CN111796013B - Zeolite imidazolate framework/metal oxide/molybdenum sulfide composite material - Google Patents

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

Zeolite Imidazolate Framework/Metal Oxide/Molybdenum Sulfide Composite

technical field

The invention belongs to the technical field of nanomaterials and electrochemical sensing, in particular to a graded zeolite imidazolate framework structure (ZIFs)/metal oxide/molybdenum sulfide composite material and its preparation method and application.

Background technique

With the rapid development of sensing technology, electrochemical biosensors have the advantages of high sensitivity, easy operation, and low cost compared with traditional large-scale detection equipment, and have broad application prospects in fields including medical diagnosis. The combination of two or more nanomaterials forms a three-dimensional composite material with a multi-level layered structure, which not only combines the advantages of each structural unit, but also gives the composite material new properties due to the synergistic enhancement effect between different components. Thus, the performance of the electrochemical biosensor is improved.

Two-dimensional molybdenum sulfide (MoS ₂ ) thin-layer materials, as a typical representative of transition metal chalcogenides, have the advantages of large specific surface area, good biocompatibility, and adjustable band gap; electrochemical devices based on two-dimensional layered molybdenum sulfide Sensors have great application potential in electrochemical biosensing due to their special electrochemical properties, abundant edge catalytic active sites, and good biocompatibility. By functionally modifying materials such as metal oxides on the surface of thin-layer molybdenum sulfide materials, the aggregation of layered molybdenum sulfide is avoided, the electrocatalytic area is effectively increased, and the direct electron transport ability with target analytes is improved. However, it is still difficult to solve the selective capture and high-sensitivity detection of analytes in electrochemical biosensors simply by functionalizing metal oxides on the surface of thin-layer molybdenum sulfide materials. Zeolitic imidazolate framework materials (ZIFs) are a class of porous crystalline materials with zeolite topology formed by the coordination of transition metals such as zinc or cobalt and imidazolate. Zeolitic imidazolate framework materials have the characteristics of high specific surface area, controllable pore and pore structure, high thermal and chemical stability, and have shown great potential in the selective capture and enrichment of biomolecules. Based on the above three nano-elements to construct composite nano-sensitive materials, it is expected to improve the signal transmission and signal amplification efficiency of the biosensing interface, thereby effectively improving the detection ability of the sensor.

Contents of the invention

In order to solve the problems of the prior art, the purpose of the present invention is to overcome the deficiencies in the prior art, to provide a zeolite imidazolate framework structure/metal oxide/molybdenum sulfide composite material, its preparation and application, the composite material of the present invention is based on a layer Molybdenum sulfide material is used as the substrate, metal oxides are grown on the surface, and zeolite imidazolate framework materials are grown on the surface of the metal oxides. Layered molybdenum sulfide has many physical and chemical properties such as adjustable band gap structure, large specific surface area, high electrocatalytic activity, good biocompatibility, and easy functionalization; relying on the support of metal oxides, the two-dimensional molybdenum sulfide interlayer Form a new active space and provide a transport channel for small biological molecules; increase the effective contact area with the molecule to be tested and accelerate the electron transfer and material transfer rate on the electrode surface; Selective immobilization to achieve highly sensitive and specific detection of the antigen or antibody to be tested.

In order to achieve the above invention creation purpose, the present invention adopts the following technical solutions:

A zeolite imidazolate framework structure/transition metal oxide/molybdenum sulfide composite material, based on a layered molybdenum sulfide material, first grows a transition metal oxide on the surface of the molybdenum sulfide material, and then grows a zeolite on the surface of the transition metal oxide The imidazolate framework material (ZIFs) forms a composite material structure; the mass ratio of the layered molybdenum sulfide, transition metal oxide and zeolite imidazolate framework structure is: 5:5:1˜400:20:1.

The above-mentioned metal oxides are preferably zinc oxide nanocolumn arrays, zinc oxide nanocrystals, tricobalt tetroxide nanocolumn arrays or tricobalt tetroxide nanocrystals.

The above-mentioned zeolite imidazolate framework material (ZIFs) is preferably ZIF-8, ZIF-67 or ZIF-90.

