Preparation method of integrated high-entropy monatomic electrode

Abstract

The application provides a preparation method of an integrated high-entropy monatomic electrode, comprising the following steps: constructing heteroatom anchor points on the surface of a carbon substrate by using plasma; preparing an electrolyte; using the electrolyte, according to a deposition sequence of standard reduction potentials from high to low of metals to be deposited, performing step-by-step underpotential deposition; and obtaining the integrated high-entropy monatomic electrode through post-processing. The application can directly construct a high-activity electrode on a large-size carbon substrate, realize stable coexistence of various metal monatoms, and is suitable for large-scale industrial application.

Description

Technical Field

[0001] This application relates to the field of single-atom electrodes, and more specifically, to a method for preparing an integrated high-entropy single-atom electrode. Background Technology

[0002] Atomically dispersed metal catalysts (single-atom catalysts) are cutting-edge materials in the field of energy conversion due to their 100% atomic utilization and unique coordination environment. However, metal single atoms are prone to aggregation due to their extremely high surface free energy. Currently, electrodeposition is considered a potential low-cost route for preparing single-atom catalysts, especially surface confinement techniques based on underpotential deposition (UPD). However, existing electrodeposition techniques for preparing single-atom catalysts (such as Nature Communications, 2020, 11:4558) have the following limitations, particularly posing significant challenges for applications on carbon substrates: The inertness of carbon substrates limits the application of underpotential deposition (a key challenge): traditional underpotential deposition typically requires the binding energy between the deposited metal and the substrate to be significantly greater than the metal's own binding energy. This phenomenon often occurs on noble metal substrates. Ordinary industrial-grade carbon cloth / carbon fiber surfaces are chemically inert and lack strong coordination sites. Metal ions on carbon surfaces tend to aggregate into nanoparticles via the Volmer-Weber mode (island growth) rather than forming a single atomic layer. Therefore, directly preparing single atoms on carbon substrates using underpotential deposition is extremely difficult.

[0003] The challenge of "displacement reaction" in multi-component metals: When constructing a multi-metal (high-entropy) system, if the deposition order is not controlled, the more active (more negative potential) metals will be deposited first. Once they come into contact with an electrolyte containing more inert (more positive potential) metal ions, a spontaneous galvanic replacement reaction will occur, which will cause the deposited atomic layers to be destroyed and agglomerated, making it impossible to obtain an ordered high-entropy structure.

[0004] Large-size integration is difficult to achieve: Existing technologies mostly rely on expensive specific carriers (such as MoS2 powder), which need to be coated on the electrode after preparation. The process is complicated and there is interfacial resistance, making it difficult to meet the continuous production needs of industrial-grade large-size electrodes.

[0005] A search revealed a patent with application publication number CN 119243219 A, which discloses a supported metal atom catalyst, its preparation method, and its application. This patent utilizes pyridine nitrogen defect sites on the surface of nitrogen-doped porous graphene as sites for underpotential deposition of metal single atoms. The metal single-atom catalyst is obtained through a first step of underpotential deposition. It can also prepare a first-metal and second-metal diatomic catalyst using underpotential deposition and electrodisplacement. However, this patent cannot construct high-entropy (>4 metals) systems, and the substrate preparation is complex and expensive. The technology relies on "nitrogen-doped porous graphene," which is typically a powdered nanomaterial with a complex preparation process. Furthermore, it requires a binder coating during application, increasing interfacial resistance and making it unsuitable for direct assembly of large-size devices.

