CN111796013B - Zeolite imidazolate framework/metal oxide/molybdenum sulfide composite material - Google Patents
Zeolite imidazolate framework/metal oxide/molybdenum sulfide composite material Download PDFInfo
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- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
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Abstract
The invention discloses a zeolite imidazole ester framework structure/metal oxide/molybdenum sulfide composite material, and a preparation method and application thereof. The composite material takes a layered molybdenum sulfide material as a substrate, metal oxide grows on the surface of the substrate, and then a zeolite imidazole ester framework structure material grows on the surface of the metal oxide. The layered molybdenum sulfide has a plurality of physicochemical properties such as adjustable band gap structure, large specific surface area, high electrocatalytic activity, good biocompatibility, easy functionalization and the like; a new active space is formed between two-dimensional molybdenum sulfide layers by means of the supporting action of metal oxide, and a transport channel is provided for biological small molecules; the effective contact area with the molecules to be detected is increased, and the electron transfer and substance transmission rate on the surface of the electrode are accelerated; the zeolite imidazole ester framework structure material selectively fixes the recognition antibody or the antigen, and realizes the high-sensitivity and specific detection of the antigen or the antibody to be detected.
Description
Technical Field
The invention belongs to the technical field of nano materials and electrochemical sensing, and particularly relates to a hierarchical Zeolite Imidazolate Framework (ZIFs)/metal oxide/molybdenum sulfide composite material as well as a preparation method and application thereof.
Background
With the rapid development of sensing technology, compared with the traditional large-scale detection equipment, the electrochemical biosensor has the advantages of high sensitivity, simplicity and convenience in operation, low cost and the like, and has wide application prospects in the fields of medical diagnosis and the like. The three-dimensional composite material with the multilevel layered structure is formed by combining two or more than two nano materials, not only combines the advantages of each structural element, but also endows the composite material with new characteristics by the synergistic enhancement effect among different components, thereby improving the performance of the electrochemical biosensor.
Two-dimensional molybdenum sulfide (MoS) 2 ) The thin-layer material is taken as a typical representative of the transition metal chalcogenide and has the advantages of large specific surface area, good biocompatibility, adjustable band gap and the like; the electrochemical sensor constructed based on the two-dimensional layered molybdenum sulfide has special electrochemical performance, abundant edge catalytic active sites and good biocompatibility, so that the electrochemical sensor has huge application potential in the aspect of electrochemical biosensing. By functionally modifying materials such as metal oxides and the like on the surface of the thin-layer molybdenum sulfide material, the aggregation of the layered molybdenum sulfide is avoided, the electrocatalytic area is effectively increased, and the direct electron transport capability with a target analyte is improved. However, the functional modification of the metal oxide on the surface of the thin molybdenum sulfide material is difficult to solve the problems of selective capture and high-sensitivity detection of the substance to be detected by the electrochemical biosensor. Zeolite imidazolate framework materials (ZIFs) are porous crystalline materials with zeolite topological structures formed by coordination of transition metals such as zinc or cobalt and imidazolate. The zeolite imidazole ester framework material has the characteristics of high specific surface area, controllable pore and pore channel structures, high thermal stability and chemical stability, and has great potential in the selective capture and enrichment of biomolecules. The composite structure nano sensitive material is constructed based on the three nano elements, and the signal transmission and signal amplification efficiency of a biosensing interface is expected to be improved, so that the detection capability of the sensor is effectively improved.
