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CN-122007409-A - Preparation and application of core-shell MOFs-derived Fe/Ni carbon-based material

CN122007409ACN 122007409 ACN122007409 ACN 122007409ACN-122007409-A

Abstract

The invention relates to a Fe/Ni carbon-based material derived from core-shell MOFs, which is prepared by synthesizing iron-based MOF-MIL-101 (Fe) by a hydrothermal method, taking MIL-101 (Fe) as a core MOF, guiding by PVP, inducing and growing Ni-MOF outside the core-shell MOF as a shell, and synthesizing a novel Fe/Ni carbon-based material derived from the core-shell MOFs through pyrolysis. The invention also relates to a preparation method and application of the electrochemical sensor for neurotransmitter detection, wherein the prepared core-shell MOFs-derived Fe/Ni carbon-based material is fixed on a carbon paper electrode, so that the electrochemical sensor is prepared and applied to neurotransmitter detection. The core-shell MOFs-derived Fe/Ni carbon-based material has unique sensing property, and the obtained electrochemical sensor system has the characteristics of high sensitivity, wide detection range, low detection limit, good stability and the like.

Inventors

  • ZHOU YANLI
  • HUANG ZIHAN
  • DONG HUI
  • XU MAOTIAN

Assignees

  • 商丘师范学院

Dates

Publication Date
20260512
Application Date
20241111

Claims (10)

  1. 1. The Fe/Ni carbon-based material derived from the core-shell MOFs is characterized in that the Fe/Ni carbon-based material is obtained by pyrolysis of an iron-nickel MOF precursor, wherein an iron-core layer and a nickel-coating layer are arranged in the iron-nickel MOF precursor, the iron-core layer is of an iron-containing MOF structure, and the nickel-coating layer is of a nickel-containing MOF structure which is combined with the iron-core layer through in-situ reaction.
  2. 2. The core-shell MOFs-derived Fe/Ni carbon-based material according to claim 1, wherein the iron-nickel MOF precursor is prepared by: s1, preparing MIL-101 (Fe) by reacting trivalent ferric salt and terephthalic acid (H 2 BDC); S2, activating MIL-101 (Fe) prepared in the step S1 by polyvinylpyrrolidone (PVP), and then adding nickel salt and H 2 BDC for reaction to obtain the iron-nickel MOF precursor.
  3. 3. The core-shell MOFs-derived Fe/Ni carbon-based material of claim 2 wherein in step S1, the reaction temperature is 100-120 ℃, the reaction time is 20-25 hours, and the solvent is N, N-Dimethylformamide (DMF).
  4. 4. The core-shell MOFs-derived Fe/Ni carbon-based material of claim 2 wherein in step S2, the activation reaction is performed in a solvent having a mass ratio of DMF, water and ethanol of 15:1:1 for 5-10 hours.
  5. 5. The core-shell MOFs-derived Fe/Ni carbon-based material according to claim 2, wherein in the step S2, PVP is added in an amount which is 3-6 times that of MIL-101 (Fe) in the activation step, and the activation time is 5-24 hours.
  6. 6. The core-shell MOFs-derived Fe/Ni carbon-based material according to claim 1, wherein the pyrolysis temperature is 700-900 ℃, the pyrolysis time is 1-3 hours, and the heating rate is 5-10 ℃ per minute.
  7. 7. The core-shell MOFs-derived Fe/Ni carbon-based material according to claim 1, wherein the particle size of the core-shell MOFs-derived Fe/Ni carbon-based material is 600-1500 nm.
  8. 8. A method for preparing an electrochemical sensor for neurotransmitter detection by using the core-shell MOFs-derived Fe/Ni carbon-based material prepared in claim 1 is characterized by comprising the following steps of taking a Carbon Paper (CP) electrode as a base electrode, treating the base electrode with acetone, ethanol and water, coating the core-shell MOFs-derived Fe/Ni carbon-based material on the treated CP electrode, and drying the treated CP electrode to obtain the electrochemical sensor for neurotransmitter detection.
  9. 9. Use of an electrochemical sensor for neurotransmitter detection prepared according to claim 8, for neurotransmitter detection.
  10. 10. Use of an electrochemical sensor for neurotransmitter detection according to claim 9, characterized in that in a three-electrode system, the electrochemical sensor modified with core-shell MOFs-derived Fe/Ni carbon-based materials is used as working electrode, and a platinum electrode and an Ag/AgCl electrode are used as counter electrode and reference electrode, respectively, for quantitative determination of neurotransmitter by differential pulse voltammetry.

