CN114931954B - Two-stage photocatalyst of ferrate composite titanium-zinc layered double hydroxide, and preparation method and application thereof - Google Patents
Two-stage photocatalyst of ferrate composite titanium-zinc layered double hydroxide, and preparation method and application thereof Download PDFInfo
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- CN114931954B CN114931954B CN202210445386.1A CN202210445386A CN114931954B CN 114931954 B CN114931954 B CN 114931954B CN 202210445386 A CN202210445386 A CN 202210445386A CN 114931954 B CN114931954 B CN 114931954B
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- ldh
- ferrate
- titanium
- photocatalyst
- layered double
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- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 35
- YJVLWFXZVBOFRZ-UHFFFAOYSA-N titanium zinc Chemical compound [Ti].[Zn] YJVLWFXZVBOFRZ-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 title claims description 20
- 239000011701 zinc Substances 0.000 claims abstract description 96
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 4
- 239000010936 titanium Substances 0.000 claims description 101
- 239000000463 material Substances 0.000 claims description 51
- 230000001699 photocatalysis Effects 0.000 claims description 28
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 17
- 229910052719 titanium Inorganic materials 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 13
- 239000004202 carbamide Substances 0.000 claims description 13
- 239000012876 carrier material Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 11
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- 230000003197 catalytic effect Effects 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- UMPKMCDVBZFQOK-UHFFFAOYSA-N potassium;iron(3+);oxygen(2-) Chemical group [O-2].[O-2].[K+].[Fe+3] UMPKMCDVBZFQOK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 239000004065 semiconductor Substances 0.000 claims description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical group Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 5
- 230000015556 catabolic process Effects 0.000 claims description 4
- 238000006731 degradation reaction Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000002351 wastewater Substances 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical group [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 3
- 238000000975 co-precipitation Methods 0.000 claims description 3
- 238000011010 flushing procedure Methods 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 239000000356 contaminant Substances 0.000 claims 2
- 230000008021 deposition Effects 0.000 claims 1
- 238000011065 in-situ storage Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 150000004692 metal hydroxides Chemical class 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000002344 surface layer Substances 0.000 abstract description 2
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 65
- 230000033558 biomineral tissue development Effects 0.000 description 22
- 239000005906 Imidacloprid Substances 0.000 description 13
- 229940056881 imidacloprid Drugs 0.000 description 13
- YWTYJOPNNQFBPC-UHFFFAOYSA-N imidacloprid Chemical compound [O-][N+](=O)\N=C1/NCCN1CC1=CC=C(Cl)N=C1 YWTYJOPNNQFBPC-UHFFFAOYSA-N 0.000 description 13
- 229960005286 carbaryl Drugs 0.000 description 10
- CVXBEEMKQHEXEN-UHFFFAOYSA-N carbaryl Chemical compound C1=CC=C2C(OC(=O)NC)=CC=CC2=C1 CVXBEEMKQHEXEN-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000010586 diagram Methods 0.000 description 10
- 239000003344 environmental pollutant Substances 0.000 description 8
- 231100000719 pollutant Toxicity 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 206010021198 ichthyosis Diseases 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002917 insecticide Substances 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 239000005583 Metribuzin Substances 0.000 description 5
- 239000011229 interlayer Substances 0.000 description 5
- FOXFZRUHNHCZPX-UHFFFAOYSA-N metribuzin Chemical compound CSC1=NN=C(C(C)(C)C)C(=O)N1N FOXFZRUHNHCZPX-UHFFFAOYSA-N 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000007853 buffer solution Substances 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- -1 fe (VI) alone Substances 0.000 description 3
- 238000010952 in-situ formation Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 2
- VCUVETGKTILCLC-UHFFFAOYSA-N 5,5-dimethyl-1-pyrroline N-oxide Chemical compound CC1(C)CCC=[N+]1[O-] VCUVETGKTILCLC-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 239000000370 acceptor Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002363 herbicidal effect Effects 0.000 description 2
- 239000004009 herbicide Substances 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical group [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 2
- 230000005298 paramagnetic effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical group [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical group [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 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
- 238000000151 deposition Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012629 purifying agent Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
- JRFBNCLFYLUNCE-UHFFFAOYSA-N zinc;oxygen(2-);titanium(4+) Chemical group [O-2].[O-2].[O-2].[Ti+4].[Zn+2] JRFBNCLFYLUNCE-UHFFFAOYSA-N 0.000 description 1
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
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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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
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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
- C02F2101/306—Pesticides
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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
- C02F2101/36—Organic compounds containing halogen
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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
- C02F2101/00—Nature of the contaminant
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- C02F2101/40—Organic compounds containing sulfur
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/08—Nanoparticles or nanotubes
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
The invention discloses a two-stage photocatalyst of ferrate composite titanium-zinc layered double metal hydroxide, a preparation method and application thereof. The photocatalyst is prepared by a low-temperature hydrothermal method for controlling the alkalinity of a reaction system, and can effectively solve the problems that Fe (VI) is unstable when being compounded with Ti/Zn LDH, is easy to self-decompose, and ferric oxide generated in situ cannot be effectively attached to the Ti/Zn LDH surface layer to form a heterojunction structure in practical application. The preparation method of the photocatalyst has the advantages of low energy consumption, no toxic or harmful byproducts, simple preparation process and easy mass production.
