Method for synthesizing nano-enzyme with ascorbic acid oxidase and catalase double-enzyme activity based on iron-doped zinc-based metal organic framework material
Nanozymes with ascorbic acid oxidase and catalase activity were synthesized through the high-temperature calcination method of iron-doped zinc-based metal-organic framework materials, which solved the problems of insufficient material activity and stability in the existing technology and achieved efficient catalytic effects.
Patent Information
- Application Number
- CN202510675877.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-23
- Publication Date
- 2025-10-10
AI Technical Summary
It is difficult to synthesize nanozyme materials with dual enzyme activities of ascorbic acid oxidase and catalase with existing technologies, and zinc-based metal-organic framework materials have the problem of nanoparticle aggregation during high-temperature calcination.
Iron-doped zinc-based metal-organic framework materials are used as precursors and calcined at high temperature in inert gas to synthesize iron-active nanoparticles dispersed in nitrogen-doped or nitrogen-oxygen-doped carbon matrices, forming nanozymes with dual enzyme activities of ascorbate oxidase and catalase.
The high-efficiency catalytic activity of ascorbic acid and hydrogen peroxide was achieved, the aggregation of nanoparticles was avoided, and the catalytic performance and stability of the material were improved.
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Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the field of doped zinc-based metal organic framework materials and nanoscale enzyme synthesis, in particular to a method for synthesizing a nanoscale enzyme with ascorbate oxidase and catalase dual enzyme activity based on iron-doped zinc-based metal organic framework materials. BACKGROUND
[0002] Zinc-based metal organic framework (MOF) material is a porous coordination polymer crystal formed by coordination of zinc ions and organic ligands. Metal organic framework material has rich active sites, large specific surface area, controllable structure, high porosity, and significant catalytic performance. Further, metal organic framework material as a precursor, in inert gas such as argon or nitrogen, or air, calcination pyrolysis synthesis of new porous materials, with large specific surface area, good thermal stability and chemical stability, and unique catalytic performance. On the other hand, the melting point and boiling point of zinc are relatively low, 420 o C and 900 o C, other metals doped zinc metal organic framework material as a precursor, in inert gas atmosphere and high temperature calcination, part or all of the reduced zinc occupies the site but will evaporate later, thereby avoiding the aggregation of doped metal particles during simultaneous calcination and reduction, and having good dispersibility and high unique catalytic activity. The present application discloses a method for synthesizing a unique nanoscale enzyme with ascorbate oxidase and catalase dual enzyme activity by calcining iron-doped zinc metal organic framework material as a precursor in an inert gas atmosphere at high temperature. SUMMARY
[0003] The present application introduces iron-doped zinc-based metal organic framework material as a precursor, calcination in inert gas at high temperature, to obtain single-atom, sub-nanometer to less than 100 nanometer iron active nanoparticles, which are dispersed in nitrogen-doped or nitrogen-oxygen-doped carbon matrix produced during calcination. The resulting composite material is a nanoscale enzyme with ascorbate oxidase and catalase dual enzyme activity.
[0004] Further, according to the method of claim 1, the iron-doped zinc-based metal organic framework material as a precursor is calcined in inert gas at high temperature, and the synthesis method with the nanoscale enzyme with ascorbate oxidase and catalase dual enzyme activity as the synthesis target is synthesized.
[0005] Furthermore, the method according to claim 1 is characterized in that the iron-doped zinc-based metal-organic framework material refers to a metal-organic framework material synthesized using divalent iron ions or trivalent iron ions mixed with divalent zinc ions as metal coordination centers, and its ligand is an organic compound containing two or more coordinating atoms, including but not limited to imidazoles, bipyridines and other organic compounds;
[0006] Furthermore, the method according to claim 1 is characterized in that the calcination temperature of the iron-doped zinc-based metal-organic framework material is 300 degrees Celsius or higher;
[0007] Furthermore, the method according to claim 1 is characterized in that the required inert gas refers to pure nitrogen, pure argon or other pure inert gases, which contain no or a small amount of residual oxygen. BRIEF DESCRIPTION OF THE DRAWINGS
[0008] Figure 1. (A) Transmission electron microscopy (TEM) image of pFe-20; (B) EDS distribution of iron (nanoparticles) in pFe-20 [partial view in the lower left corner of (A)].
