Preparation method and application of CoFe-PBA chalcogenized carbon cloth composite material
By in situ growing CoFe-PBA sulfide on carbon cloth to form CoS2/FeS2 or CoSe2/FeSe2 heterostructures, the problems of easy agglomeration and weak binding force of carbon-based support material catalysts were solved, and efficient water electrolysis catalytic performance was achieved.
Patent Information
- Application Number
- CN202511107254.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-08-08
- Publication Date
- 2025-10-17
AI Technical Summary
The surface of existing carbon-based carrier materials is highly chemically inert and catalysts are prone to agglomeration when directly loaded. Traditional cobalt-iron Prussian blue-derived catalysts have weak binding force and are prone to structural collapse during electrolysis. Traditional powdered catalysts have active site embedding and increased interfacial impedance, which limits their application.
By electrochemically activating the carbon cloth surface, oxygen-containing functional groups are introduced, CoFe-PBA nanoparticles are grown in situ, and CoFe-PBA sulfide is formed on the carbon cloth. The electronic structure is optimized by sulfidation/selenization treatment to form CoS2/FeS2 or CoSe2/FeSe2 heterostructures, thereby enhancing the loading uniformity and bonding strength of the catalyst.
A highly active and stable water electrolysis catalyst has been achieved, which significantly improves the catalytic performance of hydrogen and oxygen evolution reactions, reduces the overpotential, and enhances the material's conductivity and resistance to electrolyte corrosion.
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Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the technical field of electrocatalytic materials, and relates to a preparation method of a CoFe-PBA chalcogenide carbon cloth composite material and application thereof, in particular to a preparation method of a cobalt sulfide / iron sulfide heterostructure material based on electrochemical activation of a carbon cloth loaded cobalt-iron Prussian blue and application thereof in the field of water electrolysis hydrogen production. BACKGROUND
[0002] With the increasing demand for clean energy worldwide, water electrolysis hydrogen production technology has become a research hotspot due to its zero carbon emission and high energy conversion efficiency. The core reactions of water electrolysis include oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), but the kinetic process is slow, and high-efficiency catalysts are needed to reduce the overpotential. At present, although noble metal-based materials (such as IrO2 and Pt / C) exhibit excellent performance, their high cost and scarcity seriously restrict their large-scale application. Therefore, developing low-cost and high-activity non-noble metal catalysts has become a key challenge in this field.
[0003] Carbon-based carrier materials (such as carbon cloth and carbon paper) are considered as ideal catalyst support substrates due to their high electrical conductivity, chemical stability and flexibility. However, the original carbon cloth surface has strong chemical inertness, and when the catalyst is directly loaded, it is easy to agglomerate, resulting in insufficient exposure of active sites. Studies have shown that pre-oxidation treatment can introduce oxygen-containing functional groups and defect sites on the surface of carbon cloth, significantly improving its hydrophilicity and catalyst anchoring ability. However, the existing pre-oxidation process (such as strong acid treatment and high-temperature oxidation) has problems such as complicated steps and risk of structural damage, and it is urgent to develop a more efficient and controllable surface modification method.
[0004] Prussian blue analogues (PBAs) are a class of metal-organic framework materials with a clear crystal structure and adjustable metal coordination environment. However, the preparation of traditional PBA-derived catalysts mostly relies on solution-phase reactions, which can easily lead to weak binding between active components and carriers, and the risk of structural collapse during electrolysis. How to achieve uniform loading of PBAs on conductive substrates and optimize the electron transport path through interface engineering is still a difficult point in current research.
[0005] In recent years, transition metal compounds (such as sulfides, selenides and phosphides) have attracted attention due to their adjustable electronic structure and rich active sites. Chalcogenization (sulfidation / selenization) treatment can further optimize the charge distribution of metal centers, enhance the electrical conductivity and catalytic stability. However, traditional powder catalysts need to be loaded on the electrode surface with the help of a binder, which can easily lead to problems such as embedding of active sites and increased interface impedance, limiting their practical application. SUMMARY
[0006] To solve the above problems, the cobalt (Co) and iron (Fe) bimetallic system exhibits higher intrinsic activity than single metal due to synergistic effect, and the CoFe-PBA is converted into porous chalcogenide by sulfidation / selenization treatment, while the multi-level structure advantage of the precursor is retained; the converted material is loaded on carbon cloth to prepare an electrolytic water catalyst with high activity, high stability and low cost.
