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CN-122006703-A - Manganese-doped MOF (metal oxide fiber) derived nano laccase and preparation method and application thereof

CN122006703ACN 122006703 ACN122006703 ACN 122006703ACN-122006703-A

Abstract

The invention discloses a manganese doped MOF (metal oxide fiber) derivative nano laccase and a preparation method and application thereof, and relates to the technical field of nano enzyme catalysis, wherein ZIF-8 synthesized by water phase is taken as a substrate, and is obtained by low-temperature calcination and derivative of a precursor in an oxygen atmosphere; the water phase synthesis is that the solvent is ultrapure water in the synthesis process, the ZIF-8 is a zeolite-like topological structure MOF material formed by self-assembly of Zn 2+ and 2-methylimidazole, and the ZIF-8 is derived by low-temperature calcination of a precursor in an oxygen atmosphere. According to the invention, the substrate material of ZIF-8 is prepared by taking ultrapure water as a solvent, manganese is introduced through metal impregnation, low-temperature calcination and acid washing treatment are utilized, ZIF is used as a sacrificial template for calcination and heat treatment to be converted into a porous carbon material, and the morphology and the pore structure of the ZIF are reserved and the ZIF has higher stability.

Inventors

  • Mu Jianshuai
  • HU YUE
  • LIU ZHIXUE
  • WANG FANJUN

Assignees

  • 天津师范大学
  • 天津塞纳酶科技有限公司

Dates

Publication Date
20260512
Application Date
20260409

Claims (9)

  1. 1. A manganese-doped MOF (metal oxide fiber) derivative nanometer laccase is characterized in that a ZIF-8 synthesized by an aqueous phase is used as a substrate, the ZIF-8 is obtained by low-temperature calcination of a precursor in an oxygen atmosphere, the aqueous phase synthesis is that a solvent is ultrapure water in a synthesis process, the ZIF-8 is a zeolite-like topological structure MOF material formed by self-assembly of Zn 2+ and 2-methylimidazole, and the ZIF-8 is obtained by low-temperature calcination of the precursor in the oxygen atmosphere.
  2. 2. The manganese-doped MOF-derived nano laccase according to claim 1, wherein the precursor is introduced with manganese element by a metal impregnation method, and raw materials used for metal impregnation are potassium permanganate and ZIF-8 with a mass ratio of 0-0.5.
  3. 3. The manganese-doped MOF-derived nano laccase according to claim 1, wherein the low-temperature calcination method uses a tube furnace, the atmosphere is air, the temperature is 200-300 ℃, the holding time is 1-3h, and the heating rate is 1-5 ℃ per minute.
  4. 4. The manganese-doped MOF-derived nano laccase according to claim 1, wherein the low temperature calcination temperature is 250 ℃, the retention time is 2h, and the temperature rise rate is 2 ℃.
  5. 5. The manganese-doped MOF-derived laccase according to claim 1, further comprising a pickling step, wherein the pickling is carried out at a temperature of 50-70 ℃ for 0.5-2 hours, and the acid is sulfuric acid.
  6. 6. The manganese doped MOF derivative nano laccase according to claim 5, wherein the pickling treatment is performed at a temperature of 60 ℃ for a pickling time of 1h.
  7. 7. The manganese-doped MOF-derived laccase nanoparticle according to claims 1-6 provides a method for preparing the manganese-doped MOF-derived laccase nanoparticle, comprising the steps of: Step one, synthesizing ZIF-8 by adopting a water phase synthesis method; Step two, introducing manganese element into ZIF-8 by a metal impregnation method to obtain a precursor; step three, calcining the precursor at a low temperature; And fourthly, carrying out acid washing treatment on the calcined material to obtain the manganese doped ZIF derivative nano enzyme.
  8. 8. The method for preparing the manganese-doped MOF-derived nano laccase according to claim 7, wherein the aqueous phase synthesis method is characterized in that zinc nitrate hexahydrate and 2-methylimidazole are added into ultrapure water and stirred, and the ZIF-8 is obtained by vacuum drying after centrifugation.
  9. 9. The method for preparing the manganese-doped MOF-derived nano laccase according to claim 7, wherein the metal impregnation method is characterized in that ZIF-8 is added into ultrapure water for stirring, potassium permanganate is added for stirring, and then the mixture is centrifuged and dried in vacuum to obtain a precursor.