Description
Technical Field
The invention relates to a two-stage photocatalyst of ferrate composite titanium-zinc layered double hydroxide, and a preparation method and application thereof.
Background
Layered Double Hydroxides (LDHs) are brucite-like layered inorganic materials composed of divalent (M 2+), trivalent (M 3+) or tetravalent (M 4+) metal ions, thereby forming a positively charged outer layer structure, so anions and inorganic solids are inserted into interlayer gaps to maintain charge balance, and due to their own thin layer structure, they have the characteristics of large specific surface area, good dispersion effect in solution, etc., and are often used as adsorption materials. In addition, LDHs are surrounded by oxygen bridges and contain key cations, such as Zn, ni, cr, ti and Sn, which facilitate electron transfer, have the potential to become semiconductor photocatalysts, with titanium/zinc LDHs (Ti/Zn LDHs) being the most typical photocatalytic material.
The titanium-based material is used as the most commonly used semiconductor photocatalytic material, has the characteristics of chemical stability, strong oxidization, light resistance, availability, low cost and the like, however, because the wide band gap (Eg is about 2.9 eV-3.2 eV) of the titanium-based material is required to be smaller than 380 nm (ultraviolet light), and the ultraviolet light accounts for 4% of sunlight, so that the material cannot effectively utilize solar energy. In addition, the low carrier transfer rate and high recombination rate of photo-generated electron-hole pairs on the surface of the material also make the material incapable of being applied on a large scale.
Ferrate (Fe (VI)) is generally widely used in the fields of water purification pretreatment, special water treatment and the like as a novel water purifying agent integrating oxidation, flocculation and disinfection. In addition, the special outer layer electronic structure has strong electrophilicity, can be used as an effective electron acceptor, and simultaneously generates 4-valent and 5-valent iron oxidation intermediate substances with stronger oxidability. According to this characteristic, ferrate can effectively separate electrons and holes as electron acceptors of titanium-based materials to thereby increase the carrier transfer rate and inhibit the repetition of electron-hole pairs. Meanwhile, the band gap of ferric oxide particles of a ferrate reduction product is narrower (Eg < 1.9 eV) and the valence conduction band position is different from that of titanium-based materials, so that after the ferrate is consumed, the ferric oxide is deposited on the surface of Ti/ZnLDH by in-situ reduction, and a p-n type heterojunction is formed to reduce the band gap, so that the utilization rate of visible light and the separation rate of photo-generated carriers are continuously improved. In addition, the anionic form (FeO 4 2-、HFeO4 -) of ferrate in the solution can be inserted into an LDH interlayer, and the characteristic of poor dispersibility of the ferrate and a reduction product (ferric oxide) can be improved by virtue of the characteristic of good LDH dispersibility.
