Self-reconfigurable high-entropy sulfide electrocatalyst and preparation method and application thereof

Abstract

The present application relates to the technical field of electrocatalytic materials, in particular to a deep self-reconstruction high-entropy sulfide electrocatalyst and a preparation method and application thereof.The deep self-reconstruction high-entropy sulfide electrocatalyst provided by the present application has a current density close to 600mA cm ‑2 when the potential reaches 1.8V vs.RHE, exhibits a lower overpotential and a higher current density, significantly improves the overall efficiency of water electrolysis hydrogen production, and provides strong support for the utilization of renewable energy and the large-scale preparation of hydrogen energy.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of electrocatalytic materials, in particular to a deep self-reconstruction high-entropy sulfide electrocatalyst and a preparation method and application thereof. BACKGROUND

[0002] The information disclosed in this Background section is only for the purpose of increasing the understanding of the background of the present application and should not be taken as an acknowledgement or any form of suggestion that this information forms prior art that is already commonly known in the art.

[0003] At present, hydrogen, as an energy carrier with the highest energy density, is attracting much attention in many new energy raw materials. Hydrogen energy not only has high energy density and is clean and pollution-free, but also has a wide range of sources, and has broad prospects in the field of new energy development. The most ideal way to prepare hydrogen is to prepare hydrogen by electrolysis of water. On the one hand, the raw material is simple and easy to obtain, and can be applied on a large scale. On the other hand, the prepared hydrogen is pure and does not need further desulfurization, and the process is simple. The hydrogen prepared by the process can be directly used for electric vehicles and other applications.

[0004] Electrolysis of water to produce hydrogen mainly includes two half-reactions, namely, oxygen evolution reaction (OER) at the anode and hydrogen evolution reaction (HER) at the cathode. HER and OER are two-electron transfer reactions and four-electron transfer reactions, respectively. OER is considered to be the bottleneck of water electrolysis for hydrogen production due to its large overpotential and slow kinetics. At present, the catalysts for efficient electrolysis of water to produce hydrogen mainly use noble metals and noble metal oxides. For OER reaction, the main catalysts used are IrO2 and RuO2, etc. However, this type of noble metal-based catalyst has the problems of scarcity of raw materials, high price, and easy poisoning, which makes it difficult to be applied on a large scale in practical applications. In recent years, many researchers have devoted to developing catalysts without noble metal elements, among which transition metal compounds have the advantages of low price and excellent performance. SUMMARY

[0005] In order to overcome the above problems, the present application provides a self-reconstruction high-entropy sulfide electrocatalyst and a preparation method and application thereof.

[0006] To achieve the above technical purposes, the present application adopts the following technical solutions:

[0007] In a first aspect of the present application, a self-reconstruction high-entropy sulfide electrocatalyst is provided,

[0008] The high-entropy sulfide is loaded on the working electrode, and after self-reconstruction treatment by cyclic voltammetry scanning in an alkaline solution, a material with a nanosheet array structure is obtained;

[0009] The high-entropy sulfide comprises transition metal elements and sulfur elements, the molar ratio of the transition metal elements and the sulfur elements is 1:2, and the transition metal elements are selected from five of Fe, Co, Ni, Cu, Mn, V, Zn and Cr.

[0010] In a second aspect of the present application, a preparation method of the self-reconstructed high-entropy sulfide electrocatalyst is provided, and the preparation method comprises the following steps:

[0011] (1) The transition metal salt solution and the organic sulfur source solution are mixed, and then a high-entropy sulfide is synthesized through a hydrothermal reaction;

[0012] (2) The high-entropy sulfide is loaded on a working electrode, and then a material with a nanosheet array structure is obtained through a self-reconstruction treatment in an alkaline solution by a cyclic voltammetry scanning method, that is, the self-reconstructed high-entropy sulfide electrocatalyst.

[0013] In a third aspect of the present application, an electrocatalytic anode material is provided, and the electrocatalytic anode material comprises a conductive substrate and the self-reconstructed high-entropy sulfide electrocatalyst.

