CN113559857B - Magnetic visible light heterogeneous Fenton core-shell structure CuFe 2 O 4 Catalyst and application thereof - Google Patents
Magnetic visible light heterogeneous Fenton core-shell structure CuFe 2 O 4 Catalyst and application thereof Download PDFInfo
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- CN113559857B CN113559857B CN202110889802.2A CN202110889802A CN113559857B CN 113559857 B CN113559857 B CN 113559857B CN 202110889802 A CN202110889802 A CN 202110889802A CN 113559857 B CN113559857 B CN 113559857B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 70
- 239000011258 core-shell material Substances 0.000 title claims abstract description 32
- 239000002077 nanosphere Substances 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 26
- 239000001257 hydrogen Substances 0.000 claims abstract description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910001868 water Inorganic materials 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000002244 precipitate Substances 0.000 claims abstract description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 7
- 238000005336 cracking Methods 0.000 claims abstract description 7
- 229960003638 dopamine Drugs 0.000 claims abstract description 7
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims abstract description 7
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 26
- 238000004519 manufacturing process Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- UOFRJXGVFHUJER-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;hydrate Chemical compound [OH-].OCC[NH+](CCO)CCO UOFRJXGVFHUJER-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 4
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 claims 1
- 229920001690 polydopamine Polymers 0.000 claims 1
- DXKGMXNZSJMWAF-UHFFFAOYSA-N copper;oxido(oxo)iron Chemical compound [Cu+2].[O-][Fe]=O.[O-][Fe]=O DXKGMXNZSJMWAF-UHFFFAOYSA-N 0.000 abstract description 31
- 229910016516 CuFe2O4 Inorganic materials 0.000 abstract description 30
- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 abstract description 15
- 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 abstract description 15
- 229940043267 rhodamine b Drugs 0.000 abstract description 15
- 229960004989 tetracycline hydrochloride Drugs 0.000 abstract description 15
- OGJPXUAPXNRGGI-UHFFFAOYSA-N norfloxacin Chemical compound C1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNCC1 OGJPXUAPXNRGGI-UHFFFAOYSA-N 0.000 abstract description 14
- 229960001180 norfloxacin Drugs 0.000 abstract description 14
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 abstract description 13
- 229940012189 methyl orange Drugs 0.000 abstract description 13
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 abstract description 12
- 238000003756 stirring Methods 0.000 abstract description 9
- 229960003280 cupric chloride Drugs 0.000 abstract description 6
- KIPLYOUQVMMOHB-MXWBXKMOSA-L [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O Chemical compound [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O KIPLYOUQVMMOHB-MXWBXKMOSA-L 0.000 abstract description 5
- 229940063650 terramycin Drugs 0.000 abstract description 5
- 238000004065 wastewater treatment Methods 0.000 abstract description 4
- 239000000047 product Substances 0.000 abstract description 2
- 150000002431 hydrogen Chemical class 0.000 abstract 1
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 238000007885 magnetic separation Methods 0.000 abstract 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 20
- 230000015556 catabolic process Effects 0.000 description 18
- 238000006731 degradation reaction Methods 0.000 description 18
- 239000002351 wastewater Substances 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 9
- 238000005286 illumination Methods 0.000 description 9
- 239000004100 Oxytetracycline Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 229960000625 oxytetracycline Drugs 0.000 description 8
- 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 8
- 235000019366 oxytetracycline Nutrition 0.000 description 8
- 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 8
- 230000001699 photocatalysis Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 241000282414 Homo sapiens Species 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000985 reactive dye Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000012028 Fenton's reagent Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 229940088710 antibiotic agent Drugs 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- -1 iron ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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- B01J35/33—
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
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Abstract
A magnetic visible light heterogeneous Fenton core-shell structure CuFe2O4 nanosphere catalyst and application thereof in organic wastewater treatment and water hydrogen cracking belong to the technical field of water treatment. Adding ferric nitrate nonahydrate into deionized water, uniformly stirring, adding dopamine and ethylenediamine, and finally adding ammonia water and cupric chloride dihydrate; and (3) carrying out centrifugal separation after hydrothermal reaction, washing the obtained precipitate with deionized water and ethanol for 2-3 times, and drying to obtain the product. The obtained nanospheres take PAA-NH4 as a core and CuFe2O4 as a shell, the size of the core is 100-150 nm, the size of the shell is 250-300 nm, and the shell is formed by assembling a plurality of CuFe2O4 secondary units with the particle size smaller than 5 nm. The catalyst can degrade or reduce terramycin, norfloxacin, tetracycline hydrochloride, rhodamine B, methyl orange and Cr (VI) under the irradiation of visible light, is used for cracking aquatic hydrogen, and can be repeatedly recovered and reused through magnetic separation.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a magnetic visible light heterogeneous Fenton core-shell structure CuFe 2 O 4 Nanosphere catalyst and application thereof in organic wastewater treatment and water hydrogen cracking.
