CN111939981B - CoFeMOF-P/b-CNF composite electrocatalyst and preparation method thereof - Google Patents
CoFeMOF-P/b-CNF composite electrocatalyst and preparation method thereof Download PDFInfo
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- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 40
- 239000002131 composite material Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
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- 239000005016 bacterial cellulose Substances 0.000 claims abstract description 30
- 150000003839 salts Chemical class 0.000 claims abstract description 28
- 239000012528 membrane Substances 0.000 claims abstract description 25
- 150000003017 phosphorus Chemical class 0.000 claims abstract description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
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- 239000011259 mixed solution Substances 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
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- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
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- 239000011261 inert gas Substances 0.000 claims description 4
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- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention belongs to the technical field of new materials, and particularly relates to a CoFeMOF-P/b-CNF composite material electrocatalyst and a preparation method thereof. The technical key points are as follows: coFeMOF-P/b-CNF electrocatalysts include Co salts, fe salts and bacterial cellulose membranes, and the CoFeMOF-P/b-CNF electrocatalysts are high temperature phosphated by phosphorus salts. According to the CoFeMOF-P/b-CNF composite material electrocatalyst and the preparation method thereof, the prepared CNF by taking the bacterial cellulose membrane as a precursor has the advantages of multiple pore channels of a three-dimensional structure and high toughness, and is used as a conducting wire between a framework supporting material of the CoFeMOF and MOFs particles, so that the appearance of the MOFs material is complete, and the conductivity and the electrocatalysis capability are improved.
Description
Technical Field
The invention belongs to the technical field of new materials, and particularly relates to a CoFeMOF-P/b-CNF composite material electrocatalyst and a preparation method thereof.
Background
Energy is an inexhaustible motive power for human development, and is also an important standard for measuring national economic development and quality of life of people. In the past few decades, rapid population growth, popularization of automobiles, and increased use of machines have led to a gradual decline in reserves of fossil fuels, and eventually energy will be exhausted, and moreover, use of fossil fuels has led to serious environmental pollution and global warming. In recent years, therefore, environmental-friendly new energy sources have been vigorously developed. Clean, pollution-free, sustainable resources, hydrogen energy, are recognized as the most promising alternative to fossil fuels in the 21 st century. The electrocatalytic water decomposition hydrogen production (HER) is a hydrogen production method which is simple and convenient to operate, can convert electric energy into chemical energy in an environment-friendly mode, can be used in combination with other intermittent energy sources (such as wind energy and solar energy), and provides a solution for high-purity hydrogen production. However, hydrogen evolution reaction requires high power consumption as one of the indispensable reactions in the water splitting process. There is therefore an urgent need for an effective HER catalyst to increase the efficiency of electrocatalytic hydrogen production. Platinum group metals have heretofore been recognized as the most advanced, effective electrocatalysts, but their use in industry on a large scale has been limited due to their scarcity and high cost.
In view of the defects existing in the prior electrocatalyst technology, the inventor actively researches and innovates based on the rich practical experience and expertise of the design and manufacture of the product for many years and the application of the theory, so as to create a CoFeMOF-P/b-CNF composite electrocatalyst and a preparation method thereof, which have good conductivity, long-term electrochemical stability, good catalytic activity, low overpotential, large surface area and low cost. After continuous research and design and repeated sample test and improvement, the invention with practical value is finally created.
Disclosure of Invention
The invention provides a CoFeMOF-P/b-CNF composite electrocatalyst, which takes a bacterial cellulose film as a precursor to prepare the obtained CNF, has the advantages of multiple three-dimensional structure pore channels and high toughness, is used as a conducting wire between a framework supporting material of the CoFeMOF and MOFs particles, ensures the integrity of the morphology of the MOFs, improves the conductivity and the electrocatalysis capability, and ensures that the composite electrocatalyst has good conductivity, long-term electrochemical stability, good catalytic activity, low overpotential, large surface area and low cost.
