic framework compound Co-MOF as a carrier, and Fe is adhered to the surface and the holes of the carrier3O4Nanoparticles. The preparation method comprises mixing Fe3O4Dissolving the nano material, soluble cobalt salt and trimesic acid in deionized water, placing the mixture in a closed reaction kettle, heating the mixture to 135-150 ℃, and keeping the temperature for 20-28 hours; then, reducing the temperature to 118-122 ℃, and keeping for 4.5-6 hours; then cooling to 98-105 ℃, preserving heat for 4.5-6 hours, and finally naturally cooling to room temperature and standing for 11-14 hours; washing the precipitate, performing suction filtration, and naturally drying to obtain Fe3O4a/Co-MOF composite material. The obtained material has good thermal stability and chemical stability.
Existing Fe3O4the/MOF composite material has weak catalytic performance and cannot be generally used for catalyzing the oxidative degradation of organic matters.
Disclosure of Invention
The invention aims to overcome at least one defect of the prior art and provides a MOF material loaded with ferroferric oxide and application thereof.
The technical scheme adopted by the invention is as follows:
in a first aspect of the present invention, there is provided:
a MOF material loaded with ferroferric oxide is prepared by the following steps:
s1) dissolving water-soluble ferric salt and ferrous salt in water, and adding ammonia water at 25-35 ℃ until no precipitate is generated to obtain a suspension;
s2) heating the suspension to 75-85 ℃, stirring to react completely, cleaning, performing magnetic separation, drying and grinding the product obtained by magnetic separation into powder to obtain Fe3O4Powder;
s3) adding Fe3O4Powder dispersionIn absolute ethanol to obtain Fe3O4Suspension;
s4) dissolving trimesic acid in a mixed solvent consisting of DMF and absolute ethyl alcohol to obtain a trimesic acid solution;
s5) adding Fe3O4Heating the suspension and the trimesic acid solution to 65-75 ℃, uniformly mixing, adding a copper acetate solution, and continuing to react;
s6), washing and drying after the reaction is finished, and obtaining the MOF material loaded with ferroferric oxide.
In some examples, the mixed solvent is a mixture of DMF and absolute ethanol.
In some examples, the volume ratio of DMF to absolute ethanol in the mixed solvent is 1: (0.9-1.1).
In some examples, the trimesic acid solution has a concentration of (0.5-0.7) g/100mL trimesic acid.
In some examples, the copper acetate solution is an aqueous solution of copper acetate.
In some examples, the molar ratio of copper to iron is (0.1-0.3): 1.
in some examples, the copper acetate solution has a concentration of (1-3) g/100mL of copper acetate.
In some examples, the water-soluble iron salt is selected from iron sulfate or iron trichloride; the water-soluble ferrous salt ferrous sulfate or ferrous chloride.
In a second aspect of the present invention, there is provided:
a treatment method for degrading organic wastewater comprises the steps of adding an MOF material loaded with ferroferric oxide and hydrogen peroxide into the organic wastewater, and carrying out Fenton oxidation reaction to degrade organic pollutants in the organic wastewater, wherein the MOF material is as described in the first aspect of the invention.
In some examples, the Fenton oxidation reaction is performed using sonication. By using ultrasonic oscillation treatment, the degradation of organic matters can be better promoted.
In some examples, the Fenton oxidation reaction is carried out, and the pH of the reaction system is controlled to be 3-10.
The invention has the beneficial effects that:
the MOF material loaded with ferroferric oxide in some examples of the invention has good catalytic performance, can well catalyze the Fenton oxidation reaction, improve the utilization rate of hydroxyl free radicals (HO.), and better degrade organic pollutants, in particular dye organic pollutants.
According to the MOF material loaded with ferroferric oxide, disclosed by the invention, the MOF material can be conveniently recovered through magnetic adsorption, so that Fe is avoided2+Secondary pollution of (2).
The MOF material loaded with ferroferric oxide in some examples of the invention has good catalytic capacity in a wider pH range and is wider in application range.
Drawings
FIG. 1 is a UV scan of rhodamine B;
FIG. 2 is a rhodamine B standard curve;
FIG. 3 is Fe prepared in example 13O4X-ray diffraction patterns of (a);
FIG. 4 shows Fe prepared in example 13O4X-ray diffraction pattern of @ MOF;
FIG. 5 is the influence of single factor conditions on the rhodamine B chroma removal rate;
FIG. 6 shows catalyst Fe3O4Researching the utilization rate;
FIG. 7 is Fe of example 13O4The influence of the concentration of the @ MOF catalyst on the color removal rate of rhodamine B;
FIG. 8 shows the effect of hydrogen peroxide concentration on rhodamine B chroma removal rate;
FIG. 9 is the effect of initial pH on rhodamine B chroma removal;
FIG. 10 shows catalyst Fe3O4Studies of the utilization of @ MOF;
FIG. 11 is a three-dimensional fluorescence spectrum of rhodamine B raw water (diluted five times);
FIG. 12 is a three-dimensional fluorescence spectrum of water (diluted five times) after rhodamine B treatment.
Detailed Description
The technical scheme of the invention is further explained by combining the examples and experiments.
Example 1
Fe3O4Preparation of
2.7g of ferric chloride (FeCl) was accurately weighed3·6H2O) and 2.7g of ferrous sulfate (FeSO)4·2H2O) is dissolved in 60mL of ultrapure water, the solution is immediately transferred into a constant temperature water bath box at 30 ℃ after the dissolution is finished, and ammonia water (NH) with the mass fraction of 25 percent is dropwise added when the temperature of the solution is raised to 30 DEG3·H2O) until no precipitate is formed. After the dropwise addition is finished, the beaker is moved into a water bath thermostat at 80 ℃, the mixture is stirred for 30min by hand, after the stirring is finished, the obtained product is washed by ultrapure water until the filtered water is no longer alkaline, the product is subjected to magnetic separation, and after vacuum drying at 40-45 ℃, the product is ground into powder for later use.
