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Spinel type ZnFeMnO4 nano material, and preparation method and application thereof

A nano-material and spinel-type technology, applied in the direction of nanotechnology, nanotechnology, chemical instruments and methods, etc., can solve the problems of poor chemical stability, poor activation of PMS performance, large consumption of PMS, etc., to achieve highly selective degradation, Good pollutant removal effect, low efficiency effect

Active Publication Date: 2022-01-28
UNIV OF SCI & TECH OF CHINA
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  • Abstract
  • Description
  • Claims
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Problems solved by technology

Among all kinds of heterogeneous catalysts, spinel-type transition metal oxides are considered to be a kind of advanced oxidation catalytic materials with great development potential because of their economical, high-efficiency, stable structure and many other advantages, especially iron- and manganese-based Oxides are not only low in cost, easy to prepare and environmentally friendly, they are very suitable for water treatment applications, but their performance in activating PMS is generally poor, and a large amount of PMS is consumed, resulting in secondary pollutants such as sulfate radicals
In addition, the catalytic reaction pathway of this kind of material is mainly the free radical pathway (that is, the formation of SO 4 ·- or · OH), there are problems such as poor reaction selectivity (interferenced by various environmental ions and dissolved organic compounds), and the generation of toxic intermediate products, which limits its practical application.
[0003] In view of the above-mentioned problems existing in free radical pathway catalysts, some researchers have developed catalyst materials based on non-free radical pathways, but currently they mainly focus on carbon nanomaterials and copper oxide, which not only have low catalytic activity, but also have poor chemical stability.
Spinel-type oxide catalysts with high efficiency, stability, and high selectivity (i.e., activation of PMS through non-radical pathways) are still lacking

Method used

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  • Spinel type ZnFeMnO4 nano material, and preparation method and application thereof
  • Spinel type ZnFeMnO4 nano material, and preparation method and application thereof
  • Spinel type ZnFeMnO4 nano material, and preparation method and application thereof

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preparation example Construction

[0032] The invention provides a spinel type ZnFeMnO 4 The preparation method of nanometer material, comprises the following steps:

[0033] A) stirring and mixing zinc acetylacetonate, iron acetylacetonate, manganese acetylacetonate and an ethylene glycol solution containing polyvinylpyrrolidone to obtain a mixed solution;

[0034] B) reacting the mixed solution at 185-190°C;

[0035] C) Calcining the reacted solid product to obtain spinel ZnFeMnO 4 nanomaterials.

[0036] In the invention, zinc acetylacetonate, iron acetylacetonate, manganese acetylacetonate and ethylene glycol solution containing polyvinylpyrrolidone are first stirred and mixed to obtain a mixed solution.

[0037] In the present invention, the polyvinylpyrrolidone (PVP) is used as a surfactant to control the morphology and growth of crystals.

[0038] In some embodiments of the present invention, the average molecular weight of the polyvinylpyrrolidone is 50000-60000 g / mol. In certain embodiments, the p...

Embodiment 1

[0076] Spinel ZnFeMnO 4 Preparation of nanomaterials:

[0077] Dissolve 0.3g of polyvinylpyrrolidone (average molecular weight of 58000g / mol) in 150mL of ethylene glycol, add 1.5mmol of zinc acetylacetonate, 1.5mmol of iron acetylacetonate and 1.5mmol of manganese acetylacetonate after the solution is clarified, and stir for 2 hours. Heat the reaction in an oil bath at 190°C for 6 hours, collect and wash the solid product by centrifugation (washing three times with water and three times with ethanol), dry it in vacuum for 12 hours, and calcinate at 500°C in air for 3 hours to obtain spinel-type ZnFeMnO 4 nanomaterials.

[0078] The resulting spinel ZnFeMnO 4 After the nanomaterials are ground uniformly, X-ray diffraction (XRD) analysis and transmission electron microscope (TEM) analysis are performed. figure 1 Be the spinel type ZnFeMnO of the embodiment 1 of the present invention 4 XRD patterns of nanomaterials. from figure 1 It can be seen that the Mn element is succe...

Embodiment 2

[0082] Spinel ZnFeMnO 4 Performance and mechanism of nanomaterials activated PMS to degrade bisphenol A:

[0083] (1) Degrade bisphenol A (BPA): get the spinel type ZnFeMnO of embodiment 1 4 Ultrasonic dispersion of 2mg of nanomaterials in 20mL of 10mg / L bisphenol A solution (solvent is deionized water), stirring for 15min to reach adsorption equilibrium, adding 1mg of persulfate (PMS), reacting at room temperature, taking fixed Quantitative reaction solution (referring to be mixed with ZnFeMnO in the above-mentioned reaction 4 and the reaction solution of bisphenol A of PMS) to join mass concentration as 2% Na 2 SO 3 The reaction was terminated in solution and the BPA concentration was tested using HPLC. After reacting for 15 minutes, the catalyst was collected by centrifugation, washed with deionized water, and then the above steps were repeated. A total of 5 cycles of testing were performed, and the reaction time of each cycle was 15 minutes. The material collected aft...

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Abstract

The invention relates to the technical field of water treatment, in particular to a spinel type ZnFeMnO4 nano material and a preparation method and application thereof. The preparation method of the spinel type ZnFeMnO4 nano material comprises the following steps: A) stirring and mixing zinc acetylacetonate, ferric acetylacetonate, manganese acetylacetonate and an ethylene glycol solution containing polyvinylpyrrolidone to obtain a mixed solution; B) enabling the mixed solution to make reaction at the temperature of 185-190 DEG C; and C) calcining a solid product after the reaction to obtain the spinel type ZnFeMnO4 nano material. In the spinel type ZnFeMnO4 nano material, the unique occupation mode of each element enhances the electron interaction between Fe / Mn, enhances the conductivity of the material and the binding capacity of the material and peroxymonosulfate (PMS), and obviously improves the catalytic activity and selectivity, thereby effectively degrading organic pollutants in water.

Description

technical field [0001] The invention relates to the technical field of water treatment, in particular to a spinel type ZnFeMnO 4 Nanomaterials, their preparation methods and applications. Background technique [0002] The Fenton-like advanced oxidation technology based on persulfate has been widely used in the treatment of various organic wastewater and water environment restoration. This type of technology often uses metal ions or metal oxide catalysts to activate PMS (peroxymonosulfate) to generate sulfate radicals (SO 4 ·- ),Hydroxyl radicals( · OH), singlet oxygen ( 1 o 2 ) or PMS oxidation intermediates (PMS*) and other active species, so as to achieve the oxidative degradation of pollutants in water. Among all kinds of heterogeneous catalysts, spinel-type transition metal oxides are considered to be a kind of advanced oxidation catalytic materials with great development potential because of their economical, high-efficiency, stable structure and many other advant...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/889C02F1/72C01G49/00C01G49/02B82Y30/00B82Y40/00C02F101/30C02F101/34C02F101/36C02F101/38C02F103/16
CPCB01J23/8892B01J23/005C02F1/725C02F1/722C01G49/0063C01G49/0072C01G49/009C02F2101/30C02F2101/345C02F2101/36C02F2101/38C02F2101/40C02F2305/08C02F2305/02C02F2103/007C02F2103/16B01J35/23
Inventor 李文卫郭智妍司洋柳后起王帆
Owner UNIV OF SCI & TECH OF CHINA
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