CN111939923A - Magnetic iron-based polyatomic coupling self-assembly two-dimensional nanosheet catalyst and preparation method and application thereof - Google Patents
Magnetic iron-based polyatomic coupling self-assembly two-dimensional nanosheet catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 156
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 53
- 230000005291 magnetic effect Effects 0.000 title claims abstract description 53
- 230000008878 coupling Effects 0.000 title claims abstract description 50
- 238000010168 coupling process Methods 0.000 title claims abstract description 50
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 50
- 239000002135 nanosheet Substances 0.000 title claims abstract description 38
- 238000001338 self-assembly Methods 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000003756 stirring Methods 0.000 claims abstract description 40
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052751 metal Inorganic materials 0.000 claims abstract description 35
- 239000002184 metal Substances 0.000 claims abstract description 35
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000011701 zinc Substances 0.000 claims abstract description 26
- 239000007864 aqueous solution Substances 0.000 claims abstract description 23
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 20
- 239000000243 solution Substances 0.000 claims abstract description 19
- 239000011777 magnesium Substances 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 12
- 238000000227 grinding Methods 0.000 claims abstract description 11
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000002696 manganese Chemical class 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 229960005404 sulfamethoxazole Drugs 0.000 claims description 45
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical group O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 claims description 45
- 239000011259 mixed solution Substances 0.000 claims description 28
- 238000006731 degradation reaction Methods 0.000 claims description 27
- 239000011572 manganese Substances 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000012266 salt solution Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 230000000593 degrading effect Effects 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
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- 239000000919 ceramic Substances 0.000 claims description 12
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- 230000008569 process Effects 0.000 claims description 10
- 238000001179 sorption measurement Methods 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 7
- 150000002505 iron Chemical class 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 229910052724 xenon Inorganic materials 0.000 claims description 5
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical group [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- 239000000356 contaminant Substances 0.000 claims description 4
- 159000000003 magnesium salts Chemical class 0.000 claims description 4
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical group O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 claims description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 3
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical group C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical group [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 150000003751 zinc Chemical class 0.000 claims description 2
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical group O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 claims 1
- 238000007885 magnetic separation Methods 0.000 abstract description 14
- 230000001699 photocatalysis Effects 0.000 abstract description 14
- 238000007146 photocatalysis Methods 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 239000002086 nanomaterial Substances 0.000 abstract description 5
- 238000003980 solgel method Methods 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract 3
- 239000000084 colloidal system Substances 0.000 abstract 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 abstract 1
- 230000015556 catabolic process Effects 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 16
- 229910019077 Mg—F Inorganic materials 0.000 description 14
- 230000000694 effects Effects 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 229910018672 Mn—F Inorganic materials 0.000 description 9
- 230000005389 magnetism Effects 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 239000003344 environmental pollutant Substances 0.000 description 7
- 238000005070 sampling Methods 0.000 description 7
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
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- 239000006228 supernatant Substances 0.000 description 3
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- 238000011161 development Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000011943 nanocatalyst Substances 0.000 description 2
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- 206010034133 Pathogen resistance Diseases 0.000 description 1
- 241000607598 Vibrio Species 0.000 description 1
- 229910001308 Zinc ferrite Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 239000003302 ferromagnetic material Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical group 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 description 1
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
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- 150000007530 organic bases Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
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- 238000006116 polymerization reaction Methods 0.000 description 1
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- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution 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
- B01J23/76—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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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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
- B01J23/005—Spinels
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- 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
- B01J35/33—Electric or magnetic properties
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- 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
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- B01J35/61—Surface area
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
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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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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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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
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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
- C02F2305/10—Photocatalysts
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Abstract
The application discloses a magnetic iron-based polyatomic coupling self-assembly two-dimensional nanosheet catalyst and a preparation method and application thereof, wherein the preparation method of the catalyst comprises the following steps: uniformly mixing zinc, magnesium and manganese salts, dissolving the zinc, magnesium and manganese salts and a certain amount of ferric salt in water, fully mixing the zinc, magnesium and manganese salts with a citric acid aqueous solution prepared in advance to form a polynuclear metal atom citrate complex, adjusting the pH value of the solution to 6.8-7.5 by dropwise adding ammonia water under rapid stirring, adding a certain amount of glycol, obtaining colloid by a sol-gel method, then grinding the colloid into powder, and calcining the powder by a muffle furnace to obtain a magnetic self-assembly two-dimensional sheet-structured nano material which is an iron-based catalyst coupled with a plurality of metal atoms. The catalyst can effectively degrade organic pollutants under visible light through photocatalysis, realizes high-efficiency utilization of sunlight, can simultaneously give consideration to energy saving and environmental purification functions, is expected to combine with a magnetic separation technology to accelerate the separation of nano materials, avoid secondary environmental pollution and reduce the post-treatment cost.
Description
Technical Field
The invention relates to the technical field of organic pollutant treatment in an environmental system, in particular to a magnetic iron-based polyatomic coupling self-assembly two-dimensional nanosheet catalyst and a preparation method and application thereof.
Background
Novel environmental pollutants such as Persistent Organic Pollutants (POPs), drugs and personal care products (PPCPs), disinfection by-products (DBPs) in the environment have attracted wide attention in various social circles due to their potential threats to the ecological environment and human health. Sulfonamides, as an antibiotic and personal care product, are a new class of organic pollutants of the world's water environment and are considered as potential threats to natural ecosystems and human health due to their low biodegradability, low removal efficiency by sewage treatment plants (WWTPs), and widespread use leading to bacterial resistance and resistance genes. The photocatalysis technology is one of the new technologies with development prospects for treating environmental organic pollutants, and has energy saving and sustainable development.
