Method for synthesizing nano-enzyme with peroxidase-like activity based on Prussian blue analogue

By calcining and pyrolyzing the copper-yl Prussian blue analog in a high-temperature inert gas, a copper-iron nanoparticle composite material with peroxidase-like activity was obtained, which solved the problem of insufficient research on the product performance of the Prussian blue analog after calcining and pyrolyzing in an inert gas, and achieved efficient nanoenzyme synthesis.

CN119793509APending Publication Date: 2025-04-11GUILIN UNIVERSITY OF TECHNOLOGY
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Patent Information

Application Number
CN202411895629.7
Authority / Receiving Office
CN · China
Patent Type
Applications(China)
Current Assignee / Owner
Filing Date
2024-12-22
Publication Date
2025-04-11

AI Technical Summary

Technical Problem

In the prior art, there are not much research on the product performance of Prussian blue analogs as precursors after calcination and pyrolysis in an inert gas, and it is difficult to obtain nanoenzymes with peroxidase-like activity.

Method used

The Prussian blue analogue formed by copper ions and ferrocyanone ions is used as the precursor, and calcination and pyrolysis is performed in an inert gas at high temperature to obtain a composite material of copper-iron nanoparticles dispersed in a nitrogen-doped or nitrogen-oxygen-doped carbon matrix.

Benefits of technology

The obtained composite material exhibited peroxidase-like activity, and the synthesis method is easy to operate and simple to process.

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Abstract

The invention discloses a method for synthesizing a nano enzyme with peroxidase-like activity based on a Prussian blue analogue. The Prussian blue analogues (PBAs) are cyanide coordination polymer materials formed by non-ferrous metal ions and ferrous cyanide ions, have a unique three-dimensional open metal frame structure and a high specific surface area, and are widely applied to the fields of electro-catalysis, photocatalysis and the like. On the other hand, the Prussian blue analogue is used as a precursor, and the performance of a product obtained after calcination pyrolysis in inert gas is studied rarely. The invention discloses a synthesis method of a nano-enzyme with peroxidase-like activity, which comprises the following steps: by taking a Prussian blue analogue formed by copper ions and ferrous cyanide ions as a precursor, calcining and pyrolyzing the Prussian blue analogue in an inert gas atmosphere at high temperature to obtain the nano-enzyme with peroxidase-like activity. The method has the advantages of simple operation, simple procedure and the like.
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Description

Technical Field

[0001] The present invention relates to the field of Prussian blue analogs and nanozyme synthesis, and in particular to a method for synthesizing nanozymes with peroxidase-like activity based on Prussian blue analogs. Background Art

[0002] Prussian blue analogs (Prussian Blue Analogs, PBAs) are a cyanide coordination polymer material formed by non-ferrous metal ions and ferrocyanide ions, with a unique three-dimensional open metal framework structure and high specific surface area, and are widely used in the fields of electrocatalysis, photocatalysis, etc. On the other hand, Prussian blue analogs also belong to metal organic framework materials. As a precursor, the product synthesized by calcination and pyrolysis in an inert gas such as argon or nitrogen, or air has a large specific surface area, good thermal stability and chemical stability, and unique catalytic performance. In fact, there are few cases where Prussian blue analogs are used as precursors to study the performance of the products after calcination and pyrolysis in an inert gas. The present invention discloses a method for synthesizing a nanozyme having peroxidase-like activity by calcining and pyrolyzing a Prussian blue analog formed by copper ions and ferrocyanide ions as a precursor. The method has the advantages of simple operation and simple procedures. Summary of the invention

[0003] The present invention introduces a Prussian blue analog formed by copper ions and ferrocyanide ions, that is, a copper-based Prussian blue analog, as a precursor, and calcines and pyrolyzes it at high temperature in an inert gas to obtain copper-iron nanoparticles, which are dispersed in a nitrogen-doped or nitrogen-oxygen-doped carbon matrix generated during the calcination and pyrolysis process. The obtained composite material is the nanozyme with peroxidase-like activity described in the present invention. The synthesis method has the advantages of easy operation and simple procedures.