Therefore, the preparation technology of the Fe (VI) composite Ti/Zn LDH can change the current situation that the titanium-based photocatalytic material cannot be applied to large-scale practical application, improve the utilization efficiency of solar energy, and simultaneously, the ferric iron oxide formed by reduction of the Fe (VI) can also form a p-n heterojunction photocatalyst with the Ti/Zn LDH, so that the purpose of prolonging the oxidation pollutant of the material is realized. The invention provides a new technical choice for the application of the photocatalysis technology in water treatment.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a two-stage photocatalyst of ferrate composite titanium-zinc layered double hydroxide, and a preparation method and application thereof. The photocatalyst prepared by the low-temperature hydrothermal method for controlling the alkalinity of the reaction system can effectively solve the problems that Fe (VI) is unstable and is easy to self-decompose when being compounded with Ti/Zn LDH, ferric oxide generated in situ cannot be effectively attached to the Ti/Zn LDH surface layer in practical application to form a heterojunction structure photocatalyst, and the like. The preparation method of the photocatalyst has the advantages of low energy consumption, no toxic or harmful byproducts, simple preparation process and easy mass production, and the prepared photocatalyst has two-stage oxidability, and can continuously catalyze and oxidize pollutants by means of the reduced Fe (III) oxide and the heterojunction photocatalyst formed by Ti/Zn after the Fe (VI) is consumed.
In order to achieve the above object, the present invention provides the following technical solutions:
A two-stage photocatalyst of ferrate composite titanium zinc layered double metal hydroxide is a composite material which takes titanium zinc layered double metal hydroxide Ti/Zn LDH as a carrier and ferrate as a composite substance, wherein the ferrate is abbreviated as Fe (VI). When the two-stage photocatalyst is applied to treating pollutants in water, two different stages exist, wherein the photocatalyst mainly playing a role in the first stage is Fe (VI) -Ti/Zn LDH composite material, and the catalyst playing a role in the second stage is p-n heterojunction photocatalytic material formed by depositing ferric oxide Fe (III) formed by decomposing Fe (VI) on the surface of LDH.
Further, the mass ratio of Fe (VI) to Ti/Zn LDH is 1:1-2:1.
Further, the ratio of Zn to Ti species in the Ti/Zn LDH support material is in the range of 1.5:1 to 4:1, preferably 2:1.
The Ti/Zn LDH carrier material is prepared from a titanium source, a zinc source and urea, wherein the ratio of the urea to the Ti in the titanium source is 20:1-30:1, and is preferably 25:1.
The preparation method of the ferrate composite titanium zinc layered double hydroxide photocatalyst comprises the following steps:
1) Adding a titanium source, a zinc source and urea into deionized water, stirring at a rotating speed of 400-500 r/min for 30-60 minutes to realize coprecipitation, pouring the obtained mixed solution into a reaction kettle, and carrying out hydrothermal reaction at a temperature of 110-150 ℃ for 40-60 hours;
2) Centrifugally separating the mixed solution after the hydrothermal reaction, flushing surface impurities of the obtained solid by deionized water, and drying to obtain a Ti/Zn LDH carrier material;
3) Mixing the Ti/Zn LDH carrier material obtained in the step 2) with ferrate powder, adding the mixture into an alkaline solution with the pH of 9-10 (Fe (VI), namely ferrate cannot exist stably for more than 10 minutes under a non-alkaline condition, so that the preparation condition needs to be maintained at about pH 9-10), vigorously stirring and carrying out ultrasonic treatment for 0.5-2 hours, then adding into a reaction kettle, carrying out low-temperature hydrothermal reaction at the temperature lower than 50 ℃ for 0.5-8 hours;
4) And 3) after the reaction is finished, centrifugally separating the reaction solution, washing the obtained solid by a solvent, and then blowing off and drying by nitrogen to obtain the Fe (VI) composite Ti/Zn LDH semiconductor photocatalytic material, namely the preparation is finished.
Further, in the step 1), the titanium source is titanium tetrachloride, the zinc source is zinc nitrate, and the ratio of Ti in the titanium source to the Zn and urea in the zinc source is 1:1.5-4:20-30, preferably 1:2:25; in the step 1), the hydrothermal reaction temperature is 125-130 ℃, and the hydrothermal reaction time is 48-50 hours.
Further, in the step 3), the mass ratio of the Ti/Zn LDH carrier material to the ferrate powder is 1:1-1.2, preferably 1:1.1, and the ferrate is potassium ferrate; the alkaline solution is a potassium hydroxide aqueous solution, and the pH value of the alkaline solution is 9-9.5.
Further, the low-temperature hydrothermal reaction temperature in the step 3) is 40 ℃, and the reaction time is 4-6 hours.
Further, in step 4), the solid is washed several times with cyclohexane, ethanol, diethyl ether in this order.