[0014] In a fourth aspect of the present application, a preparation method of the electrocatalytic anode material is provided, and the preparation method comprises the following steps:

[0015] The transition metal salt solution and the organic sulfur source solution are mixed to obtain a mixed solution, the conductive substrate is immersed in the mixed solution, and then a foam nickel composite material loaded with a high-entropy sulfide is synthesized through a hydrothermal reaction;

[0016] The foam nickel composite material loaded with the high-entropy sulfide is used as a working electrode, and then an electrocatalytic anode material is obtained through a self-reconstruction treatment in an alkaline solution by a cyclic voltammetry scanning method.

[0017] In a fifth aspect of the present application, the self-reconstructed high-entropy sulfide electrocatalyst or the electrocatalytic anode material is applied to water electrolysis to produce hydrogen and oxygen.

[0018] The present application has the following beneficial effects:

[0019] (1) The present application relates to the technical field of electrocatalytic materials, in particular to a deeply self-reconstructed high-entropy sulfide electrocatalyst and a preparation method and application thereof. The deeply self-reconstructed high-entropy sulfide electrocatalyst provided by the present application realizes effective enrichment of active sites and effectively improves catalytic activity. The high-entropy characteristic enables the synergistic effect of multiple metal elements, optimizes the local electronic structure, promotes charge transfer, increases the number of active sites, and at the same time, the deep self-reconstruction not only increases the surface area of the high-entropy sulfide, but also activates the high-entropy sulfide to form high-valence active species, so that the active sites are enriched in situ, and the catalytic activity is further improved.

[0020] (2) The deep self-reconstruction high-entropy sulfide electrocatalyst provided by the application has a current density close to 600 mA cm when the potential reaches 1.8 V vs. RHE, which shows a lower overpotential and a higher current density, significantly improves the overall efficiency of hydrogen production by water electrolysis, and provides strong support for the utilization of renewable energy and the large-scale preparation of hydrogen energy. -2

[0021] (3) The deep self-reconstruction high-entropy sulfide electrocatalyst provided by the application significantly improves the overall efficiency of hydrogen production by water electrolysis in the water electrolysis anode OER reaction by adding glycerol as an electron sacrificial agent. When the current density is 100 mA cm -2 , the difference in current density corresponding to the two LSV curves reaches ΔE = 359 mV before and after the addition of glycerol. BRIEF DESCRIPTION OF DRAWINGS

[0022] The drawings accompanying the specification of the present application serve to provide a further understanding of the present application, and the schematic embodiments of the present application and the description thereof serve to explain the present application and do not constitute an improper limitation on the present application.

[0023] Figure 1 is the morphology of the high-entropy sulfide before self-reconstruction, wherein A is a TEM image and B is a SEM image;

[0024] Figure 2 is the morphology of the high-entropy sulfide after self-reconstruction, wherein A is a TEM image and B is a SEM image;

[0025] Figure 3 is the valence of Co (A), Cu (B), Fe (C), Mn (D) and Ni (E) in the high-entropy sulfide before self-reconstruction;

[0026] Figure 4 is the valence of Co (A), Cu (B), Fe (C), Mn (D) and Ni (E) in the high-entropy sulfide after self-reconstruction;

[0027] Figure 5 is the XRD image of the self-reconstruction high-entropy sulfide electrocatalyst prepared in Examples 1-5 and the comparative product Ni3S2;

[0028] Figure 6 is the LSV curve of the electrocatalytic anode material prepared in Example 1 in 1M KOH and 1M KOH + 0.1M glycerol electrolyte, respectively;

[0029] Figure 7 is the LSV curve of the electrocatalytic anode material prepared in Examples 1-5 in 1M KOH + 0.1M glycerol electrolyte, respectively. DETAILED DESCRIPTION

[0030] ​It should be noted that the following detailed description is exemplary in nature and is intended to provide further description of the application. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.

[0031] It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments in accordance with the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms "comprises" and / or "comprising," when used in this specification, specify the presence of stated features, steps, operations, elements, and / or components, but do not preclude the presence or addition of one or more other features, steps, operations, elements, components, and / or groups thereof.

[0032] In a first exemplary embodiment of the present application, there is provided a self-reconfigurable high-entropy sulfide electrocatalyst,

[0033] The high-entropy sulfide is loaded on a working electrode, and after self-reconfiguration treatment by cyclic voltammetry scanning in an alkaline solution, a material with a nanosheet array structure is obtained.

[0034] The high-entropy sulfide includes transition metal elements and sulfur elements; the molar ratio of the transition metal elements and the sulfur elements is 1:2; and the transition metal elements are selected from five of Fe, Co, Ni, Cu, Mn, V, Zn, and Cr.