[0004] Furthermore, the synthesis method and related processes described in this patent refer to a method for synthesizing a nanozyme having peroxidase-like activity by calcining and pyrolyzing a copper-based Prussian blue analogue as a precursor in an inert gas at a high temperature;

[0005] Furthermore, the nanozyme is a composite nanomaterial composed of copper-iron nanoparticles dispersed in a nitrogen-doped or nitrogen-oxygen-doped carbon matrix generated during the calcination and pyrolysis process described in this patent;

[0006] Furthermore, the Prussian blue analogue described in this patent refers to a Prussian blue analogue formed by copper ions and ferrocyanide ions, i.e., a copper-based Prussian blue analogue;

[0007] Furthermore, the calcination and pyrolysis temperature of the copper-based Prussian blue analog in the synthesis process described in this patent refers to 300 degrees Celsius or higher;

[0008] Furthermore, the inert gas required in the synthesis process described in this patent 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

[0009] Figure 1. Using copper-based Prussian blue analog (Cu-PBA) as a precursor, it was calcined and pyrolyzed at high temperature in an inert gas to obtain copper iron (CuFe) nanoparticles dispersed in a nitrogen (N)-doped or nitrogen oxide (N, O)-doped carbon (C) matrix generated during the calcination and pyrolysis process, namely CuFe@NOC. Verification and comparison of the peroxidase-like activity of CuFe@NOC and Cu-PBA: Hydrogen peroxide oxidized 3,3',5,5'-tetramethylbenzidine (TMB) under the catalysis of CuFe@NOC or Cu-PBA. The oxidized TMB has a characteristic absorption peak at 652 nm. It can be seen that the peroxidase-like activity of CuFe@NOC is much higher than that of its precursor Cu-PBA. Working buffer: pH 3.5, 0.2 M HAc-NaAc. [CuFe@NOC] = [Cu-PBA]: 30 μg / mL. [TMB]: 0.1 mM; [H2O2]: 0.1 mM. Incubation temperature: 25 o C. Duration: 2 min. DETAILED DESCRIPTION

[0010] The following is a detailed description of an example of the synthesis method of the present invention in conjunction with the accompanying drawings.

[0011] Synthesis example:

[0012] 0.3633 g of copper acetate and 0.53 g of sodium citrate dihydrate were dissolved in 40 mL of water, referred to as solution A, and 0.3380 g of potassium ferrocyanide trihydrate was dissolved in 30 mL of water, referred to as solution B. Solution B was slowly added to solution A under magnetic stirring (700 rpm / min), and stirring was continued for 20 minutes. The mixed solution was transferred to a 100 mL polytetrafluoroethylene-lined high-temperature reactor and reacted at 120°C for 24 hours. The synthesized copper-based Prussian blue analog (Cu-PBA) was washed with ethanol and centrifuged three times (10,000 g, 5 minutes), and then dried at 60°C for 12 hours. Under a nitrogen atmosphere, Cu-PBA was pyrolyzed and calcined at 800°C for 2 hours to obtain a black powder, which is the nanozyme (CuFe@NOC) with peroxidase-like activity synthesized based on the copper-based Prussian blue analog described in this patent.

Claims

1. A method for synthesizing nanozymes with peroxidase-like activity based on Prussian blue analogs, characterized in that: A Prussian blue analogue formed by copper ions and ferrocyanide ions, i.e., a copper-based Prussian blue analogue, is introduced as a precursor, which is calcined and pyrolyzed in an inert gas at a high temperature to obtain copper-iron nanoparticles. These copper-iron nanoparticles are dispersed in a nitrogen-doped or nitrogen-oxygen-doped carbon matrix generated during the calcination and pyrolysis process. The resulting composite material is the nanozyme with peroxidase-like activity described in the present invention.

2. The method according to claim 1, characterized in that The method and related processes refer to a method for synthesizing a nanozyme having peroxidase-like activity by calcining and pyrolyzing a copper-based Prussian blue analogue as a precursor at high temperature in an inert gas.

3. The method according to claim 1, characterized in that The nanozyme is a composite nanomaterial composed of copper-iron nanoparticles dispersed in a nitrogen-doped or nitrogen-oxygen-doped carbon matrix generated during the calcination and pyrolysis process described in this patent.

4. The method according to claim 1, characterized in that The Prussian blue analogue refers to a Prussian blue analogue formed by copper ions and ferrocyanide ions, that is, a copper-based Prussian blue analogue.

5. The method according to claim 1, characterized in that The calcination and pyrolysis temperature of the copper-based Prussian blue analog during the synthesis process is 300 degrees Celsius or higher.

6. The method according to claim 1, characterized in that The inert gas required in the synthesis process refers to pure nitrogen, pure argon or other pure inert gases, which contain no or a small amount of residual oxygen.