CN112886024B

CN112886024B - Preparation method of myrica cobalt nickel boron composite carbon material proton membrane fuel cell catalyst

Info

Publication number: CN112886024B
Application number: CN202110246709.XA
Authority: CN
Inventors: 肖高; 张梦瑶
Original assignee: Fuzhou University
Current assignee: Fuzhou University
Priority date: 2021-03-05
Filing date: 2021-03-05
Publication date: 2022-04-08
Anticipated expiration: 2041-03-05
Also published as: CN112886024A

Abstract

The invention relates to a preparation method of a myrica cobalt nickel boron composite carbon material proton membrane fuel cell catalyst, wherein a nano material active substance is a myrica cobalt nickel boron composite carbon material, which is called CoNi @ TA/B for short. The problems of the existing fuel cell catalyst are solved, the defects of the prior art, the problems of single precursor obstacle and synthesis cost of the existing fuel cell catalyst are overcome, and the defects of high cost, toxicity and the like of a Pt-based catalytic material are overcome; based on the unique structure of CoNi MOF, a metal organic framework nano composite material for a proton membrane fuel cell is developed, and the nano composite material has the advantages of high initial potential, half-slope potential, excellent limiting current, excellent stability, good methanol tolerance, strong methanol poisoning resistance and the like.

Description

Preparation method of myrica cobalt nickel boron composite carbon material proton membrane fuel cell catalyst

Technical Field

The invention discloses a myrica cobalt nickel boron composite carbon material proton membrane fuel cell catalyst, and relates to a CoNi @ TA/B nano material prepared by a thermal decomposition process and application of the CoNi @ TA/B nano material as an oxygen reduction catalyst material.

Background

Generally, to ensure that an electrocatalyst can operate stably at high current densities, its active sites should have a high surface area, high intrinsic activity, high tolerance, be readily accessible to reactants, and conduct electrons to an external circuit at the same time. Traditional MOFs-derived materials are mainly based on simple MOFs as single precursors and therefore mainly exhibit a relatively simple configuration, and the catalysts prepared therefrom have poor ORR catalytic performance.

To this end, the present invention provides a method for achieving the synthesis of high performance ORR catalysts in a controlled manner, CoNiMOF with multilayer spherical hollow nanostructure is prepared by using reagents such as cobalt nitrate hexahydrate and zinc nitrate hexahydrate through a hydrothermal synthesis method, CoNiMOF @ TA is coated on a CoNiMOF precursor by using TA, metal atoms are tightly wrapped in a polymer chain by using the TA, the "wrapped" structure effectively protects the metal species from large aggregation of metal species leading to low catalyst activity, and in addition, the TA-metal composition has high thermal stability, therefore, the high yield of the catalyst is ensured, 1, 4-benzene diboronic acid is added for heat treatment, the obtained catalyst CoNi @ TA/B shows good ORR catalytic performance in alkaline solution, and the unique multilayer hollow structure can effectively improve the oxygen reduction reaction.

Disclosure of Invention

The invention aims to solve the problems of the existing fuel cell catalyst, overcome the defects of the prior art, solve the problems of single precursor obstacle and synthesis cost of the existing fuel cell catalyst, and overcome the defects of high cost, toxicity and the like of a Pt-based catalytic material; based on the unique structure of CoNi MOF, a metal organic framework nano composite material for a proton membrane fuel cell is developed, and the nano composite material has the advantages of high initial potential, half-slope potential, excellent limiting current, excellent stability, good methanol tolerance, strong methanol poisoning resistance and the like.

The simple thermal decomposition preparation process provided by the invention is used for synthesizing the myrica-shaped cobalt-nickel-boron composite carbon material proton membrane fuel cell catalyst, and comprises the following steps:

（1）436 mg Ni(NO₃)₂·6H₂O、436 mg Co(NO₃)₂·6H₂o, 300 mg of trimesic acid, and 3 g of PVP were dissolved in 60mL of a mixed solution (distilled water: DMF: ethanol =1:1:1 v/v/v) and sufficiently stirred;

(2) transferring the stirred solution into a 100 mL high-pressure reaction kettle for hydrothermal reaction;

(3) washing the obtained product with ethanol for several times, and drying to obtain a CoNi MOF crystal;

(4) 400 mg CoNi MOF was dispersed in 10 mL deionized water;

(5) the pH of a 12 mM, 6 mL TA solution was adjusted to 7.5 with a prepared KOH (6M) solution;