Background
Antibiotic contamination has become a major problem to be solved in the last decades. The serious pollution of antibiotics to water body threatens the future of human beings, which not only causes more and more environmental problems, but also seriously threatens the health of human beings, and in recent years, many researches search for biological, electrochemical, physical and other methods to solve the pollution of antibiotics. Meanwhile, due to the rapid development of society, the excessive consumption of fossil fuel causes serious resource shortage and environmental pollution, and causes great harm to human life and health. It is urgent to find new clean energy sources that can be recycled without pollution. Hydrogen has been widely studied as a renewable clean energy source. The photo-Fenton reaction is widely focused due to high stability, high efficiency, low toxicity and simple operation, and the problem is to propose a photo-Fenton reaction solution as an advanced oxidation process.
Since 1964, H.R. Eisehnonser used Fenton reagent for the first time to treat phenol and alkylbenzene wastewater (EISENSHAUER H R, oxidation of Phenolic Wastes [ J ]. Water Pollution Control Federation,1964, 36:1116-1128.), the homogeneous Fenton oxidation technique was widely used as an advanced oxidation technique for degradation of industrial wastewater. Wang Binsong et al studied the homogeneous Fenton oxidation technique for the treatment of three vinyl sulfone-type commercial reactive dyes (Wang Binsong, huang Junli, zhang Jie. Fenton reagent oxidation reactive dye wastewater study [ J ]. University of Harbin Industrial journal, 2005,37 (9): 1280-1282, 1302.), found: the pH is 2-5, nFe2+ is 0.5mmol/L, the concentration of hydrogen peroxide is 167-333mg/L, the dye of 400mg/L is degraded, and the removal rate of chromaticity of the three reactive dyes can reach more than 99% within 20 min. 1972. In the year, the Fujishima experiment of Japanese scientist discovers that the photoelectrochemical system is composed of the TiO2 electrode and the Pt electrode, the Pt electrode generates H2 under illumination, and the TiO2 electrode generates O2, namely the photocatalytic material decomposes the aquatic hydrogen. (Fujishima A, honda K. Electrochemical photolysis of water at a semiconductor electrode [ J ]. Nature, 1972, 238 (5358): 37-38.). The photocatalytic material is irradiated by light with energy larger than the forbidden band width, photons are absorbed to generate electron transition to generate hole pairs, the hole pairs are separated into electrons and holes, the holes react with electrolyte solution in a solid-liquid interface to generate O2, and the electrons migrate to the surface of the photocatalytic material to reduce and decompose H2O to generate H2. Numerous studies have shown that: the homogeneous Fenton process uses dissolved Fe2+ and H2O2 to generate hydroxyl radicals (. OH), which are the second strongest oxidants, only weaker than fluorine and OH. Can selectively attack and decompose various organic pollutants into CO2, H2O and inorganic ions. However, the system has some problems when applied to degradation of wastewater and cracking of water to produce hydrogen: the homogeneous Fenton system requires optimal conditions of strong acid pH value (2.8-3.5); under alkaline conditions, iron ions are easy to precipitate to form iron mud, so that the catalyst is lost; the H2O2 demand is large; the recombination rate of photo-generated electrons and holes in the homogeneous Fenton system is high, so that the hydrogen production efficiency is reduced. Because of the limitation of homogeneous Fenton reaction conditions and expensive raw materials, the degradation efficiency of the homogeneous Fenton system is low, and the treatment cost is high. Therefore, the development of an efficient, low-cost, green and environment-friendly advanced treatment technology has very important significance.