A kind of preparation method of zeolite imidazolate framework structure/transition metal oxide/molybdenum sulfide composite material of the present invention, the steps are as follows:

a. Uniformly disperse layered molybdenum sulfide in absolute ethanol to obtain a dispersion solution with a layered molybdenum sulfide concentration of 0.1-1 mg/mL; apply the dispersion solution evenly on the surface of a silicon wafer and wait for it to dry to form a sulfide solution Molybdenum film layer;

b. be that concentration is the dehydrated alcohol solution of the transition metal salt of 1～20mM coating on the molybdenum sulfide film layer that is combined on the obtained silicon chip of step a, dry, obtain the molybdenum sulfide film layer and transition metal material film layer that combine successively Silicon wafer; then calcined at 200-500°C for 10-50 minutes, took out the silicon wafer and cooled it naturally to obtain a silicon wafer combined with a transition metal oxide/molybdenum sulfide composite material;

c. Prepare a mixed solution containing metal salt, amide, alkali source and water, the metal salt adopts metal nitrate or metal chloride, the amide adopts urea or polyetherimide, and the alkali source adopts hexamethylene tetramine or ammonium fluoride, the silicon chip obtained in step b is placed above the mixed solution, sealed and reacted at a temperature of 60-95°C for 2-12 hours;

After taking out the silicon chip, wash it with absolute ethanol and deionized water respectively, and obtain the transition metal oxide/molybdenum sulfide composite material after drying; the molar concentration of the metal salt in the solution is 10-50mM, and the molar concentration of the alkali source is 10-50mM, the molar concentration of amide is 1-30mM; the molar ratio of the metal salt, alkali source and amide is 2:2:1-10:10:1;

d. Place the zeolite imidazolate skeleton structure ligand in an airtight container, and hang the silicon chip obtained in step c above the zeolite imidazolate skeleton structure ligand solution, and react at 100-200° C. for 0.2-8 hours after sealing; then The sample is taken out and placed in a vacuum drying oven at 100-200°C for 5min-12h, and cooled to room temperature to obtain a zeolite imidazolate framework structure/transition metal oxide/molybdenum sulfide composite material.

As a preferred technical solution of the present invention, in the step d, configure a 20-80 mM zeolite imidazolate skeleton structure ligand/N,N-dimethylformamide solution, and place the silicon wafer obtained in step c above the solution , sealed and reacted at a temperature of 40-120°C for 0.5-8h; then the silicon chip was taken out and cooled to room temperature, washed with absolute ethanol and deionized water, and dried to obtain the zeolite imidazolate skeleton structure/transition metal oxide Molybdenum/molybdenum sulfide composites.

An electrochemical immunobiological sensor adopts the zeolite imidazolate framework structure/transition metal oxide/molybdenum sulfide composite material of the present invention, and the sensor is deposited with the zeolite imidazolate framework structure/on the surface of the working electrode of the electrochemical sensing chip. Transition metal oxide/molybdenum sulfide composites to form composite electrodes.

A preparation method of the electrochemical immune biosensor of the present invention, the steps are as follows: the zeolite imidazolate framework structure/metal oxide/molybdenum sulfide composite material is dispersed in absolute ethanol and Nafion solution, i.e. perfluorosulfonic acid polymer In the solution, the volume ratio of V _ethanol : V _Nafion is 12:1~2:1, and it is prepared into a solution with a concentration of 1~50mg/mL, and it is ultrasonically treated for 15-45min to obtain a uniformly dispersed ink, and the ink is deposited on the electrochemical sensor After the surface of the working electrode of the chip is dried at room temperature, an electrochemical immunological biosensor based on the zeolite imidazolate framework structure/metal oxide/molybdenum sulfide composite material is obtained.

An application of the electrochemical immune biosensor of the present invention, the electrochemical immune biosensor is used in detecting antigens or antibodies.

As a preferred technical solution of the present invention, the prepared electrochemical sensor chip is soaked in the recognition antibody or antigen solution, and reacted at 4°C for 8-18 hours. The taken out sensor chip was rinsed with phosphate buffer solution, then put into blocking buffer (Blocking Buffer) with a volume fraction of 10%, and incubated at a constant temperature of 37°C for 40-80min. After taking out the sensor chip, wash it with phosphate buffer solution to remove the residual blocking buffer, soak it in the antigen or antibody solution to be tested, and incubate at 37°C for 40-80min at a constant temperature before testing. The above antibody solution, blocking buffer solution and antigen solution are all prepared from phosphate buffer solution; the pH value of the above phosphate buffer solution is 6.8-7.4.