[0007] To achieve the above object, the technical scheme adopted by the present application is as follows: The first aspect of the present application discloses a preparation method of CoFe-PBA chalcogenide carbon cloth composite material, comprising the following steps: S1: electrochemically activating and pre-oxidizing the carbon cloth to obtain an activated carbon cloth with oxygen-containing functional groups on the surface; S2: immersing the activated carbon cloth in a CoFe-PBA precursor solution to grow cobalt-iron Prussian blue (CoFe-PBA) nanoparticles in situ on the surface of the activated carbon cloth, thereby obtaining a CoFe-PBA-loaded carbon cloth; S3: placing the CoFe-PBA-loaded carbon cloth and a sulfur source or a selenium source in a tube furnace, heating at 2-5 ℃ / min to 400-600 ℃ under an inert atmosphere, and keeping the temperature for 1-5 hours to generate a CoFe-PBA chalcogenide carbon cloth composite material; The mass ratio of the CoFe-PBA-loaded carbon cloth to the sulfur source or the selenium source is 1:(2-6).
[0008] Preferably, in S1, the method of electrochemical activation and pre-oxidation treatment is: The carbon cloth is immersed in 0.1-1 M H2SO4 (strong acidic environment promotes carbon surface oxidation), the working electrode is the pretreated carbon cloth, the counter electrode is a platinum sheet, the reference electrode is Ag / AgCl, and the cyclic voltammetry scanning voltage is-0.5-2.0 V (vs. RHE) at a scanning rate of 10-50 mV / s, and the cycle is 10-20 times; after 10-30 minutes of activation treatment, a uniform nanoscale rough structure is formed on the surface of the carbon cloth, and carboxyl / hydroxyl functional groups are also generated, and after washing with deionized water, an activated carbon cloth (denoted as CC-O) is obtained.
[0009] Preferably, the preparation method of the pretreated carbon cloth is: sequentially ultrasonic cleaning the carbon cloth with deionized water and ethanol to remove surface impurities, then washing with deionized water to neutral, and vacuum drying for standby.
[0010] Preferably, in S2, the preparation method of the CoFe-PBA precursor solution is: Weighing potassium ferricyanide into deionized water, stirring for 10-30 minutes to form a yellow transparent solution; weighing cobalt salt into 50 mL deionized water to obtain a pink transparent solution; mixing the two solutions and adding trisodium citrate dihydrate as a complexing agent, adjusting the pH of the solution to 2 to inhibit side reactions, and obtaining CoFe-PBA precursor solution after the reaction is completed; The molar ratio of the potassium ferricyanide, the cobalt salt and the trisodium citrate dihydrate is 2:2:(1-8).
[0011] The cobalt salt is selected from cobalt acetate tetrahydrate or cobalt chloride hexahydrate.
[0012] Preferably, the preparation method of the CoFe-PBA loaded carbon cloth is as follows: The activated carbon cloth is immersed in the precursor solution, sealed in a polytetrafluoroethylene high-pressure reaction kettle, and reacted at 120-180℃ for 2-6 h, so that the CoFe-PBA nanoparticles grow in situ on the surface of the carbon cloth fibers; after the reaction is completed, the product is washed with ethanol and deionized water alternately, and dried to obtain the CoFe-PBA loaded carbon cloth.
[0013] The sulfur source is any one of sulfur powder, thiourea or thioacetamide; and the selenium source is selected from selenium powder.
[0014] The second aspect of the present application discloses a CoFe-PBA chalcogenated carbon cloth composite material, characterized in that it is prepared by the above-mentioned preparation method. The CoFe-PBA chalcogenated carbon cloth composite material comprises: a) a carbon cloth substrate with a surface oxygen functional group density of ≥5 at%; b) CoS2 / FeS2 heterostructure or CoSe2 / FeSe2 heterostructure nanoparticles with a particle size of 10-100 nm; c) sulfur-doped carbon layer with a carbon layer thickness of 1-5 nm.