Disclosure of Invention
In order to solve the problems of the prior art, the invention aims to overcome the defects in the prior art and provide a zeolite imidazolate framework/metal oxide/molybdenum sulfide composite material, and preparation and application thereof. The layered molybdenum sulfide has a plurality of physicochemical properties such as adjustable band gap structure, large specific surface area, high electrocatalytic activity, good biocompatibility, easy functionalization and the like; a new active space is formed between two-dimensional molybdenum sulfide layers by means of the supporting action of metal oxides, and a transportation channel is provided for biological small molecules; the effective contact area with the molecules to be detected is increased, and the electron transfer and substance transmission rate of the electrode surface is accelerated; the zeolite imidazole ester framework structure material selectively fixes the recognition antibody or the antigen, and realizes the high-sensitivity and specificity detection of the antigen or the antibody to be detected.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
a zeolite imidazole ester framework structure/transition metal oxide/molybdenum sulfide composite material takes a layered molybdenum sulfide material as a substrate, firstly, a transition metal oxide grows on the surface of the molybdenum sulfide material, and then a zeolite imidazole ester framework structure material (ZIFs) grows on the surface of the transition metal oxide to form a composite material structure; the mass ratio of the layered molybdenum sulfide, the transition metal oxide and the zeolite imidazolate framework structure is as follows: 5.
The metal oxide preferably adopts a zinc oxide nano-pillar array, a zinc oxide nano-crystal, a cobaltosic oxide nano-pillar array or a cobaltosic oxide nano-crystal.
The above zeolite imidazolate framework material (ZIFs) preferably adopts ZIF-8, ZIF-67 or ZIF-90.
The invention relates to a preparation method of a zeolite imidazolate framework structure/transition metal oxide/molybdenum sulfide composite material, which comprises the following steps:
a. uniformly dispersing the layered molybdenum sulfide in absolute ethyl alcohol to obtain a dispersion liquid with the concentration of the layered molybdenum sulfide of 0.1-1 mg/mL; uniformly coating the dispersion solution on the surface of a silicon wafer, and drying to form a molybdenum sulfide film layer;
b. b, coating an absolute ethyl alcohol solution of transition metal salt with the concentration of 1-20 mM on the molybdenum sulfide film layer combined on the silicon wafer obtained in the step a, and drying to obtain the silicon wafer sequentially combining the molybdenum sulfide film layer and the transition metal material film layer; then calcining for 10-50 min at the temperature of 200-500 ℃, taking out the silicon wafer, and naturally cooling to obtain the silicon wafer combined with the transition metal oxide/molybdenum sulfide composite material;
c. preparing a mixed solution containing metal salt, amide, an alkali source and water, wherein the metal salt adopts metal nitrate or metal chloride, the amide adopts urea or polyetherimide, the alkali source adopts hexamethylenetetramine or ammonium fluoride, the silicon wafer obtained in the step b is placed above the mixed solution, and the silicon wafer is sealed and reacts for 2 to 12 hours at the temperature of between 60 and 95 ℃;
taking out the silicon wafer, respectively washing the silicon wafer by absolute ethyl alcohol and deionized water, and drying to obtain a transition metal oxide/molybdenum sulfide composite material; the molar concentration of the metal salt in the solution is 10-50 mM, the molar concentration of the alkali source is 10-50 mM, and the molar concentration of the amide is 1-30 mM; the molar ratio of the metal salt, the alkali source and the amide is 2:2:1 to 10:10:1;
d. placing the zeolite imidazole ester framework structure ligand in a closed container, hanging the silicon wafer obtained in the step c above the solution of the zeolite imidazole ester framework structure ligand, sealing, and reacting for 0.2-8 h at 100-200 ℃; and then taking out a sample, placing the sample in a vacuum drying oven at 100-200 ℃ for treatment for 5 min-12 h, and cooling to room temperature to obtain the zeolite imidazole ester framework structure/transition metal oxide/molybdenum sulfide composite material.
As a preferable technical scheme of the invention, in the step d, 20-80 mM zeolite imidazole ester framework ligand/N, N-dimethylformamide solution is prepared, the silicon chip obtained in the step c is placed above the solution, and the reaction is carried out for 0.5-8 h at the temperature of 40-120 ℃ after sealing; and then taking out the silicon wafer, cooling to room temperature, respectively washing with absolute ethyl alcohol and deionized water, and drying to obtain the zeolite imidazole ester framework structure/transition metal oxide/molybdenum sulfide composite material.