The technical aim of the invention is realized by the following technical scheme:
the CoFeMOF-P/b-CNF composite electrocatalyst provided by the invention comprises Co salt, fe salt and bacterial cellulose membrane, and the CoFeMOF-P/b-CNF electrocatalyst is subjected to high-temperature phosphating through phosphorus salt. The novel MOFs material and the derivatives thereof are used as development catalysts, can effectively promote reaction kinetics, and improve the energy utilization rate so as to improve the catalytic performance of the electrochemical catalyst.
Further, the Co salt is Co (NO 3 ) 2 、CoCl 2 Or Co (CH) 3 COO) 2 The concentration of any one of the above is 5-11 mg/mL.
Further, the Fe salt is Fe (NO 3 ) 3 、FeCl 3 Or Fe (CH) 3 COO) 3 Any one of the concentrations is 3-8 mg/mL.
Further, co salt and Fe salt are Co (CH 3 COO) 2 •6H 2 O and FeCl 3 •6H 2 O, the concentration of Co (CH) 3 COO) 2 •6H 2 O 11mg/mL，FeCl 3 •6H 2 O 6mg/mL。
Further, the phosphorus salt is NaH 2 PO 2 Or KH 2 PO 2 The mass is 0.5-3 g.
The invention provides a preparation method of a CoFeMOF-P/b-CNF composite material electrocatalyst, which is used for preparing the CoFeMOF-P/b-CNF electrocatalyst by simple hydrothermal and phosphating modes and the like and has the same effect.
The technical effects of the invention are realized by the following technical scheme:
the preparation method of the CoFeMOF-P/b-CNF composite material electrocatalyst provided by the invention comprises the following operation steps:
s1. Preparation of CoFeMOF-supported bacterial cellulose membrane: dissolving Co salt and Fe salt, adding the dissolved Co salt and Fe salt into a bacterial cellulose membrane, shaking to enable the Co salt and the Fe salt to be uniformly adsorbed on the surface of the bacterial cellulose membrane, transferring the mixture to a high-pressure reaction kettle, and preparing the CoFeMOF-loaded bacterial cellulose membrane by a one-step hydrothermal method;
s2. Preparation of CoFeMOF-P/b-CNF electrocatalyst: transferring the product obtained in the step S1 to a tubular furnace, putting phosphorus salt into an upper air port of an air path of the tubular furnace, introducing inert gas, carbonizing the bacterial cellulose membrane obtained in the step S1 at high temperature, and phosphating to obtain a CoFeMOF-P/b-CNF electrocatalyst; the electro-catalyst after phosphating can improve the conductivity of the electro-catalyst due to the doping of phosphorus element.
As a preferable mode of the technical scheme, the one-step hydrothermal method in the step S1 is to adsorb Co salt and Fe salt on the surface of the bacterial cellulose membrane in advance, wherein the adsorption time is 8-24 hours.
As the optimization of the technical scheme, the one-step hydrothermal method in the step S1 is to carry out hydrothermal reaction for 24-72 hours at the temperature of 100-200 ℃.
As the optimization of the technical scheme, the phosphating temperature in the step S2 is 200-400 ℃ and the phosphating time is 1-5 hours.
Preferably, the inert gas in step S2 is either nitrogen or argon.