[0015] Preferably, the heterostructure is core-shell type (CoS@FeS) and / or inlay type (CoS / FeS interface coupling).
[0016] The third aspect of the present application discloses the application of the above-mentioned CoFe-PBA chalcogenated carbon cloth composite material in water electrolysis hydrogen production.
[0017] Compared with the prior art, the present application has the following beneficial effects: 1. By introducing oxygen-containing functional groups (such as -COOH, -OH) on the surface of carbon cloth through electrochemical method, the hydrophilicity and catalyst anchoring ability of carbon cloth are significantly improved. The activated carbon cloth surface is rich in functional groups and defect sites, providing an ideal substrate for the uniform growth of CoFe-PBA nanoparticles, which improves the uniformity and binding strength of CoFe-PBA on carbon cloth.
[0018] 2. The present application utilizes the bimetallic framework of CoFe-PBA and the cyano ligand to achieve uniform mixing of Co / Fe atoms at the atomic level and controlled growth of heterostructures during sulfidation, forming CoS2 / FeS2 heterostructures with strong interface coupling effect, which can optimize the electronic structure and improve the catalytic activity. The synergistic effect of the bimetallic system (Co and Fe) significantly improves the intrinsic catalytic activity of the material, especially in the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), which shows lower overpotential.
[0019] 3. The present application utilizes sulfur-doped carbon layers to form nitrogen / sulfur co-doped carbon layers by carbonizing PBA, which enhances the electrical conductivity and inhibits the dissolution of sulfides. The synergistic effect of sulfur-doped carbon layers and heterostructures effectively resists electrolyte corrosion, and the material shows excellent stability in constant current tests.
[0020] 4. The present application grows CoS2 / FeS2 heterostructures on the surface of carbon cloth by electrochemical activation method, which has dual functional catalytic performance of HER and OER, realizing the integrated application of dual functional catalysts. BRIEF DESCRIPTION OF DRAWINGS
[0021] Figure 1 X-ray diffraction (XRD) pattern of the cobalt disulfide / iron disulfide heterostructure loaded on carbon cloth prepared in Example 1.
[0022] Figure 2 Scanning electron microscope (SEM) image of the cobalt disulfide / iron disulfide carbon heterostructure loaded on carbon cloth prepared in Example 2.
[0023] Figure 3 Durability test data graph of the cobalt disulfide / iron disulfide carbon heterostructure loaded on carbon cloth prepared in Example 2. DETAILED DESCRIPTION
[0025] The technical solutions of the present application will be described in detail below in combination with the drawings and examples, but the present application is not limited to the scope of the described examples. The process parameters not mentioned in the examples of the present application can be carried out according to conventional methods, and the raw materials used can be obtained through commercial channels.
[0026] Example 1: (1) The carbon cloth is cut to the required size (such as 1x2 cm 2 ), and is sequentially ultrasonically cleaned with acetone, ethanol, and deionized water for 20 minutes each to remove surface impurities. The carbon cloth is immersed in an HNO3 / deionized water mixture and heated in a water bath at 80°C for 2 hours to introduce oxygen-containing functional groups (-COOH, -OH) and enhance the surface hydrophilicity, thereby obtaining an activated carbon cloth.
[0027] (2) 0.329 g of potassium ferricyanide is added to 50 mL of deionized water and stirred for 10-30 minutes. 0.291 g of cobalt nitrate hexahydrate is dissolved in 50 mL of deionized water. After mixing the two solutions, 0.582 g of trisodium citrate dihydrate is added as a complexing agent, and the solution pH is adjusted to 2 to inhibit side reactions.
[0028] (3) The activated carbon cloth is immersed in the precursor solution and sealed in a polytetrafluoroethylene high-pressure reaction kettle, and reacted at 120°C for 6 hours. After removal, it is alternately cleaned with ethanol and deionized water, and dried at 60°C to obtain the sample.
[0029] (4) The sample is placed in the middle of a tube furnace, 0.4 g of sulfur powder is placed upstream of the tube furnace, and the temperature is raised to 400°C at a rate of 3°C / min under an Ar atmosphere, and held for 2 hours to obtain a CoFe-PBA chalcogenized carbon cloth composite material containing CoS2 / FeS2 heterostructures.