Fe3O4Preparation of @ MOF
1) The magnetic ferroferric oxide (Fe) is prepared3O4) Dispersing the powder in 110mL of absolute ethyl alcohol, and uniformly stirring to prepare a solution A;
2) simultaneously preparing 80mL of the mixture with the volume ratio of 1: 1 in DMF (40mL) and absolute ethanol (40mL), 0.5g H was accurately weighed3BTC (trimesic acid) is dissolved in the mixed solution and stirred evenly to prepare solution B;
3) adding 10mL of the solution A into the solution B, stirring uniformly, immediately transferring into a constant temperature water bath box at 70 ℃, adding 40mL of aqueous solution dissolved with 0.86g of copper acetate monohydrate into the solution when the temperature of the solution rises to 70 ℃, and heating in a water bath for 4 hours. And performing magnetic separation on the obtained product, washing the product with absolute ethyl alcohol and ultrapure water for three times respectively, performing vacuum drying at 40-45 ℃, and grinding the product into powder for later use.
Example 2
Fe3O4Preparation of
1.35g of ferric chloride (FeCl) was accurately weighed3·6H2O) and 1.35g of ferrous sulfate (FeSO)4·2H2O) is dissolved in 60mL of ultrapure water, and immediately moved into a constant-temperature water bath box at 30 ℃ after the dissolution is finished, until the solution risesWhen the temperature is 30 ℃, dropwise adding ammonia water (NH) with the mass fraction of 25 percent3·H2O) until no precipitate is formed. After the dropwise addition is finished, the beaker is moved into a water bath thermostat at 80 ℃, the mixture is stirred for 30min by hand, after the stirring is finished, the obtained product is washed by ultrapure water until the filtered water is no longer alkaline, the product is subjected to magnetic separation, and after vacuum drying at 40-45 ℃, the product is ground into powder for later use.
Fe3O4Preparation of @ MOF
1) The magnetic ferroferric oxide (Fe) is prepared3O4) Dispersing the powder in 110mL of absolute ethyl alcohol, and uniformly stirring to prepare a solution A;
2) simultaneously preparing 80mL of the mixture with the volume ratio of 1: 1 in DMF (40mL) and absolute ethanol (40mL), 0.25g H was accurately weighed3BTC (trimesic acid) is dissolved in the mixed solution and stirred evenly to prepare solution B;
3) and adding 10mL of the solution A into the solution B, stirring uniformly, immediately transferring into a 70 ℃ constant temperature water bath box, adding 40mL of an aqueous solution in which 0.43g of copper acetate monohydrate is dissolved into the solution when the temperature of the solution rises to 70 ℃, heating in a water bath for 4 hours, carrying out magnetic separation on the obtained product, washing with absolute ethyl alcohol and ultrapure water for three times respectively, carrying out vacuum drying at 40-45 ℃, and grinding into powder for later use.
Example 3
Fe3O4Preparation of
Accurately weigh 5.4g of ferric chloride (FeCl)3·6H2O) and 5.4g ferrous sulfate (FeSO)4·2H2O) is dissolved in 60mL of ultrapure water, the solution is immediately transferred into a constant temperature water bath box at 30 ℃ after the dissolution is finished, and ammonia water (NH) with the mass fraction of 25 percent is dropwise added when the temperature of the solution is raised to 30 DEG3·H2O) until no precipitate is formed. After the dropwise addition is finished, the beaker is moved into a water bath thermostat at 80 ℃, the mixture is stirred for 30min by hand, after the stirring is finished, the obtained product is washed by ultrapure water until the filtered water is no longer alkaline, the product is subjected to magnetic separation, and after vacuum drying at 40-45 ℃, the product is ground into powder for later use.
Fe3O4Preparation of @ MOF
1) The magnetic ferroferric oxide (Fe) is prepared3O4) Dispersing the powder in 110mL of absolute ethyl alcohol, and uniformly stirring to prepare a solution A;
2) simultaneously preparing 80mL of the mixture with the volume ratio of 1: 1 in DMF (40mL) and absolute ethanol (40mL), 1.0g H was accurately weighed3BTC (trimesic acid) is dissolved in the mixed solution and stirred evenly to prepare solution B;
3) adding 10mL of the solution A into the solution B, stirring uniformly, immediately transferring into a constant temperature water bath box at 70 ℃, adding 40mL of aqueous solution dissolved with 1.72g of copper acetate monohydrate into the solution when the temperature of the solution rises to 70 ℃, and heating in a water bath for 4 hours. And performing magnetic separation on the obtained product, washing the product with absolute ethyl alcohol and ultrapure water for three times respectively, performing vacuum drying at 40-45 ℃, and grinding the product into powder for later use.
Comparative example 1
Fe3O4Preparation of
2.7g of ferric chloride (FeCl) was accurately weighed3·6H2O) and 2.7g of ferrous sulfate (FeSO)4·2H2O) is dissolved in 60mL of ultrapure water, the solution is immediately transferred into a constant temperature water bath box at 30 ℃ after the dissolution is finished, and ammonia water (NH) with the mass fraction of 25 percent is dropwise added when the temperature of the solution is raised to 30 DEG3·H2O) until no precipitate is formed. After the dropwise addition is finished, the beaker is moved into a water bath thermostat at 80 ℃, the mixture is stirred for 30min by hand, after the stirring is finished, the obtained product is washed by ultrapure water until the filtered water is no longer alkaline, the product is subjected to magnetic separation, and after vacuum drying at 40-45 ℃, the product is ground into powder for later use.