A typical photocatalyst is titanium dioxide (TiO)2) In the last 80 th century, TiO2Has already established a position in the photocatalysis technology, realizes industrial mass production (such as P25), and is applied to various fields. However, TiO2By ultraviolet light (l) of short wavelength only<390 nm), solar energy (solar energy contains 3-5% of ultraviolet light and 47% of visible light) cannot be fully utilized. The catalyst absorbs and utilizes the characteristic of the material inherent to sunlight and has a forbidden band width of (E g ) Are closely related. Research shows that TiO2Forbidden band width of (E g = 3.2 eV) can be controlled from the microstructure level by means of atomic doping, but the modulation range is limited, and the modified catalyst is unstable and easy to deactivate, causing secondary environmental pollution. Thus, researchers have been working on catalysts with narrow forbidden bandwidths, such as Fe2O3（E g = 2.3 eV), a large number of studies were carried out. However, the results show Fe2O3Is not ideal in exciting light catalysis technique because of Fe2O3The generated carriers (photo-generated electron-hole pairs) have high recombination rate and low quantum effect.
Different from TiO2、Fe2O3In the single metal material system, the iron-based polyatomic coupling material has a unique crystal structure, and the microstructure is regulated and controlled from the material bulk phase, so that the material is stable and uniform. The material is a multifunctional material and can be used for constructing heterogeneous catalysis technologies such as photocatalysis, Fenton-like oxidation, sulfate radical activation and the like. Based on the multi-metal atom coupling effect in the catalyst microstructure, photons in a wider wavelength range can be absorbed, the generation rate of photo-generated electrons and holes is improved, and efficient migration of electrons is induced, so that the degradation efficiency of organic matters is improved.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide a magnetic iron-based polyatomic coupling self-assembly two-dimensional nanosheet catalyst, and a preparation method and application thereof.
The preparation method of the magnetic iron-based polyatomic coupling self-assembly two-dimensional nanosheet catalyst is characterized by comprising the following steps of:
1) uniformly mixing zinc, manganese and manganese salt according to a molar ratio of 0.2-1: 0.2-1 to form mixed metal salt A for later use; dissolving a mixed metal salt A and an iron salt into water, wherein the ratio of the total molar weight of zinc, manganese and magnesium salts in the mixed metal salt A to the molar weight of the iron salt is 1: 1.9-2.1, and forming a metal salt solution B for later use;
adding a citric acid aqueous solution into the metal salt solution B under stirring, wherein the ratio of the total molar weight of zinc, manganese salt and ferric salt in the metal salt solution B to the molar weight of citric acid is 1: 0.5-5, and stirring and reacting the obtained mixed solution to form a multi-core Zn/Mg/Mn/Fe-citrate complex;
2) slowly dripping ammonia water into the mixed liquid obtained in the step 1) under rapid stirring, adjusting the pH to be 6.8-7.5, then adding ethylene glycol, and stirring and mixing uniformly;
3) transferring the mixed solution obtained in the step 2) into an oven, heating to 95 ℃, and keeping for 2-5 hours to form transparent soft glue; further heating to 110-150 ℃, and keeping the temperature overnight to form transparent hard glue;
4) cooling the hard rubber obtained in the step 3) to room temperature, grinding the hard rubber into fine powder, putting the fine powder into a ceramic utensil, transferring the ceramic utensil to a muffle furnace, and calcining the fine powder for 1 to 4 hours at the temperature of 400 to 500 ℃ in the air atmosphere; and cooling to room temperature after the reaction is finished to obtain the magnetic iron-based polyatomic coupling self-assembly two-dimensional nanosheet catalyst.
The preparation method of the magnetic iron-based polyatomic coupling self-assembly two-dimensional nanosheet catalyst is characterized in that in the step 1), zinc salt is zinc nitrate hexahydrate, magnesium salt is magnesium nitrate hexahydrate, manganese salt is manganese nitrate, and ferric salt is ferric nitrate nonahydrate.
The preparation method of the magnetic iron-based polyatomic coupling self-assembly two-dimensional nanosheet catalyst is characterized in that the ratio of the volume of ethylene glycol added in the step 2) to the mass of iron salt added in the step 1) is 1: 0.6-5.9, preferably 1: 1.5, the unit of mass is g, and the unit of volume is mL.
The magnetic iron-based polyatomic coupling self-assembly two-dimensional nanosheet catalyst prepared by the method.
The application of the magnetic iron-based polyatomic coupling self-assembly two-dimensional nanosheet catalyst in degrading organic pollutants in a water body is characterized in that the method for degrading the organic pollutants comprises the following steps: the catalyst is driven by visible light to carry out photocatalytic reaction to degrade organic pollutants in water.
The application of the magnetic iron-based polyatomic coupling self-assembly two-dimensional nanosheet catalyst in degrading organic pollutants in a water body is characterized in that the specific process of degrading the organic pollutants in the water body by the catalyst is as follows: placing the catalyst in a water body containing organic pollutants, performing ultrasonic dispersion uniformly, then adjusting the pH value to 3.5-7, performing adsorption balance for 0.5-2 hours under a dark condition, and performing photocatalytic degradation reaction under a visible light irradiation condition; wherein the dosage of the catalyst in the water body is controlled to be 0.05-5.0 g/L.