(6) pouring the adjusted TA solution into a CoNiMOF solution, and carrying out ultrasonic treatment for 30min to obtain a solution A, CoNiMOF @ TA for short;

(7) weighing 24 mg of 1, 4-phenyl diboronic acid to be dissolved in 10 ml of deionized water;

(8) pouring the prepared TA solution (6 mL, 12 mM, pH = 7.5) into the 1, 4-benzenediboronic acid solution, and performing ultrasonic treatment for 5 min to obtain a solution B, TA/B for short;

(9) pouring the obtained solution A into the solution B, performing ultrasonic treatment for 30min, washing for several times by using deionized water and ethanol respectively, and drying to obtain a precursor;

(10) and calcining the prepared precursor in Ar atmosphere, and performing thermal annealing to obtain the myrica cobalt nickel boron composite carbon material CoNi @ TA/B.

In the technical scheme, the hydrothermal reaction in the step (2) is carried out at 150 ℃ and is kept for 10 hours;

in the technical scheme, the drying temperature in the step (3) is preferably 80 ℃, and the time is 12 hours, so that the deformation of the precursor structure is avoided;

in the technical scheme, the drying temperature in the step (9) is preferably 60 ℃ and the time is 12 h, so that the deformation of the precursor structure is avoided;

in the technical scheme, the heat treatment temperature in the step (10) is 700 ℃, the reaction time is 3 hours, and the heating rate is controlled to be 1-5 ℃/min, because the heating rate is too high, the structure collapse is easily caused during calcination.

Compared with a commercial Pt/C catalyst, the myrica cobalt nickel boron composite carbon material proton membrane fuel cell catalyst has the following advantages:

(1) the preparation process of the catalyst adopts a thermal decomposition method with simple equipment, simple operation steps, environmental protection and easily controlled reaction conditions, and not only shows high initial potential, half-slope potential, excellent limiting current, excellent stability and good methanol tolerance, but also has the advantages of strong methanol poisoning resistance and the like.

(2) Prepared CoThe current density of Ni @ TA/B is-5 mA cm^-2It is demonstrated that an increase in the oxygen reduction reactivity of boron-doped MOF catalysts by boron content correlates with an increase in boron content. Experimental results show that CoNi @ TA/B has similar limiting current with commercial Pt/C.

(3) The CoNi @ TA/B composite carbon material prepared by the invention is characterized in that a metal organic framework material framework containing a cobalt nickel metal element is taken as a template, the excellent metal nonmetal chelating capacity of TA is utilized, a boron element is anchored on the template framework of CoNiMOF in situ, the composite precursor is taken as a carbon source, then high-temperature oxygen separation carbonization is carried out, so that a multi-metal composite carbon material is obtained, and under the synergistic action of metal nanoparticles and a porous carbon material taking the metal organic framework as the carbon source, an electrocatalyst with excellent oxygen reduction performance is prepared, and the electrocatalyst is expected to be widely used for a proton membrane fuel cell cathode material.

(4) The CoNi @ TA/B composite carbon material has excellent oxygen electrocatalytic performance and good stability, and is obtained by the combined action of the following aspects: 1) the CoNi @ TA/B composite carbon material has high specific surface area and porosity; 2) TA has stronger chelating ability to metal ions as plant-derived polyphenol, and metal atoms are tightly wrapped in a polymer chain by the TA, so that the metal species are effectively protected by the wrapping structure, the condition that the activity of the catalyst is low due to the large aggregation of the metal species is avoided, and in addition, the TA-metal composition has higher thermal stability, so that the high yield of the catalyst is ensured; 3) the 2pz empty orbit of boron can be conjugated with the delocalized pi orbit of carbon, so that the oxygen reduction activity of carbon is improved; 4) the active sites can be generated by the synergistic effect generated by the N and B dopants, so that the change value of free energy in the rate determination step is reduced, which shows that the uniform synergistic coupling of B-N in a carbon structure and a hierarchical porous structure enables the prepared CoNi @ TA/B to enhance the ORR parameter, and the crystal defect density of the carbon material is increased, the active sites are increased, and the oxygen reduction performance, the methanol resistance performance and the durability are improved along with the increase of the addition amount of a boron source.