Compared with the prior art, the present invention has the following obvious outstanding substantive features and significant advantages:

1. The graded zeolite imidazolate framework structure (ZIFs)/metal oxide/molybdenum sulfide composite material of the present invention is based on layered molybdenum sulfide material, adopts hydrothermal method to grow metal oxide on the layered molybdenum sulfide material surface, and then passes Growth of zeolite imidazolate framework materials on the surface of metal oxides by gas-phase or liquid-phase methods;

2. The layered molybdenum sulfide of the present invention has many physical and chemical properties such as adjustable bandgap structure, large specific surface area, high electrocatalytic activity, good biocompatibility, and easy functionalization; relying on the support of metal oxides in two-dimensional A new active space is formed between molybdenum sulfide layers, which provides a transport channel for small biological molecules; the composite material composed of layered molybdenum sulfide and metal oxide increases the effective contact area with the analyte molecule and accelerates the electron transfer on the electrode surface and material transmission rate; and then use zeolite imidazolate framework material to selectively immobilize antibodies or antigens to achieve highly sensitive and specific detection of the analyte; the invention has high detection sensitivity, simple operation, short response time, and low cost. low merit;

3. The method of the present invention is simple and easy to implement, low in cost, and suitable for popularization and use.

Description of drawings

Figure 1 shows the morphology and structure characterization results of ZIF-90/ZnO/MoS ₂ composites. Where a is the SEM image of ZIF-90/ZnO/MoS ₂ at low magnification; b is the SEM image of ZIF-90/ZnO/MoS ₂ at high magnification; c is the TEM image of ZIF-90/ZnO/MoS ₂ at low magnification Figure; d is the TEM image of ZIF-90/ZnO/MoS ₂ at high magnification.

Fig. 2 is the detection result of different concentrations of human IgG (immunoglobulin G, IgG) by the electrochemical sensor chip modified by ZIF-90/ZnO/MoS ₂ composite material. Wherein a is the DPV test curve of human IgG in the concentration range of 10-100 μg/mL; b is the DPV test curve of human IgG in the concentration range of 0.001-1 μg/mL.

Figure 3 shows the detection results of different concentrations of CD-63 by the electrochemical sensor chip modified by ZIF-90/ZnO/MoS ₂ composites.

Detailed ways

Below in conjunction with specific implementation example, above-mentioned scheme is described further, and preferred embodiment of the present invention is described in detail as follows:

Embodiment one:

In this embodiment, a zeolite imidazolate framework structure/transition metal oxide/molybdenum sulfide composite material is based on a layered molybdenum sulfide material. First, a transition metal oxide is grown on the surface of the molybdenum sulfide material, and then the transition Zeolite imidazolate framework materials (ZIFs) were grown on the surface of metal oxides to form a composite structure.

In this embodiment, the preparation method of the zeolite imidazolate framework structure/transition metal oxide/molybdenum sulfide composite material, the steps are as follows:

a. Weigh 5 mg of pre-prepared layered MoS ₂ and add it to 25 mL of absolute ethanol. After ultrasonic treatment for 30 minutes, a uniformly dispersed MoS ₂ solution is obtained. Use a pipette gun to evenly deposit the dispersed solution on the surface of a clean silicon wafer, and After it dries, a molybdenum sulfide film layer is formed;

b. Prepare a zinc acetate absolute ethanol solution with a concentration of 5mM, use a pipette gun to evenly drop the solution on the surface of the molybdenum sulfide film layer, dry it naturally at room temperature, then transfer it to a tube furnace at 350°C for calcination for 20min, take it out and cool it naturally; The concentration is 200mL aqueous solution of 25mM zinc chloride hexahydrate and 25mM hexamethylenetetramine. After dissolving, pour the above solution into the reaction kettle, and place the calcined silicon wafer above the precursor solution, and seal it at 90 ℃ oven for 5 hours; after the reaction, the silicon chip was taken out and washed several times with deionized water and ethanol to obtain a silicon chip of ZnO/MoS ₂ composite material;

c. 0.5g imidazole- ₂ -formaldehyde (ICA) is put into a wide-mouth glass bottle with a volume of 100mL; then, the silicon chip loaded with ZnO/MoS2 composite material is suspended in the bottle; ℃ for 30 minutes; then the sample was transferred from the bottle into a vacuum oven at 150 ℃ for 10 minutes, and cooled to room temperature to obtain the ZIF-90/ZnO/MoS ₂ composite material.