The application of the magnetic iron-based polyatomic coupling self-assembly two-dimensional nanosheet catalyst in degrading organic pollutants in water is characterized in that the specific process of adjusting the pH to 3.5-7 comprises the following steps: adding NaOH solution or H with the concentration of 0.2-0.8M2SO4And adjusting the initial pH value of the system to be 3.5-7.
The application of the magnetic iron-based polyatomic coupling self-assembly two-dimensional nanosheet catalyst in degrading organic pollutants in water is characterized in that a light source irradiated by visible light is a xenon lamp light source, and the wavelength range is controlled to be 420-680 nm.
The application of the magnetic iron-based polyatomic coupling self-assembly two-dimensional nanosheet catalyst in degrading organic pollutants in water is characterized in that after the catalytic degradation reaction is finished, the catalyst in the water can be separated and recovered in a mode of an external magnetic field.
The application of the magnetic iron-based polyatomic coupling self-assembly two-dimensional nanosheet catalyst in degrading organic pollutants in a water body is characterized in that the organic pollutants in the water body are sulfamethoxazole.
The beneficial effects obtained by the invention are as follows:
1) the invention adopts a simple sol-gel method to successfully prepare the iron-based polyatomic coupling catalyst. A specific two-dimensional nanosheet structure is formed through self-assembly, so that more active sites are endowed under a higher specific surface area, and the problem that nanoparticles are difficult to separate is avoided. In addition, the prepared material has better magnetism and can be quickly separated and recycled under an external magnetic field.
2) The iron-based polyatomic coupling catalyst provided by the invention has the advantages that a polyatomic coupling synergistic effect is formed in the iron-based polyatomic coupling catalyst, the generation rate and the electron migration rate of photoproduction electron-hole pairs can be effectively improved under the irradiation of visible light, the yield of free radicals such as hydroxyl is improved, and the degradation rate of pollutants is accelerated.
3) The catalyst can realize the high-efficiency utilization of sunlight, simultaneously has the functions of energy conservation and environmental purification, is expected to combine with a magnetic separation technology to accelerate the separation of nano materials, avoid the secondary environmental pollution and reduce the post-treatment cost.
Drawings
FIG. 1 is a comparison of XRD patterns of catalysts prepared in examples 1-4;
FIG. 2 is a SEM image comparison of catalysts prepared in examples 1-4; in fig. 2: a-example 1 catalyst, B-example 2 catalyst, C-example 3 catalyst, D-example 4 catalyst;
FIG. 3 is a comparative photograph of a water sample containing the catalysts of examples 1-4 before and after magnetic separation; in fig. 3: a-the graph of the magnetic separation effect of the catalyst in example 1, B-the graph of the magnetic separation effect of the catalyst in example 2, C-the graph of the magnetic separation effect of the catalyst in example 3 and D-the graph of the magnetic separation effect of the catalyst in example 4;
FIG. 4 is a graph comparing the degradation effect of the catalysts of examples 1-4 on SMX as a target pollutant in a visible light photocatalytic system;
FIG. 5 shows the Zn-F catalyst prepared in example 1, the ZnMgMn-F catalyst prepared in example 4, and commercial Fe3O4Results of magnetic strength test of nanospheres respectivelyComparing the images;
FIG. 6 is a SEM photograph comparing the catalysts prepared in comparative examples 1-2.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example 1 degradation of Sulfamethoxazole (SMX) by visible light photocatalysis of magnetic iron-based polyatomic coupling self-assembly two-dimensional nanosheet catalyst
The preparation method of the magnetic iron-based polyatomic coupling self-assembly two-dimensional nanosheet catalyst comprises the following steps:
1) 1.10g of Zn (NO)3)2·6H2O and 2.987g Fe (NO)3)3·9H2Dissolving O in 10mL of water to form a metal salt solution A for later use; weighing 2.13g of citric acid, and dissolving in 5mL of water to prepare a water solution B; adding the aqueous solution B into the metal salt solution A under stirring, and stirring the obtained mixed solution to react to form a polynuclear Zn/Fe-citrate complex (citric acid is a chelating agent, is beneficial to the uniform distribution and stability of various metal ions in a system, and has steric effect to influence the self-assembly and growth process of the material);
2) dropwise and slowly adding 4.5mL of ammonia water with the concentration of 25-28% by weight into the mixed solution obtained in the step 1) (the ammonia water is an organic base and has the function of buffering the pH value) under the condition of rapid stirring to enable the pH value to reach 7, then adding 2mL of glycol (playing the role of reaction liquid gelation), and continuously stirring for 2 hours to enable the mixture to be uniformly mixed;
3) transferring the mixed solution obtained in the step 2) into an oven, heating to 95 ℃, and keeping for 3 hours to form transparent soft glue; further heating to 120 ℃ and preserving the temperature overnight to form transparent hard glue;
4) cooling the hard rubber obtained in the step 3) to room temperature, grinding the hard rubber into fine powder, putting the fine powder into a ceramic utensil, transferring the ceramic utensil to a muffle furnace, and calcining the fine powder for 2 hours at 450 ℃ in the air atmosphere; and cooling to room temperature after the reaction is finished, grinding to obtain the magnetic iron-based multi-atom coupling two-dimensional nanostructured catalyst, and marking the catalyst as a Zn-F catalyst.