Drawings

FIG. 1 is a graph of the apparent CoNi @ TA/B values produced;

FIG. 2 is an XRD pattern of a CoNi @ TA/B sample (scan interval: 5 deg. -80 deg., step size: 0.02 deg., scan rate: 1.5 deg./min), (a) XRD patterns of Co @ TA and CoNi @ TA/B calcined at different calcination temperatures (B)700 deg.C;

FIG. 3 is a scanning electron micrograph of CoNi @ TA/B;

FIG. 4 is a transmission electron micrograph and selected area electron diffractogram of CoNi @ TA/B;

FIG. 5 is a CoNi @ TA/B initial XPS spectrum survey (a), C (B), O (C), B (d), Ni (e), Co (f);

FIG. 6 shows CoNi @ TA/B nano material in N₂And O₂CV plot in saturated 0.1M KOH (scan range-0.9-0.1V, scan rate 50 mv/s);

FIG. 7 is the CoNi @ TA/B nano material prepared at different temperatures under O₂LSV profile in saturated 0.1M KOH (scan range-0.9-0.1V, scan rate 10 mv/s);

FIG. 8 is a graph of CoNi @ TA/B and Pt/C at O for different B loadings₂LSV profile in saturated 0.1M KOH (scan range-0.9-0.1V, scan rate 10 mv/s);

FIG. 9 LSV plot of CoNi @ TA/B at different speeds (speeds of 400 rmp, 625 rmp, 900 rmp, 1225 rmp, 1600 rmp, 2025 rmp, scan rate of 10 mv/s);

FIG. 10 is a K-L equation plot of CoNi @ TA/B;

FIG. 11 CoNi @ TA/B and Pt/C at O₂I-t curves run in saturated 0.1M KOH for long periods of time;

FIG. 12 i-t curves run after CoNi @ TA/B and Pt/C addition of methanol.

Detailed Description

The invention provides a method for synthesizing a myrica-shaped cobalt-nickel-boron composite carbon material proton membrane fuel cell catalyst by a simple thermal decomposition preparation process, which comprises the following steps:

（1）436 mg Ni(NO₃)₂·6H₂O、436 mg Co(NO₃)₂·6H₂o, 300 mg of trimesic acid, and 3 g of PVP were dissolved in 60mL of a mixed solution (distilled water: DMF: ethanol =1:1:1 v/v/v) and sufficiently stirredStirring;

(4) 400 mg CoNi MOF was dispersed in 10 mL deionized water;

(6) pouring the adjusted TA solution into a CoNiMOF solution, and carrying out ultrasonic treatment for 30min to obtain a solution A;

(8) pouring the prepared TA solution (6 mL, 12 mM, pH = 7.5) into the 1, 4-benzenediboronic acid solution, and performing ultrasonic treatment for 5 min to obtain a solution B;

The invention provides a metal organic framework-biopolymer nano composite material and an electro-catalytic material using the material.

The active substance is abbreviated as CoNi @ TA/B.

The CoNi @ TA/B catalyst is prepared by thermal decomposition.

The invention uses a platinum electrode as a counter electrode, a saturated silver chloride electrode (Ag/AgCl) as a reference electrode and a Pt/C electrode as a working electrode.

The concentration of Nafion added in the preparation process of the catalyst ink was 5wt%, and the amount used was 15 ul.

A catalyst ink (ink) was prepared by dispersing 4 mg of the catalyst of the present invention in 1 mL of a mixed solution (250. mu.L of deionized water, 735. mu.L of isopropyl alcohol and 15. mu.L of a 5wt% Nafion solution) using a scale. Then gradually dropping 28 μ L ink to the surface of the glassy carbon electrode (catalyst loading 0.25 mg cm)^-2) And carrying out an electrocatalysis performance test after naturally drying.

All electrocatalytic performance tests described in the present invention were performed in 0.1M KOH (pH = 13.62) electrolyte, and the experimentally measured potential was converted to a potential relative to a Reversible Hydrogen Electrode (RHE) by the following formula:

the potential values referred to in the present invention are all potentials relative to the reversible hydrogen electrode.

The catalyst of the present invention requires CV activation for 3 cycles before electrochemical testing.

The catalyst is tested at normal temperature, and the influence of large temperature change difference on the performance of the catalyst is prevented.

The invention will be further illustrated with reference to the following specific examples. In order to further clarify the present invention, preferred embodiments of the present invention are described in connection with the examples which are intended to illustrate various features and advantages of the present invention, but not to limit the scope of the invention which is not defined by the claims. In addition, it should be understood that various changes or modifications can be made by those skilled in the art after reading the disclosure of the present invention, and such equivalents also fall within the scope of the invention.

The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.