The morphology and structural characterization results of the composite material in this example are shown in Figure 1. From Figure 1(a), it can be seen that a layer of ZnO nanowire arrays is uniformly grown on the surface of the two-dimensional layered molybdenum sulfide material, and in Figure 1(b), it can be seen that a layer of rough ZIF- 90 material; the transmission electron microscope characterization result of accompanying drawing 1 (c) and (d) further shows that the ZIF-90 material that thickness is about 10nm is evenly wrapped on the surface of ZnO nanowire; Above-mentioned result shows, adopts the present embodiment method to obtain ZIF _- 90/ZnO/MoS2 composites with multilayer hierarchical structure.

Disperse 2 mg of the above-prepared ZIF-90/ZnO/MoS ₂ composite material in 50 μL of absolute ethanol and 12.5 μL of Nafion solution (perfluorosulfonic acid polymer solution), ultrasonically treat for 30 min to obtain a uniformly dispersed ink, and deposit the ink on After the surface of the working electrode of the electrochemical sensor chip is dried at room temperature, the electrochemical sensor chip modified by the ZIF-90/ZnO/MoS ₂ composite material is obtained.

The prepared electrochemical sensor chip was soaked in the goat anti-human IgG antibody solution, and placed at 4°C for 12 hours to react. The taken out sensor chip was rinsed with PBS, put into blocking buffer (BlockingBuffer) with a volume fraction of 10%, and incubated at 37° C. for 1 hour. After taking out the sensor chip, wash it with PBS to remove the residual blocking buffer, put it into different concentrations of human IgG solution and incubate at 37°C for 1 hour. Pipette 10 μL of the fully reacted solution and place it on the surface of the working electrode of the sensor, and use differential pulse voltammetry to test the electrochemical response performance to human IgG within the potential range of 0-0.6V. The results are shown in Figure 2. Figure 2 (a) and (b) are the results measured in the concentration ranges of 1ng/mL-1μg/mL and 10-100μg/mL human IgG respectively. As can be seen from the figure, the electrochemical immunosensor based on the ZIF-90/ZnO/MoS ₂ composite material can reach a detection limit of 1 ng/mL for human IgG. And as the concentration of human IgG increased, the current response signal in the DPV curve gradually increased.

The preparation of the zeolite imidazolate framework material (ZIF-90)/ZnO/molybdenum sulfide composite material in this embodiment and its detection of different concentrations of human IgG (immunoglobulin G, IgG), the layered vulcanization of the composite material in this embodiment Molybdenum has many physical and chemical properties such as adjustable bandgap structure, large specific surface area, high electrocatalytic activity, good biocompatibility, and easy functionalization; relying on the support of metal oxides to form a new two-dimensional molybdenum sulfide layer The active space provides a transport channel for small biological molecules; the composite material composed of layered molybdenum sulfide and metal oxide increases the effective contact area with the analyte molecule and accelerates the electron transfer and material transfer rate on the electrode surface; and then utilizes The selective immobilization of antibodies or antigens by zeolite imidazolate framework materials enables highly sensitive and specific detection of analytes. The invention has the characteristics of high detection sensitivity, simple operation, short response time and low cost.

Embodiment two:

This embodiment is basically the same as Embodiment 1, especially in that:

In this example, the zeolite imidazolate framework material (ZIF-90)/ZnO/molybdenum sulfide composite material is used for the detection of exosome-associated antibody CD-63 (tetraspanner), and the specific steps are as follows:

The preparation method of the ZIF-90/ZnO/MoS ₂ composite modified electrochemical sensor chip and the CD-63 detection method are the same as in Example 1. The detection results of the electrochemical immunosensor based on the ZIF-90/ZnO/MoS ₂ composite material for different concentrations of CD-63 are shown in Figure 3. It can be seen from the figure that as the concentration of CD-63 gradually increases from 0.2 μg/mL to 2.0 μg/mL, the differential pulse voltammetry response of the ZIF-90/ZnO/MoS ₂ composite modified electrochemical sensor chip The signal increases accordingly. The above two specific implementation examples show that the ZIF-90/ZnO/MoS ₂ composite material prepared by the method of the present invention is made into an electrochemical immune sensor chip, which has a good response result to the test object.