Example 1 preparationThe XRD pattern of the Zn-F catalyst is shown in figure 1, and it can be seen from figure 1 that: the Zn-F catalyst has spinel type ZnFe2O4Characteristic peak (JCPDS-04-007-6616) shows that the prepared Zn-F catalyst has a spinel crystal structure.
The SEM image of Zn-F prepared in example 1 is shown in Panel A of FIG. 2, and it can be seen that: the Zn-F catalyst presents a self-assembled two-dimensional nanosheet structure, and the material characteristics suggest that the prepared catalyst has better catalytic degradation performance.
The Zn-F catalyst prepared in example 1 forms a photocatalytic reaction under the irradiation of visible light for degrading Sulfamethoxazole (SMX), and the specific process is as follows:
1) preparing SMX aqueous solution with the concentration of 3 mg/L. 50mL of a prepared aqueous solution of 3mg/L of SMX was added with 0.006g of the Zn-F catalyst prepared in example 1, sonicated for 1 minute to uniformly disperse the catalyst in the solution, and then 0.25mM of H was added2SO4Adjusting the pH value of the aqueous solution to 4.0, then placing the mixed solution under a dark condition, stirring, and carrying out adsorption balance for 1 hour;
2) carrying out visible light photocatalytic reaction on the mixed solution subjected to adsorption balance in the step 1) under the simulated visible light (irradiation of a xenon lamp light source, and control of the wavelength of visible light to be 420-680 nm), wherein the reaction time is 150min, and sampling and analyzing after the reaction is finished.
The operation steps of sampling analysis are as follows: separating the catalyst from the sample obtained in the above step under an external magnetic field, and measuring the concentration of SMX in the solution by high performance liquid chromatography. The effect of the Zn-F catalyst of example 1 on the degradation of the target contaminant SMX in a visible light photocatalytic system after 150min is shown in FIG. 4. As can be seen from fig. 4, SMX was degraded by around 85%.
Among them, the comparative photograph of the sample containing Zn — F catalyst before and after magnetic separation is shown in panel a in fig. 3, and it can be seen that: the Zn-F catalyst can accelerate the separation under the action of an external magnetic field, which shows that Zn-F has certain magnetism.
Example 2 degradation of Sulfamethoxazole (SMX) by visible light photocatalysis of magnetic iron-based polyatomic coupling self-assembly two-dimensional nanosheet catalyst
The preparation method of the magnetic iron-based polyatomic coupling self-assembly two-dimensional nanosheet catalyst comprises the following steps:
1) 0.948g of Mg (NO)3)2·6H2O and 2.987g Fe (NO)3)3·9H2Dissolving O in 10mL of water to form a metal salt solution A for later use; weighing 2.13g of citric acid, and dissolving in 5mL of water to prepare a water solution B; adding the aqueous solution B into the metal salt solution A under stirring, and stirring and reacting the obtained mixed solution to form a polynuclear Mg/Fe-citrate complex;
2) dropwise and slowly adding 4.0mL of ammonia water with the concentration of 25-28% by weight into the mixed solution obtained in the step 1) under rapid stirring to enable the pH value to reach 7, then adding 2mL of ethylene glycol, and continuously stirring for 2 hours to enable the mixture to be uniformly mixed;
3) transferring the mixed solution obtained in the step 2) into an oven, heating to 95 ℃, and keeping for 3 hours to form transparent soft glue; further heating to 120 ℃ and preserving the temperature overnight to form transparent hard glue;
4) cooling the hard rubber obtained in the step 3) to room temperature, grinding the hard rubber into fine powder, putting the fine powder into a ceramic utensil, transferring the ceramic utensil to a muffle furnace, and calcining the fine powder for 2 hours at 450 ℃ in the air atmosphere; and cooling to room temperature after the reaction is finished, grinding to obtain the magnetic iron-based polyatomic coupling two-dimensional nanostructured catalyst, and marking the magnetic iron-based polyatomic coupling two-dimensional nanostructured catalyst as an Mg-F catalyst.
The XRD pattern of the Mg-F catalyst prepared in example 2 is shown in fig. 1, and the Mg-F catalyst has characteristic peaks similar to those of the Zn-F catalyst, indicating that the prepared Mg-F catalyst has a spinel crystal structure.
The SEM image of the Mg — F catalyst prepared in example 2 is shown in panel B in fig. 2, and it can be seen that: the Mg-F catalyst presents a self-assembled two-dimensional nanosheet structure, and the material characteristics suggest that the prepared catalyst has better catalytic degradation performance.
The Mg-F catalyst prepared in example 2 was subjected to a photocatalytic reaction under visible light irradiation for degradation of SMX, and the procedure for degradation of SMX in example 1 was repeated except for "replacing the Zn-F catalyst in example 1 with the Mg-F catalyst prepared in example 2 of the same quality", and the other steps were the same as in example 1.
Sampling and analyzing after the degradation reaction is finished, wherein the operation steps are as follows: separating the catalyst from the sample under an external magnetic field, and measuring the concentration of SMX in the solution by using high performance liquid chromatography to obtain the supernatant. The effect of the Mg-F catalyst of example 2 on the degradation of the target contaminant SMX in a visible light photocatalytic system after 150min is shown in fig. 4. As can be seen from fig. 4, SMX degraded by about 82%.
Wherein, the comparative photograph of the sample containing the Mg-F catalyst before and after the magnetic separation is shown in panel B of FIG. 3, it can be seen that: the Mg-F catalyst can accelerate the separation under the action of an external magnetic field, which shows that the Mg-F has certain magnetism.