[0035] In one or more embodiments, the nanosheet array structure has a thickness of about 10 nm and a length of about 500 nm.

[0036] In one or more embodiments, the transition metal elements are selected from Ni, Co, Fe, Cu, and Mn.

[0037] In one or more embodiments, the transition metal elements are selected from Ni, Co, Fe, Cu, and Zn.

[0038] In one or more embodiments, the transition metal elements are selected from Ni, Co, V, Cu, and Mn.

[0039] In one or more embodiments, the transition metal elements are selected from Ni, Co, Fe, Cu, and Cr.

[0040] In one or more embodiments, the transition metal elements are selected from Ni, Co, Fe, Zn, and Cr.

[0041] In one or more embodiments, each transition metal element in the high-entropy sulfide is in an equal molar ratio or a near equal molar ratio.

[0042] In a second typical embodiment of the present application, a preparation method of the self-reconstructed high-entropy sulfide electrocatalyst of the first aspect is provided, comprising the following steps:

[0043] (1) mixing a transition metal salt solution and an organic sulfur source solution, and then performing hydrothermal reaction to synthesize a high-entropy sulfide;

[0044] (2) loading the high-entropy sulfide on a working electrode, and then performing self-reconstruction treatment in an alkaline solution by cyclic voltammetry to obtain a material with a nanosheet array structure, i.e., the self-reconstructed high-entropy sulfide electrocatalyst.

[0045] In one or more embodiments, in step (1), the organic sulfur source is selected from thioacetamide.

[0046] In one or more embodiments, in step (1), the temperature of the hydrothermal reaction is 130-150°C, and preferably 140°C; and the time of the hydrothermal reaction is 11-13h, and preferably 12h.

[0047] In one or more embodiments, in step (2), the alkaline solution is a KOH solution or a NaOH solution, and the concentration of the KOH solution or the NaOH solution is 0.8-1.2M, and preferably 1M.

[0048] In one or more embodiments, in step (2), the voltage range of the cyclic voltammetry is 1.0-1.8V vs. RHE.

[0049] In one or more embodiments, in step (2), the scan rate of the cyclic voltammetry is 90-110mV s -1 , and preferably 100mV s -1 .

[0050] In one or more embodiments, in step (2), the number of cycles of the cyclic voltammetry is 90-110 cycles, and preferably 100 cycles.

[0051] In a third typical embodiment of the present application, an electrocatalytic anode material is provided, comprising a conductive substrate and the self-reconstructed high-entropy sulfide electrocatalyst of the first aspect.

[0052] In one or more embodiments, the conductive substrate is selected from a nickel foam.

[0053] In a fourth typical embodiment of the present application, a preparation method of the above electrocatalytic anode material is provided, comprising the following steps:

[0054] mixing a transition metal salt solution and an organic sulfur source solution to obtain a mixed solution, and then immersing a conductive substrate in the mixed solution to perform hydrothermal reaction and synthesize a nickel foam composite material loaded with a high-entropy sulfide.

[0055] The self-reconstructed high-entropy sulfide electrocatalyst of the first aspect or the electrocatalytic anode material of the third aspect is used in the electrolysis of water to produce hydrogen and oxygen.

[0056] In a fifth typical embodiment of the present application, the self-reconstructed high-entropy sulfide electrocatalyst of the first aspect or the electrocatalytic anode material of the third aspect is used in the electrolysis of water to produce hydrogen and oxygen.

[0057] In one or more embodiments, glycerol is added as an electron sacrificial agent in the process of electrolysis of water to produce hydrogen and oxygen.

[0058] In order to enable those skilled in the art to more clearly understand the technical solutions of the present application, the technical solutions of the present application will be described in detail below with specific examples.

[0059] Example 1

[0060] (1) Pretreatment of the foam nickel: Place the foam nickel (1 x 4 cm) in a beaker, add anhydrous ethanol to it, and ultrasonicate for 5 min to remove organic matter from the surface of the foam nickel; then ultrasonicate with a 1% mass fraction dilute hydrochloric acid solution for 5 min to remove the oxide layer from the surface of the foam nickel. Finally, wash with deionized water for 3-5 times, and it can be used for subsequent experimental steps.

