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CN-122011415-A - Ce/Zr bimetal doped UiO-67 material for nitric oxide detection, method and application

CN122011415ACN 122011415 ACN122011415 ACN 122011415ACN-122011415-A

Abstract

The invention discloses a Ce/Zr bimetal doped UiO-67 material for detecting nitric oxide, a method and application thereof, and belongs to the technical field of functional materials and electrochemical sensing. The preparation method comprises the steps of dissolving 4,4' -biphenyl dicarboxylic acid in a polar solvent, ultrasonically dispersing, adding a mixed solution of cerium salt and zirconium salt, stirring to obtain a precursor solution, adding a carboxylic acid modifier into the precursor solution, then carrying out solvothermal reaction to obtain a reaction product, and carrying out post-treatment on the reaction product to obtain the Ce/Zr bimetal doped UiO-67 material for detecting nitric oxide. The method solves the problems of insufficient activity and poor stability of the traditional MOF material in electrochemical sensing.

Inventors

  • MA FEI
  • YAO SHIJUN
  • CHEN SHIMENG
  • YANG SHUHAN

Assignees

  • 西安交通大学

Dates

Publication Date
20260512
Application Date
20260224

Claims (10)

  1. 1. The preparation method of the Ce/Zr bimetal doped UiO-67 material for detecting nitric oxide is characterized by comprising the following steps of: dissolving 4,4' -biphenyl dicarboxylic acid in a polar solvent, performing ultrasonic dispersion, adding a mixed solution of cerium salt and zirconium salt, and stirring to obtain a precursor solution; adding a carboxylic acid modifier into the precursor solution, and then carrying out solvothermal reaction to obtain a reaction product; and (3) after post-treating the reaction product, obtaining the Ce/Zr bimetal doped UiO-67 material for detecting nitric oxide.
  2. 2. The method for preparing a Ce/Zr bimetal doped UiO-67 material for detecting nitric oxide according to claim 1, wherein said carboxylic acid modulating agent is glacial acetic acid; The polar solvent is N, N-dimethylformamide, the cerium salt is ceric ammonium nitrate, and the zirconium salt is zirconyl nitrate.
  3. 3. The preparation method of the Ce/Zr bimetal doped UiO-67 material for nitric oxide detection according to claim 1, wherein the mixed solution of cerium salt and zirconium salt is obtained by mixing cerium salt and zirconium salt in deionized water; In the mixed solution of cerium salt and zirconium salt, the molar ratio of cerium to zirconium is 1:4-4:1, and the concentration of the mixed solution of cerium salt and zirconium salt is 0.3-0.6M.
  4. 4. The preparation method of the Ce/Zr bimetal doped UiO-67 material for nitric oxide detection according to claim 1, wherein the dosage ratio of the 4,4' -biphenyl dicarboxylic acid to the polar solvent is 0.5-1 g:20-30 mL.
  5. 5. The preparation method of the Ce/Zr bimetal doped UiO-67 material for nitric oxide detection according to claim 1, wherein the dosage ratio of the mixed solution of 4,4' -biphenyl dicarboxylic acid and cerium salt to zirconium salt is 0.5-1 g/10-20 mL.
  6. 6. The preparation method of the Ce/Zr bimetal doped UiO-67 material for nitric oxide detection according to claim 1, wherein the dosage ratio of the precursor solution to the carboxylic acid modulating agent is 20-30 mL:1-2 mL.
  7. 7. The preparation method of the Ce/Zr bimetal doped UiO-67 material for nitric oxide detection according to claim 1, wherein the solvothermal reaction is carried out at a temperature of 80-120 ℃ for 15-30 min under an oil bath.
  8. 8. The method for preparing a Ce/Zr bimetal doped UiO-67 material for detecting nitric oxide according to claim 1, wherein said post-treatment comprises centrifugation, washing and vacuum drying treatments carried out in sequence; the washing is sequentially performed by using DMSO, DMF and absolute ethyl alcohol; the temperature of the vacuum drying is 65-75 ℃.
  9. 9. The Ce/Zr bimetal doped UiO-67 material for nitric oxide detection, which is characterized by being prepared by adopting any one of the preparation methods in claims 1-8, and being characterized in that the Ce/Zr bimetal doped UiO-67 material has a porous crystal structure.
  10. 10. The application of the Ce/Zr bimetal doped UiO-67 material nitric oxide electrochemical sensor for detecting nitric oxide as claimed in claim 9, wherein the detection limit of the sensor on nitric oxide is lower than 50 nM, the linear detection range is 280 nM-127 mu M, and the current response retention rate is more than 87% after continuous operation for four weeks.