Example 3 degradation of Sulfamethoxazole (SMX) by visible light photocatalysis of magnetic iron-based polyatomic coupling self-assembly two-dimensional nanosheet catalyst
The preparation method of the magnetic iron-based polyatomic coupling self-assembly two-dimensional nanosheet catalyst comprises the following steps:
1) 1.323g of Mn (NO)3)2(50% by weight aqueous solution) and 2.987g Fe (NO)3)3·9H2Dissolving O in 5mL of water to form a metal salt solution A for later use; weighing 2.13g of citric acid, and dissolving in 5mL of water to prepare a water solution B; adding the aqueous solution B into the metal salt solution A under stirring, and stirring and reacting the obtained mixed solution to form a polynuclear Mn/Fe-citrate complex;
2) dropwise and slowly adding 3.9mL of ammonia water with the concentration of 25-28% by weight into the mixed solution obtained in the step 1) under rapid stirring to enable the pH value to reach 7, then adding 2mL of ethylene glycol, and continuously stirring for 2 hours to enable the mixture to be uniformly mixed;
3) transferring the mixed solution obtained in the step 2) into an oven, heating to 95 ℃, and keeping for 3 hours to form transparent soft glue; further heating to 120 ℃ and preserving the temperature overnight to form transparent hard glue;
4) cooling the hard rubber obtained in the step 3) to room temperature, grinding the hard rubber into fine powder, putting the fine powder into a ceramic utensil, transferring the ceramic utensil to a muffle furnace, and calcining the fine powder for 2 hours at 450 ℃ in the air atmosphere; and cooling to room temperature after the reaction is finished, grinding to obtain the magnetic iron-based multi-atom coupling two-dimensional nanostructured catalyst, and marking the catalyst as the Mn-F catalyst.
The XRD pattern of the Mn-F catalyst prepared in example 3 is shown in FIG. 1, and the Mn-F catalyst has characteristic peaks similar to those of the Zn-F catalyst, indicating that the Mg-F catalyst prepared has a spinel crystal structure.
The SEM image of the Mn — F catalyst prepared in example 3 is shown in panel C of fig. 2, and it can be seen that: the Mn-F catalyst presents a self-assembled two-dimensional nanosheet structure, and the material characteristics suggest that the prepared catalyst has better catalytic degradation performance.
The Mn — F catalyst prepared in example 3 was subjected to a photocatalytic reaction under visible light irradiation for degradation of SMX, and the detailed experimental procedure was repeated for the degradation of SMX of example 1, except that "the Zn — F catalyst in example 1 was replaced with the Mn-F catalyst prepared in example 3 of the same quality", and the remaining steps were the same as in example 1.
Sampling and analyzing after the degradation reaction is finished, wherein the operation steps are as follows: separating the catalyst from the sample under an external magnetic field, and measuring the concentration of SMX in the solution by using high performance liquid chromatography to obtain the supernatant. The effect of the Mn — F catalyst of example 3 on the degradation of the target contaminant SMX in a visible light photocatalytic system after 150min is shown in fig. 4. As can be seen from fig. 4, SMX degraded by about 92%.
Among them, the comparative photographs of the sample containing the Mn — F catalyst before and after the magnetic separation are shown in panel C in fig. 3, and it can be seen that: the Mn-F catalyst can accelerate the separation under the action of an external magnetic field, which shows that Mn-F has certain magnetism.
Example 4 degradation of Sulfamethoxazole (SMX) by visible light photocatalysis of magnetic iron-based polyatomic coupling self-assembly two-dimensional nanosheet catalyst
The preparation method of the magnetic iron-based polyatomic coupling self-assembly two-dimensional nanosheet catalyst comprises the following steps:
1) 0.367g of Zn (NO)3)2·6H2O、0.316g Mg(NO3)2·6H2O and 0.441g Mn (NO)3)2(50% by weight aqueous solution) to form mixed metal salt A for use. Mixed Metal salt A with 2.987g Fe(NO3)3·9H2Dissolving O in 10mL of water to form a metal salt solution B for later use; weighing 2.13g of citric acid, dissolving in 5mL of water, and preparing a water solution C; adding the aqueous solution C into the metal salt solution B under stirring, and stirring and reacting the obtained mixed solution to form a polynuclear Zn/Mg/Mn/Fe-citrate complex;
2) dropwise and slowly adding 4.1mL of ammonia water with the concentration of 25-28% by weight into the mixed solution obtained in the step 1) under rapid stirring to enable the pH value to reach 7, then adding 2mL of ethylene glycol, and continuously stirring for 2 hours to uniformly mix the mixture;
3) transferring the mixed solution obtained in the step 2) into an oven, heating to 95 ℃, and keeping for 3 hours to form transparent soft glue; further heating to 120 ℃ and preserving the temperature overnight to form transparent hard glue;
4) cooling the hard rubber obtained in the step 3) to room temperature, grinding the hard rubber into fine powder, putting the fine powder into a ceramic utensil, transferring the ceramic utensil to a muffle furnace, and calcining the fine powder for 2 hours at 450 ℃ in the air atmosphere; and cooling to room temperature after the reaction is finished, grinding to obtain the magnetic iron-based multi-atom coupling two-dimensional nanostructured catalyst, and marking the catalyst as a ZnMgMn-F catalyst.