The invention discloses an electrochemical immunosensor, which adopts a zeolite imidazole ester framework structure/transition metal oxide/molybdenum sulfide composite material, wherein the zeolite imidazole ester framework structure/transition metal oxide/molybdenum sulfide composite material is deposited on the surface of a working electrode of an electrochemical sensing chip to form a composite electrode.
The invention relates to a preparation method of an electrochemical immune biosensor, which comprises the following steps: combining said zeolitic imidazolate frameworkThe metal oxide/molybdenum sulfide composite material is dispersed in absolute ethyl alcohol and Nafion solution, namely perfluorosulfonic acid polymer solution, and the volume ratio is V Ethanol ：V Nafion Preparing a solution with the concentration of 1-50 mg/mL for 12-2:1, performing ultrasonic treatment for 15-45min to obtain uniformly dispersed ink, depositing the ink on the surface of a working electrode of an electrochemical sensing chip, and drying at room temperature to obtain the electrochemical immunosensor based on the zeolite imidazole ester framework structure/metal oxide/molybdenum sulfide composite material.
The invention relates to an application of an electrochemical immune biosensor, which is applied to detecting antigen or antibody.
As a preferred technical scheme of the invention, the prepared electrochemical sensing chip is soaked in a recognition antibody or antigen solution and is placed at 4 ℃ for reaction for 8-18 hours. And (3) washing the taken-out sensing chip by using a phosphoric acid Buffer solution, then putting the sensing chip into a Blocking Buffer solution (Blocking Buffer) with the volume fraction of 10%, and incubating at the constant temperature of 37 ℃ for 40-80min. And (3) taking out the sensor chip, washing the sensor chip by using a phosphoric acid buffer solution to remove residual blocking buffer solution, soaking the sensor chip in an antigen or antibody solution to be tested, and incubating the sensor chip in a constant temperature of 37 ℃ for 40-80min to test. The antibody solution, the closed buffer solution and the antigen solution are all prepared from phosphoric acid buffer solution; the pH value of the phosphoric acid buffer solution is 6.8-7.4.
Compared with the prior art, the invention has the following obvious substantive characteristics and remarkable advantages:
1. the invention relates to a graded zeolite imidazole ester Framework Structure (ZIFs)/metal oxide/molybdenum sulfide composite material, which takes a layered molybdenum sulfide material as a substrate, adopts a hydrothermal method to grow metal oxide on the surface of the layered molybdenum sulfide material, and then adopts a gas phase method or a liquid phase method to grow a zeolite imidazole ester framework structure material on the surface of the metal oxide;
2. the layered molybdenum sulfide has a plurality of physicochemical properties such as adjustable band gap structure, large specific surface area, high electrocatalytic activity, good biocompatibility, easy functionalization and the like; a new active space is formed between two-dimensional molybdenum sulfide layers by means of the supporting action of metal oxides, and a transportation channel is provided for biological small molecules; the composite material composed of the layered molybdenum sulfide and the metal oxide improves the effective contact area with molecules to be detected and accelerates the electron transfer and substance transmission rate of the electrode surface; then, the zeolite imidazole ester framework material is used for selectively fixing the antibody or the antigen, so that the high-sensitivity and high-specificity detection on the object to be detected is realized; the invention has the advantages of high detection sensitivity, simple operation, short response time and lower cost;
3. the method is simple and easy to implement, low in cost and suitable for popularization and application.
Drawings
FIG. 1 is ZIF-90/ZnO/MoS 2 And (5) characterizing the morphology and the structure of the composite material. Wherein a is ZIF-90/ZnO/MoS under low multiple 2 SEM picture of (g); b is ZIF-90/ZnO/MoS under high multiple 2 SEM picture of (1); c is ZIF-90/ZnO/MoS under low multiple 2 A TEM image of (B); d is ZIF-90/ZnO/MoS under high multiple 2 A TEM image of (a).