Fe3O4Preparation of @ MOF
1) The magnetic ferroferric oxide (Fe) is prepared3O4) Dispersing the powder in 110mL of absolute ethyl alcohol, and uniformly stirring to prepare a solution A;
2) simultaneously preparing 80mL of the mixture with the volume ratio of 1: 1 in DMF (40mL) and absolute ethanol (40mL), 0.5g H was accurately weighed3BTC (trimesic acid) is dissolved in the mixed solution and stirred evenly to prepare solution B;
3) adding 10mL of the solution A into the solution B, stirring uniformly, immediately transferring into a constant temperature water bath box at 40 ℃, adding 40mL of an aqueous solution dissolved with 0.86g of copper acetate monohydrate into the solution when the temperature of the solution rises to 40 ℃, and heating in a water bath for 4 hours. And performing magnetic separation on the obtained product, washing the product with absolute ethyl alcohol and ultrapure water for three times respectively, performing vacuum drying at 40-45 ℃, and grinding the product into powder for later use.
Comparative example 2
Fe3O4Preparation of
2.7g of ferric chloride (FeCl) was accurately weighed3·6H2O) and 2.7g of ferrous sulfate (FeSO)4·2H2O) is dissolved in 60mL of ultrapure water, the solution is immediately transferred into a constant temperature water bath box at 30 ℃ after the dissolution is finished, and ammonia water (NH) with the mass fraction of 25 percent is dropwise added when the temperature of the solution is raised to 30 DEG3·H2O) until no precipitate is formed. After the dropwise addition is finished, the beaker is moved into a water bath thermostat at 80 ℃, the mixture is stirred for 30min by hand, after the stirring is finished, the obtained product is washed by ultrapure water until the filtered water is no longer alkaline, the product is subjected to magnetic separation, and after vacuum drying at 40-45 ℃, the product is ground into powder for later use.
Fe3O4Preparation of @ MOF
1) The magnetic ferroferric oxide (Fe) is prepared3O4) Dispersing the powder in 110mL of absolute ethyl alcohol, and uniformly stirring to prepare a solution A;
2) simultaneously preparing 80mL of the mixture with the volume ratio of 1: 1 in DMF (40mL) and absolute ethanol (40mL), 0.5g H was accurately weighed3BTC (trimesic acid) is dissolved in the mixed solution and stirred evenly to prepare solution B;
3) adding 10mL of the solution A into the solution B, stirring uniformly, immediately transferring into a constant temperature water bath box at 100 ℃, adding 40mL of an aqueous solution dissolved with 0.86g of copper acetate monohydrate into the solution when the temperature of the solution rises to 100 ℃, and heating in a water bath for 4 hours. And performing magnetic separation on the obtained product, washing the product with absolute ethyl alcohol and ultrapure water for three times respectively, performing vacuum drying at 40-45 ℃, and grinding the product into powder for later use.
Degradation experiment of rhodamine
The experimental method comprises the following steps:
the rhodamine B is widely applied in the industrial production of the dye, and the dye has large chroma, is easy to dissolve in water and has carcinogenicity, thereby being a representative substance for preventing and treating printing and dyeing wastewater. The research adopts 10mg/L rhodamine B to simulate the dye wastewater, and researches the problem of removing the chromaticity of the dye wastewater.
Preparation of rhodamine B dye solution
Accurately weighing 0.01g of rhodamine B powder in a 100mL beaker, adding water to dissolve the rhodamine B powder, transferring the rhodamine B powder into a 1000mL volumetric flask, and fixing the volume for later use.
Fe3O4Research on participating in Fenton-like reaction for degrading rhodamine B
Transferring a certain volume and concentration of rhodamine B dye solution into a 250mL conical flask, and adding a certain concentration of Fe3O4Powder and 30% H2O2Placing the mixed solution in an ultrasonic generator to carry out Fenton oxidation reaction, and changing the concentration of the catalyst and H2O2And (3) concentration and initial pH value, further filtering and decoloring the treated solution by a sand core, measuring the absorbance value of the mixed solution at the maximum absorption wavelength of the rhodamine B, and converting the absorbance value into the concentration of the residual dye solution through a rhodamine B standard curve to obtain the removal rate of the reaction on the chroma of the rhodamine B.
Fe3O4Research on degrading rhodamine B through Fenton-like reaction with participation of @ MOF
Transferring a certain volume and concentration of rhodamine B dye solution into a 250mL conical flask, and adding a certain concentration of Fe3O4@ MOF powder and 30% H2O2Placing the mixed solution in an ultrasonic generator to carry out Fenton oxidation reaction, and changing the concentration of the catalyst and H2O2And (3) concentration and initial pH value, carrying out suction filtration and decoloration on the treated solution by a sand core, measuring the absorbance value of the mixed solution at the maximum absorption wavelength of rhodamine B, and converting the absorbance value into the concentration of the residual dye solution through a rhodamine B standard curve to obtain the removal rate of the reaction on the chroma of the rhodamine B.
Sand core suction filtration
And (4) carrying out suction filtration treatment on the sand core on the treated water sample by adopting a solvent filter.
The main parameters of the solvent filter used in this experiment were as follows:
the volume of the filter cup is as follows: 300 ml;
receiving bottle volume: 1000 ml;
the aperture of a filter head sieve plate is as follows: 30 mu m;
diameter of sand core: Φ 41;
the material is as follows: high borosilicate glass;
the filter membrane is an organic mixed membrane (namely a nylon membrane) with the pore diameter of 0.22 mu m and the diameter of 50mm, which is produced by a new inferior purification device factory in Shanghai.