Description

Manganese-doped MOF (metal oxide fiber) derived nano laccase and preparation method and application thereof Technical Field The invention mainly relates to the technical field of nano enzyme catalysis, in particular to manganese doped MOF derived nano laccase and a preparation method and application thereof. Background Laccase is an oxidation-reduction enzyme with wide substrate range and excellent catalytic efficiency, catalyzes molecular oxygen to oxidize various organic pollutants such as phenols, aromatic amines and the like, only generates water in the reaction, and has excellent green catalytic performance. However, the natural laccase has many defects in practical application, such as poor stability, high production cost, difficult recovery and the like. Compared with natural enzymes, the nano-enzyme has excellent structural stability and environmental condition tolerance, and plays an important role in the catalysis field as a substitute for biological enzymes. In various emerging nano-enzyme structure researches, the development and innovation of an artificial simulated enzyme system are promoted by the class enzyme based on the metal organic framework. MOFs class enzymes have precisely mimicked catalytic centers and highly dispersed catalytic sites compared to the native enzyme, which is also the main reason for the greatly improved substrate affinity and catalytic efficiency of mimicking enzymes compared to native enzymes. Besides, MOFs enzyme has the advantages of low cost, simple preparation, high stability and durability. The MOFs laccase is synthesized by a solvothermal method, high temperature, high pressure and expensive organic ligand are needed, the process is complex, the yield is low, the batch stability is poor, the cost of the post-treatment (solvent removal and activation) of the MOFs is high, and the requirement of industrialized mass production is difficult to meet. Moreover, although active, the affinity for the substrate is insufficient, resulting in a higher substrate concentration being required to function. Disclosure of Invention Based on the method, the zeolite imidazole ester skeleton-8 is synthesized by adopting a water phase synthesis method, and the manganese element is introduced into the ZIF-8 structure by taking potassium permanganate as a precursor. The manganese-doped ZIF-8 derivative is obtained through low-temperature air calcination. The synthesis condition is mild, and the method is green and pollution-free. The material has higher laccase-like activity, and provides a manganese-doped MOF derivative nano laccase as well as a preparation method and application thereof, so as to solve the technical problems in the background art. In order to achieve the above purpose, the present invention provides the following technical solutions: A manganese-doped MOF-derived nano laccase is prepared by taking ZIF-8 synthesized in an aqueous phase as a substrate and calcining the precursor at a low temperature in an oxygen atmosphere, wherein the aqueous phase synthesis is that a solvent is ultrapure water in the synthesis process, the ZIF-8 is a zeolite-like topological structure MOF material formed by self-assembling Zn 2+ and 2-methylimidazole, and the ZIF-8 is derived by calcining the precursor at a low temperature in the oxygen atmosphere. Preferably, the precursor is introduced with manganese element by a metal impregnation method, and the raw materials used for metal impregnation are potassium permanganate and ZIF-8 with a mass ratio of 0-0.5. Preferably, the low-temperature calcination method uses a tube furnace, the atmosphere is air, the temperature is 200-300 ℃, the holding time is 1-3h, and the temperature rising rate is 1-5 ℃ per minute. Preferably, the low-temperature calcination temperature is 250 ℃, the retention time is 2h, and the temperature rising rate is 2 ℃ per minute. Preferably, the method further comprises a pickling treatment step, wherein the temperature is 50-70 ℃, the pickling time is 0.5-2h, and the acid is sulfuric acid. Preferably, the temperature during the pickling treatment is 60 ℃, and the pickling time is 1h. The preparation method of the manganese doped MOF derivative nano laccase comprises the following steps: Step one, synthesizing ZIF-8 by adopting a water phase synthesis method; Step two, introducing manganese element into ZIF-8 by a metal impregnation method to obtain a precursor; step three, calcining the precursor at a low temperature; And fourthly, carrying out acid washing treatment on the calcined material to obtain the manganese doped ZIF derivative nano enzyme. Preferably, the aqueous phase synthesis method specifically comprises the steps of adding zinc nitrate hexahydrate and 2-methylimidazole into ultrapure water, stirring, centrifuging and vacuum drying to obtain ZIF-8. Preferably, the metal impregnation method specifically comprises the steps of adding ZIF-8 into ultrapure water, stirring, adding potassium permanganate, sti