In summary, the invention has the following beneficial effects:
(1) The adsorption quantity of the CoFeMOF prepared by a subsequent hydrothermal method on the surface of the bacterial cellulose is greatly increased and the adsorption is more uniform by the way of pre-mixing and adsorbing the Co salt and the Fe salt with the bacterial cellulose film after dissolving;
(2) The method has the advantages that the (CNF) which has excellent performance, is environment-friendly, is simple to prepare and has been industrially produced is selected, and carbon fibers are obtained in the high-temperature phosphating process, so that the method is simple;
(3) The CNF prepared by taking the bacterial cellulose film as a precursor has the advantages of multiple pore channels of a three-dimensional structure and high toughness, and is used as a conducting wire between a framework supporting material of CoFeMOF and MOFs particles, so that the integrity of the morphology of the MOFs is ensured, and the conductivity and the electrocatalytic capacity are improved;
(4) CoFeMOF bimetallic MOFs are selected to prepare the CoFeMOF-P/b-CNF electrocatalyst, new bimetallic bonds are introduced to promote the rupture of O-H and accelerate the formation of H-H bonds, so that the electrocatalyst performance of the catalyst is improved. And the bimetallic MOF has two metal centers, and has more catalytic active sites and adsorption sites than the single metal MOF, so that the catalytic performance, the structural stability and the like are improved.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the embodiments of the invention, serve to explain the invention. In the drawings:
FIG. 1 is a scanning electron microscope view and a schematic diagram of a CoFeMOF-P/b-CNF electrocatalyst;
FIG. 2 is a linear sweep voltammogram of CoFeMOF, coFeMOF-P, coFeMOF/b-CNF, coFeMOF-P/b-CNF and commercial Pt/C;
FIG. 3 is a Taphillips slope plot of CoFeMOF, coFeMOF-P, coFeMOF/b-CNF, coFeMOF-P/b-CNF and commercial Pt/C.
Detailed Description
In order to further illustrate the technical means and effects adopted by the invention to achieve the preset aim, the invention provides a CoFeMOF-P/b-CNF composite material electrocatalyst and a preparation method thereof, and specific embodiments, characteristics and effects thereof are described in detail below.
Example 1: coFeMOF-P/b-CNF composite electrocatalyst and preparation method thereof
The CoFeMOF-P/b-CNF composite material electrocatalyst comprises Co salt, fe salt and bacterial cellulose membrane, and the CoFeMOF-P/b-CNF electrocatalyst is subjected to high-temperature phosphating through phosphorus salt.
The preparation method comprises the following steps:
s1, preparing 10 mL of mixed solution of N, N-Dimethylformamide (DMF) and ethanol in a volume ratio of 1:1, and adding 11mg/mL of Co (CH) 3 COO) 2 •6H 2 FeCl of O,6 mg/mL 3 •6H 2 O,6 mg/mL terephthalic acid and 50 mg/mL polyvinylpyrrolidone are dissolved uniformly at room temperature, then 1g of bacterial cellulose membrane is added, the mixture is shaken and adsorbed for 12 hours, and then the mixture is transferred into a polytetrafluoroethylene reaction kettle and heated to 150 ℃ for hydrothermal reaction for 48 hours; after cooling to room temperature, washing with DMF for three times, drying the brownish-black product in a 100 ℃ oven to obtain a CoFeMOF-loaded bacterial cellulose membrane;
s2, placing a bacterial cellulose membrane loaded by CoFeMOF in a porcelain plate, placing in a tube furnace, and simultaneously placing at an upper tuyere of the tube furnacePlacing 1g NaH 2 PO 2 Lead to N 2 Setting the phosphating temperature to 300 ℃, keeping for 2 hours, cooling to room temperature, washing the product with deionized water, and drying to obtain CoFeMOF-P/b-CNF.
The scanning electron microscope of the obtained product is shown in figure 1, the appearance of the shuttle-shaped CoFeMOF is regular, and b-CNF is used as a conducting wire between a framework supporting material of the CoFeMOF and CoFeMOF particles, so that the appearance of the MOFs material is ensured to be complete. As shown in FIG. 2, the initial potential of the prepared CoFeMOF-P/b-CNF is 60 mV, and the initial potential (eta) of 138 mV can reach 10mA/cm 2 Is used for the current density of the battery. As shown in FIG. 3, the CoFeMOF-P/b-CNF Tafil slope of the prepared CoFeMOF-P/b-CNF is 66.8 mV/dec, which is very close to 48.3 mV/dec of the commercial PtC catalyst, and the electrochemical performance of the prepared CoFeMOF-P/b-CNF electrocatalyst is greatly improved compared with that of comparative examples 1, 2 and 3.