The solvent filter is composed of an oil-free vacuum pump and a filter bottle device, and is integrally divided into a funnel type filter cup, a middle sand core filter head (sintering filter head), a triangular liquid collection bottle and a stainless steel fixing clamp. The filter bottle is made of extra hard glass, resists temperature change up to 280 ℃, and has good pressure resistance.
Because some water samples of rhodamine B for suction filtration are darker in color, the filter membrane gasket is easy to discolor and block. Therefore, cleaning is required in a certain period, and the main cleaning method used in the experiment is as follows:
(1) soaking with an acidic solvent: the filter membrane gasket has the advantages that particles blocked on the filter membrane gasket can be melted, but the problems of color change and the like of the filter membrane gasket cannot be solved, and the filter membrane gasket cannot be effectively improved. And the cleaning effect is not determined.
(2) Cleaning by an ultrasonic cleaning machine: the cleaning method is also a physical cleaning method, has better effect than the cleaning method by a high-pressure water gun, but has no effect on the filter element with polluted color.
(3) Flushing by a high-pressure water gun: through stronger water pressure, the particulate matters blocked in the filter element are flushed out.
Experimental analytical testing
Rhodamine B ultraviolet visible spectrum
10mg/L rhodamine B dye solution is scanned by an ultraviolet visible spectrophotometer under the wavelength of 250-800nm, and the scanning result is shown in figure 1. As is obvious from FIG. 1, the maximum absorption peak of rhodamine B is located at 554nm, so that the characteristic absorption peak of rhodamine B is at 554nm, and the decoloring effect of rhodamine B is researched at 554 nm.
Rhodamine B dye liquor standard curve
In order to determine the concentration of the remaining rhodamine B dye after the Fenton reaction, a standard curve drawing work of the rhodamine B dye solution is carried out to obtain a curve of the relationship between the concentration and the absorbance under the wavelength of 554nm, so that the concentration of the remaining rhodamine B dye is calculated through a formula.
In order to ensure the data to be accurate and reliable, 1mg/L, 2mg/L, 3mg/L, 4mg/L and 5mg/L rhodamine B dye solutions are respectively prepared by using 10mg/L colorimetric tubes, absorbance values corresponding to various concentrations are respectively measured by an ultraviolet-visible spectrophotometer at 554nm (shown in the following table 1), and a relation curve between the concentrations and the absorbance is fitted (shown in the following table 2).
TABLE 1 rhodamine B Standard Curve data
The analysis of the following figure 2 shows that the matching degree of the standard curve of the rhodamine B and the linear relation is highest, so that the concentration of the rhodamine B dye solution and the absorbance thereof are presumed to be in a linear relation, the linear equation is that y is 0.061x +0.059, and the linear regression coefficient R is20.993. Therefore, after the Fenton oxidation reaction is finished, the solution concentration of the rhodamine B dye solution can be calculated through the linear equation.
Method for calculating rhodamine B dye decolorization rate
Preparing 10mg/L rhodamine B dye solution, carrying out Fenton oxidation reaction under different conditions, after the reaction is finished, carrying out sand core filtration treatment on the mixed solution, taking an appropriate amount, carrying out ultraviolet-visible spectrophotometer detection at 554nm, determining the absorbance value of the solution, and if the absorbance value exceeds the range of the absorbance value, diluting a water sample, and then carrying out detection calculation. According to the measured absorbance value, after the concentration is calculated corresponding to the rhodamine B standard curve, the chroma removal rate is calculated according to the following formula:
in the formula: c0Rhodamine B solution concentration (mg/L) before reaction; concentration of rhodamine B solution (mg/L) after C-reaction.
Fe in the following Experimental data3O4@ MOF, unless otherwise specified, is Fe of example 13O4@MOF。
Fe3O4X-ray diffraction analysis (XRD)
As shown in fig. 3, Fe having paramagnetism synthesized by a coprecipitation method3O4XRD diffractogram of the material. Analysis of paramagnetic Fe by Jade Spectroscopy3O4The material has obvious diffraction peaks at 2 theta (30.241 degrees), 35.460 degrees, 62.620 degrees and the like, and Fe3O4The standard chart is consistent, so that the sample can be determined to be Fe3O4And has higher purity and better crystal phase structure. And the material has part of Fe at 2 theta (43.195 degrees) and 57.141 degrees2O3Diffraction peak of (1) indicates Fe3O4Will be gradually oxidized into Fe when exposed to air2O3Fe thus prepared3O4Before use, the product needs to be stored in a sealed way to prevent the product from being oxidized.
Fe3O4X-ray diffraction analysis of @ MOF
As shown in fig. 4, it is Fe having paramagnetism synthesized by a coprecipitation method3O4The XRD diffractogram of the @ MOF material. Analysis of paramagnetic Fe by Jade Spectroscopy3O4The material has obvious diffraction peaks at 2 theta (30.260 degrees), 35.580 degrees, 62.800 degrees and the like, and Fe3O4The standard chart is consistent, so that the sample can be determined to contain a larger part of Fe3O4And has higher purity and good crystal phase stable structure. And the material has part of Fe at 2 theta (43.320 degrees) and 57.240 degrees2O3Diffraction peak of (1) indicates Fe3O4Will be gradually oxidized into Fe when exposed to air2O3Fe thus prepared3O4Before use, it needs to be stored in a sealed manner to preventIt is oxidized. In addition, compared with the catalyst before modification, the modified catalyst has more obvious diffraction peaks in a wave band of 10-20: among them, the diffraction peak of copper ions at 2 θ of 18.322 ° is more prominent. While the other, less pronounced diffraction peaks are the stable organics added to the MOF material to stabilize the structure-m-benzenetricarboxylic acid and N, N-dimethylacetamide.