[0061] (2) Dissolve 0.3 mmol of Ni(NO3)2·6H2O, Co(NO3)2·6H2O, Fe(NO3)3·9H2O, Cu(NO3)2·3H2O and Mn(NO3)2·4H2O in a total amount of 17 mL of deionized water in an equimolar ratio, stir uniformly to form solution A. Then weigh 0.6 mmol of thioacetamide into 17 mL of deionized water to form a uniform transparent solution B. Slowly add solution B to solution A, stir at room temperature for 30 min to form a mixed solution, then place the foam nickel substrate treated in advance into a 50 mL polytetrafluoroethylene liner, then add the mixed solution into the liner and seal, then transfer to a stainless steel autoclave, and keep at 140°C for 12 hours. After the reaction is completed, naturally cool to room temperature, take out the solid catalyst, i.e. the foam nickel composite material loaded with high-entropy sulfide, rinse with deionized water and ethanol, and dry in a vacuum drying oven overnight.

[0062] (3) Electrochemical self-reconstruction is carried out by cyclic voltammetry using a CHI660 electrochemical workstation in a 1M KOH electrolyte. The foam nickel composite material loaded with high-entropy sulfide is used as the working electrode, a platinum sheet is used as the counter electrode, and a Hg / HgO electrode is used as the reference electrode. The voltage range of the cyclic voltammetry is 1.0-1.8V vs. RHE, and the scan rate is 100mV s-1 After 100 cycles, the material with nanosheet array structure was obtained, and then washed with deionized water and ethanol respectively, and dried in a vacuum drying oven at 40℃ overnight to obtain the foam nickel composite loaded with self-reconstructed high-entropy sulfide electrocatalyst, i.e. electrocatalytic anode material.

[0063] Figure 1 Fig. 1 is the morphology of high-entropy sulfide before self-reconstruction, wherein A is a TEM image and B is a SEM image; Figure 2 Fig. 2 is the morphology of high-entropy sulfide after self-reconstruction, wherein A is a TEM image and B is a SEM image, from Figure 1 and Figure 2 It can be seen from the above that after electrochemical reconstruction, the original irregular block is derived into nanosheet, which increases the electrochemical surface area and enhances the catalytic ability of the catalyst.

[0064] Figure 3 and Figure 4 are the valence of Co (A), Cu (B), Fe (C), Mn (D) and Ni (E) in high-entropy sulfide before and after self-reconstruction, Co 3+ , Fe 3+ , Ni 3+ , Mn 3+ and Mn 4+ in the respective elements increase, the valence increases, indicating the formation of high-valence active species, which can further enrich the active sites in situ and further improve the catalytic activity.

[0065] Example 2

[0066] (1) Pretreatment of foam nickel: Put the foam nickel (1x4cm) into a beaker, add anhydrous ethanol into the beaker, and ultrasonic for 5min to remove the organic matter on the surface of the foam nickel; then ultrasonic for 5min with 1% mass fraction of dilute hydrochloric acid solution to remove the oxide layer on the surface of the foam nickel. Finally, wash with deionized water for 3-5 times, and then use for subsequent experimental steps.

[0067] (2) The total amount of metal salt is 0.3 mmol of Ni(NO3)2·6H2O, Co(NO3)2·6H2O, Fe(NO3)3·9H2O, Cu(NO3)2·3H2O and Zn(NO3)2·6H2O, which are dissolved in 17 mL of deionized water in an equimolar ratio, stirred uniformly to form solution A. Then 0.6 mmol of thioacetamide is dissolved in 17 mL of deionized water to form a uniform transparent solution B. Slowly add solution B to solution A, stir at room temperature for 30 min to form a mixed solution, then place the previously treated foam nickel substrate into a 50 mL polytetrafluoroethylene liner, then add the mixed solution to the liner and seal, then transfer to a stainless steel autoclave, and keep at 140°C for 12 hours. After the reaction is completed, it is naturally cooled to room temperature, and the solid catalyst, i.e. the foam nickel composite loaded with high-entropy sulfide, is washed with deionized water and ethanol and dried in a vacuum drying oven overnight.