[0030] Example 2: (1) The carbon cloth is cut to the required size (such as 1x2 cm 2 ), and is sequentially ultrasonically cleaned with deionized water and ethanol for 20 minutes each to remove surface impurities. Finally, it is rinsed with deionized water until neutral and vacuum dried at 60°C for 12 hours. The carbon cloth is immersed in 0.5 M H2SO4, the working electrode is the pretreated carbon cloth, the counter electrode is a platinum sheet, and the reference electrode is Ag / AgCl. The scan voltage is -0.5-2.0 V using cyclic voltammetry, and the activated carbon cloth (denoted as CC-O) is obtained after 30 minutes of activation and deionized water washing.
[0031] (2) 0.329 g of potassium ferricyanide is added to 50 mL of deionized water and stirred for 10-30 minutes. 0.291 g of cobalt nitrate hexahydrate is dissolved in 50 mL of deionized water. After mixing the two solutions, 0.582 g of trisodium citrate dihydrate is added as a complexing agent, and the solution pH is adjusted to 2 to inhibit side reactions.
[0032] (3) The activated carbon cloth is immersed in the precursor solution and sealed in a polytetrafluoroethylene high-pressure reaction kettle, and reacted at 120°C for 6 hours. After removal, it is alternately cleaned with ethanol and deionized water, and dried at 60°C to obtain CoFe-PBA@CC-O.
[0033] (4) The sample CoFe-PBA@CC-O is placed in the middle of a tube furnace, 0.4 g of sulfur powder is placed upstream of the tube furnace, and the temperature is raised to 400 ℃ at a rate of 3 ℃ / min under an Ar atmosphere, and the temperature is kept constant for 2 hours to obtain a CoFe-PBA sulfurized carbon cloth composite material containing CoS2 / FeS2 heterostructures.
[0034] Example 3: (1) The carbon cloth is cut to the required size (for example, 1×2 cm 2 ), and is sequentially ultrasonically cleaned with deionized water and ethanol for 20 minutes to remove surface impurities. Finally, the carbon cloth is rinsed with deionized water until it is neutral, and is vacuum dried at 60 ℃ for 12 hours. The carbon cloth is immersed in 0.5 M H2SO4, the working electrode is the pretreated carbon cloth, the counter electrode is a platinum sheet, and the reference electrode is Ag / AgCl. The scan voltage is -0.5-2.0 V by cyclic voltammetry, and the carbon cloth is activated for 30 minutes, and then is washed with deionized water to obtain an activated carbon cloth (denoted as CC-O).
[0035] (2) 0.329 g of potassium ferricyanide is weighed into 50 mL of deionized water, and is stirred for 10-30 minutes. 0.291 g of cobalt nitrate hexahydrate is dissolved in 50 mL of deionized water, and the two solutions are mixed. 0.582 g of trisodium citrate dihydrate is added as a complexing agent, and the pH of the solution is adjusted to 2 to inhibit side reactions.
[0036] (3) The activated carbon cloth is immersed in the precursor solution, and is sealed in a polytetrafluoroethylene high-pressure reaction kettle, and is reacted at 120 ℃ for 6 hours. After being taken out, the carbon cloth is alternately cleaned with ethanol and deionized water, and is dried at 60 ℃ to obtain CoFe-PBA@CC-O.
[0037] (4) The sample CoFe-PBA@CC-O is placed in the middle of a tube furnace, 0.4 g of sulfur powder is placed upstream of the tube furnace, and the temperature is raised to 500 ℃ at a rate of 3 ℃ / min under an Ar atmosphere, and the temperature is kept constant for 2 hours to obtain a CoFe-PBA sulfurized carbon cloth composite material containing CoS2 / FeS2 heterostructures.
[0038] Example 4: (1) The carbon cloth is cut to the required size (for example, 1×2 cm 2 ), and is sequentially ultrasonically cleaned with deionized water and ethanol for 20 minutes to remove surface impurities. Finally, the carbon cloth is rinsed with deionized water until it is neutral, and is vacuum dried at 60 ℃ for 12 hours. The carbon cloth is immersed in 0.5 M H2SO4, the working electrode is the pretreated carbon cloth, the counter electrode is a platinum sheet, and the reference electrode is Ag / AgCl. The scan voltage is -0.5-2.0 V by cyclic voltammetry, and the carbon cloth is activated for 30 minutes, and then is washed with deionized water to obtain an activated carbon cloth (denoted as CC-O).