Comparative example 1
Comprises the following steps of
S1, preparing 10 mL of mixed solution of N, N-Dimethylformamide (DMF) and ethanol in a volume ratio of 1:1, and adding 11mg/mL of Co (CH) 3 COO) 2 •6H 2 FeCl of O,6 mg/mL 3 •6H 2 O,6 mg/mL terephthalic acid and 50 mg/mL polyvinylpyrrolidone are dissolved uniformly at room temperature, then the mixture is transferred into a polytetrafluoroethylene reaction kettle, the mixture is heated to 150 ℃ for hydrothermal reaction for 48 hours, the mixture is cooled to room temperature and then washed three times by DMF, and a brownish black product is dried in a baking oven at 100 ℃ to obtain CoFeMOF;
as shown in FIG. 2, the initial potential of the prepared CoFeMOF is 209mV, and the overpotential (. Eta.) of 368mV can reach 10mA/cm 2 Compared with example 1, the current density is larger than the overpotential 138 and mV of example 1, and the same catalytic effect is achieved, so that more electric energy is required to be consumed. And as shown in fig. 3, the CoFeMOF taffel slope prepared was 108.8 mV/dec, which is 48.3 mV/dec higher than commercial Pt/C compared to example 1, and the catalytic effect was inferior to example 1. Thus, compared to example 1, the electrochemical performance of comparative example 1 is better than that of example 1, since no bacterial cellulose membrane was added and no high temperature phosphating was performedDescending.
Comparative example 2
The method comprises the following operation steps:
s1, preparing 10 mL of mixed solution of N, N-Dimethylformamide (DMF) and ethanol in a volume ratio of 1:1, and adding 11mg/mL of Co (CH) 3 COO) 2 •6H 2 FeCl of O,6 mg/mL 3 •6H 2 O,6 mg/mL terephthalic acid and 50 mg/mL polyvinylpyrrolidone are dissolved uniformly at room temperature, then the mixture is transferred into a polytetrafluoroethylene reaction kettle, the mixture is heated to 150 ℃ for hydrothermal reaction for 48 hours, the mixture is cooled to room temperature and then washed three times by DMF, and a brownish black product is dried in a baking oven at 100 ℃ to obtain CoFeMOF;
s2, placing CoFeMOF in a porcelain plate, placing in a tube furnace, and simultaneously placing 1 gNaH at an upper tuyere of the tube furnace 2 PO 2 Lead to N 2 Setting the phosphating temperature to 300 ℃, keeping for 2 hours, cooling to room temperature, washing the product with deionized water, and drying to obtain CoFeMOF-P.
As shown in FIG. 2, the initial potential of the prepared CoFeMOF-P is 100mV, and the overpotential (. Eta.) of 199mV is required to reach 10mA/cm 2 Compared with example 1, the current density is larger than the overpotential 138 and mV of example 1, and the same catalytic effect is achieved, so that more electric energy is required to be consumed. And as shown in fig. 3, the CoFeMOF-P tafel slope prepared was 81.1 mV/dec, which is 48.3 mV/dec higher than commercial Pt/C compared to example 1, and the catalytic effect was inferior to example 1. Thus, as can be seen from the results, the electrochemical performance of the electrocatalyst of example 1 was superior to that of comparative example 2, without the addition of a bacterial cellulose membrane in comparative example 2.
Comparative example 3
The method comprises the following operation steps:
s1, preparing 10 mL of mixed solution of N, N-Dimethylformamide (DMF) and ethanol in a volume ratio of 1:1, and adding 11mg/mL of Co (CH) 3 COO) 2 •6H 2 FeCl of O,6 mg/mL 3 •6H 2 O,6 mg/mL terephthalic acid and 50 mg/mL polyvinylpyrrolidone are dissolved uniformly at room temperature, followed by addition of bacterial cellulose membrane1g, shaking and adsorbing for 12 hours, transferring the mixture into a polytetrafluoroethylene reaction kettle, and heating the mixture to 150 ℃ for hydrothermal reaction 48 h. After cooling to room temperature, the resulting mixture was washed three times with DMF and the brownish-black product was dried in an oven at 100℃to give a CoFeMOF-loaded bacterial cellulose membrane.