[0068] (3) Electrochemical self-reconstruction is carried out by cyclic voltammetry using CHI660 electrochemical workstation in 1M KOH electrolyte. The foam nickel composite loaded with high-entropy sulfide is used as the working electrode, platinum sheet as the counter electrode, and Hg / HgO electrode as the reference electrode. The voltage range of cyclic voltammetry is 1.0-1.8V vs. RHE, and the scanning rate is 100mV s -1 , followed by 100 cycles to obtain a material with nanosheet array structure, which is washed with deionized water and ethanol respectively and dried in a vacuum drying oven at 40°C overnight to obtain a foam nickel composite loaded with self-reconstructed high-entropy sulfide electrocatalyst, i.e. electrocatalytic anode material.

[0069] Example 3

[0070] (1) Pretreatment of foam nickel: Place the foam nickel (1×4 cm) in a beaker, add anhydrous ethanol, and ultrasonic for 5 min to remove organic matter on the surface of the foam nickel; then ultrasonic for 5 min with 1% dilute hydrochloric acid solution to remove the oxide layer on the surface of the foam nickel. Finally, wash with deionized water for 3-5 times, and it can be used for subsequent experimental steps.

[0071] (2) The total amount of metal salt is 0.3 mmol of Ni(NO3)2·6H2O, Co(NO3)2·6H2O, V(NO3)3·6H2O, Cu(NO3)2·3H2O and Mn(NO3)2·4H2O, which are dissolved in 17 mL of deionized water in an equimolar ratio, stirred uniformly to form solution A. Then 0.6 mmol of thioacetamide is dissolved in 17 mL of deionized water to form a uniform transparent solution B. Slowly add solution B to solution A, stir at room temperature for 30 min to form a mixed solution, then place the previously treated foam nickel substrate into a 50 mL polytetrafluoroethylene liner, then add the mixed solution to the liner and seal, then transfer to a stainless steel autoclave, and keep at 140°C for 12 hours. After the reaction is completed, it is naturally cooled to room temperature, and the solid catalyst, i.e. the foam nickel composite loaded with high-entropy sulfide, is washed with deionized water and ethanol and dried in a vacuum drying oven overnight.

[0072] (3) Electrochemical self-reconstruction is carried out by cyclic voltammetry using CHI660 electrochemical workstation in 1M KOH electrolyte. The foam nickel composite loaded with high-entropy sulfide is used as the working electrode, platinum sheet as the counter electrode, and Hg / HgO electrode as the reference electrode. The voltage range of cyclic voltammetry is 1.0-1.8V vs. RHE, and the scanning rate is 100mV s -1 , followed by 100 cycles to obtain a material with nanosheet array structure, which is washed with deionized water and ethanol respectively and dried in a vacuum drying oven at 40°C overnight to obtain a foam nickel composite loaded with self-reconstructed high-entropy sulfide electrocatalyst, i.e. electrocatalytic anode material.

[0073] Example 4

[0074] (1) Pretreatment of foam nickel: Place the foam nickel (1×4 cm) in a beaker, add anhydrous ethanol, and ultrasonic for 5 min to remove organic matter on the surface of the foam nickel; then ultrasonic for 5 min with 1% dilute hydrochloric acid solution to remove the oxide layer on the surface of the foam nickel. Finally, wash with deionized water for 3-5 times, and it can be used for subsequent experimental steps.

[0075] (2) The total amount of metal salt is 0.3 mmol of Ni(NO3)2·6H2O, Co(NO3)2·6H2O, Fe(NO3)3·9H2O, Cu(NO3)2·3H2O and Cr(NO3)3·9H2O, which are dissolved in 17 mL of deionized water in an equimolar ratio, stirred uniformly to form solution A. Then 0.6 mmol of thioacetamide is dissolved in 17 mL of deionized water to form a uniform transparent solution B. Slowly add solution B to solution A, stir at room temperature for 30 min to form a mixed solution, then place the previously treated nickel foam substrate into a 50 mL polytetrafluoroethylene liner, then add the mixed solution to the liner and seal, then transfer to a stainless steel autoclave, and keep at 140°C for 12 hours. After the reaction is completed, it is naturally cooled to room temperature, and the solid catalyst, i.e. the high-entropy sulfide-loaded nickel foam composite, is taken out, washed with deionized water and ethanol, and dried in a vacuum drying oven overnight.