The application of the ferrate composite titanium-zinc layered double hydroxide photocatalyst in catalyzing and degrading organic pollutants in wastewater under visible light is that ferric oxide (Fe (III)) formed in situ along with reduction of ferrate is deposited on the surface of the titanium-zinc layered double hydroxide to form a novel p-n heterojunction photocatalyst, so that the forbidden bandwidth is reduced, the utilization rate of visible light and the separation rate of photo-generated carriers are continuously improved, and the photocatalyst still has a good photocatalysis effect.
The invention has the following beneficial effects:
a. Titanium tetrachloride solution, zinc nitrate hexahydrate and urea are used as Ti/Zn LDH preparation raw materials, so that the LDH interlayer spacing can be expanded to the greatest extent, and Fe (VI) compositing is easier. The purpose of adding urea as a nitrogen source in the preparation method is that the urea is a substance which is decomposed into ammonia gas and carbon dioxide after being heated at a low temperature, ammonia monohydrate is generated with water along with the generation of the ammonia gas, hydroxide is ionized along with the ammonia monohydrate, basic LDH is formed by the ammonia monohydrate and titanium zinc oxide, and an interlayer structure of the LDH is spread by the generation of the carbon dioxide. While other kinds of nitrogen-containing compounds hardly have the above two characteristics and the urea hydrothermal process is one of the basic processes for preparing LDH, the present invention uses only urea as a synthetic raw material for LDH.
B. The alkaline low-temperature hydrothermal method can relieve the self-decomposition of ferrate in the solution, and ensure the activity of Fe (VI) in the Fe (VI) -Ti/Zn LDH photocatalytic composite material after the preparation is completed.
C. Fe (VI) and Ti/Zn LDH are compounded into the LDH, so that the effective extraction of photo-generated electrons is facilitated, the recombination of hole electrons and heavy electrons is inhibited, meanwhile, the carrier migration efficiency is improved, and the defect of low sunlight utilization rate of the titanium-based photocatalytic material is overcome.
D. in the process of degrading organic pollutants in wastewater, ferric oxide formed in situ after Fe (VI) oxidizes the pollutants can be adsorbed by LDH to form heterojunction structure materials, so that the forbidden bandwidth of titanium-based materials is reduced, the energy required for excitation is reduced, the energy-saving effect is achieved, and meanwhile, the pollutant adsorption performance of the LDH is enhanced due to the coordination effect of the ferric oxide.
E. The successful combination of Fe (VI) and Ti/Zn LDH enhances the dispersibility of Fe (VI) and the ferric oxide of the reduction product thereof in the wastewater solution of organic pollutants, and increases the contact probability with the pollutants in practical application.
F. The material of the invention is applied to the field of environmental water treatment, has the characteristics of rapid and thorough pollutant oxidative degradation, simple and convenient production and low cost, and thus has important industrial application value.
Drawings
FIG. 1a is a scanning electron microscope image of a layered double hydroxide of titanium zinc (hereinafter referred to as Ti/Zn LDH) prepared in example 1 of the present invention.
FIG. 1b is a scanning electron microscope image of a ferrate composite titanium zinc layered double hydroxide (hereinafter referred to as Fe (VI) -Ti/Zn LDH) photocatalytic material prepared in example 1 of the present invention.
FIG. 2a is an X-ray diffraction pattern of a Fe (VI) -Ti/Zn LDH photocatalytic material;
FIG. 2b is a high resolution transmission electron microscopy image of Fe (VI) -Ti/Zn LDH photocatalytic material.
FIG. 3 is a nitrogen adsorption and desorption isotherm plot of Fe (VI) -Ti/Zn LDH photocatalytic material.
FIG. 4 is a scanning electron microscope image of a photocatalytic material for in situ formation of a ferric iron-LDH heterojunction structure after application of the material of the present invention;
fig. 5 is an optical property diagram (a) of a photocatalytic material for forming a ferric iron-LDH heterojunction structure in situ after application of the material of the invention, which is an absorbance diagram of Ti/Zn LDH, and an inner diagram is a forbidden band width diagram obtained after treatment; (b) The absorbance diagram is the absorbance diagram of Fe (III) oxide, and the inner diagram is the forbidden bandwidth diagram obtained after treatment; (c) a valence band x-ray photoelectron spectrum of a Ti/Zn LDH; (d) Is a valence band x-ray photoelectron spectrum of Fe (III) oxide.