[0006] Patent application CN 118308754 A discloses a method for preparing a high-entropy compound / carbon self-supporting integrated electrode. The method includes using carbon cloth as a substrate and constructing a vertical graphene array on its surface using plasma technology; immersing the carbon cloth with the vertical graphene array on its surface in a mixed solution of metal precursor ions / ethanol / urea; after the carbon cloth is fully wetted, it is removed and subjected to a combustion process in air, collecting the combustion products; the combustion products are repeatedly rinsed and then air-dried to obtain the finished product. In this patent, plasma is used to grow the vertical graphene array to change its physical morphology. The combustion method used in this patent is a violent thermochemical process with high reaction temperatures that are difficult to control precisely. Under these conditions, metals tend to aggregate and oxidize through thermal diffusion, forming micron / nanoscale high-entropy compound particles / crystals (such as oxides and alloys) rather than atomically dispersed single atoms. Summary of the Invention

[0007] In view of the deficiencies in the prior art, the purpose of this application is to provide a method for preparing an integrated high-entropy single-atom electrode.

[0008] This application provides a method for preparing an integrated high-entropy single-atom electrode, comprising: Using plasma to construct heteroatom anchor points on the surface of a carbon substrate; Preparation of electrolyte; Using the electrolyte, a stepwise underpotential deposition process is performed according to the deposition sequence of the metal to be deposited, from high to low standard reduction potential. After post-processing, an integrated high-entropy single-atom electrode is obtained.

[0009] Optionally, the method of constructing heteroatom anchors on the surface of a carbon substrate using plasma, wherein the heteroatom is O.

[0010] Optionally, the method of constructing heteroatom anchors on the carbon substrate surface using plasma is described, wherein the gas used for plasma treatment is O2.

[0011] Optionally, the method of constructing heteroatom anchors on the surface of a carbon substrate using plasma, wherein the heteroatom is N.

[0012] Optionally, the method of constructing heteroatom anchors on the carbon substrate surface using plasma is wherein the gas used for plasma treatment is N2 or NH3.

[0013] Optionally, the preparation of the electrolyte includes: For each deposited metal, a corresponding metal solution is prepared using a metal salt to obtain an electrolyte corresponding to each deposited metal.

[0014] Optionally, the electrolyte is prepared in the form of a solution with a concentration of 0.001-0.05 M.

[0015] Optionally, the stepwise underpotential deposition using the electrolyte, based on a deposition sequence from high to low standard reduction potential determined by the metal to be deposited, includes: Based on the metal to be deposited, the metal with the most positive equilibrium potential is determined as the most inert metal. The underpotential deposition range of the metal on the carbon substrate is determined by cyclic voltammetry. In the underpotential deposition range, a potential that is more positive than the equilibrium potential of the most inert metal is selected for constant potential deposition. Following the order of standard reduction potential from high to low, the working electrodes are sequentially moved to the corresponding electrolytes for underpotential deposition.

[0016] Optionally, the underpotential deposition is performed at room temperature using a standard three-electrode system, with a carbon substrate containing heteroatom anchors as the working electrode, a graphite electrode as the counter electrode, and an Ag / AgCl electrode as the reference electrode.

[0017] Optionally, the post-processing includes: first washing with deionized water, and then drying with nitrogen or vacuum.

[0018] The method for fabricating an integrated high-entropy single-atom electrode provided in this application utilizes plasma to implant heteroatoms as anchor points on an inert carbon substrate. The lone pair electrons of these heteroatoms can form strong coordination bonds with metal ions. This bonding significantly reduces the Gibbs free energy of the metal on the carbon surface. Furthermore, by utilizing the difference in standard reduction potentials of the metals, metal atoms are locked in a stepwise manner from positive to negative, achieving the stable coexistence of multiple metal single atoms. This application overcomes the limitations of underpotential deposition on carbon substrates, offers flexible metal combinations, stable processes, eliminates substitution side reactions, and enables the fabrication of large-size integrated high-entropy single-atom electrodes, making it suitable for large-scale industrial applications.