Description

Ce/Zr bimetal doped UiO-67 material for nitric oxide detection, method and application Technical Field The invention belongs to the technical field of functional materials and electrochemical sensing, and particularly relates to a Ce/Zr bimetal doped UiO-67 material for nitric oxide detection, a method and application. Background Nitric Oxide (NO) is a vital gas signal molecule in organisms and is widely involved in and regulates various core physiological and pathological processes such as cardiovascular function, neurotransmission, immune response, apoptosis and the like. The concentration level of the polypeptide in a biological system (generally in the range of nanomoles to micromoles) is closely related to the occurrence, development and prognosis of a plurality of important diseases such as inflammation, septicemia, cardiovascular diseases, neurodegenerative diseases, cancers and the like. Therefore, development of detection technology capable of realizing real-time, high sensitivity, high selectivity and high stability on NO in complex biological environment has great scientific value and urgent clinical requirements for deep understanding of disease mechanism, discovery of early diagnosis markers and dynamic evaluation of therapeutic effect. Currently, detection of NO is mainly dependent on spectroscopic and electrochemical methods. Spectroscopy methods, such as chemiluminescence and fluorescent probe methods, generally have higher sensitivity, but often require complex sample pretreatment, rely on large precision instruments or introduce exogenous labeling molecules, are difficult to achieve true real-time, in-vivo, undisturbed detection, and are costly. In contrast, the electrochemical method is simple and convenient to operate, quick in response, easy to miniaturize and integrate, suitable for continuous monitoring, and is the most potential in-vivo NO detection method. The core is electrocatalytic material with the surface of the working electrode modified, and the material directly determines the performance of the sensor. Metal Organic Frameworks (MOFs) exhibit great potential in the field of electrochemical sensing due to their ultra-high specific surface area, adjustable pore structure and rich designable active sites. Among them, the UiO-67 series MOF is excellent in structural stability in aqueous and electrochemical environments, and is attracting attention. Attempts have been made to introduce Ce element having redox activity into MOF framework (e.g. Ce-UiO-67) and to use the catalytic activity of Ce 3+/Ce4+ pair to detect H 2O2 or gas molecules. In addition, there are studies and research to construct bimetallic MOFs aimed at enhancing specific catalytic properties through intermetallic synergistic effects. The single metal MOF represented by Ce-UiO-67 has single catalytic active site, limited adsorption capacity to polar NO molecules and generally poor conductivity, so that the sensitivity, response speed and stability of the sensor are difficult to meet the requirements of complex biological sample detection. The existing bimetallic MOF studies have focused on combining metals with similar catalytic activities or have failed to accurately design intermetallic functional division and synergy mechanisms. For the specific detection path of NO molecules, namely 'adsorption firstly and catalytic oxidation later', a directional material design strategy capable of simultaneously enhancing adsorption and accelerating electron transfer is lacking. Disclosure of Invention The invention aims to provide a Ce/Zr bimetal doped UiO-67 material for detecting nitric oxide, a method and application thereof, which are used for solving the technical problems of insufficient sensitivity, limited selectivity and poor long-term stability in the electrochemical detection of a biomarker molecule NO in the prior art. In order to achieve the above purpose, the invention is realized by adopting the following technical scheme: The invention discloses a preparation method of a Ce/Zr bimetal doped UiO-67 material for detecting nitric oxide, which comprises the following steps: dissolving 4,4' -biphenyl dicarboxylic acid in a polar solvent, performing ultrasonic dispersion, adding a mixed solution of cerium salt and zirconium salt, and stirring to obtain a precursor solution; adding a carboxylic acid modifier into the precursor solution, and then carrying out solvothermal reaction to obtain a reaction product; and (3) after post-treating the reaction product, obtaining the Ce/Zr bimetal doped UiO-67 material for detecting nitric oxide. Further, the carboxylic acid regulator is glacial acetic acid; The polar solvent is N, N-dimethylformamide, the cerium salt is ceric ammonium nitrate, and the zirconium salt is zirconyl nitrate. Further, the mixed solution of cerium salt and zirconium salt is obtained by mixing cerium salt and zirconium salt in deionized water; In the mixed solution of cerium salt and zirconium salt,