FIG. 2 is ZIF-90/ZnO/MoS 2 And (3) detecting results of the electrochemical sensing chip modified by the composite material on human IgG (immunoglobulin G, igG) with different concentrations. Wherein a is a DPV test curve of human IgG with the concentration range of 10-100 mu g/mL; b is the DPV test curve for human IgG at a concentration range of 0.001-1. Mu.g/mL.
FIG. 3 is ZIF-90/ZnO/MoS 2 And (3) detecting the results of the electrochemical sensing chip modified by the composite material on different concentrations of CD-63.
Detailed Description
The above-described scheme is further illustrated below with reference to specific embodiments, which are detailed below:
the first embodiment is as follows:
in this embodiment, a zeolite imidazolate framework/transition metal oxide/molybdenum sulfide composite material uses a layered molybdenum sulfide material as a substrate, and first a transition metal oxide grows on a surface of the molybdenum sulfide material, and then a Zeolite Imidazolate Framework (ZIFs) material grows on the surface of the transition metal oxide to form a composite material structure.
In this example, the preparation method of the zeolite imidazolate framework/transition metal oxide/molybdenum sulfide composite material includes the following steps:
a. 5mg of the layered MoS prepared beforehand are weighed 2 Adding into 25mL of absolute ethyl alcohol, and carrying out ultrasonic treatment for 30min to obtain uniformly dispersed MoS 2 Uniformly depositing the dispersion solution on the surface of a clean silicon wafer by using a liquid-transferring gun, and drying the silicon wafer to form a molybdenum sulfide film layer;
b. preparing 5mM zinc acetate absolute ethyl alcohol solution, uniformly dripping the solution on the surface of a molybdenum sulfide film layer by using a liquid transfer gun, naturally drying at room temperature, transferring into a 350 ℃ tube furnace, calcining for 20min, taking out and naturally cooling; preparing 200mL of water solution with the concentration of 25mM zinc chloride hexahydrate and 25mM hexamethylenetetramine, pouring the solution into a reaction kettle after dissolution, placing the calcined silicon wafer above the precursor solution, sealing, and reacting in an oven at 90 ℃ for 5 hours; taking out the silicon wafer after the reaction is finished, and cleaning the silicon wafer for a plurality of times by using deionized water and ethanol to obtain ZnO/MoS 2 A silicon wafer of composite material;
c. placing 0.5g of imidazole-2-carbaldehyde (ICA) in a wide-mouth glass bottle having a volume of 100 mL; then, the ZnO/MoS load is added 2 Suspending the silicon chip of the composite material in a bottle; sealing the glass bottle and reacting for 30min at 150 ℃; transferring the sample from the bottle into a vacuum drying oven at 150 deg.C for 10min, cooling to room temperature to obtain ZIF-90/ZnO/MoS 2 A composite material.
The morphology and structure characterization results of the composite material of this example are shown in FIG. 1. From the attached figure 1 (a), a layer of ZnO nanowire array is uniformly grown on the surface of a two-dimensional layered molybdenum sulfide material, and from the attached figure 1 (b), a layer of rough ZIF-90 material is grown on the surface of a ZnO nanowire; the transmission electron microscopy characterization results of FIGS. 1 (c) and (d) further show that the surface of the ZnO nanowire is uniformly wrapped with a ZIF-90 material with a thickness of about 10 nm; the results show that the method of the embodiment can be used for obtaining ZIF-90/ZnO/MoS with a multi-layer hierarchical structure 2 A composite material.
2mg of the above prepared ZIF-90/ZnO/MoS 2 The composite material was dispersed in 50. Mu.L of absolute ethanol and 12.5. Mu.L of a solution of a perfluorosulfonic acid-type polymer, and subjected to ultrasonic treatmentUniformly dispersed ink is obtained within 30min, the ink is deposited on the surface of a working electrode of an electrochemical sensing chip and dried at room temperature, and ZIF-90/ZnO/MoS is obtained 2 An electrochemical sensing chip modified by composite materials.