[0019] Other technical effects resulting from the additional features will be further illustrated in the corresponding embodiments. Attached Figure Description

[0020] Other features, objects, and advantages of this application will become more apparent from the following detailed description of non-limiting embodiments with reference to the accompanying drawings: Figure 1 This is a flowchart illustrating a method for fabricating an integrated high-entropy single-atom electrode according to an exemplary embodiment; Figure 2 This is a schematic diagram illustrating a method for fabricating an integrated high-entropy single-atom electrode according to an exemplary embodiment; Figure 3 Aberration-corrected scanning transmission electron microscope image of an integrated high-entropy single-atom electrode according to an exemplary embodiment; Figure 4 This is a high-resolution C1s XPS spectrum of a carbon substrate treated with O2 plasma according to an exemplary embodiment. Detailed Implementation

[0021] The present application will now be described in detail with reference to specific embodiments. These embodiments will help those skilled in the art to further understand the present application, but do not limit the present application in any way. It should be noted that those skilled in the art can make several modifications and improvements without departing from the concept of the present application, and these all fall within the protection scope of the present application. Parts not described in detail in the following embodiments can be implemented using existing technology.

[0022] Terminology Explanation: UPD (Underpotential Deposition) refers to the phenomenon where a metal ion deposits a single atomic layer or subatomic layer on the surface of a heterogeneous substrate at a potential that is more positive than its thermodynamic reversible deposition potential.

[0023] High-entropy single atom: refers to four or more metallic elements coexisting in an atomically dispersed form on the same substrate, with each element being uniformly distributed and not forming alloy clusters.

[0024] In existing technologies for preparing single-atom electrodes by underpotential deposition, ordinary carbon cloth cannot induce metal underpotential deposition, which limits its application in underpotential deposition. In the process of preparing high-entropy single-atom electrodes, substitution side reactions may occur between different metals, and some technologies rely on expensive carriers and binders, which are complex and costly, making it difficult to meet the needs of continuous production of industrial-grade large-size electrodes.

[0025] To address the aforementioned problems, this application provides a method for preparing an integrated high-entropy single-atom electrode.

[0026] Reference Figure 1 and Figure 2 In one embodiment of this application, the method for preparing an integrated high-entropy single-atom electrode includes the following steps: S1. Construct heteroatom anchor points on the surface of a carbon substrate using plasma; S2. Prepare the electrolyte; S3. Using the electrolyte, perform stepwise underpotential deposition according to the deposition sequence of the standard reduction potential from high to low (i.e., from strong to weak oxidizing power) based on the metal to be deposited. S4. After post-processing, an integrated high-entropy single-atom electrode is obtained.

[0027] Specifically, to address the issue that ordinary carbon cloth cannot induce underpotential metal deposition, plasma surface modification is employed to endow it with the thermodynamic ability to capture metal single atoms, overcoming the surface inertia of the carbon substrate and creating "UPD-like" conditions. To suppress substitution reactions during multi-metal assembly, a universal deposition sequence rule is established to prevent substitution between different metals, achieving the stable coexistence of multiple metal single atoms, referencing... Figure 3 The image shown is an AC-STEM image of PtNi bimetallic single atoms prepared by this method. It can be seen that the prepared bimetallic single atoms exhibit no aggregation and are uniformly dispersed. Due to overcoming the interference of substitution reactions, four or more metal single atoms can also coexist stably. This application eliminates expensive carriers and binders, directly constructing highly active electrodes on a macroscopic conductive substrate, achieving the integrated fabrication of inexpensive, large-size electrodes. This application provides a more universal, lower-cost solution for directly fabricating large-size integrated high-performance electrodes.

[0028] The core mechanism of the preparation method in this application is plasma defect engineering and stepwise underpotential deposition based on potential gradient. This application does not follow the traditional UPD's reliance on a metal substrate, but creatively utilizes plasma treatment to "implant" strongly electronegative nonmetallic heteroatoms as anchor points on an inert carbon substrate, obtaining a modified carbon substrate. The lone pair electrons of these anchor points can form strong coordination bonds with metal ions, and this bonding significantly reduces the Gibbs free energy of the metal on the carbon surface. Based on this, the difference in the standard reduction potential of the metal is used to lock the metal atoms stepwise in a "from positive to negative" order.