The photocatalysis technology can generate electron transition under the irradiation of sunlight to generate electron-hole pairs with strong oxidizing capability, so that not only can organic pollutants in wastewater be oxidized and decomposed into carbon dioxide, water and inorganic small molecules, but also can generate oxidation-reduction reaction on the surface of the material to reduce and decompose the water into O2. In order to improve the catalytic activity of the catalyst, composite catalytic technology is receiving a great deal of attention. The heterogeneous Fenton composite photocatalyst is characterized in that a Fenton technology and a photocatalysis technology are combined, so that the catalytic activity of the catalyst can be effectively improved, the wastewater treatment efficiency and the hydrogen production efficiency are improved, the technology is simple to operate and environment-friendly, and therefore, how to construct an efficient sewage treatment and H2 renewable clean energy system becomes a focus of research for pursuing people. The heterogeneous Fenton technology combines the advantages of photocatalysis and Fenton oxidization, so that energy conservation can be achieved, recycling is convenient, good waste water degradation and hydrogen production effects can be guaranteed, and the heterogeneous Fenton technology has great potential in practical application.
Disclosure of Invention
The invention aims to provide a recoverable magnetic visible light heterogeneous Fenton core-shell structure CuFe2O4 nanosphere catalyst which has the advantages of simple preparation method, low cost, high degradation rate and hydrogen production rate, and contains magnetic Fe < 3+ > (shown in figure 6), and application of the catalyst in organic wastewater treatment and water hydrogen cracking.
The invention adopts a one-step method to prepare the magnetic visible light heterogeneous (the catalyst and the reactant belong to heterogeneous phases, namely the catalyst prepared by the patent is a solid phase, and the reactant is a liquid phase) Fenton core-shell structure CuFe2O4 nanosphere catalyst, and the nanosphere catalyst is a shell-core structure, and the one-step method specifically comprises:
adding 250-500 mg of ferric nitrate nonahydrate into 10-20 mL of deionized water, stirring and mixing uniformly, stirring and reacting for 2-4 hours at room temperature, adding 300-400 mg of dopamine, adding 40-70 mL of ethylenediamine into the solution, and finally adding 600-1400 mu L of ammonia water (2M) and 250-350 mg of cupric chloride dihydrate; and pouring the obtained mixed solution into a 100mL reaction kettle, keeping the temperature of 160-200 ℃ for reaction for 24-30 hours, and then performing centrifugal separation (3000-6000 rpm, 5-10 minutes), washing the obtained precipitate with deionized water and ethanol for 2-3 times, and drying (the drying temperature is 60-70 ℃ and the drying time is 12-20 hours) to obtain the magnetic visible light heterogeneous Fenton core-shell structure CuFe2O4 nanosphere catalyst.
The obtained magnetic visible light Fenton core-shell structure CuFe2O4 nanosphere catalyst takes PAA-NH4 as a core and CuFe2O4 as a shell, the size of the core is 100-150 nm, the size of the shell is 250-300 nm, and the shell is formed by assembling a plurality of CuFe2O4 secondary units with the particle size smaller than 5 nm.
The obtained magnetic visible light Fenton core-shell structure CuFe2O4 nanosphere catalyst has more active sites due to a hollow core-shell structure (shown in figure 2), is favorable for charge transfer and has good effect in the aspect of being applied to cracking of aquatic hydrogen. When the catalyst is applied to the treatment of organic wastewater, the catalyst has better composite use effect with hydrogen peroxide catalyst.
The magnetic visible light Fenton core-shell structure CuFe2O4 nanosphere catalyst can degrade terramycin (OTC), norfloxacin (NFX), tetracycline hydrochloride (TCH), rhodamine B (RhB) and Methyl Orange (MO) and reduce Cr (VI) in organic wastewater within 5-60 minutes respectively, the degradation rate (reduction rate) is as high as 95-98%, the concentration of terramycin (OTC), norfloxacin (NFX), tetracycline hydrochloride (TCH), rhodamine B (RhB), methyl Orange (MO) and Cr (VI) in 100mL of organic wastewater is 30-150 ppm, and the dosage of the catalyst prepared by the method is 20-100 mg, and the dosage of hydrogen peroxide is 150-250 mu L.
In addition, 30-70 mg of the magnetic visible light Fenton core-shell structure CuFe2O4 nanosphere catalyst is subjected to water splitting decomposition under the condition that 50-100 mL of a 15vol% triethanolamine aqueous solution is used as a sacrificial agent, and the hydrogen production data of the water splitting product is 1200-1400 mu mol g-1h-1.