The XRD pattern of the ZnMgMn-F catalyst prepared in example 4 is shown in FIG. 1, and the ZnMgMn-F catalyst has characteristic peaks similar to those of the Zn-F catalyst, thus indicating that the ZnMgMn-F catalyst prepared has a spinel crystal structure.
The SEM image of the ZnMgMn — F catalyst prepared in example 4 is shown in panel D of fig. 2, and it can be seen that: the ZnMgMn-F catalyst presents a self-assembled two-dimensional nanosheet structure, and the material characteristics imply that the prepared catalyst has better catalytic degradation performance.
The ZnMgMn-F catalyst prepared in example 4 is subjected to photocatalytic reaction under the irradiation of visible light for degrading SMX, and the SMX degrading process of example 1 is repeated in the specific experimental process, except that the Zn-F catalyst in example 1 is replaced by the ZnMgMn-F catalyst prepared in example 4 with the same quality, and the rest steps are the same as those in example 1.
Sampling and analyzing after the degradation reaction is finished, wherein the operation steps are as follows: separating the catalyst from the sample under an external magnetic field, and measuring the concentration of SMX in the solution by using high performance liquid chromatography to obtain the supernatant. The effect of the ZnMgMn-F catalyst of example 4 on the degradation of the target pollutant SMX in a visible light photocatalytic system after 150min is shown in FIG. 4. As can be seen in fig. 4, SMX was degraded by about 99%.
Wherein, the comparative photograph of the sample containing ZnMgMn-F catalyst before and after magnetic separation is shown in the panel D in FIG. 3, which can be seen: the ZnMgMn-F catalyst can be quickly separated under the action of an external magnetic field, which shows that the ZnMgMn-F has certain magnetism.
From the results of comparing the degradation effects of the catalysts of examples 1 to 4 of fig. 4 on the target pollutant SMX under the visible light photocatalytic system, it can be seen that: under the same other conditions, the iron-based bimetallic atom coupled catalyst (namely Fe in Zn-F is coupled with Zn atoms, Fe in Mg-F is coupled with Mg atoms, and Fe in Mn-F is coupled with Mn atoms) shows different efficiencies on the degradation of pollutants, which shows that the iron-based bimetallic atom coupled catalyst is influenced by the properties of the coupled atoms, and the obtained Mn atoms in multiple valence states are more beneficial to improving the catalytic activity of the iron-based catalyst than single valence state Zn or Mg. When an iron atom is coupled with a plurality of metal atoms to form an iron-based polyatomic coupling catalyst (namely, Fe in ZnMgMn-F is coupled with Zn, Mg and Mn atoms at the same time), the efficiency of photocatalytic degradation of SMX is improved to 99 percent, which shows that the coupling of Zn-Mg-Mn multi-metal atoms is an effective means for effectively improving the iron-based catalyst. The internal reason may be that the coupling synergistic effect occurs among polyatomic atoms, and the recombination rate of photogenerated electron-hole pairs is reduced, so that the yield of free radicals in a system is improved, and the degradation of pollutants is accelerated.
According to the results shown in fig. 3, the iron-based oxides, such as Zn-F, Mg-F, Mn-F, ZnMgMn-F, prepared in examples 1 to 4, respectively, all had magnetic separation characteristics, are a type of magnetic material, and all had a spinel-type crystal structure (see fig. 1), which is advantageous for accelerating separation after environmental regulations.
For the Zn-F catalyst prepared in example 1, the ZnMgMn-F catalyst prepared in example 4, and commercial Fe3O4The nanospheres (Stremchemials Newbury Pork) were individually subjected to a magnetic strength test (Vibrio specimen magnetometer, VSM), and the test results are shown in FIG. 5. From the figure5, it can be seen that: comparative ferromagnetic commercial Fe3O4The magnetization intensity of the nanospheres reaches 38.7 emu/g, and the Zn-F is found to have poor magnetism, and the magnetization intensity is only 8.8 emu/g. After Mg and Mn atoms are coupled to form a ZnMgMn-F iron-based multi-atom coupling catalyst, the magnetism of the catalyst can surpass that of a ferromagnetic material Fe3O4The magnetization exceeds 41 emu/g. The reason for this is probably mainly that (1) Zn (or Mg) is a non-magnetic element, while Fe, Mn, etc. are magnetic elements; (2) forming polyatomic coupling synergy in the microstructure; (3) polyatomic coupling causes lattice changes in the same crystal structure.
The ZnMgMn-F prepared in the embodiment 4 of the invention has good magnetism, is beneficial to the magnetic separation and recovery of the catalyst, and reduces the time for the magnetic separation and recovery.
Comparative example 1
The preparation method of the magnetic iron-based polyatomic coupling nano-catalyst comprises the following steps:
1) 1.10g of Zn (NO)3)2·6H2O and 2.987g Fe (NO)3)3·9H2Dissolving O in 10mL of water to form a metal salt solution A for later use; weighing 2.13g of citric acid, and dissolving in 5mL of water to prepare a water solution B; adding the aqueous solution B into the metal salt solution A under stirring, and stirring and reacting the obtained mixed solution to form a polynuclear Zn/Fe-citrate complex;
2) the mixed solution obtained in the step 1) is transferred to a water bath condition of 65 ℃ for heating, and an aqueous solution of NaOH (a solution of 2.49g of NaOH dissolved in 10mL of water) is slowly dropped dropwise under vigorous stirring, and stirring is maintained for 60 minutes. And then transferring the obtained mixed solution into a polytetrafluoroethylene container, adding 40mL of ammonia water (the concentration of the analytically pure ammonia water is 25-28%) under stirring, magnetically stirring for 5 minutes, and transferring into a 200 ℃ oven to react for 5 hours. And after the reaction is finished, cooling to room temperature, centrifugally separating a product, washing with deionized water and acetone, and collecting to obtain the Zn-F catalyst product.