[0039] (2) 0.329 g of potassium ferricyanide was weighed into 50 mL of deionized water and stirred for 10-30 minutes, 0.291 g of cobalt nitrate hexahydrate was dissolved in 50 mL of deionized water, and then the two solutions were mixed and 0.582 g of trisodium citrate dihydrate was added as a complexing agent to inhibit side reactions by adjusting the pH of the solution to 2.
[0040] (3) The activated carbon cloth was immersed in the precursor solution and sealed in a polytetrafluoroethylene high-pressure reaction kettle, and reacted at 120 °C for 6 hours. After taking out, it was washed alternately with ethanol and deionized water, and dried at 60 °C to obtain CoFe-PBA@CC-O.
[0041] (4) The sample CoFe-PBA@CC-O was placed in the middle of the tube furnace, 0.4 g of sulfur powder was placed upstream of the tube furnace, and the temperature was raised to 600 °C at a rate of 3 °C / min under an Ar atmosphere, and held for 2 hours to obtain a CoFe-PBA chalcogenized carbon cloth composite containing CoS2 / FeS2 heterostructures.
[0042] Example 5: (1) The carbon cloth was cut to the required size (such as 1×2 cm 2 ), and was sequentially ultrasonically cleaned with deionized water and ethanol for 20 minutes to remove surface impurities. Finally, it was washed with deionized water until neutral, and vacuum dried at 60 °C for 12 hours. The carbon cloth was immersed in 0.5 M H2SO4, the working electrode was the pretreated carbon cloth, the counter electrode was a platinum sheet, and the reference electrode was Ag / AgCl. The scanning voltage was -0.5-2.0 V by cyclic voltammetry, and the activated carbon cloth (denoted as CC-O) was obtained after activation treatment for 30 minutes and deionized water washing.
[0043] (2) 0.329 g of potassium ferricyanide was weighed into 50 mL of deionized water and stirred for 10-30 minutes, 0.291 g of cobalt nitrate hexahydrate was dissolved in 50 mL of deionized water, and then the two solutions were mixed and 0.582 g of trisodium citrate dihydrate was added as a complexing agent to inhibit side reactions by adjusting the pH of the solution to 2.
[0044] (3) The activated carbon cloth was immersed in the precursor solution and sealed in a polytetrafluoroethylene high-pressure reaction kettle, and reacted at 120 °C for 6 hours. After taking out, it was washed alternately with ethanol and deionized water, and dried at 60 °C to obtain CoFe-PBA@CC-O.
[0045] (4) The sample CoFe-PBA@CC-O was placed in the middle of the tube furnace, 0.5 g of selenium powder was placed upstream of the tube furnace, and the temperature was raised to 400 °C at a rate of 3 °C / min under an Ar atmosphere, and held for 2 hours to obtain a CoFe-PBA chalcogenized carbon cloth composite containing CoSe2 / FeSe2 heterostructures.
[0046] Example 6, performance test: The CoFe-PBA sulfide carbon cloth composites (including CoS2 / FeS2@CC-O or CoSe2 / FeSe2@CC-O) obtained from Examples 1-5 were subjected to electrochemical performance test. A three-electrode system was used to carry out electrochemical performance evaluation: the sample to be tested was used as the working electrode, an Ag / AgCl electrode was used as the reference electrode, a graphite rod was used as the counter electrode, and the electrolyte was a 1 M KOH solution. The hydrogen evolution / oxygen evolution polarization curve (hydrogen evolution reaction HER, oxygen evolution reaction OER) was determined by linear sweep voltammetry at a scan rate of 50 mV / s, and the solution resistance compensation was carried out synchronously during the test. The working potential obtained was uniformly converted to the reversible hydrogen electrode (RHE) scale for data analysis.