Compared with the prior art, the invention has the advantages that:
1) The invention provides the magnetic visible light Fenton core-shell structure CuFe2O4 nanosphere catalyst which is simple to operate, low in cost, high in degradation rate and hydrogen production rate, good in stability, green and economical, and is suitable for industrial production.
The CuFe2O4 nanosphere catalyst with the magnetic visible light Fenton core-shell structure has a large number of active sites on the surface of a material due to the unique shell-core structure, and the sites provide channels for charge transfer and promote separation of photo-generated electrons and holes, so that the photocatalysis effect of the catalyst is improved.
The magnetic visible light Fenton core-shell structure CuFe2O4 nanosphere catalyst can be separated magnetically, is easy to recycle and can be used repeatedly.
The magnetic visible light Fenton core-shell structure CuFe2O4 nanosphere catalyst is applicable to a wider pH range; by using a composite catalytic system (the catalyst is used after being mixed with hydrogen peroxide, the addition amount of the hydrogen peroxide is 150-250 mu L, and the addition amount of the catalyst is 20-100 mg), the technology discovers that a synergistic effect can be generated among various catalytic systems, the utilization rate of visible light can be obviously improved, and finally the pollutant removal effect is enhanced.
The magnetic visible light Fenton core-shell structure CuFe2O4 nanosphere catalyst has higher photo-generated electron-hole separation rate. The catalyst disclosed by the invention has the advantages that the addition amount of 30-70 mg, and the hydrogen production performance of the pyrolysis water is good under the condition that 50-100 mL and 5% of triethanolamine are taken as sacrificial agents.
The invention provides a research thought for heterogeneous Fenton composite photocatalysts.
Description of the drawings:
fig. 1: XRD patterns of the magnetic visible light Fenton core-shell structure CuFe2O4 nanosphere catalyst obtained in the example 1 are obtained.
Fig. 2: a transmission photo diagram of the magnetic visible light Fenton core-shell structure CuFe2O4 nanosphere catalyst obtained in the example 1 is obtained. PAA-NH4 forms a core and CuFe2O4 forms a shell, and the core is polycondensed after high-temperature calcination to obtain the following picture-shell-core structure. The size of the inner core ranges from 100 nm to 150nm, and the size of the outer shell ranges from about 250 nm to 300nm.
Fig. 3: the performance diagram of the magnetic visible light Fenton core-shell structure CuFe2O4 nanosphere catalyst obtained in the example 1 on degradation of terramycin (OTC), norfloxacin (NFX), tetracycline hydrochloride (TCH), rhodamine B (RhB) and Methyl Orange (MO) and reduction of Cr (VI) is obtained.
Fig. 4: the magnetic visible light Fenton core-shell structure CuFe2O4 nanosphere catalyst obtained in the example 1 has a cycle performance diagram for degrading terramycin (OTC) and Methyl Orange (MO) and reducing Cr (Cr6+).
Fig. 5: the magnetic visible light Fenton core-shell structure CuFe2O4 nanosphere catalyst obtained in example 1 has cyclic performance graphs of Norfloxacin (NFX), tetracycline hydrochloride (TCH) and rhodamine B (RhB).
Fig. 6: the magnetic visible light Fenton core-shell structure CuFe2O4 nanosphere catalyst obtained in example 1 has 15vol% triethanolamine water solution as sacrificial agent, and the cycle stability performance of hydrogen production is shown by 12h (4 cycles) of light irradiation.
Fig. 7: hysteresis loop diagrams of the magnetic visible light Fenton core-shell structure CuFe2O4 nanosphere catalyst obtained in the example 1 are obtained.
Detailed Description
Example 1
300mg of ferric nitrate nonahydrate is weighed and added into 15mL of deionized water, the mixture is stirred and mixed uniformly, after stirring for 2 hours at room temperature, 300mg of dopamine is added into the solution, 55mL of ethylenediamine is added into the solution, 700 mu L of ammonia water (2M) is added dropwise into the solution, ultrasonic treatment is carried out for 30min, and finally 280mg of cupric chloride dihydrate is weighed and added into the solution, and the solution is stirred uniformly. Transferring the obtained mixed solution into a 100mL reaction kettle, heating to 170 ℃ and keeping the temperature for reaction for 28h, centrifuging the solution (5000 rpm,8 min), washing the precipitate with deionized water and ethanol for 2 times, and drying in a 65 ℃ oven for 15h to obtain the magnetic visible light heterogeneous Fenton core-shell structure CuFe2O4 nanosphere catalyst. The average size of the CuFe2O4 nanospheres shown in FIG. 2 is 300nm, and the nanospheres are assembled by a plurality of CuFe2O4 secondary units with particle sizes smaller than 5 nm.