The SEM image of Zn — F prepared in comparative example 1 is shown in panel a in fig. 6, and it can be seen that the resulting catalyst is in the form of nanoparticles.
The Zn-F catalyst prepared in the comparative example 1 forms a photocatalytic reaction under the irradiation of visible light for degrading Sulfamethoxazole (SMX), and the specific process is as follows:
1) preparing SMX aqueous solution with the concentration of 3 mg/L. 50mL of a prepared aqueous solution of 3mg/L of SMX was added with 0.006g of the Zn-F catalyst prepared in comparative example 1, sonicated for 1 minute to uniformly disperse the catalyst in the solution, and then 0.25mM of H was added2SO4Adjusting the pH value of the aqueous solution to 4.0, then placing the mixed solution under a dark condition, stirring, and carrying out adsorption balance for 1 hour;
2) and (2) carrying out visible light photocatalytic reaction on the mixed solution subjected to adsorption balance in the step 1) under the simulated visible light (irradiation of a xenon lamp light source, and control of the wavelength of visible light to be 420-680 nm), wherein the reaction time is 150min, and sampling analysis is carried out after the reaction is finished, so that the SMX is degraded by about 43%.
Comparative example 2
The preparation method of the magnetic iron-based polyatomic coupling nano-catalyst comprises the following steps:
1) 0.367g of Zn (NO)3)2·6H2O、0.316g Mg(NO3)2·6H2O and 0.441g Mn (NO)3)2(50% by weight aqueous solution) to form mixed metal salt A for use. Mixed metal salt A with 2.987g Fe (NO)3)3·9H2Dissolving O in 10mL of water to form a metal salt solution B for later use; weighing 2.13g of citric acid, dissolving in 5mL of water, and preparing a water solution C; adding the aqueous solution C into the metal salt solution B under stirring, and stirring and reacting the obtained mixed solution to form a polynuclear Zn/Mg/Mn/Fe-citrate complex;
2) the mixed solution obtained in the step 1) is transferred to a water bath condition of 65 ℃ for heating, and an aqueous solution of NaOH (a solution of 2.49g of NaOH dissolved in 10mL of water) is slowly dropped dropwise under vigorous stirring, and stirring is maintained for 60 minutes. And then transferring the obtained mixed solution into a polytetrafluoroethylene container, adding 40mL of ammonia water (the concentration of the analytically pure ammonia water is 25-28%) under stirring, magnetically stirring for 5 minutes, and transferring into a 200 ℃ oven to react for 5 hours. And after the reaction is finished, cooling to room temperature, centrifugally separating a product, washing by deionized water and acetone, and collecting to obtain the ZnMgMn-F catalyst.
The SEM image of ZnMgMn — F prepared in comparative example 2 is shown in panel B of fig. 6, and it can be seen that the resulting catalyst is in the form of nanoparticles.
The ZnMgMn-F catalyst prepared in the comparative example 2 forms a photocatalytic reaction under the irradiation of visible light for degrading Sulfamethoxazole (SMX), and the specific process is as follows:
1) preparing SMX aqueous solution with the concentration of 3 mg/L. 50mL of the prepared SMX aqueous solution of 3mg/L was added with 0.006g of the ZnMgMn-F catalyst prepared in comparative example 2, sonicated for 1 minute to uniformly disperse the catalyst in the solution, and then 0.25mM of H was added2SO4Adjusting the pH value of the aqueous solution to 4.0, then placing the mixed solution under a dark condition, stirring, and carrying out adsorption balance for 1 hour;
2) and (2) carrying out visible light photocatalytic reaction on the mixed solution subjected to adsorption balance in the step 1) under the simulated visible light (irradiation of a xenon lamp light source, and control of the wavelength of visible light to be 420-680 nm), wherein the reaction time is 150min, and sampling analysis is carried out after the reaction is finished, so that the SMX is degraded by about 76%.
According to the comparison results of fig. 6 and fig. 2, under the same metal salt formula, the iron-based polyatomic coupling spinel type nano materials prepared by the coprecipitation-hydrothermal method in the comparative examples 1-2 all have nanoparticle morphology, while the catalyst prepared by the sol-gel method in the application is consistently represented by a self-assembled two-dimensional nano sheet nano structure. The sol-gel method successfully prepares the two-dimensional nano-sheet structured spinel type iron-based polyatomic coupling catalyst, is related to the citric acid molecules and ammonia ions to play a role of a soft template, guides metal atoms to be regularly arranged according to a plane on a microscopic level, simultaneously plays a role of cross-linking polymerization along with the heating of added glycol, fixes the atomic arrangement in the solution gelling, and finally successfully prepares the catalyst with the self-assembled two-dimensional nano-sheet structure through calcination.
The statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular forms set forth in the examples.