Research on decolorizing effect of rhodamine B by various different methods
Research on effect of single-factor condition on rhodamine B chroma removal rate
The influence of various different single-factor treatment conditions on the rhodamine B chroma removal rate is specifically considered in the experiment. In the experimental process, if no temperature influence exists, the temperature is 27-30 ℃ at room temperature. The reaction experimental conditions of the individual ultrasound were: the concentration of rhodamine B is 10mg/L, the initial pH value of the solution is 4.7, the ultrasonic power is 490W, the ultrasonic time is 0-90 min, and the ultrasonic reaction temperature is controlled to be 40 ℃; the reaction experimental conditions for the individual sand core filtration are as follows: the concentration of rhodamine B is 10mg/L, the initial pH value of the solution is 4.7, and the standing time is 0-90 min; fe alone3O4The reaction conditions of (A) are as follows: the concentration of rhodamine B is 10mg/L, Fe3O4The concentration is 0.35g/L, the initial pH value of the solution is 4.7, and the standing time is 0-90 min; h alone2O2The reaction conditions of (A) are as follows: the concentration of rhodamine B is 10mg/L, H2O2The concentration is 0.1mol/L, the initial pH value of the solution is 4.7, and the standing time is 0-90 min. The results are shown in FIG. 5 below.
As can be obtained from FIG. 5, the single-factor condition has a certain influence on the chroma removal rate of the rhodamine B. The removal rate of the chromaticity is maintained between 20% and 22% by pure sand core filtration, and the sand core filtration has a certain decolorizing effect because the low-pressure reverse osmosis membrane selectively filters out some micromolecule chromogenic substances. The removal rate does not change obviously with the increase of time, and the standing time of the visible solution has no obvious influence on the filtering effect of the sand core; by simple addition of Fe3O4The maximum chroma removal rate is only 19.84% because of Fe3O4As a Fenton reactionThe corresponding catalyst cannot generate hydroxyl free radical (HO) with strong oxidizability to catalyze the reaction, so that the chroma of the rhodamine B cannot be effectively removed; by simple addition of H2O2Without the action of a catalyst, a hydroxyl radical (HO. cndot.) can not be generated, and the chroma of rhodamine B can not be effectively removed; the maximum chroma removal rate can reach 35.14% by pure ultrasound, the ultrasound has a cavitation effect on the aqueous solution, and the high-frequency ultrasound can degrade organic matters to different degrees, so that the additional condition of ultrasound has a more obvious effect on removing the chroma of rhodamine B.
Fe3O4Study of catalyst utilization problem
This section of the experiment investigated catalyst Fe3O4The utilization rate of the process is low. In the experimental process, if no temperature influence exists, the temperature is 27-30 ℃ at room temperature. The experimental conditions were as follows: the concentration of the rhodamine B dye solution is 10mg/L, the concentration of the catalyst is 0.35g/L, the adding amount of hydrogen peroxide is 0.1mol/L, the initial pH value of the solution is 4.77, the ultrasonic power is 490W, the reaction temperature is 40 ℃, and the reaction time is 30min +90 min. Wherein the first 30min is the catalyst Fe in Ultrasonic (US) dispersion dye liquor3O4The reaction time of the second half period of 90min is the reaction time of the US/Fenton reaction system.
After carrying out an experiment, carrying out magnetic separation on the product, washing the product for multiple times by using ultrapure water, repeating the experiment after vacuum drying, and so on. The results are shown in FIG. 6 below.
As can be seen from FIG. 6, the catalyst Fe was reused for the second time3O4Then, the removal rate of the rhodamine B dye solution is reduced from 94.26% to 43.11%, and the catalyst Fe is repeatedly used for the third time3O4Then, the removal rate of the rhodamine B dye solution is reduced from 43.11 percent to 23.77 percent, and the catalyst Fe is repeatedly used for the fourth time3O4Then, the removal rate of the rhodamine B dye solution is reduced from 23.77 percent to 8.52 percent. So that the catalyst Fe3O4The repeated utilization rate of the catalyst is extremely low, and the effect of repeated use of the catalyst cannot be well exerted. Probably due to Fe3O4The cube is stable after being subjected to ultrasonic treatment, sand core filtration and Fenton system reactionThe crystals are destroyed and a small amount of Fe (OH) may adhere to the magnetically separated solid surface3Precipitation, therefore, to increase the catalyst utilization, Fe is added to the catalyst3O4The improvement is made.
Fe3O4Research on influence factors of chroma removal rate of rhodamine B treated by @ MOF catalytic Fenton reaction
Influence factors of catalyst concentration on chromaticity removal rate
The experiment specifically inspects the influence of different catalyst concentrations on the chroma removal rate of the rhodamine B dye solution. In the experimental process, if no temperature influence exists, the temperature is 27-30 ℃ at room temperature. The experimental conditions were as follows: rhodamine B dye liquor concentration is 10mg/L, hydrogen peroxide (H)2O2) The concentration is 1mol/L, the initial pH value of the solution is 4.77, the ultrasonic power is 490W, and the reaction temperature is 40 ℃. The concentration of the catalyst is respectively studied by adopting 0.10g/L, 0.20g/L, 0.30g/L and 0.40g/L, the reaction time is 30min +60min in total, a trace water sample is taken every 4min for sand core filtration treatment, the absorbance of the water sample is measured, the concentration of the treated water is calculated, and the removal rate is calculated. Wherein the first 30min is the catalyst Fe in Ultrasonic (US) dispersion dye liquor3O4The time of @ MOF, and the second half period of 60min is the reaction time of the US/Fenton reaction system. The results are shown in FIG. 7 below.