In summary, zeolite imidazolate framework structure/metal oxide/molybdenum sulfide composites, their preparation and application. The composite material is based on layered molybdenum sulfide material, metal oxide is grown on the surface, and zeolite imidazolate skeleton structure material is grown on the metal oxide surface. Layered molybdenum sulfide has many physical and chemical properties such as adjustable band gap structure, large specific surface area, high electrocatalytic activity, good biocompatibility, and easy functionalization; relying on the support of metal oxides, the two-dimensional molybdenum sulfide interlayer Form a new active space and provide a transport channel for small biological molecules; increase the effective contact area with the molecule to be tested and accelerate the electron transfer and material transfer rate on the electrode surface; Selective immobilization to achieve highly sensitive and specific detection of the antigen or antibody to be tested.

The embodiment of the present invention has been described above in conjunction with the accompanying drawings, but the present invention is not limited to the above-mentioned embodiment, and various changes can also be made according to the purpose of the invention of the present invention. The changes, modifications, substitutions, combinations or simplifications should be equivalent replacement methods, as long as they meet the purpose of the present invention, as long as they do not deviate from the zeolite imidazolate framework structure/metal oxide/molybdenum sulfide composite material of the present invention, its preparation The technical principle and inventive concept of its application all belong to the protection scope of the present invention.

Claims (8)