[0076] (3) Electrochemical self-reconstruction is carried out by cyclic voltammetry using CHI660 electrochemical workstation in 1M KOH electrolyte. The high-entropy sulfide-loaded nickel foam composite is used as the working electrode, platinum sheet as the counter electrode, and Hg / HgO electrode as the reference electrode. The voltage range of cyclic voltammetry is 1.0-1.8V vs. RHE, and the scanning rate is 100mV s -1 , followed by 100 cycles to obtain a material with nanosheet array structure, which is washed with deionized water and ethanol respectively, and dried in a vacuum drying oven at 40°C overnight to obtain a high-entropy sulfide electrocatalyst-loaded nickel foam composite, i.e. an electrocatalytic anode material.

[0077] Example 5

[0078] (1) Pretreatment of nickel foam: Place the nickel foam (1×4 cm) in a beaker, add anhydrous ethanol, and ultrasonic for 5 min to remove organic matter on the surface of the nickel foam; then ultrasonic for 5 min with 1% dilute hydrochloric acid solution to remove the oxide layer on the surface of the nickel foam. Finally, wash with deionized water for 3-5 times, and it can be used for subsequent experimental steps.

[0079] (2) 0.3 mmol of Ni(NO3)2·6H2O, Co(NO3)2·6H2O, Fe(NO3)3·9H2O, Zn(NO3)2·6H2O and Cr(NO3)3·9H2O were dissolved in 17 mL of deionized water in an equimolar ratio to form solution A. 0.6 mmol of thioacetamide was dissolved in 17 mL of deionized water to form a uniform transparent solution B. Solution B was slowly added to solution A, stirred at room temperature for 30 min to form a mixed solution, then the previously treated nickel foam substrate was placed in a 50 mL polytetrafluoroethylene liner, then the mixed solution was added to the liner and sealed, and then transferred to a stainless steel autoclave and kept at 140°C for 12 hours. After the reaction was completed, it was naturally cooled to room temperature, and the solid catalyst, i.e. the high-entropy sulfide-loaded nickel foam composite, was washed with deionized water and ethanol and dried in a vacuum drying oven overnight.

[0080] (3) Electrochemical self-reconstruction was carried out by cyclic voltammetry using CHI660 electrochemical workstation in 1M KOH electrolyte. The high-entropy sulfide-loaded nickel foam composite was used as the working electrode, platinum sheet as the counter electrode, and Hg / HgO electrode as the reference electrode. The voltage range of cyclic voltammetry was 1.0-1.8V vs. RHE, and the scan rate was 100mV s -1 , followed by 100 cycles to obtain a material with nanosheet array structure, which was washed with deionized water and ethanol respectively and dried in a vacuum drying oven at 40°C overnight to obtain a high-entropy sulfide electrocatalyst-loaded nickel foam composite, i.e. an electrocatalytic anode material.

[0081] Comparative Example 1

[0082] Compared with Example 1, no electrochemical self-reconstruction was carried out.

[0083] Figure 5 The XRD images of the self-reconstructed high-entropy sulfide electrocatalyst prepared in Examples 1-5 and the comparative product Ni3S2 were compared, and it could be confirmed from the Figure 5 that the self-reconstructed high-entropy sulfide was synthesized.

[0084] Figure 6 The LSV curves of the electrocatalytic anode material prepared in Example 1 in 1M KOH and 1M KOH+0.1M glycerol electrolyte were compared, and it could be seen from the Figure 6 that the overall efficiency of water electrolysis hydrogen production was significantly improved by adding glycerol as an electron sacrificial agent in the anode OER reaction of water electrolysis. The current density difference of the two LSV curves before and after adding glycerol reached ΔE=359mV at a current density of 100mA cm -2 .

[0085] Figure 7 LSV curves of the electrocatalytic anode materials prepared in Examples 1-5 in 1 M KOH + 0.1 M glycerol electrolyte, respectively, from Figure 7 It can be seen from the above that when the current density of 50 mA cm -2 -2 reached 545.0 mA cm -2 -2, which was 1.5 to 2.8 times higher than the same catalysts.