As can be seen from FIG. 7, the concentration of different catalysts has a great influence on the removal rate of the rhodamine B chroma. Under the condition of controlling other experimental variables to be unchanged, Fe is added along with the catalyst3O4When the concentration of the @ MOF is gradually increased from 0.10g/L to 0.40g/L, after the reaction is carried out for 20min, the decolorization rate of the rhodamine B dye solution is increased from 6.74% to 72.49%, and the decolorization rate of the rhodamine B is increased by 65.75%. But the chroma removal rate of the rhodamine B is slowly increased along with the increase of the reaction time, and the catalyst Fe is used for the reaction for 36-60 min3O4The chroma removal rate of rhodamine B is kept between 80% and 100% when the concentration of the @ MOF is 0.30g/L and 0.40g/L, and the growth rate is between 0.50% and 13.50%. When the reaction is carried out to the second half period, namely the reaction time is 48 min-60 min, the catalyst Fe3O4@ MOF concentration from 0.10g/L toWhen the concentration of the iron oxide is gradually increased to 0.40g/L, the decolorization rate of the rhodamine B dye solution can reach more than 60 percent, and the iron oxide is used as a catalyst3O4When the concentration of the @ MOF is 0.30g/L and 0.40g/L, the reaction time is continuously increased, the decolorization rate of the rhodamine B dye solution is not obviously increased, and therefore, the Fe content in the dye solution is obviously increased at the moment3O4The catalytic oxidation effect of the @ MOF on the Fenton reaction system reaches an optimal value. Catalyst Fe3O4The @ MOF belongs to a porous metal organic framework, and the large specific surface area of the @ MOF enables the catalyst Fe3O4The @ MOF can achieve more than 80% of objective removal effect only by ultrasonic treatment for 35min under a certain concentration, and the catalytic oxidation capability of the whole Fenton system is greatly improved.
It can be seen that, within a certain range, Fe is associated with the catalyst3O4The concentration of the @ MOF is increased, and the decolorization rate of the rhodamine B dye solution is gradually increased. But when the catalyst is Fe3O4When the concentration of the @ MOF is increased to 0.40g/L, the catalytic oxidation effect is obviously lower than that of the reaction at 0.3g/L in the same time period, which is probably because the reaction in the solution is carried out in the reaction direction due to the excessively large adding amount of the catalyst. The hydroxyl radical (HO) separated by the hydrogen peroxide reaches a supersaturated state, and the reaction rate is reduced[39]. Therefore, Fe is selected by comprehensively considering the addition amount of the catalyst and the chroma removal rate of the rhodamine B3O4The concentration of the @ MOF catalyst is 0.30g/L, and the reaction time is 30min +60 min.
Research on influence factors of hydrogen peroxide addition on chromaticity removal rate
The experiment specifically inspects the influence of the adding amount of hydrogen peroxide on the chroma removal rate of the rhodamine B dye solution. In the experimental process, if no temperature influence exists, the temperature is 27-30 ℃ at room temperature. The experimental conditions were as follows: the concentration of rhodamine B dye solution is 10mg/L, and the catalyst is Fe3O4The concentration of @ MOF is 0.30g/L, the initial pH value of the solution is 4.77, the ultrasonic power is 490W, the reaction temperature is 40 ℃, and the reaction time is 30min +60 min. The adding amount of hydrogen peroxide is respectively as follows: 0.05mol/L, 0.10mol/L, 0.15mol/L, 0.20mol/L, 0.25mol/L, 0.30mol/L, 0.35mol/L and 0.40 mol/L. Wherein the first 30min is the catalyst Fe in Ultrasonic (US) dispersion dye liquor3O4The reaction time of the second half period of 90min is the reaction time of the US/Fenton reaction system. The results are shown in FIG. 8 below.
As can be seen from the figure 8, the adding amount of the hydrogen peroxide has a more obvious effect on the color chromaticity removal of the rhodamine B dye solution. Along with the continuous increase of the adding amount of the hydrogen peroxide, the decolorization rate of the rhodamine B dye solution is gradually increased. Under the condition of controlling other experimental variables to be unchanged, when the adding amount of the hydrogen peroxide is gradually increased from 0.05mol/L to 0.10mol/L, the removal rate is gradually increased from 88.23% to 98.56%, and the removal rate is obviously improved. Hydrogen peroxide is an important component as an oxidant in a Fenton oxidation reaction system and is indispensable. The hydroxyl free radical (HO. cndot.) decomposed from the added hydrogen peroxide is used for oxidizing refractory organic matters in the rhodamine B, thereby achieving the purpose of decoloring. When the adding amount of the hydrogen peroxide is continuously increased, namely the adding amount of the hydrogen peroxide is gradually increased from 0.10mol/L to 0.250mol/L, the chroma removal rate of the rhodamine B dye solution is basically maintained at 98.56-99.51%, and the method is stable. When the adding amount of hydrogen peroxide is increased to 0.30mol/L, the removal rate of the chroma of the rhodamine B dye solution is not increased and inversely decreased, and is decreased from 99.51 percent to 97.35 percent, and the removal rate is decreased by 2.16 percent. Therefore, the excessive hydrogen peroxide has relatively negative influence on the removal rate of the rhodamine B dye solution. The main reason for the decrease of the removal rate may be that the excess hydrogen peroxide can not regenerate hydroxyl radical (HO ·) in the Fenton system, and in addition, the excess hydrogen peroxide can react with the generated hydroxyl radical (HO ·) to generate peroxide radical (HO ·) with weaker oxidizing power than hydroxyl radical2And. The) to slightly reduce the chroma removal rate of the rhodamine B dye solution. In addition, catalyst Fe of Fenton reaction system3O4The @ MOF has the property of peroxide mimic enzyme, and excessive hydrogen peroxide can reduce the activity of the mimic enzyme[40]Excess free radicals are generated to quench the reaction itself.