FIG. 6 is a diagram of specific structure and mechanism of action of Fe (III) -Ti/Zn LDH p-n heterojunction photocatalyst;
FIG. 7 shows a graph of electron paramagnetic (spin) resonance spectrometer signals generated when Fe (VI) -Ti/Zn LDH photocatalytic materials are applied: (a) Hydroxyl radical signal of the pre-applied catalyst material, (b) superoxide radical signal of the post-applied catalyst material.
Fig. 8 is a graph comparing the removal rate (a) and mineralization (b) of the Fe (VI) -Ti/Zn LDH photocatalytic material, fe (VI) alone, and Ti/Zn LDH alone in example 1 and comparative example 1 to pesticide (carbaryl) under visible light conditions.
Fig. 9 is a graph comparing the removal rate (a) and mineralization (b) of the herbicide (metribuzin) under visible light conditions for the Fe (VI) -Ti/Zn LDH photocatalytic material, fe (VI) alone, and Ti/Zn LDH alone in example 2 and comparative example 2.
Fig. 10 is a graph comparing the removal rate (a) and mineralization (b) of the Fe (VI) -Ti/Zn LDH photocatalytic material, fe (VI) alone, and Ti/Zn LDH alone in example 3 and comparative example 3 to insecticide (imidacloprid) under visible light conditions.
FIG. 11 is a graph showing the comparative results of the removal rate (a) and mineralization (b) of the Fe (VI) -Ti/Zn LDH photocatalytic material and Fe (VI) -Al/Zn LDH in example 3 and comparative example 4 on insecticide (imidacloprid) under the condition of visible light.
Detailed Description
The invention will be further illustrated with reference to specific examples, but the scope of the invention is not limited thereto.
Example 1
1) 0.46 ML titanium tetrachloride, 2.4 g zinc nitrate hexahydrate and 6 g urea were first added to 100 mL deionized water solution and stirred at 450 r/min for 45 minutes to effect co-precipitation.
2) Pouring the obtained solution into a reaction kettle, and carrying out hydrothermal reaction for 48 hours at the temperature of 130 ℃.
3) Centrifugally separating substances in the reaction kettle at the rotating speed of 5500 r/min, washing surface impurities with deionized water, heating, drying and the like to obtain the Ti/Zn LDH carrier material.
4) The above 3.9 g Ti/Zn LDH and 4.3 g potassium ferrate powder were added to an aqueous potassium hydroxide solution at ph=9, vigorously stirred and sonicated for 1 hour, then added to the reaction vessel and reacted under low temperature hydrothermal conditions at 40 ℃ for 4 hours.
5) And (3) centrifugally separating the reaction solution obtained in the step (4) at the rotating speed of 5500 r/min, repeatedly flushing the obtained solid for 4 times by using cyclohexane, ethanol and diethyl ether respectively, and finally blowing off and drying by using nitrogen to obtain the Fe (VI) composite Ti/Zn LDH semiconductor photocatalytic material, namely Fe (VI) -Ti/Zn LDH.
Scanning electron microscope images of the Ti/Zn LDH carrier material prepared in step 3) and the Fe (VI) -Ti/Zn LDH prepared in step 5) of the invention are shown in FIG. 1a and FIG. 1b respectively. The X-ray diffraction pattern, the high resolution transmission electron microscope pattern and the nitrogen adsorption and desorption isothermal line patterns of the Fe (VI) -Ti/Zn LDH prepared in the step 5) are respectively shown in fig. 2a, 2b and 3.
The composite catalyst has the following characteristics: the results of X-ray diffraction and high resolution transmission electron microscopy (fig. 2a and 2 b) also help demonstrate the presence of and successful coupling of Fe (VI) species in LDHs, where Fe (VI) recombination into the interlayer (fig. 1 b) of LDH (fig. 1 a) is observed in the microenvironment. The result of the nitrogen adsorption and desorption isothermal line graph (figure 3) of the material shows that Fe (VI) is mainly inserted into micropores of LDH, the mesoporous and macroporous structures of the LDH are successfully reserved, the adsorption influence on the LDH is small, the specific surface area of the photocatalytic material is 55.92 m 2/g, and the particle size is 14.38 nm.
