CN-121975137-A - Copper-doped metal covalent organic framework material and preparation method and application thereof

Abstract

The invention belongs to the technical field of metal organic frame materials, and relates to a copper-doped metal covalent organic frame material, a preparation method and application thereof. The preparation method comprises the following steps of taking Cu (NO 3 ) 2 •3H 2 O, 2-amino terephthalic acid and tetrabutyl titanate) as raw materials, and synthesizing to obtain Cu doped NH 2 -MIL-125, namely a copper doped metal covalent organic framework material by a solvothermal one-step method; when the gallic acid is identified through photoelectrochemistry, the method has high selectivity and anti-interference capability on the gallic acid, improves the accuracy of gallic acid detection, and provides a new mode for gallic acid detection.

Inventors

• FAN YAN
• ZHANG MINGJIN
• BI TAO

Assignees

• 青海师范大学

Dates

Publication Date

20260505

Application Date

20260209

Claims (9)

1. 1. A method for preparing a copper-doped metal-covalent organic framework material, which is characterized by comprising the following steps: Cu (NO 3 ) 2 •3H 2 O, 2-amino terephthalic acid and tetrabutyl titanate) are used as raw materials, and Cu doped NH 2 -MIL-125, namely a copper doped metal covalent organic framework material, is synthesized through a solvothermal one-step method.
2. 2. The method of preparing a copper-doped metallic covalent organic framework material according to claim 1, characterized in that the molar ratio of Cu (NO 3 ) 2 •3H 2 O, 2-amino terephthalic acid and tetrabutyl titanate) is (0.03-0.075): 6.0:1.5.
3. 3. The method for preparing a copper-doped metal-covalent organic framework material according to claim 1, wherein the solvent used in the solvothermal one-step method is a mixed solution composed of N, N-dimethylformamide and methanol.
4. 4. The method for preparing the copper-doped metal-covalent organic framework material according to claim 1, wherein the solvothermal one-step synthesis condition is that the temperature is 150 ℃ plus or minus 20 ℃ and the time is 12-24 hours.
5. 5. The method of preparing a copper-doped metal-covalent organic framework material according to claim 1, wherein the forbidden bandwidth of the copper-doped metal-covalent organic framework material is at least 2.60eV.
6. 6. A copper-doped metal-covalent organic framework material, characterized in that it is obtained by a preparation process according to any one of claims 1 to 5.
7. 7. The use of the copper-doped metal-covalent organic framework material of claim 6 as photoelectrochemical sensing electrode in gallic acid detection.
8. 8. The application of claim 7, wherein the application is specifically that copper-doped metal covalent organic framework material is dispersed in a dispersing agent to form suspension, the suspension is uniformly dripped on the surface of an FTO substrate, a photoelectrochemical sensing electrode is obtained after drying, and the content of gallic acid is detected by utilizing the photoelectrochemical sensing electrode and combining a transient photocurrent method ‌.
9. 9. The use according to claim 8, wherein the dispersant is water, N-dimethylformamide, ethanol or methanol.

Description

Copper-doped metal covalent organic framework material and preparation method and application thereof Technical Field The invention belongs to the technical field of metal organic frame materials, and relates to a copper-doped metal covalent organic frame material, a preparation method and application thereof. Background Food additives play a key role in the modern food industry, wherein phenolic antioxidants play a critical role in preventing oxidative spoilage of foods and in extending the shelf life of foods. Gallic acid (GALLIC ACID GA) is widely used as a natural polyphenol compound in foods such as tea, grapes, apples and the like, has various physiological activities such as natural antioxidation, anti-inflammatory and anticancer, and meanwhile, gallic acid is one of key indexes for evaluating the total antioxidants of the foods. Along with the continuous improvement of food quality and safety requirements of people, the rapid and accurate detection requirements of gallic acid are increasingly improved. The presently disclosed gallic acid (GALLIC ACID GA) detection techniques are high performance liquid chromatography (CN 102759584A), fluorescence sensing and electrochemical sensing. Although detection of gallic acid can be achieved, the inherent limitations of High Performance Liquid Chromatography (HPLC), fluorescence sensing and electrochemical sensing are manifested in: high Performance Liquid Chromatography (HPLC), while advantageous in terms of separation efficiency and reproducibility, has high equipment costs, need for operator expertise, and cumbersome sample pretreatment, limiting its application requirements for rapid detection and timeliness in the field; the fluorescence sensing technology has the advantages that although the sensitivity is high and the response is quick, the fluorescence sensing technology is easily influenced by problems such as autofluorescence interference, photobleaching effect, scattering, fluorescence quenching caused by complex matrixes and the like, meanwhile, gallic acid exists in food, the detection matrixes are complex, the background interference is obvious, and the accuracy and the quantitative performance of a detection result are reduced; the electrochemical sensing technology has the advantages of low cost, portability and easiness in miniaturization, but biological pollution caused by nonspecific adsorption is easy to occur on the surface of an electrode, so that the long-term stability and reproducibility of the sensor are affected, and in addition, the co-response and slow redox reaction kinetics of an electroactive interferent can also cause poor selectivity and insufficient anti-interference capability. In view of the shortcomings of the existing methods for detecting gallic acid, a new mode for detecting gallic acid needs to be developed. Photoelectrochemical (Photoelectrochemical, PEC) sensing technology is an emerging detection technology, combines the advantages of optics and electrochemistry, and improves selectivity, anti-interference capability and accuracy by spatially separating photoexcitation from charge recognition/conversion, and the photoexcitation-electric signal detection mode enables extremely low noise floor. However, the photoelectrochemical detection of gallic acid belongs to the technical blank at present, and secondly, the sensing performance of the PEC sensing technology is closely related to photoelectrode materials, and the performance (light absorption capacity, charge transfer capacity and carrier separation efficiency) of the photoelectrode materials determines the performance of the PEC sensor. Therefore, the development of a novel photoelectrode material for photoelectrochemical detection of gallic acid is an important subject in the current research and development. Disclosure of Invention Aiming at the technical problems of reduced accuracy, poor selectivity and insufficient anti-interference capability in the existing detection of gallic acid, the invention provides a copper-doped metal covalent organic framework material and a preparation method and application thereof. The invention takes Cu (NO 3)2•3H2 O, 2-amino terephthalic acid and tetrabutyl titanate) as raw materials, synthesizes Cu doped NH 2 -MIL-125 by adopting an in-situ solvothermal method, thereby obtaining a copper doped metal covalent organic framework material, can promote the separation of photo-generated electron-hole pairs, improve the photoelectric conversion efficiency, has high selectivity and anti-interference capability on gallic acid when the gallic acid is identified by photoelectrochemistry, improves the detection accuracy of the gallic acid, and provides a new mode for the detection of the gallic acid. In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: A method for preparing a copper-doped metal-covalent organic framework material, comprising the following steps: Cu (NO 3)2•3H2 O, 2-amino t