Description

Preparation and application of core-shell MOFs-derived Fe/Ni carbon-based material Technical Field The invention belongs to the field of electrochemical sensors, and particularly relates to a core-shell MOFs-derived Fe/Ni carbon-based material for neurotransmitter detection, a preparation method of an electrochemical sensor and application of the electrochemical sensor. Background Neurotransmitters (Neurotransmitter, NTs) are endogenous molecules of chemical messengers involved in the regulation of neurotransmission between neurons and a range of physiological functions, wherein Dopamine (DA) and serotonin (5-HT) are important neurotransmitters that regulate a variety of physiological and behavioral processes, and imbalance of DA is associated with physiological and psychological disorders, while 5-HT can regulate emotional, sleep patterns, appetite, body temperature and hormonal activities. Deregulation of DA and 5-HT levels is associated with many neurological disorders such as Parkinson's disease, schizophrenia and depression, and the realization of mechanisms by which the monitoring of these two neurotransmitters contributes to an in-depth understanding of animal behavior. Various methods of analyzing NTs such as chromatography, fluorescence, chemiluminescence, and capillary electrophoresis have been reported. The electrochemical sensing method has the advantages of simple operation, low use cost, high response speed and the like, but the bare electrode has the problems of low sensitivity, poor selectivity and the like, and often cannot completely meet the requirements of practical application. Since DA and 5-HT are typically present at ultra-low levels in biological fluids, new materials need to be developed to build new electrochemical sensors for high sensitivity and selectivity detection of DA and 5-HT. Currently, conductive elements comprising carbon materials, conductive polymers, conductive Metal Organic Framework (MOFs) materials, or metal nanoparticles are often used to improve the selectivity, sensitivity, and accuracy of electrochemical sensors. The MOFs are crystalline porous materials with periodic network structures, which are formed by connecting inorganic metal centers and bridged organic ligands through self-assembly, are different from inorganic porous materials and common organic complexes, and have the rigidity of inorganic materials and the flexibility characteristics of organic materials, so that the MOFs have great development potential in the field of electrochemical sensors. Unfortunately, although MOFs can be used alone as electrode modifications, there are problems of poor stability, weak anti-interference ability, low sensitivity, etc., and it is difficult to meet the requirements of trace DA and 5-HT assays in complex samples. Disclosure of Invention The first technical problem to be solved by the invention is to prepare a core-shell MOFs-derived Fe/Ni carbon-based material, which is used as a porous carbon material, partially reserves an octahedral carbon skeleton, disperses two nano particles of Fe 3O4 and Ni inside and outside, is more beneficial to electron transmission, and can effectively improve conductivity. The second technical problem to be solved by the invention is to provide a preparation method of an electrochemical sensor for neurotransmitter detection, the method adopts a core-shell MOFs-derived Fe/Ni carbon-based material modified electrode, and Fe 3O4 nano particles and Ni nano particles have roles in improving target catalytic effect, and the synergistic catalytic effect enables the sensor to have excellent performance and high sensitivity. The third technical problem to be solved by the invention is the application of the electrochemical sensor for neurotransmitter detection, and the electrochemical sensor modified by the Fe/Ni carbon-based material derived from the core-shell MOFs is used for preparing a system for detecting neurotransmitter, and the system comprises a working electrode, a counter electrode, a reference electrode and an electrolytic cell, and is used for quantitatively determining the neurotransmitter and has the advantages of low detection limit, strong anti-interference capability, high stability and the like. To solve the first technical problem, the invention provides a core-shell MOFs-derived Fe/Ni carbon-based material, which is obtained by pyrolysis of an iron-nickel MOF precursor, wherein the iron-nickel MOF precursor is provided with an iron-core layer and a nickel-coating layer, the iron-core layer is of an iron-containing MOF structure, and the nickel-coating layer is of a nickel-containing MOF structure combined with the iron-core layer through in-situ reaction. Preferably, the iron-nickel MOF precursor is prepared by the following method: s1, preparing MIL-101 (Fe) by reacting trivalent ferric salt and terephthalic acid (H 2 BDC); S2, activating MIL-101 (Fe) prepared in the step S1 by polyvinylpyrrolidone (PVP), and then add