[0029] The embodiments of this application overcome the limitations of underpotential deposition on carbon substrates, offer flexible metal combinations, have stable processes, eliminate substitution side reactions, and enable the fabrication of large-size integrated high-entropy single-atom electrodes, making them suitable for large-scale industrial applications.

[0030] Compared to existing technologies such as (CN119243219A), the embodiments of this application overcome the interference of substitution reactions and can stably integrate four or more metal single atoms, such as Ag, Cu, Ni, Co, Fe, and Mn, on the same substrate. The embodiments of this application utilize plasma to in-situ etch strongly electronegative defects (heteroatom anchors) on ordinary carbon cloth, changing the chemical surface energy to create the thermodynamic conditions required for underpotential deposition. By combining plasma anchoring with potential gradient underpotential deposition, the embodiments of this application not only solve the problem of underpotential deposition on inexpensive carbon substrates (such as carbon cloth), but also successfully incorporate highly reactive metals (such as Mn), which are generally considered extremely difficult to deposit, into a high-entropy single-atom system, achieving the ordered assembly of all transition metals. This achieves the integrated effect of "activating inexpensive inert substrates" and "precisely assembling high-entropy single atoms."

[0031] In step S1 above, substrate defect treatment is a key step. To improve the treatment effect, the carbon substrate (carbon cloth) is first cleaned, and then the cleaned carbon cloth is treated with plasma technology.

[0032] In some specific embodiments of this application, plasma is used to construct heteroatom anchor points on the surface of a carbon substrate, wherein the heteroatom is O.

[0033] In order to introduce oxygen anchors, in some specific embodiments of this application, plasma is used to construct heteroatom anchors on the surface of a carbon substrate, wherein the gas used for plasma treatment is O2.

[0034] By employing O2 in plasma processing, oxygen-containing functional groups, mainly including oxygen anchors such as hydroxyl (-OH) and carboxyl (-COOH) groups, can be efficiently introduced onto the surface of carbon cloth. (Refer to...) Figure 4 As shown, the XPS results for oxygen-doped carbon cloth (O2 plasma treated carbon cloth at different times) show that as time increases, more and more oxygen functional groups are introduced into the surface of the carbon cloth, providing more oxygen anchoring sites for underpotential deposition.

[0035] In some specific embodiments of this application, plasma is used to construct heteroatom anchor points on the surface of a carbon substrate, wherein the heteroatom is N.

[0036] In order to introduce nitrogen anchors, in some specific embodiments of this application, plasma is used to construct heteroatom anchors on the surface of a carbon substrate, wherein the gas used for plasma treatment is N2 or NH3.

[0037] By using N2 or NH3 in plasma treatment, nitrogen-containing functional groups, mainly pyridine nitrogen / pyrrole nitrogen anchors, can be efficiently introduced into the surface of carbon cloth.

[0038] In the embodiments described above, plasma treatment is used to "implant" strongly electronegative nonmetallic heteroatoms (O, N, etc.) on an inert carbon substrate as anchor points. The lone pair electrons of these anchor points can form strong coordination bonds (MO / NC) with metal ions. This bonding effect significantly reduces the Gibbs free energy of the metal on the carbon surface.

[0039] Specifically, the plasma treatment power is 50 W to 300 W, the treatment pressure is 20 Pa to 100 Pa, and the treatment time is 1 min to 15 min. The atmosphere includes oxygen, nitrogen, and ammonia. For example, the power is 100 W, the treatment pressure is 50 Pa, and the treatment time is 4 min. By adjusting the above parameters, defect sites can be etched in situ on the carbon substrate surface and specific functional groups can be introduced, so that the substrate surface can meet the thermodynamic requirements of subsequent underpotential deposition.

[0040] Through the plasma treatment described above, high-density defect sites are etched in situ in the carbon lattice (meaning that after plasma treatment, the atomic percentage of heteroatoms (O or N) on the carbon substrate surface reaches 5% to 20%), which greatly increases the surface energy of the substrate and provides a thermodynamic driving force for the adsorption of metal single atoms.