The main reaction of hydrogen peroxide in the dye solution is as follows:
H2O2→HO·+HO·
HO·+H2O2→HO2·+H2O
HO2·+HO2·→H2O2+O2
HO·+HO2·→H2O+O2
therefore, the optimal adding amount of the hydrogen peroxide is selected to be 0.10mol/L by comprehensively considering the adding amount of the hydrogen peroxide and the chroma removal rate of the rhodamine B.
Influence factors of different initial pH values on chroma removal rate are researched
The influence of different initial pH values of the dye solution on the chroma removal rate of the rhodamine B dye solution is specifically considered in the experiment. In the experimental process, if no temperature influence exists, the temperature is 27-30 ℃ at room temperature. The experimental conditions were as follows: the concentration of rhodamine B dye solution is 10mg/L, and the catalyst is Fe3O4The concentration of @ MOF is 0.30g/L, the adding amount of hydrogen peroxide is 0.1mol/L, the initial pH value of the solution is 4.77, the ultrasonic power is 490W, the reaction temperature is 40 ℃, and the reaction time is 30min +60 min. Wherein the first 30min is the catalyst Fe in Ultrasonic (US) dispersion dye liquor3O4The reaction time of the second half period of 60min is the reaction time of the US/Fenton reaction system. The results are shown in FIG. 9 below.
As can be seen from FIG. 9, the pH value of the rhodamine B dye solution has a more obvious influence on the chroma removal rate of the rhodamine B dye solution. When the pH value is within the range of 2-4, the chroma removal rate of the rhodamine B dye solution is 56.98% -82.36%, and the condition that H is possibly reacted under the reaction condition+Too much, the generation of hydroxyl radical (HO. cndot.) which is a strongly oxidizing group is suppressed, resulting in a great decrease in removal efficiency. As can be seen from the graph, the removal rate of the rhodamine B color becomes maximum at pH 5. When the initial pH value is 6-11, the color removal rate of the rhodamine B dye solution begins to be in a slow descending trend possibly due to the fact that excessive OH exists in the solution-The generation of HO is also suppressed. The pH value of the raw water of the rhodamine B is at 4.77, the removal rate of the raw water can reach 99.32 percent and is slightly higher than 95.67 percent when the initial pH value is 5, so the original pH value of the rhodamine B dye solution is adopted for reaction.
Fe3O4Research on the problem of the utilization ratio of the @ MOF catalyst
Part of the experiment investigates the catalystAgent Fe3O4The utilization problem of @ MOF. In the experimental process, if no temperature influence exists, the temperature is 27-30 ℃ at room temperature. The experimental conditions were as follows: the concentration of rhodamine B dye solution is 10mg/L, and the catalyst is Fe3O4The concentration of @ MOF is 0.30g/L, the adding amount of hydrogen peroxide is 0.10mol/L, the initial pH value of the solution is 4.77, the ultrasonic power is 490W, the reaction temperature is 40 ℃, and the reaction time is 30min +60 min. Wherein the first 30min is the catalyst Fe in Ultrasonic (US) dispersion dye liquor3O4The time of @ MOF, and the reaction time of the US/Fenton reaction system is 60min in the second half.
After carrying out an experiment, carrying out magnetic separation on the product, washing the product for multiple times by using ultrapure water, repeating the experiment after vacuum drying, and so on. The results are shown in FIG. 10 below.
As can be seen from FIG. 10, the catalyst Fe was reused for the second time3O4After @ MOF, the removal rate of rhodamine B dye liquor is changed from 99.79 percent to 99.69 percent, and the catalyst Fe is repeatedly used for the third time3O4After @ MOF, the removal rate of rhodamine B dye liquor is changed from 99.69 percent to 99.36 percent, and the catalyst Fe is repeatedly used for the fourth time3O4After @ MOF, the removal rate of the rhodamine B dye solution is changed from 99.36 percent to 98.76 percent. It can be seen that Fe3O4The metal-organic framework of @ MOF not only having Fe3O4The catalyst has paramagnetism and stability of MOF material, and is a good Fenton reaction system catalyst.
UV-VIS spectral analysis of aqueous solutions before and after reaction
Aiming at the rhodamine B raw water and under the optimal reaction conditions (namely the rhodamine B dye solution concentration is 10mg/L, the initial pH value of the solution is 4.77, the ultrasonic power is 490W, the reaction temperature is 40 ℃, and Fe is added3O4The concentration of the @ MOF catalyst is 0.30g/L, the adding amount of hydrogen peroxide is 0.10mol/L, the reaction time is 30min +60min, and the catalyst Fe in the Ultrasonic (US) dispersion dye solution is obtained in the first 30min3O4The reaction time of the US/Fenton reaction system is 60min in the second half period), and ultraviolet-visible spectrophotometer scanning is carried out on the rhodamine B dye solution before and after the treatment, and the ultraviolet-visible spectrums are respectively shown in FIG. 11 and FIG. 12:
as can be seen from the graphs in FIGS. 11 and 12, the absorption intensity of the treated rhodamine B dye solution is reduced to a certain extent at the wavelength of 300-700 nm, wherein the absorption intensity is obviously reduced at the wavelength of 525-555 nm; particularly, the absorption intensity is reduced from 0.266 to 0.06 at the maximum absorption wavelength of 554nm of rhodamine B, which indicates that more than 93 percent of organic matters in the rhodamine B dye solution catalytically oxidized by a Fenton reaction system are catalytically degraded into carbon dioxide (CO)2) And water (H)2O)。
Comparison of the Performance of the different examples and comparative examples
The 10mg/L rhodamine B is adopted to simulate the dye wastewater, the chroma removal effect of the dye wastewater in the examples 1, 2, 3, 1 and 2 is explored, and the experimental result is shown in the table 2. As can be seen from table 2, example 2 in the examples had the lowest removal rate because the removal rate was low due to insufficient amount of catalyst; the removal effect of the embodiment 3 is equivalent to that of the embodiment 1, but the embodiment 3 has the problem of high treatment cost because the amount of the catalyst is 2 times that of the embodiment 1; comparative example 1 the catalyst productivity was low and the degradation effect was poor due to the too low temperature for the preparation of the catalyst; comparative example 2 the catalyst productivity was low and the degradation effect was poor due to the solvent volatilization too fast due to the too high temperature for preparing the catalyst. From the above, the preparation conditions of the catalyst and the effect of degrading rhodamine B in example 1 are optimal.