The prepared electrochemical sensing chip is soaked in a goat anti-human IgG antibody solution and is placed at 4 ℃ for reaction for 12 hours. The removed sensor chip was washed with PBS and then placed in 10% volume fraction Blocking Buffer (Blocking Buffer), and incubated at 37 ℃ for 1 hour. After the sensor chip was removed, the blocking buffer remained was removed by washing with PBS, and the sensor chip was incubated in human IgG solutions of different concentrations at a constant temperature of 37 ℃ for 1 hour. 10 mu L of the fully reacted solution is transferred and placed on the surface of a working electrode of the sensor, and the electrochemical response performance of human IgG is tested in a potential interval of 0-0.6V by adopting a differential pulse voltammetry method, and the result is shown in figure 2. FIGS. 2 (a) and (b) are the results obtained for human IgG concentrations ranging from 1ng/mL to 1. Mu.g/mL and from 10 to 100. Mu.g/mL, respectively. As can be seen from the figure, the ZIF-90/ZnO/MoS-based alloy is based on 2 The detection limit of the electrochemical immunosensor of the composite material to human IgG can reach 1ng/mL. And the current response signal in the DPV curve gradually increased with increasing human IgG concentration.
The preparation of the zeolite imidazolate framework material (ZIF-90)/ZnO/molybdenum sulfide composite material and the detection of human IgG (immunoglobulin G, igG) with different concentrations, the layered molybdenum sulfide of the composite material of the embodiment has a plurality of physicochemical properties such as an adjustable band gap structure, large specific surface area, high electrocatalytic activity, good biocompatibility, easy functionalization and the like; a new active space is formed between two-dimensional molybdenum sulfide layers by means of the supporting action of metal oxide, and a transport channel is provided for biological small molecules; the composite material composed of the layered molybdenum sulfide and the metal oxide improves the effective contact area with the molecules to be detected and accelerates the electron transfer and substance transmission rate of the electrode surface; and then the high-sensitivity and high-specificity detection of the object to be detected is realized by utilizing the selective fixation of the zeolite imidazole ester framework material on the antibody or the antigen. The invention has the characteristics of high detection sensitivity, simple operation, short response time and lower cost.
The second embodiment:
this embodiment is substantially the same as the first embodiment, and is characterized in that:
in this embodiment, the detection of the exosome-associated antibody CD-63 (four-transmembrane transporter) by the zeolite imidazolate framework material (ZIF-90)/ZnO/molybdenum sulfide composite material specifically comprises the following operation steps:
ZIF-90/ZnO/MoS 2 the preparation method and the CD-63 detection method of the electrochemical sensing chip modified by the composite material are the same as those of the first embodiment. Based on ZIF-90/ZnO/MoS 2 The detection results of the electrochemical immunosensor made of the composite material on CD-63 with different concentrations are shown in the attached figure 3. As can be seen from the graph, ZIF-90/ZnO/MoS was gradually increased from 0.2. Mu.g/mL to 2.0. Mu.g/mL as the concentration of CD-63 was increased 2 The differential pulse volt-ampere response signal of the electrochemical sensing chip modified by the composite material is enhanced. The two specific embodiments show that the ZIF-90/ZnO/MoS prepared by the method of the invention 2 The electrochemical immunosensor chip made of the composite material has a good response result to an object to be detected.
In conclusion, the zeolite imidazolate framework structure/metal oxide/molybdenum sulfide composite material, the preparation and the application thereof are provided. The composite material takes a layered molybdenum sulfide material as a substrate, metal oxide grows on the surface of the substrate, and then a zeolite imidazole ester framework structure material grows on the surface of the metal oxide. The layered molybdenum sulfide has a plurality of physicochemical properties such as adjustable band gap structure, large specific surface area, high electrocatalytic activity, good biocompatibility, easy functionalization and the like; a new active space is formed between two-dimensional molybdenum sulfide layers by means of the supporting action of metal oxide, and a transport channel is provided for biological small molecules; the effective contact area with the molecules to be detected is increased, and the electron transfer and substance transmission rate on the surface of the electrode are accelerated; the zeolite imidazole ester framework structure material selectively fixes the recognition antibody or the antigen, and realizes the high-sensitivity and specific detection of the antigen or the antibody to be detected.