[0009] Figure 2. Kinetic monitoring of ascorbic acid oxidation catalyzed by pFe-20. Comparative samples are nitrogen-doped or nitrogen-oxygen-doped carbon-based materials, prepared using undoped ZIF-8 as a precursor and calcined under the same conditions. Reaction temperature: 25°C; buffer: pH 5.0, 0.2 M sodium acetate; [AA]: 80 μM.
[0010] Figure 3. Kinetic monitoring of the catalytic decomposition of H₂O₂ by pFe-20. Comparative samples are nitrogen-doped or nitrogen-oxygen-doped carbon-based materials, prepared using undoped ZIF-8 as a precursor and calcined under the same conditions. Reaction temperature: 25°C; buffer: pH 5.0, 50 mM sodium phosphate; [H₂O₂]: 10 mM. DETAILED DESCRIPTION
[0011] The specific embodiments of the present invention are described in detail below with reference to the accompanying drawings.
[0012] Examples:
[0013] 32 mmol of aniline and 32 mmol of 2-methylimidazole were dissolved in 80 mL of H₂O, mixed and stirred vigorously at room temperature to obtain a homogeneous solution, designated Solution A. 8 mmol of Zn(NO₃)₂·6H₂O and 0.4 mmol of FeCl₂·4H₂O were dissolved in 80 mL of H₂O, designated Solution B, which was then added to Solution A. The resulting mixture (with a molar ratio of iron to zinc ions of 1:20) was stirred at room temperature for 4 hours. After the reaction was complete, the mixture was washed with water, collected by centrifugation, and dried to yield iron-doped ZIF-8. Finally, the resulting powder was pyrolyzed in a tube under a nitrogen atmosphere at a heating rate of 5°C / min from room temperature to 900°C and maintained at this temperature for 2 hours. This yielded iron-active nanoparticles (pFe-20) dispersed in a nitrogen- or nitrogen-oxygen-doped carbon matrix generated during the calcination process (the molar ratio of iron to zinc ions was 1:20 in the precursor synthesis described above). When the molar ratio of iron to zinc ions in the precursor synthesis was 1:10 or 1:40, the iron active nanoparticles dispersed in the nitrogen-doped or nitrogen-oxygen-doped carbon matrix obtained by similar calcination were called pFe-10 and pFe-40, respectively. Under the same conditions, undoped ZIF-8 was synthesized and calcined under the same conditions. The products were nitrogen-doped or nitrogen-oxygen-doped carbon matrix materials, which served as comparison samples. Taking pFe-20 as an example, its dual enzyme activity of ascorbate oxidase and catalase was determined, see Figure 2 and Figure 3 .
Claims
1. A method for synthesizing a nanozyme having dual enzymatic activities of ascorbate oxidase and catalase based on an iron-doped zinc-based metal-organic framework, characterized in that: The present invention introduces an iron-doped zinc-based metal-organic framework material as a precursor, and calcines it at high temperature in an inert gas to obtain iron-active nanoparticles ranging from single atoms, sub-nanometers to less than 100 nanometers. These iron-active nanoparticles are dispersed in the nitrogen-doped or nitrogen-oxygen-doped carbon matrix generated during the calcination process. The resulting composite material is a nanozyme with dual enzyme activities of ascorbic acid oxidase and catalase.
2. The method according to claim 1, characterized in that A synthesis method is provided in which an iron-doped zinc-based metal-organic framework material as a precursor is calcined at high temperature in an inert gas, and a nanozyme having dual enzyme activities of ascorbic acid oxidase and catalase is synthesized as the target.
3. The method according to claim 1, characterized in that Iron-doped zinc-based metal-organic framework materials refer to metal-organic framework materials synthesized using divalent iron ions or trivalent iron ions mixed with divalent zinc ions as metal coordination centers, and their ligands are organic compounds containing two or more coordinating atoms, including but not limited to imidazoles, bipyridines and other organic compounds.
4. The method according to claim 1, wherein The calcination temperature of the iron-doped zinc-based metal organic framework material is 300 degrees Celsius or higher.
5. The method according to claim 1, wherein The required inert gas refers to pure nitrogen, pure argon or other pure inert gases, which contain no or a small amount of residual oxygen.