[0047] To quantitatively characterize the number of catalytic active sites, cyclic voltammetry tests (hydrogen evolution reaction HER, oxygen evolution reaction OER) were carried out at a multi-stage scan rate of 10-100 mV / s, and the electrochemical active surface area (ECSA) was further derived by calculating the double-layer capacitance value. The durability evaluation was carried out by chronoamperometry, and the full water splitting performance test was carried out by a symmetric double electrode device in a 1 M KOH system. All electrochemical tests were completed in a constant temperature environment of 25 °C to ensure data comparability.
[0048] The LSV performance, ECSA performance and full water splitting performance of CoS2 / FeS2@CC-O or CoSe2 / FeSe2@CC-O in Examples 1-5 are shown in Table 1. As can be seen from Table 1, compared with Example 1, the electrochemical performance of the electrochemically activated carbon cloth in Example 2 is obviously better, and the electrochemically activated carbon cloth is the core step to improve the performance, which enhances the catalyst loading and electron transport, realizes the in-situ growth of CoFe-PBA, and generates uniform dispersed CoS2 / FeS2 heterostructure by calcination in a sulfur atmosphere. At the same time, changing the pyrolysis temperature has a certain influence on the performance of the electrode material, and the pyrolysis temperature will affect the graphitization degree and thus affect the hydrogen evolution and oxygen evolution performance of water electrolysis.
[0049] Table 1
[0050] As can be seen from the data in Table 1, at a current density of 10 mA / cm², the overpotential of HER of Example 2 (electrochemical activation + sulfurization at 400 °C) is 63 mV, which is the best performance, and the electrochemical activation significantly improves the HER activity, and the surface oxygen-containing functional groups enhance the interface combination of the catalyst and the carbon cloth, and the sulfurization temperature affects the activity, and 400 °C (Example 2) is better than 500 °C (Example 3) and 600 °C (Example 4), and it may be due to the sintering of part of the active sites or the excessive graphitization of the carbon layer at too high a temperature; The overpotential in OER is 276 mV, and it is speculated that the synergistic effect of Co-Fe bimetal and the heterostructure optimize the electron transport path of OER.
[0051] The carbon cloth after electrochemical activation (Example 2) has a higher ECSA than Example 1, indicating that it exposes more active sites, which is consistent with the improvement of HER / OER performance; the increase of sulfidation temperature (400-600 ℃) leads to the decrease of ECSA, which may be related to the aggregation of particles or the densification of carbon layers.
[0052] The integrated design of the bifunctional catalyst (HER+OER) avoids the impedance matching problem between different materials and improves the overall water splitting efficiency.
[0053] Figure 1 The XRD pattern of Example 2, Figure 2 indicates that the phases are cobalt disulfide (JCPDS No. 41-1471) with a cobalt pyrite structure and iron disulfide (JCPDS No. 42-1340) with a pyrite structure. Figure 2 The SEM image of the nanoflower-shaped CoS2 / FeS2@CC-O prepared in Example 2 is shown, and it can be seen that the cubic block structure and the nanoflower structure are alternately present. The average diameter of the nanoflower composed of small cubic blocks is about 400 nm. Figure 3 The constant current test in Example 2, at a current density of 10 mA / cm 2 The voltage of the anode cell composed of CoS2 / FeS2@CC-O is 1.54 V, indicating that CoS2 / FeS2@CC-O exhibits excellent stability in long-term testing and can effectively resist electrolyte corrosion.
[0054] The present application is not limited to the above embodiments, and any changes in shape or structure fall within the scope of the present application. The scope of protection of the present application is defined by the appended claims, and those skilled in the art can make various changes, modifications, substitutions, combinations and simplifications to these embodiments without departing from the principles and essence of the present application. All such equivalent replacement methods fall within the scope of protection of the present application.
Claims
1. A method for preparing a CoFe-PBA chalcogenide carbon cloth composite material, characterized in that: The following steps are involved: S1: electrochemically activating and pre-oxidizing the carbon cloth to obtain activated carbon cloth with a surface rich in oxygen-containing functional groups; S2: Immersing the activated carbon cloth in a CoFe-PBA precursor solution, in situ growing cobalt iron Prussian blue (CoFe-PBA) nanoparticles on the surface of the activated carbon cloth to obtain a CoFe-PBA-loaded carbon cloth; S3: placing the CoFe-PBA loaded carbon cloth and a sulfur source or selenium source in a tube furnace, heating to 400-600°C at a rate of 2-5°C / min under an inert atmosphere, and keeping the temperature for 1-5 hours to generate a CoFe-PBA chalcogenide carbon cloth composite material; The mass ratio of the carbon cloth loaded with CoFe-PBA to the sulfur source or selenium source is 1:(2-6).