Application example 1
Example 1 Fe (VI) -Ti/Zn LDH catalytic material with an effective Fe (VI) concentration of around 22.5 mg/L was added to a ph=7 borate buffer solution containing 4.6 mg/L (23.5 μmol/L) of carbaryl insecticide, supplemented with 42 mW/cm 2 of light for 60 minutes, and fig. 8 (panels a-b) are the removal rate and degree of mineralization (DOC) of carbaryl at different reaction time points.
The Fe (VI) -Ti/Zn LDH catalytic material after the degradation application described in the application example 1 is characterized, a scanning electron microscope image of the photocatalytic material with the in-situ formation of the ferric iron-LDH heterojunction structure after the application is shown in fig. 4, an optical property image of the photocatalytic material with the in-situ formation of the ferric iron-LDH heterojunction structure after the application is summarized in fig. 5, and fig. 6 is a specific structure and action mechanism image of the Fe (III) -Ti/Zn LDH p-n heterojunction photocatalyst. As can be seen from fig. 4-6: when Fe (III) oxide generated after Fe (VI) is consumed is deposited on the LDH surface (microstructure thereof in fig. 4), a new p-n heterojunction catalyst material is formed, specific optical properties are shown in fig. 5 (plots a-d), the forbidden band width and valence band positions of two substances constituting the heterojunction catalyst are included, and a specific structure diagram is shown in fig. 6.
In addition, electron paramagnetic (spin) resonance spectrometer signal patterns generated when Fe (VI) -Ti/Zn LDH photocatalytic materials are applied are analyzed, and the specific analysis method is as follows:
DMPO (final concentration 100.0 mM) and fresh Fe (VI) -Ti/Zn LDH catalytic material of example 1 (final concentration 0.22 g/L) were added to methanol and the resulting mixture was transferred to an EPR tube of 2 mm and subsequently placed in a Bruker ELEXSYS-II E500 spectrometer for analysis, fe (VI) not consumed, the catalyst generating hydroxyl radicals under visible light catalysis (visible light irradiation for 5 min) (hydroxyl radical ESR signal as shown in fig. 7 (a)).
DMPO (final concentration 100.0 mM) and Fe (VI) -Ti/Zn LDH catalytic material (final concentration 0.22 g/L) after the above degradation application were added to methanol, and the resulting mixture was transferred to an EPR tube of 2 mm and then put into Bruker ELEXSYS-II E500 spectrometer for analysis, and in the second stage of catalyst explanation application (heterojunction catalyst formation stage), the reactive species (radicals) were converted into superoxide radicals under visible light catalysis (visible light irradiation for 5 min) (fig. 7 (b) is signal intensity of superoxide radicals for different periods of time).
Application example 2
Example 1 Fe (VI) -Ti/Zn LDH catalytic material with an effective Fe (VI) concentration of around 22.5 mg/L was added to a ph=7 borate buffer solution containing 3.97 mg/L (23.5 μmol/L) of zinone herbicide, with an illumination of around 42 mW/cm 2 for 60 minutes, figure 9 (panels a-b) for the removal and mineralization (DOC) of carbaryl at different reaction time points.
Application example 3
Example 1 Fe (VI) -Ti/Zn LDH catalytic material with an effective Fe (VI) concentration of around 22.5 mg/L was added to a ph=7 borate buffer solution containing 6.00 mg/L (23.5 μmol/L) imidacloprid insecticide, supplemented with 42 mW/cm 2 of light for 60 minutes, and fig. 10 (panels a-b) are the removal rate and degree of mineralization (DOC) of imidacloprid at different reaction time points.
Comparative example 1
The removal rates and mineralization rates (DOC) of the carbaryl insecticide at different reaction time points are summarized in FIG. 8 (panels a-b) by adding Fe (VI) potassium ferrate and Ti/Zn LDH, respectively, at a final concentration of 22.5 mg/L to the solution under the same experimental conditions as in application example 1. The results show that the removal rate and removal rate of the Fe (VI) -Ti/Zn LDH composite material for the carbaryl (30 s carbaryl removal rate reaches 100%, 120-minute mineralization reaches 64%) are obviously better than those of the Fe (VI) (60-minute carbaryl removal rate 83%, 120-minute mineralization 32%) and the Ti/Zn LDH (60-minute carbaryl removal rate 10%, 120-minute mineralization 9%).