1. A zeolite imidazolate framework structure/transition metal oxide/molybdenum sulfide composite material is characterized in that: with layered molybdenum sulfide material as substrate, at first transition metal oxide is grown on the surface of molybdenum sulfide material, and then on the transition A zeolite imidazolate framework material is grown on the surface of the metal oxide to form a composite material structure; the mass ratio of the layered molybdenum sulfide, transition metal oxide and zeolite imidazolate framework structure is: 5:5:1～400:20:1 ; The preparation steps of the zeolite imidazolate framework structure/transition metal oxide/molybdenum sulfide composite material are as follows: a. Uniformly disperse layered molybdenum sulfide in absolute ethanol to obtain a dispersion solution with a layered molybdenum sulfide concentration of 0.1-1 mg/mL; apply the dispersion solution evenly on the surface of a silicon wafer and wait for it to dry to form a sulfide solution Molybdenum film layer; b. be that concentration is the dehydrated alcohol solution of the transition metal salt of 1～20mM coating on the molybdenum sulfide film layer that is combined on the obtained silicon chip of step a, dry, obtain the molybdenum sulfide film layer and transition metal material film layer that combine successively Silicon wafers; then calcining at 200-500°C for 10-50 minutes, taking out the silicon wafers and cooling naturally to obtain silicon wafers combined with transition metal oxide/molybdenum sulfide composite materials; c. Prepare a mixed solution containing metal salt, amide, alkali source and water, the metal salt adopts metal nitrate or metal chloride, the amide adopts urea or polyetherimide, and the alkali source adopts hexamethylene tetramine or ammonium fluoride, the silicon chip obtained in step b is placed above the mixed solution, sealed and reacted at a temperature of 60-95°C for 2-12 hours; After taking out the silicon chip, wash it with absolute ethanol and deionized water respectively, and obtain the transition metal oxide/molybdenum sulfide composite material after drying; the molar concentration of the metal salt in the solution is 10-50mM, and the molar concentration of the alkali source is 10-50mM, the molar concentration of amide is 1-30mM; the molar ratio of the metal salt, alkali source and amide is 2:2:1-10:10:1; d. Place the zeolite imidazolate skeleton structure ligand in an airtight container, and hang the silicon chip obtained in step c above the zeolite imidazolate skeleton structure ligand solution, and react at 100-200° C. for 0.2-8 hours after sealing; then The sample is taken out and placed in a vacuum drying oven at 100-200°C for 5min-12h, and cooled to room temperature to obtain a zeolite imidazolate framework structure/transition metal oxide/molybdenum sulfide composite material. 2. according to the described zeolite imidazolate framework structure/transition metal oxide/molybdenum sulfide composite material of claim 1, it is characterized in that: described metal oxide is zinc oxide nanocolumn array, zinc oxide nanocrystal, tricobalt oxide nanocolumn array or Cobalt tetraoxide nanocrystals. 3. The zeolite imidazolate framework structure/transition metal oxide/molybdenum sulfide composite material according to claim 1, characterized in that: the zeolite imidazolate framework structure material is ZIF-8, ZIF-67 or ZIF-90. 4. a preparation method of zeolite imidazolate framework structure/transition metal oxide/molybdenum sulfide composite material described in any one of claims 1 to 3, is characterized in that, the steps are as follows: a. Uniformly disperse layered molybdenum sulfide in absolute ethanol to obtain a dispersion solution with a layered molybdenum sulfide concentration of 0.1-1 mg/mL; apply the dispersion solution evenly on the surface of a silicon wafer and wait for it to dry to form a sulfide solution Molybdenum film layer; b. be that concentration is the dehydrated alcohol solution of the transition metal salt of 1～20mM coating on the molybdenum sulfide film layer that is combined on the obtained silicon chip of step a, dry, obtain the molybdenum sulfide film layer and transition metal material film layer that combine successively Silicon wafer; then calcined at 200-500°C for 10-50 minutes, took out the silicon wafer and cooled it naturally to obtain a silicon wafer combined with a transition metal oxide/molybdenum sulfide composite material; c. Prepare a mixed solution containing metal salt, amide, alkali source and water, the metal salt adopts metal nitrate or metal chloride, the amide adopts urea or polyetherimide, and the alkali source adopts hexamethylene tetramine or ammonium fluoride, the silicon chip obtained in step b is placed above the mixed solution, sealed and reacted at a temperature of 60-95°C for 2-12 hours; After taking out the silicon chip, wash it with absolute ethanol and deionized water respectively, and obtain the transition metal oxide/molybdenum sulfide composite material after drying; the molar concentration of the metal salt in the solution is 10-50mM, and the molar concentration of the alkali source is 10-50mM, the molar concentration of amide is 1-30mM; the molar ratio of the metal salt, alkali source and amide is 2:2:1-10:10:1; d. Place the zeolite imidazolate skeleton structure ligand in an airtight container, and hang the silicon chip obtained in step c above the zeolite imidazolate skeleton structure ligand solution, and react at 100-200° C. for 0.2-8 hours after sealing; then The sample is taken out and placed in a vacuum drying oven at 100-200°C for 5min-12h, and cooled to room temperature to obtain a zeolite imidazolate framework structure/transition metal oxide/molybdenum sulfide composite material. 5. The preparation method according to claim 4, characterized in that: in the step d, a 20-80 mM zeolite imidazolate skeleton structure ligand/N,N-dimethylformamide solution is configured, and the Place the silicon chip above the solution, seal it and react at 40-120°C for 0.5-8 hours; then take out the silicon chip and cool it to room temperature, wash it with absolute ethanol and deionized water, and dry it to obtain zeolite imidazole Ester skeleton structure/transition metal oxide/molybdenum sulfide composite. 6. An electrochemical immune biosensor, adopting the zeolite imidazolate framework structure/transition metal oxide/molybdenum sulfide composite material according to any one of claims 1 to 3, characterized in that: the sensor is electrochemically The zeolite imidazolate framework structure/transition metal oxide/molybdenum sulfide composite material is deposited on the surface of the working electrode of the sensor chip to form a composite electrode. 7. a preparation method of the described electrochemical immune biosensor of claim 6, is characterized in that, step is as follows: described zeolite imidazolate framework structure/metal oxide/molybdenum sulfide composite material is dispersed in dehydrated alcohol and Nafion solution , that is, in the perfluorosulfonic acid polymer solution, the volume ratio V _ethanol :V _Nafion is 12:1~2:1, and the solution is prepared into a solution with a concentration of 1~50mg/mL, and the ultrasonic treatment is 15-45min to obtain a uniformly dispersed ink. The ink is deposited on the surface of the working electrode of the electrochemical sensor chip and dried at room temperature to obtain an electrochemical immunological biosensor based on the zeolite imidazolate framework structure/metal oxide/molybdenum sulfide composite material. 8. An application of the electrochemical immunological biosensor according to claim 6, characterized in that: the electrochemical immunological biosensor is used in the detection of antigens or antibodies.

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