Example 1:

this example demonstrates a method for synthesizing a CoNi @ TA/B catalyst, comprising the steps of:

(4) 400 mg CoNi MOF was dispersed in 10 mL deionized water;

(10) calcining the prepared precursor at 700 ℃, 800 ℃ and 900 ℃ respectively in Ar atmosphere, and respectively marking products obtained after thermal annealing as CoNi₄₀₀@TA/B₂₄-700℃，CoNi₄₀₀@TA/B₂₄-800℃，CoNi₄₀₀@TA/B₂₄-900℃；

in the technical scheme, the calcination time in the step (10) is 3 h, and the heating rate is controlled at 5 ℃/min, because the heating rate is too high, the structure collapse is easily caused during calcination.

Comparative example: the preparation method of Co @ TA comprises the following steps:

1）436 mg Co(NO₃)₂·6H₂o, 300 mg of trimesic acid, and 3 g of PVP were dissolved in 60mL of a mixed solution (distilled water: DMF: ethanol =1:1:1 v/v/v) and sufficiently stirred;

2) transferring the stirred solution into a 100 mL high-pressure reaction kettle for hydrothermal reaction;

3) washing the obtained product with ethanol for several times, and drying to obtain a Co precursor;

4) weighing 400 mg of Co precursor and dispersing in 10 mL of deionized water;

5) the pH of a 12 mM, 6 mL TA solution was adjusted to 7.5 with a prepared KOH (6M) solution;

6) pouring the adjusted TA solution into the Co precursor solution, carrying out ultrasonic treatment for 30min, and washing with deionized water and ethanol for several times respectively to obtain a Co @ TA precursor;

7) and calcining the prepared Co @ TA precursor in Ar atmosphere at 700 ℃ to obtain the Co @ TA.

FIG. 1 is CoNi prepared₄₀₀@TA/B₂₄-700 ℃ appearance.

Phase identification and microstructure and structure characterization of the CoNi @ TA/B material obtained in this example 1 were performed: and phase identification is carried out on the prepared material by using a powder X-ray diffractometer and an X-ray photoelectron spectrometer, and the microscopic morphology and the structural characterization are carried out on the obtained material by using a scanning electron microscope and a transmission electron microscope.

FIG. 2 XRD patterns (a) of CoNi @ TA/B samples at different calcination temperatures (700 deg.C, 800 deg.C, 900 deg.C), XRD patterns (B) of calcined Co @ TA and CoNi @ TA/B at 700 deg.C (scan interval: 5 deg. -80 deg., scan rate: 8 deg./min). The characteristic peaks of all the CoNi @ TA/B samples in the figure correspond to the (002) graphitic carbon and the (111), (200), (220) CoNi alloy faces, and since the BN crystal structure is very similar to that of graphite and the B loading in the samples is very low, the peaks corresponding to NB in the XRD pattern are lower in intensity than the associated peaks of graphitic carbon and are therefore masked. In which the (002) peaks of the two substantially coincide and the (100) peak is slightly enhanced in intensity due to the presence of BN, indicating that this experiment has succeeded in complexing B to CoNiMOF. The XRD pattern was magnified to 43 to 45, as is evident in FIG. 2 (B), and the diffraction peak position of Co (111) in Co @ TA was shifted slightly to the right compared to CoNi @ TA/B, further confirming the formation of CoNi duplex in the obtained CoNi @ TA/B sample.

FIG. 3 FIG. 4 are CoNi₄₀₀@TA/B₂₄-700 ℃ scanning electron micrograph, transmission electron micrograph and selected area electron diffraction pattern. As can be seen from the figure, the CoNi @ TA/B sample powder is composed of waxberry-like particles, and a few holes are formed in the middle of the waxberry-like particles. The particle size distribution is 3 um-5 um, and the lattice spacing is 0.204 nm, 0.217 nm, 0.106 nm and 0.125 nm, which is beneficial to enhancing the catalytic action of the catalyst.