2. The method for preparing a CoFe-PBA chalcogenide carbon cloth composite material according to claim 1, characterized in that: In S1, the electrochemical activation pre-oxidation treatment method is: The carbon cloth was immersed in 0.1~1 M H2SO4, the working electrode was the pretreated carbon cloth, the counter electrode was a platinum sheet, and the reference electrode was Ag / AgCl. Cyclic voltammetry was used with a scanning voltage of -0.5-2.0 V, a scanning rate of 10-50 mV / s, and 10-20 cycles. After activation treatment for 10-30 minutes, a uniform nanoscale rough structure was formed on the surface of the carbon cloth, and carboxyl / hydroxyl functional groups were generated at the same time. The activated carbon cloth was obtained after washing with deionized water.
3. The method for preparing a CoFe-PBA chalcogenide carbon cloth composite material according to claim 2, characterized in that: The preparation method of the pretreated carbon cloth is as follows: ultrasonically clean the carbon cloth with deionized water and ethanol in sequence to remove surface impurities, then rinse with deionized water until neutral, and vacuum dry the carbon cloth for later use.
4. The method for preparing a CoFe-PBA chalcogenide carbon cloth composite material according to claim 1, characterized in that: The preparation method of CoFe-PBA precursor solution in S2 is: Weigh potassium ferrocyanide and add it to deionized water. Stir for 10-30 minutes to form a yellow transparent solution. Weigh cobalt salt and dissolve it in 50 mL of deionized water to obtain a pink transparent solution. Mix the two solutions and add trisodium citrate dihydrate as a complexing agent. Adjust the pH of the solution to 2 to inhibit side reactions. After the reaction is completed, a CoFe-PBA precursor solution is obtained. The molar ratio of the potassium ferricyanide, the cobalt salt and the trisodium citrate dihydrate is 2:2:(1-8).
5. The method for preparing a CoFe-PBA chalcogenide carbon cloth composite material according to claim 4, characterized in that: The cobalt salt is selected from cobalt acetate tetrahydrate or cobalt chloride hexahydrate.
6. The method for preparing a CoFe-PBA chalcogenide carbon cloth composite material according to claim 1, characterized in that: The preparation method of the CoFe-PBA loaded carbon cloth is as follows: The activated carbon cloth was immersed in the precursor solution, sealed in a polytetrafluoroethylene high-pressure reactor, and reacted at 120-180 ° C for 2-6 h to allow CoFe-PBA nanoparticles to grow in situ on the surface of the carbon cloth fiber. After the reaction was completed, the carbon cloth was taken out and washed alternately with ethanol and deionized water, and dried to obtain the CoFe-PBA-loaded carbon cloth.
7. The method for preparing a CoFe-PBA chalcogenide carbon cloth composite material according to claim 1, characterized in that: The sulfur source is any one of sulfur powder, thiourea or thioacetamide; and the selenium source is selected from selenium powder.
8. A CoFe-PBA chalcogenide carbon cloth composite material, characterized in that: Prepared by the preparation method according to any one of claims 1 to 7; The CoFe-PBA chalcogenide carbon cloth composite material comprises: a) Carbon cloth substrate, surface oxygen functional group density ≥5 at%; b) CoS2 / FeS2 heterostructure or CoSe2 / FeSe2 heterostructure nanoparticles, with a particle size of 10-100 nm; c) Sulfur-doped carbon layer with a thickness of 1~5 nm.
9. The CoFe-PBA chalcogenide carbon cloth composite material according to claim 8, characterized in that: The heterostructure is a core-shell type (CoS@FeS) and / or a mosaic type (CoS / FeS interface coupling).
10. Use of the CoFe-PBA sulfide carbon cloth composite material according to any one of claims 8 or 9 in hydrogen production by water electrolysis.