Adding 200 mu L of hydrogen peroxide and 30mg of prepared catalyst into 100mL of organic wastewater containing 40ppm of norfloxacin under illumination condition, stirring for 50min for degradation, wherein the degradation rate of the Norfloxacin (NFX) reaches 96.7% as shown in figure 3; under the same conditions, the catalyst of the embodiment has higher degradation rate and reduction rate on Oxytetracycline (OTC), tetracycline hydrochloride (TCH), rhodamine B (RhB), methyl Orange (MO) and Cr (VI). The catalyst used was recovered and then degraded by the same degradation conditions as described above to give Norfloxacin (NFX), oxytetracycline (OTC), tetracycline hydrochloride (TCH), rhodamine B (RhB), methyl Orange (MO) and Cr (vi) reduction, which were repeated 5 times, and the catalyst prepared as shown in fig. 4 was excellent in cycle stability.
The catalyst 50 and mg of the embodiment takes 50mL of 15vol% triethanolamine water solution as a sacrificial agent, and the hydrogen production performance of the pyrolysis water under the illumination condition is 1280 mu mol g-1h-1. After the above test experiment of 12h (4 cycles) under irradiation of visible light as shown in fig. 5, the stability of hydrogen production cycle reached 86%, and the stability was good.
Example 2
280mg of ferric nitrate nonahydrate is weighed, added into 10mL of deionized water, stirred and uniformly mixed, stirred at room temperature for 2.5 hours, 380mg of dopamine is added into the solution, 70mL of ethylenediamine is added into the solution, 900 mu L of ammonia water (2M) is added dropwise into the solution, ultrasonic treatment is carried out for 30 minutes, 260mg of cupric chloride dihydrate is weighed, the solution is added into a 100mL reaction kettle for stirring and dissolution, the obtained mixed solution is transferred into a 100mL reaction kettle, the temperature is raised to 185 ℃ for reaction for 25 hours, centrifugal separation (4000 rpm,8 minutes) is carried out, the precipitate is washed with deionized water and ethanol for 3 times, and the precipitate is dried in a 65 ℃ oven for 12 hours, thus obtaining the magnetic visible light heterogeneous Fenton nuclear shell structure CuFe2O4 nanosphere catalyst.
Under the illumination condition, 150 mu L of hydrogen peroxide and 50mg of prepared catalyst are added into 100mL of organic wastewater containing 30ppm of rhodamine B, the degradation is carried out by stirring for 35min, the degradation rate is up to 98.0%, the rhodamine B is degraded by the same degradation condition after the catalyst is recovered, and the result shows that the prepared catalyst has excellent cycling stability.
In the catalyst 40 mg of the embodiment, 70mL of 15vol% triethanolamine water solution is used as a sacrificial agent, the hydrogen production performance under the illumination condition is 1310 mu mol g-1h-1, and the hydrogen production effect is good.
Example 3
320mg of ferric nitrate nonahydrate is weighed, added into 20mL of deionized water, stirred and mixed uniformly, after stirring for 3 hours at room temperature, 330mg of dopamine is added into the solution, 50mL of isopropanol is added into the solution, 1200 mu L of ammonia water (2M) is added dropwise into the solution, ultrasonic treatment is carried out for 30min, 250mg of cupric chloride dihydrate is weighed, added into the solution, stirred and dissolved. And transferring the obtained mixed solution into a 100mL reaction kettle, heating to 190 ℃, keeping the temperature for reaction for 27h, performing centrifugal separation (4500 rpm,8 min), washing the precipitate with deionized water and ethanol for 3 times, and drying in a 65 ℃ oven for 16h to finally obtain the magnetic visible light heterogeneous Fenton core-shell structure CuFe2O4 nanosphere catalyst.
180 mu L of hydrogen peroxide and 70mg of the prepared catalyst are added into 100mL of organic wastewater containing 40ppm of tetracycline hydrochloride under the illumination condition, and the degradation rate is up to 97.1 percent. The catalyst is recycled and then the tetracycline hydrochloride is degraded under the same degradation conditions, and the catalyst is repeated for 5 times, so that the prepared catalyst has excellent cycling stability.