TABLE 2 comparison of the measurements
Conclusion
The main findings are summarized as follows:
1) in the presence of Fe3O4Under the condition of a catalyst, single-factor experiments are carried out on various reaction conditions to obtain the following sequence of the influence of various factors on the chroma removal rate of rhodamine B: fenton reaction system + ultrasound + sand core suction filtration > Fenton reaction system + ultrasound > Fenton reaction system + sand core suction filtration > hydrogen peroxide + ultrasound > hydrogen peroxide + sand core suction filtration > Fe3O4+ ultrasound > Fe3O4Sand core suction filtration > hydrogen peroxide single action > ultrasonic single action > sand core suction filtration single action > Fe3O4Acting alone;
2) in the presence of Fe3O4Under the condition that @ MOF is used as a catalyst, the optimal chroma removal rate of 10mg/L rhodamine B degraded by a Fenton catalytic oxidation system can reach more than 99%, and the optimal reaction conditions are as follows: catalyst Fe3O4The concentration of @ MOF is 0.30g/L, the adding amount of hydrogen peroxide is 0.10mol/L, the initial pH value of the solution is 4.77, the ultrasonic power is 490W, the reaction temperature is 40 ℃, and the reaction time is 30min +60 min. Wherein the first 30min is the catalyst Fe in Ultrasonic (US) dispersion dye liquor3O4The time of @ MOF, and the reaction time of the US/Fenton reaction system is 60min in the second half period;
3) the research of the magnetic separation on the utilization rate experiment of the reacted catalyst under the optimal reaction conditions of the two catalysts respectively shows that the Fe3O4The @ MOF is stable, has large specific surface area and high reaction catalysis efficiency, and has the performance far better than that of Fe3O4；
4) By XRD characterization and analysis of MOF materials, Fe contained in MOF materials synthesized by a coprecipitation method can be obtained3O4And Cu2+And the like, so that a Fenton catalytic oxidation reaction system can be efficiently catalyzed;
5) the ultraviolet visible spectrum and the three-dimensional fluorescence spectrum are adopted to compare and characterize the water samples before and after treatment, and the results show that the two catalysts have the effect of degrading the rhodamine B dye solution, but the latter has better efficiency and higher utilization rate.
Claims (10)
1. An MOF material loaded with ferroferric oxide, which is characterized in that: the preparation method comprises the following operations:
s1) dissolving water-soluble ferric salt and ferrous salt in water, and adding ammonia water at 25-35 ℃ until no precipitate is generated to obtain a suspension;
s2) heating the suspension to 75-85 ℃, stirring to react completely, cleaning, performing magnetic separation, drying and grinding the product obtained by magnetic separation into powder to obtain Fe3O4Powder;
s3) adding Fe3O4Dispersing the powder in absolute ethyl alcohol to obtain Fe3O4Suspension;
s4) dissolving trimesic acid in a mixed solvent consisting of DMF and absolute ethyl alcohol to obtain a trimesic acid solution;
s5) adding Fe3O4Heating the suspension and the trimesic acid solution to 65-75 ℃, uniformly mixing, adding a copper acetate solution, and continuing to react;
s6), washing and drying after the reaction is finished, and obtaining the MOF material loaded with ferroferric oxide.
2. A MOF material according to claim 1 wherein: in the mixed solvent, the volume ratio of DMF to absolute ethyl alcohol is 1: (0.9-1.1).
3. A MOF material according to claim 1 wherein: in the trimesic acid solution, the concentration of trimesic acid is (0.5-0.7) g/100 mL.
4. A MOF material according to claim 1 wherein: the copper acetate solution is an aqueous solution of copper acetate.
5. A MOF material according to any one of claims 1 to 4, wherein: the molar ratio of the copper element to the iron element is (0.1-0.3): 1.
6. a MOF material according to any one of claims 1 to 4, wherein: in the copper acetate solution, the concentration of copper acetate is (1-3) g/100 mL.
7. A MOF material according to any one of claims 1 to 4, wherein: the water-soluble ferric salt is selected from ferric sulfate or ferric trichloride; the water-soluble ferrous salt ferrous sulfate or ferrous chloride.
8. A treatment method for degrading organic wastewater comprises the steps of adding an MOF material loaded with ferroferric oxide and hydrogen peroxide into the organic wastewater to carry out Fenton oxidation reaction, and degrading organic pollutants in the organic wastewater, wherein the MOF material is as defined in any one of claims 1 to 7.
9. The processing method according to claim 8, characterized in that: and (3) carrying out Fenton oxidation reaction by using ultrasonic oscillation treatment.
10. The processing method according to claim 8 or 9, characterized in that: and (3) controlling the pH of the reaction system to be 3-10 during the Fenton oxidation reaction.
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