S2, placing a bacterial cellulose membrane loaded by CoFeMOF in a porcelain plate, placing in a tube furnace, and introducing N 2 The temperature was set at 300℃and maintained for 2 hours. After cooling to room temperature, the product was rinsed with deionized water and dried to give CoFeMOF/b-CNF.
As shown in FIG. 2, the initial potential of the prepared CoFeMOF-P/b-CNF is 118mV, and the overpotential (. Eta.) of 216mV is required to reach 10mA/cm 2 Compared with example 1, the current density is larger than the overpotential 138 and mV of example 1, and the same catalytic effect is achieved, so that more electric energy is required to be consumed. And as shown in fig. 3, the CoFeMOF/b-CNF tafel slope prepared was 66.8 mV/dec, which is 48.3 mV/dec higher than commercial Pt/C compared to example 1, and the catalytic effect was inferior to example 1. Comparative example 3 was not subjected to high temperature phosphating compared to example 1, which resulted in a decrease in electrochemical performance of the electrocatalyst of comparative example 3.
The present invention is not limited to the above-mentioned embodiments, but is not limited to the above-mentioned embodiments, and any simple modification, equivalent changes and modification made to the above-mentioned embodiments according to the technical matters of the present invention can be made by those skilled in the art without departing from the scope of the present invention.
Claims (5)
1. The preparation method of the CoFeMOF-P/b-CNF composite electrocatalyst is characterized by comprising the following operation steps:
s1. Preparation of CoFeMOF-supported bacterial cellulose membrane: dissolving Co salt and Fe salt with deionized water, adding the dissolved Co salt and Fe salt into a bacterial cellulose membrane, shaking to enable the Co salt and the Fe salt to be uniformly adsorbed on the surface of the bacterial cellulose membrane, transferring the mixture to a high-pressure reaction kettle, and preparing the bacterial cellulose membrane loaded by CoFeMOF through a one-step hydrothermal method;
s2. Preparation of CoFeMOF-P/b-CNF electrocatalyst: transferring the product obtained in the step S1 to a tubular furnace, putting phosphorus salt into an upper air port of an air path of the tubular furnace, introducing inert gas, carbonizing the bacterial cellulose membrane obtained in the step S1 at high temperature, and phosphating to obtain a CoFeMOF-P/b-CNF electrocatalyst;
the specific method in the step S1 is as follows:
10 mL of a mixed solution of N, N-Dimethylformamide (DMF) and ethanol in a volume ratio of 1:1 was prepared, and 11. 11mg/mL of Co (CH) was added thereto 3 COO) 2 •6H 2 FeCl of O,6 mg/mL 3 •6H 2 O,6 mg/mL terephthalic acid and 50 mg/mL polyvinylpyrrolidone are dissolved uniformly at room temperature, then 1g of bacterial cellulose membrane is added, the mixture is shaken and adsorbed for 12 hours, and then the mixture is transferred into a polytetrafluoroethylene reaction kettle and heated to 150 ℃ for hydrothermal reaction for 48 hours; after cooling to room temperature, the resulting mixture was washed three times with DMF and the brownish-black product was dried in an oven at 100℃to give a CoFeMOF-loaded bacterial cellulose membrane.
2. The method for preparing the CoFeMOF-P/b-CNF composite electrocatalyst according to claim 1, wherein the phosphating temperature in the step S2 is 200-400 ℃ and the phosphating time is 1-5 hours.
3. The method for preparing the CoFeMOF-P/b-CNF composite electrocatalyst according to claim 1, wherein the inert gas in step S2 is any one of nitrogen and argon.
4. A CoFeMOF-P/b-CNF composite electrocatalyst prepared according to the method of claim 1, wherein the CoFeMOF-P/b-CNF electrocatalyst comprises a Co salt, a Fe salt and a bacterial cellulose membrane, and the CoFeMOF-P/b-CNF electrocatalyst is high temperature phosphatized by a phosphorus salt.
5. The CoFeMOF-P/b-CNF composite electrocatalyst according to claim 4, wherein the phosphorus salt is NaH 2 PO 2 Or KH 2 PO 2 The mass is 0.5-3 g.
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