Comparative example 2
The removal rates and mineralization Degrees (DOCs) of zinone at different reaction time points are summarized in FIG. 9 (panels a-b) by adding Fe (VI) potassium ferrate and Ti/Zn LDH, respectively, to solutions having a final concentration of 22.5 mg/L, under the same experimental conditions as in application example 2. The results show that the removal rate and the removal rate of the Fe (VI) -Ti/Zn LDH composite material on the metribuzin (the metribuzin removal rate reaches 88% in 10 minutes, the mineralization degree reaches 64% in 120 minutes) are obviously better than those of the Fe (VI) (the metribuzin removal rate is 52% in 60 minutes, the mineralization degree is 32% in 120 minutes) and the Ti/Zn LDH (the metribuzin removal rate is 10% in 60 minutes and the mineralization degree is 9% in 120 minutes).
Comparative example 3
The removal rates and mineralization Degrees (DOC) of imidacloprid at different reaction time points are summarized in FIG. 10 (panels a-b) by adding Fe (VI) potassium ferrate and Ti/Zn LDH, respectively, at a final concentration of 22.5 mg/L, to the solution under the same experimental conditions as in application example 3. The results show that the removal rate and the removal rate of the Fe (VI) -Ti/Zn LDH composite material for the imidacloprid (the imidacloprid removal rate reaches 100% in 20 minutes, the mineralization degree reaches 46% in 120 minutes) are obviously better than those of the Fe (VI) (the imidacloprid removal rate of 86% in 60 minutes, the mineralization degree of 24% in 120 minutes) and the Ti/Zn LDH (the imidacloprid removal rate of 27% in 60 minutes, and the mineralization degree of 14.1% in 120 minutes).
Comparative example 4
The procedure 1) to 3) for synthesizing Ti/Zn LDH in example 1 was repeated except that "0.46 mL of titanium tetrachloride was replaced with aluminum nitrate in the same molar amount as that", and the remaining operation conditions were unchanged, to prepare an Al/Zn LDH carrier material. And repeating the operation steps 4) to 5) of synthesizing Fe (VI) -Ti/Zn LDH in example 1, replacing Ti/Zn LDH in the Fe (VI) -Ti/Zn LDH in example 1 with Al/Zn LDH, and synthesizing Fe (VI) -Al/Zn LDH by the same synthesis method.
The removal and mineralization (DOC) of imidacloprid at various reaction time points is summarized in fig. 11 (panels a-b) by adding the above-described synthetic Fe (VI) -Al/Zn LDH or example 1 Fe (VI) -Ti/Zn LDH catalytic material (wherein the effective Fe (VI) concentration is around 22.5 mg/L) to a ph=7 borate buffer solution containing 4.6 mg/L (23.5 μmol/L) of carbaryl insecticide, while being supplemented with 42 mW/cm 2 of light for 60 minutes. The result shows that the removal rate and the removal rate of the Fe (VI) -Ti/Zn LDH composite material for imidacloprid (the imidacloprid removal rate reaches 100% in 20 minutes and the mineralization degree reaches 46% in 120 minutes) are superior to those of the Fe (VI) -Al/Zn LDH (the imidacloprid removal rate reaches 68% in 60 minutes and the mineralization degree reaches 25% in 120 minutes).
The above examples and comparative examples show that the composite material has excellent photocatalytic pollutant degradation performance, successfully complements the respective disadvantages by compositing Fe (VI) with Ti/Zn LDH and shows the effect of synergistically treating water pollutants.
What has been described in this specification is merely an enumeration of possible forms of implementation for the inventive concept and may not be considered limiting of the scope of the present invention to the specific forms set forth in the examples.