FIG. 5 is an XPS spectrum survey of CoNi @ TA/B showing the full spectrum (a), C (B), O (C), B (d), Ni (f), Co (e); the electronic state of the surface element was analyzed by XPS technique using CoNi400@ TA/B24-700 ℃ as a representative sample. C1 s is broken down into 3 peaks corresponding to aromatic chain carbons (C = C, 284.7 eV), carbon-nitrogen double bonds (C-O, 285.8 eV) and carboxylic acid carbons (O-C = O, 288.8 eV). The presence of O in CoNi @ TA/B is primarily due to H₂Adsorption of O molecules on the sample surface. Another distinct peak, referred to as element B, appears at 192 eV in the full spectrum. We decomposed the B1 s spectrogram in FIG. 5 (d), which was divided into B-C (191.5 eV), B-O (192.3 eV) and B-N (190.7 eV), demonstrating that this experiment has successfully complexed B to CoNiMOF. XPS spectra of Ni 2p and Co 2p, with main Co peaks of 778.2 eV and 793.3 eV and main Ni peak of 8529 eV and 870.3 eV, indicating the presence of the zero valent metals Ni and Co, consistent with the XRD results for CoNi @ TA/B, the other two peaks at higher binding energies are attributable to the metal oxide, probably due to partial oxidation of CoNiMOF. The remaining peak of the Co spectrum, 786.3 eV and 859.7 eV for the Ni 2p remaining peak, respectively, is considered a rocking satellite (denoted "saturation") due to plasma depletion and end-state effects. The results, combined with XRD and XPS analysis, further confirmed the formation of CoNi400@ TA/B24.

Example 2:

this example shows a study of the electrochemical properties of a catalyst based on the nanomaterial CoNi @ TA/B.

A catalyst ink (ink) was prepared by dispersing 4 mg of the catalyst of the present invention in 1 mL of a mixed solution (250 uL of deionized water, 735 uL of isopropyl alcohol, and 15uL of a 5wt% Nafion solution) using a scale. Then gradually dropping 28 uL ink on the surface of the glassy carbon electrode (catalyst loading amount is 0.25 mg cm)^-2) And carrying out an electrocatalysis performance test after naturally drying.

Nafion added in the preparation process of the catalyst is produced by Aldrich sigma company, and the concentration is 5%.

The catalyst is absorbed by a pipette gun to be 7 ul and dropped on a working electrode, the step is repeated for 3 times after the catalyst is naturally aired, then the working electrode slowly enters 0.1M KOH electrolyte saturated by oxygen, bubbles are prevented from being generated on the working electrode in the step, and the electrolyte is continuously introduced into oxygen in the whole testing process to ensure oxygen saturation.

Cyclic voltammetry and linear cyclic voltammetry tests were performed on the catalyst obtained in this example: the cyclic voltammetry test was carried out using an electrochemical workstation manufactured by Pine of the United states, the test voltage sweep range was-0.9-0.1V, the sweep rate was 50 mV/s, and during the test, the cyclic voltammetry test was carried out after 3 cycles of activation with a current density of 50 mV/s. Linear cyclic voltammetry tests were also performed using the Pine electrochemical workstation, with a test voltage sweep range of-0.9-0.1V and a sweep rate of 50 mV/s. The current density of the catalyst material under different rotating speeds can be obtained through rotating speed test, the number of transferred electrons can be obtained by utilizing a K-L equation, the test current density is 10mV/s, and the rotating speeds are 400 rmp, 625 rmp, 900 rmp, 1225 rmp, 1600 rmp and 2025 rmp. The stability and the methanol tolerance are also important indexes of the catalyst performance, the test is also completed on an electrochemical workstation, the stability test voltage is-0.189V, and the test time length is 20000 s; the methanol tolerance test voltage was-0.189V, the test duration was 1000 s, and a 2M methanol solution was dropped at 250 s.

FIG. 6 is CoNi₄₀₀@TA/B₂₄The cyclic voltammogram of the catalyst at 700 ℃ (test voltage sweep range: -0.9-0.1V, sweep rate: 50 mV/s), in a 0.1M KOH solution saturated with nitrogen, no significant oxidation or reduction peak was detected, in contrast to a significant cathodic oxygen reduction peak at 0.7V (vs RHE) in an electrolyte solution saturated with oxygen, indicating that sample CoNi @ TA/B has significant catalytic activity on ORR.

FIG. 7 is a linear cyclic voltammogram of CoNi @ TA/B catalyst at different temperatures (test voltage range: -0.9-0.1V, scan rate: 50 mV/s), respectively, with the CoNi @ TA/B catalyst performing best when the calcination temperature is 700 deg.C.

FIG. 8 is a graph of CoNi @ TA/B and Pt/C at O for different B loadings₂LSV plot in saturated 0.1M KOH (scan range-0.9-0.1V, scan rate 10 mv/s), with increasing boron content, the current density of the oxygen reduction reaction increased and then decreased, with the current density of the sample CoNi @ TA/B being the maximum at 24g boron content, which is-5 mA cm^-2It is demonstrated that an increase in the oxygen reduction reactivity of boron-doped MOF catalysts by boron content correlates with an increase in boron content. Experimental results show that CoNi @ TA/B has similar limiting current with commercial Pt/C.