Claims (10)
1. A preparation method of a magnetic iron-based polyatomic coupling self-assembly two-dimensional nanosheet catalyst is characterized by comprising the following steps:
1) uniformly mixing zinc, manganese and manganese salt according to a molar ratio of 0.2-1: 0.2-1 to form mixed metal salt A for later use; dissolving a mixed metal salt A and an iron salt into water, wherein the ratio of the total molar weight of zinc, manganese and magnesium salts in the mixed metal salt A to the molar weight of the iron salt is 1: 1.9-2.1, and forming a metal salt solution B for later use;
adding a citric acid aqueous solution into the metal salt solution B under stirring, wherein the ratio of the total molar weight of zinc, manganese salt and ferric salt in the metal salt solution B to the molar weight of citric acid is 1: 0.5-5, and stirring and reacting the obtained mixed solution to form a multi-core Zn/Mg/Mn/Fe-citrate complex;
2) slowly dripping ammonia water into the mixed liquid obtained in the step 1) under rapid stirring, adjusting the pH to be 6.8-7.5, then adding ethylene glycol, and stirring and mixing uniformly;
3) transferring the mixed solution obtained in the step 2) into an oven, heating to 95 ℃, and keeping for 2-5 hours to form transparent soft glue; further heating to 110-150 ℃, and keeping the temperature overnight to form transparent hard glue;
4) cooling the hard rubber obtained in the step 3) to room temperature, grinding the hard rubber into fine powder, putting the fine powder into a ceramic utensil, transferring the ceramic utensil to a muffle furnace, and calcining the fine powder for 1 to 4 hours at the temperature of 400 to 500 ℃ in the air atmosphere; and cooling to room temperature after the reaction is finished to obtain the magnetic iron-based polyatomic coupling self-assembly two-dimensional nanosheet catalyst.
2. The method for preparing the magnetic iron-based polyatomic coupling self-assembly two-dimensional nanosheet catalyst of claim 1, wherein in step 1), the zinc salt is zinc nitrate hexahydrate, the magnesium salt is magnesium nitrate hexahydrate, the manganese salt is manganese nitrate, and the iron salt is iron nitrate nonahydrate.
3. The preparation method of the magnetic iron-based polyatomic coupling self-assembly two-dimensional nanosheet catalyst according to claim 1, wherein the ratio of the volume of the ethylene glycol added in step 2) to the mass of the iron salt added in step 1) is 1: 0.6-5.9, preferably 1: 1.5, the unit of the mass is g, and the unit of the volume is mL.
4. A magnetic iron-based polyatomic coupling self-assembling two-dimensional nanosheet catalyst prepared by the method of any one of claims 1-3.
5. The application of the magnetic iron-based polyatomic coupling self-assembly two-dimensional nanosheet catalyst of claim 4 in degrading organic pollutants in a water body is characterized in that the method for degrading the organic pollutants comprises the following steps: the catalyst is driven by visible light to carry out photocatalytic reaction to degrade organic pollutants in water.
6. The application of claim 5, wherein the specific process for degrading the organic pollutants in the water body by the catalyst is as follows: placing the catalyst in a water body containing organic pollutants, performing ultrasonic dispersion uniformly, then adjusting the pH value to 3.5-7, performing adsorption balance for 0.5-2 hours under a dark condition, and performing photocatalytic degradation reaction under a visible light irradiation condition; wherein the dosage of the catalyst in the water body is controlled to be 0.05-5.0 g/L.
7. The use according to claim 6, wherein the specific process of adjusting the pH to 3.5-7 is: adding NaOH solution or H with the concentration of 0.2-0.8M2SO4And adjusting the initial pH value of the system to be 3.5-7.
8. The use according to claim 6, wherein the visible light is a xenon lamp, and the wavelength is controlled to be 420-680 nm.
9. The application of claim 6, wherein the catalyst in the water body can be separated and recovered by means of an external magnetic field after the catalytic degradation reaction is finished.
10. The use of claim 6, wherein the organic contaminant in the body of water is sulfamethoxazole.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103055771A (en) * | 2011-10-19 | 2013-04-24 | 中国科学院宁波材料技术与工程研究所 | Magnetic MFe2O4/C/AOX composite material using phenol organic molecules as carbon source and preparation method thereof |
| CN109745996A (en) * | 2019-01-16 | 2019-05-14 | 山东大学 | A kind of preparation method of high-specific area nano grade ferrous acid Mn catalyst |
| CN111268784A (en) * | 2020-03-05 | 2020-06-12 | 浙江工业大学 | Method for treating organic wastewater by multiphase Fenton-like system |
| CN111439807A (en) * | 2020-04-07 | 2020-07-24 | 浙江工业大学 | Visible light catalysis water body disinfection method based on multi-element composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103055771A (en) * | 2011-10-19 | 2013-04-24 | 中国科学院宁波材料技术与工程研究所 | Magnetic MFe2O4/C/AOX composite material using phenol organic molecules as carbon source and preparation method thereof |
| CN109745996A (en) * | 2019-01-16 | 2019-05-14 | 山东大学 | A kind of preparation method of high-specific area nano grade ferrous acid Mn catalyst |
| CN111268784A (en) * | 2020-03-05 | 2020-06-12 | 浙江工业大学 | Method for treating organic wastewater by multiphase Fenton-like system |
| CN111439807A (en) * | 2020-04-07 | 2020-07-24 | 浙江工业大学 | Visible light catalysis water body disinfection method based on multi-element composite material |
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| CN113042110A (en) * | 2021-03-26 | 2021-06-29 | 浙江工业大学 | Simple regeneration method of iron-based polyatomic coupling catalyst based on activated sulfate radical |
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