Claims (10)
1. The preparation method of the two-stage photocatalyst of ferrate composite titanium-zinc layered double hydroxide is characterized by comprising the following steps of:
1) Adding a titanium source, a zinc source and urea into deionized water, stirring at a rotating speed of 400-500 r/min for 30-60 minutes to realize coprecipitation, pouring the obtained mixed solution into a reaction kettle, and carrying out hydrothermal reaction at a temperature of 110-150 ℃ for 40-60 hours;
2) Centrifugally separating the mixed solution after the hydrothermal reaction, flushing surface impurities of the obtained solid by deionized water, and drying to obtain a Ti/Zn LDH carrier material;
3) Mixing the Ti/Zn LDH carrier material obtained in the step 2) with ferrate powder, adding the mixture into alkaline solution with pH of 8.5-10, vigorously stirring and carrying out ultrasonic treatment for 0.5-2 hours, then adding the mixture into a reaction kettle, and carrying out low-temperature hydrothermal reaction at a temperature lower than 50 ℃ for 0.5-8 hours;
4) After the reaction of the step 3), centrifugally separating the reaction solution, washing the obtained solid by a solvent, and then blowing off and drying by nitrogen to obtain the Fe (VI) composite Ti/Zn LDH semiconductor photocatalytic material, namely the composite material which takes titanium-zinc layered double-metal hydroxide Ti/Zn LDH as a carrier and ferrate as a composite substance, wherein the ferrate is called Fe (VI) for short;
the mass ratio of Fe (VI) to Ti/Zn LDH is 1:1-2:1;
the ratio of Zn to Ti substances in the Ti/Zn LDH carrier material is 1.5:1-4:1;
the ratio of the amount of urea to Ti in the titanium source is 20:1 to 30:1.
2. The method for preparing a two-stage photocatalyst of ferrate composite titanium zinc layered double hydroxide according to claim 1, wherein the amount ratio of Zn to Ti species in the Ti/Zn LDH support material is in the range of 2:1.
3. The method for preparing a two-stage photocatalyst of ferrate-composite titanium-zinc layered double hydroxide according to claim 1, wherein the ratio of urea to Ti in the titanium source is 25:1.
4. The method for preparing the two-stage photocatalyst of ferrate composite titanium-zinc layered double hydroxide according to claim 1, wherein in the step 1), the titanium source is titanium tetrachloride, the zinc source is zinc nitrate, the hydrothermal reaction temperature is 125-130 ℃, and the hydrothermal reaction time is 48-50 hours.
5. The method for preparing the two-stage photocatalyst of ferrate composite titanium-zinc layered double hydroxide according to claim 1, wherein the mass ratio of Ti/Zn LDH carrier material to ferrate powder in the step 3) is 1:1-1.2, and the ferrate is potassium ferrate; the alkaline solution is a potassium hydroxide aqueous solution, and the pH value of the alkaline solution is 9-9.5.
6. A method for preparing a two-stage photocatalyst of ferrate composite titanium-zinc layered double hydroxide according to claim 5, wherein the mass ratio of Ti/Zn LDH carrier material to ferrate powder in step 3) is 1:1.1.
7. The method for preparing the two-stage photocatalyst of ferrate composite titanium-zinc layered double hydroxide according to claim 1, wherein the low-temperature hydrothermal reaction temperature in the step 3) is 40 ℃, and the reaction time is 4-6 hours.
8. The method for preparing a two-stage photocatalyst of ferrate composite titanium-zinc layered double hydroxide according to claim 1, wherein in the step 4), the solid is washed with cyclohexane, ethanol and diethyl ether several times in sequence.
9. A two-stage photocatalyst of ferrate composite titanium zinc layered double hydroxide prepared by the method of any one of claims 1-8.
10. The use of a two-stage photocatalyst of ferrate composite titanium-zinc layered double hydroxide according to claim 9 for the catalytic degradation of organic contaminants in wastewater under visible light, wherein the two different stages exist when the photocatalyst is used for treating contaminants in a body of water, the photocatalyst which mainly functions in the first stage is a Fe (VI) -Ti/Zn LDH composite material, and the catalyst which functions in the second stage is a p-n heterojunction photocatalytic material which is formed by the deposition of ferric oxide Fe (III) formed by the decomposition of Fe (VI) on the LDH surface.
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| CN110813299A (en) * | 2019-11-11 | 2020-02-21 | 安徽理工大学 | Iron oxide/layered double-metal hydroxide compound and preparation and application thereof |
| CN111974400A (en) * | 2020-07-31 | 2020-11-24 | 浙江天地环保科技股份有限公司 | Composite nano material based on layered double hydroxides and preparation and application thereof |
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| CN110813299A (en) * | 2019-11-11 | 2020-02-21 | 安徽理工大学 | Iron oxide/layered double-metal hydroxide compound and preparation and application thereof |
| CN111974400A (en) * | 2020-07-31 | 2020-11-24 | 浙江天地环保科技股份有限公司 | Composite nano material based on layered double hydroxides and preparation and application thereof |
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