While the embodiments of the present invention have been described with reference to the accompanying drawings, the present invention is not limited to the above embodiments, and various changes, modifications, substitutions, combinations or simplifications made according to the spirit and principle of the technical solution of the present invention should be made in equivalent replacement modes, so long as the objects of the present invention are met, and the technical principles and inventive concepts of the zeolite imidazolate framework/metal oxide/molybdenum sulfide composite material, the preparation and the application thereof are not deviated from the technical principles and inventive concepts of the present invention.
Claims (8)
1. A zeolite imidazolate framework structure/transition metal oxide/molybdenum sulfide composite material is characterized in that: taking a layered molybdenum sulfide material as a substrate, firstly growing a transition metal oxide on the surface of the molybdenum sulfide material, and then growing a zeolite imidazole ester framework structure material on the surface of the transition metal oxide to form a composite material structure; the mass ratio of the layered molybdenum sulfide to the transition metal oxide to the zeolite imidazolate framework structure is as follows: 5;
the preparation steps of the zeolite imidazole ester framework structure/transition metal oxide/molybdenum sulfide composite material are as follows:
a. uniformly dispersing the layered molybdenum sulfide in absolute ethyl alcohol to obtain a dispersion liquid with the concentration of the layered molybdenum sulfide of 0.1-1 mg/mL; uniformly coating the dispersion solution on the surface of a silicon wafer, and drying to form a molybdenum sulfide film layer;
b. b, coating an absolute ethyl alcohol solution of transition metal salt with the concentration of 1-20 mM on the molybdenum sulfide film layer combined on the silicon wafer obtained in the step a, and drying to obtain the silicon wafer sequentially combining the molybdenum sulfide film layer and the transition metal material film layer; then calcining for 10-50 min at the temperature of 200-500 ℃, taking out the silicon wafer, and naturally cooling to obtain the silicon wafer combined with the transition metal oxide/molybdenum sulfide composite material;
c. preparing a mixed solution containing metal salt, amide, an alkali source and water, wherein the metal salt adopts metal nitrate or metal chloride, the amide adopts urea or polyetherimide, the alkali source adopts hexamethylenetetramine or ammonium fluoride, the silicon wafer obtained in the step b is placed above the mixed solution, and the silicon wafer is sealed and reacts for 2 to 12 hours at the temperature of between 60 and 95 ℃;
taking out the silicon wafer, respectively washing the silicon wafer by absolute ethyl alcohol and deionized water, and drying to obtain a transition metal oxide/molybdenum sulfide composite material; the molar concentration of the metal salt in the solution is 10-50 mM, the molar concentration of the alkali source is 10-50 mM, and the molar concentration of the amide is 1-30 mM; the molar ratio of the metal salt, the alkali source and the amide is 2:2:1 to 10:10:1;
d. placing the zeolite imidazole ester framework structure ligand in a closed container, hanging the silicon wafer obtained in the step c above the solution of the zeolite imidazole ester framework structure ligand, sealing, and reacting for 0.2-8 h at 100-200 ℃; and then taking out a sample, placing the sample in a vacuum drying oven at 100-200 ℃ for treatment for 5 min-12 h, and cooling to room temperature to obtain the zeolite imidazole ester framework structure/transition metal oxide/molybdenum sulfide composite material.
2. A zeolitic imidazolate framework/transition metal oxide/molybdenum sulfide composite according to claim 1, characterized in that: the metal oxide is a zinc oxide nano-pillar array, a zinc oxide nano-crystal, a cobaltosic oxide nano-pillar array or a cobaltosic oxide nano-crystal.
3. A zeolitic imidazolate framework/transition metal oxide/molybdenum sulfide composite according to claim 1, characterized in that: the zeolite imidazolate framework material is ZIF-8, ZIF-67 or ZIF-90.