In the catalyst 60mg of the embodiment, the hydrogen production performance under the illumination condition is 1250 mu mol g-1h-1 in 85mL and 15vol% of triethanolamine water solution as a sacrificial agent, and the hydrogen production effect is good.
Example 4
400mg of ferric nitrate nonahydrate is weighed and added into 18mL of deionized water, the mixture is stirred and mixed uniformly, after stirring for 3.5 hours at room temperature, 370mg of dopamine is added into the solution, 65mL of ethylenediamine is slowly added dropwise into the solution, 1300 mu L of ammonia water (2M) is added dropwise into the solution for ultrasonic treatment for 30 minutes, 300mg of cupric chloride dihydrate is weighed and added into the solution for dissolution, the obtained mixed solution is transferred into a 100mL reaction kettle, the temperature is raised to 200 ℃ for reaction for 30 hours, centrifugal separation (5000 rpm,6 minutes) is carried out, the precipitate is washed for 2 times by deionized water and ethanol, and the precipitate is dried in a 65 ℃ oven for 13 hours, thus finally the magnetic visible light heterogeneous Fenton nuclear shell structure CuFe2O4 nanosphere catalyst is obtained.
250 mu L of hydrogen peroxide and 80mg of the prepared catalyst are added into 100mL of organic wastewater containing 150ppm of Cr (VI) under the illumination condition, and the mixture is stirred for 45min, wherein the reduction rate is as high as 95.8%. After the catalyst used was recovered, cr (VI) was reduced under the same degradation conditions as described above, and the catalyst was repeated 5 times, whereby the catalyst was excellent in cycle stability.
In the catalyst 55 mg of the embodiment, 85mL of 15vol% triethanolamine water solution is used as a sacrificial agent, the hydrogen production performance under the illumination condition is 1370 mu mol g-1h-1, and the hydrogen production effect is good.
Claims (4)
1. Magnetic visible light heterogeneous Fenton core-shell structure CuFe 2 O 4 The preparation method of the nanosphere catalyst is characterized by comprising the following steps: the nanosphere catalyst takes polydopamine as a core and CuFe 2 O 4 The shell is made of a plurality of CuFe with particle size less than 5nm, the size of the inner core is 100-150 nm, the size of the outer shell is 250-300 nm 2 O 4 The secondary unit is assembled;
the magnetic visible light heterogeneous Fenton core-shell structure CuFe 2 O 4 The nanosphere catalyst is prepared by the following method: 250-500 mg of ferric nitrate nonahydrate is added into 10-20 mL of deionized water, stirred and mixed uniformly, stirred and reacted for 2-4 hours at room temperature, 300-400 mg of dopamine is added, and 40-70 mL of ethylenediamine is added into the solutionFinally, 600 to 1400 mu L of 2M ammonia water and 250 to 350mg of copper chloride dihydrate are added; pouring the obtained mixed solution into a reaction kettle, keeping the temperature of 160-200 ℃ for reaction for 24-30 hours, then performing centrifugal separation, washing the obtained precipitate with deionized water and ethanol for 2-3 times, and drying to obtain the magnetic visible light heterogeneous Fenton core-shell structure CuFe 2 O 4 Nanosphere catalysts.
2. A magnetic visible light heterogeneous Fenton core-shell structure CuFe as defined in claim 1 2 O 4 The preparation method of the nanosphere catalyst is characterized by comprising the following steps: the rotational speed of centrifugal separation is 3000-6000 rpm, and the time of centrifugal separation is 5-10 min; the drying temperature is 60-70 ℃ and the drying time is 12-20 h.
3. A magnetic visible light heterogeneous Fenton core-shell structure CuFe as defined in any one of claims 1-2 2 O 4 The catalyst prepared by the preparation method of the nanosphere catalyst is applied to hydrogen production by cracking water.
4. A use according to claim 3, wherein: 30-70 mg of magnetic visible light heterogeneous Fenton core-shell structure CuFe 2 O 4 Nanosphere catalyst, under the condition that 50-100 mL of 15vol% triethanolamine water solution is taken as a sacrificial agent, the hydrogen data of the cracked water is 1200-1400 mu mol g -1 h -1 。
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