[0086] The above description is merely preferred embodiments of the present application, but not for limiting the present application. For the skilled in the art, the present application can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A method for preparing a self-reconfigurable high-entropy sulfide electrocatalyst, comprising the following steps: (1) mixing a transition metal salt solution and an organic sulfur source solution, and then performing hydrothermal reaction to synthesize a high-entropy sulfide; (2) loading the high-entropy sulfide on a working electrode, and then performing self-reconfiguration treatment in an alkaline solution by cyclic voltammetry to obtain a material with a nanosheet array structure, i.e., a self-reconfigurable high-entropy sulfide electrocatalyst; wherein the high-entropy sulfide comprises transition metal elements and sulfur elements, and the molar ratio of the transition metal elements to the sulfur elements is 1:2; the transition metal elements are selected from five of Fe, Co, Ni, Cu, Mn, V, Zn and Cr; in step (2), the voltage range of the cyclic voltammetry is 1.0-1.8 V vs. RHE; or, in step (2), the cycle number of the cyclic voltammetry is 90-110 cycles. 2.The method for preparing a self-reconfigurable high-entropy sulfide electrocatalyst according to claim 1, wherein the nanosheet array structure has a thickness of about 10 nm and a length of about 500 nm; or the transition metal elements are selected from Ni, Co, Fe, Cu and Mn; or the transition metal elements are selected from Ni, Co, Fe, Cu and Zn; or the transition metal elements are selected from Ni, Co, V, Cu and Mn; or the transition metal elements are selected from Ni, Co, Fe, Cu and Cr; or the transition metal elements are selected from Ni, Co, Fe, Zn and Cr; or each of the transition metal elements in the high-entropy sulfide is in an equimolar ratio or a near equimolar ratio. In step (1), the organic sulfur source is selected from thioacetamide. In step (1), the temperature of the hydrothermal reaction is 130-150 ℃, and the time of the hydrothermal reaction is 11-13 h. In step (1), the temperature of the hydrothermal reaction is 140 ℃. In step (1), the time of the hydrothermal reaction is 12 h. Or, in step (2), the scan rate of the cyclic voltammetry scan method is 90-110 mV s -1 ; In step (2), the alkaline solution is a KOH solution or a NaOH solution, and the concentration of the KOH solution or the NaOH solution is 0.8-1.2 M. The concentration of the KOH solution or the NaOH solution is 1 M. In step (2), the cycle number of the cyclic voltammetry is 100 cycles. The electrocatalyst obtained by the method for preparing a self-reconfigurable high-entropy sulfide electrocatalyst according to claim 1 or 2. The conductive substrate is selected from a nickel foam. The method comprises the following steps: mixing a transition metal salt solution and an organic sulfur source solution to obtain a mixed solution, immersing a conductive substrate in the mixed solution, and then performing hydrothermal reaction to synthesize a nickel foam composite material loaded with a high-entropy sulfide; and using the nickel foam composite material loaded with the high-entropy sulfide as a working electrode, and then performing self-reconfiguration treatment in an alkaline solution by cyclic voltammetry to obtain an electrocatalytic anode material. 13.Use of the electrocatalyst obtained by the method for preparing a self-reconfigurable high-entropy sulfide electrocatalyst according to claim 1 or 2 or the electrocatalytic anode material according to claim 10 in electrolysis of water to produce hydrogen and oxygen. ​ ​ 3. The method of claim 1, wherein the self-reconfiguring high-entropy sulfide electrocatalyst is prepared by the steps of: ​ ​ 4. The method of claim 3, wherein the self-reconfiguring high-entropy sulfide electrocatalyst is prepared by the method comprising: ​ 5. The method of claim 3, wherein the self-reconfiguring high-entropy sulfide electrocatalyst is prepared by the steps of: ​ 6. The method of claim 1, wherein the self-reconfiguring high-entropy sulfide electrocatalyst is prepared by the method comprising: ​ 7. The method of claim 6, wherein the self-reconfiguring high-entropy sulfide electrocatalyst is prepared by the method comprising: ​ 8. The method of claim 1, wherein the self-reconfiguring high-entropy sulfide electrocatalyst is prepared by the method comprising: In step (2), the scan rate of the cyclic voltammetry scan is 100 mV s -1 .

9. The method of claim 1, wherein the self-reconfiguring high-entropy sulfide electrocatalyst is prepared by the method comprising: ​ 10. An electrocatalytic anode material, characterized in that, ​ 11. The electrocatalytic anode material of claim 10, wherein, ​ 12. The method of producing an electrocatalytic anode material according to claim 10, characterized in that, ​ ​ ​ ​ 14. Use according to claim 13, wherein the compound is ###0002### Glycerol is added as an electron sacrificial agent in the process of electrolysis of water to produce hydrogen and oxygen.

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