4. A method for preparing a zeolitic imidazolate framework/transition metal oxide/molybdenum sulfide composite according to any one of claims 1 to 3, characterized in that it comprises the following steps:
a. uniformly dispersing the layered molybdenum sulfide in absolute ethyl alcohol to obtain a dispersion liquid with the concentration of the layered molybdenum sulfide of 0.1-1 mg/mL; uniformly coating the dispersion solution on the surface of a silicon wafer, and drying to form a molybdenum sulfide film layer;
b. b, coating an absolute ethyl alcohol solution of transition metal salt with the concentration of 1-20 mM on the molybdenum sulfide film layer combined on the silicon wafer obtained in the step a, and drying to obtain the silicon wafer sequentially combining the molybdenum sulfide film layer and the transition metal material film layer; then calcining for 10-50 min at the temperature of 200-500 ℃, taking out the silicon wafer, and naturally cooling to obtain the silicon wafer combined with the transition metal oxide/molybdenum sulfide composite material;
c. preparing a mixed solution containing metal salt, amide, an alkali source and water, wherein the metal salt adopts metal nitrate or metal chloride, the amide adopts urea or polyetherimide, the alkali source adopts hexamethylenetetramine or ammonium fluoride, the silicon wafer obtained in the step b is placed above the mixed solution, and the silicon wafer is sealed and reacts for 2 to 12 hours at the temperature of between 60 and 95 ℃;
taking out the silicon wafer, respectively washing the silicon wafer by absolute ethyl alcohol and deionized water, and drying to obtain a transition metal oxide/molybdenum sulfide composite material; the molar concentration of the metal salt in the solution is 10-50 mM, the molar concentration of the alkali source is 10-50 mM, and the molar concentration of the amide is 1-30 mM; the molar ratio of the metal salt, the alkali source and the amide is 2:2:1 to 10:10:1;
d. placing the zeolite imidazole ester framework structure ligand in a closed container, hanging the silicon wafer obtained in the step c above the solution of the zeolite imidazole ester framework structure ligand, sealing, and reacting for 0.2-8 h at 100-200 ℃; and then taking out a sample, placing the sample in a vacuum drying oven at 100-200 ℃ for treatment for 5 min-12 h, and cooling to room temperature to obtain the zeolite imidazolate framework structure/transition metal oxide/molybdenum sulfide composite material.
5. The method according to claim 4, wherein: in the step d, preparing 20-80 mM zeolite imidazole ester framework structure ligand/N, N-dimethylformamide solution, placing the silicon chip obtained in the step c above the solution, sealing and reacting for 0.5-8 h at the temperature of 40-120 ℃; and then taking out the silicon wafer, cooling to room temperature, respectively washing with absolute ethyl alcohol and deionized water, and drying to obtain the zeolite imidazole ester framework structure/transition metal oxide/molybdenum sulfide composite material.
6. An electrochemical immunosensor comprising the zeolitic imidazolate framework/transition metal oxide/molybdenum sulfide composite according to any one of claims 1 to 3, wherein: the sensor is characterized in that the zeolite imidazole ester framework structure/transition metal oxide/molybdenum sulfide composite material is deposited on the surface of a working electrode of an electrochemical sensing chip to form a composite electrode.
7. A method for preparing the electrochemical immunosensor according to claim 6, comprising the steps of: dispersing the zeolite imidazole ester framework structure/metal oxide/molybdenum sulfide composite material in absolute ethyl alcohol and Nafion solution, namely perfluorosulfonic acid polymer solution, with the volume ratio of V Ethanol ：V Nafion The method comprises the following steps of preparing a solution with the concentration of 1-50 mg/mL from 1-2:1, carrying out ultrasonic treatment for 15-45min to obtain uniformly dispersed ink, depositing the ink on the surface of a working electrode of an electrochemical sensing chip, and drying at room temperature to obtain the electrochemical immunosensor based on the zeolite imidazolate framework structure/metal oxide/molybdenum sulfide composite material.
8. Use of the electrochemical immunobiosensor of claim 6, wherein: the electrochemical immune biosensor is applied to detecting antigen or antibody.
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