FIG. 9 shows the CoNi catalysts at different speeds (400 rmp, 625 rmp, 900 rmp, 1225 rmp, 1600 rmp, 2500 rmp)₄₀₀@TA/B₂₄The LSV curve at-700 deg.C (scan speed: 10 mV/s) shows a tendency to increase gradually with increasing rotation speed, mainly due to the fact that the increasing rotation speed effectively shortens the diffusion layer of the oxygen reduction reaction. A series of oxygen reduction curves of the catalyst show a better diffusion-limiting current platform, which means that the catalytic active sites of the catalyst are distributed more uniformly, and the speed of the oxygen reduction process is improved.

FIG. 10 is CoNi₄₀₀@TA/B₂₄The slope of the K-L curve at 700 ℃ remains substantially constant over the entire potential range, which indicates that the oxygen reduction reaction has the same number of transferred electrons at different potentials over the catalyst. It can be seen that the electron transfer number averages 3.6, indicating that the four-electron path predominates in the sample under alkaline conditions, and that the greater the potential, the greater the electron transfer number.

FIG. 11 is a test of CoNi by chronoamperometry₄₀₀@TA/B ₂₄700 ℃ and Pt/C, after testing for 20000 s, the CoNi @ TA/B current of the catalyst remained 83%, while the current of the commercial Pt/C catalyst decreased to 83% when the ORR reaction proceeded to 10000 s. The prepared catalyst CoNi @ TA/B is shown to have excellent durability in the ORR process.

FIG. 12 is CoNi₄₀₀@TA/B ₂₄700 ℃ and commercialThe methanol resistance of 20% Pt/C catalyst is shown by adding 2M methanol to 0.1M KOH electrolyte at 300 s by using i-t technology, for fuel cell catalyst, Pt/C catalyst will generate methanol oxidation reaction with anode fuel cell, accelerate cathode polarization, and have great poisoning effect on catalyst, and the influence of methanol on catalyst is tested by using a chronoamperometry. Tests show that the prepared catalyst shows excellent methanol poisoning performance in an alkaline electrolyte. During the test, when a methanol solution was added to the electrolyte, it was evident that the CoNi @ TA/B current change was small, indicating that it was somewhat resistant to methanol. On the contrary, when the methanol solution is added into the Pt/C catalyst electrolyte, the Pt/C catalyst shows very obvious instantaneous current jump and the current density is reduced, which shows that the Pt/C catalyst is very easy to poison methanol.

The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. The preparation method of the myrica cobalt nickel boron composite carbon material proton membrane fuel cell catalyst is characterized by comprising the following steps of: the preparation method comprises the following steps:

（1）Ni(NO₃)₂·6H₂O、Co(NO₃)₂·6H₂dissolving O, trimesic acid and PVP in the mixed solution and fully stirring;

(2) transferring the stirred solution into a high-pressure reaction kettle for hydrothermal reaction;

(4) dispersing the CoNi MOF in deionized water;

(5) adjusting the pH value of the tannic acid TA solution to 7.5 by using a KOH solution;

(6) pouring the adjusted tannic acid TA solution into a CoNiMOF solution, and carrying out ultrasonic treatment for 30min to obtain a solution A;

(7) dissolving 1, 4-phenyl diboronic acid in deionized water;

(8) pouring the prepared tannic acid TA solution into the 1, 4-phenyl diboronic acid solution, and carrying out ultrasonic treatment for 5 min to obtain a solution B;

2. The method of claim 1, wherein: the mixed solution in the step (1) is obtained by mixing distilled water, DMF and ethanol according to the volume ratio of 1:1: 1.

3. The method of claim 1, wherein: the hydrothermal reaction in the step (2) is carried out at 150 ℃ for 10 h.

4. The method of claim 1, wherein: the drying temperature in the step (3) is 80 ℃.

5. The method of claim 1, wherein: the concentration of the KOH solution in the step (5) was 6M.

6. The method of claim 1, wherein: the concentration of the tannic acid TA solution in the step (5) was 12 mM.

7. The method of claim 1, wherein: the drying temperature in the step (9) is 60 ℃.

8. The method of claim 1, wherein: the calcination temperature in the step (10) is 700 ℃, the calcination time is 3 h, and the heating rate is controlled to be 1-5 ℃/min.

9. The myrica cobalt nickel boron composite carbon material proton membrane fuel cell catalyst prepared by the preparation method according to any one of claims 1 to 8.