[0041] It should be noted that the above defect density range represents the optimal balance between the number of metal single-atom anchors and the conductivity of the substrate. Precise control of defect density is mainly achieved through the coordinated adjustment of process parameters such as plasma power, processing time, and gas pressure.

[0042] In some specific embodiments of this application, S2, preparing the electrolyte, includes: preparing a corresponding metal solution using a metal salt according to each deposited metal, to obtain an electrolyte corresponding to each deposited metal.

[0043] In some specific embodiments of this application, the concentration of the electrolyte is 0.001-0.05 M. This concentration setting can limit the mass transfer rate of the electrochemical reaction, creating a growth environment that is both thermodynamically and kinetically constrained. If the concentration is below 0.001 M, the deposition efficiency is too low, which is not conducive to industrial production; if the concentration is above 0.05 M, uncontrollable agglomeration is very likely to occur.

[0044] In the embodiments described above, inexpensive metal salts are used to prepare dilute solutions of various single metals, and a supporting electrolyte (such as H2SO4) is added. The addition of an acidic supporting electrolyte to the electrolyte provides an acidic environment and improves the solution conductivity.

[0045] To achieve the stable coexistence of multiple metal single atoms in the deposition, in some specific embodiments of this application, S3, using an electrolyte, a stepwise underpotential deposition is performed according to the standard reduction potential of the metal to be deposited, in descending order, including: S31. Based on the metal to be deposited, determine the metal with the most positive equilibrium potential as the most inert metal, and determine its underpotential deposition range on the carbon substrate by cyclic voltammetry. In the underpotential deposition range, select a potential that is more positive than the equilibrium potential of the most inert metal for constant potential deposition. S32. Following the order of standard reduction potential from high to low, the working electrodes are sequentially transferred to the corresponding electrolytes for underpotential deposition. Furthermore, during the transfer of the working electrodes, an intermediate cleaning is required (after completing the deposition of the previous metal, the working electrode is removed and immediately rinsed and dried with deionized water). This is to remove any residual electrolyte from the previous stage from the electrode surface and the porous structure.

[0046] In some specific embodiments of this application, underpotential deposition is carried out at room temperature using a standard three-electrode system, prepared in an H-type electrolytic cell, with a carbon substrate containing heteroatom anchors as the working electrode, a graphite electrode as the counter electrode, and an Ag / AgCl electrode as the reference electrode.

[0047] Specifically, the potential gradient stepwise UPD sequence (strictly ordered) is based on the standard reduction potential (E) of the metal to be deposited. 0 ), and formulate a deposition sequence from high to low (i.e., from strong to weak oxidizing power).

[0048] Step 1 (Most Inert Metal): Select the metal with the most positive potential (such as Ag or Cu), determine its UPD range on the modified carbon substrate using cyclic voltammetry (CV), and perform constant potential deposition at a potential more positive than its equilibrium potential. Due to the strong adsorption at the anchor sites, stable first-type single-atom sites are formed.

[0049] Subsequent steps (for more reactive metals): The electrode is sequentially moved to a metal solution with a more negative potential (such as Ni, Co, Fe, Mn). Because the previous metal has a more positive potential, it is firmly locked in and will not be replaced by subsequent more negative metal ions. At the same time, the deposited metal will synergistically regulate the electronic structure of the substrate, assisting the subsequent metal deposition at a specific UPD potential.

[0050] In some specific embodiments of this application, the post-processing includes: first washing with deionized water, and then drying with nitrogen or vacuum.

[0051] In the embodiments described above, a uniform heteroatom (O or N) anchor site is first constructed on the surface of a macroscopic carbon cloth substrate through plasma treatment. Subsequently, based on the standard reduction potential sequence of metals, a stepwise underpotential deposition technique is used to sequentially and specifically anchor various non-noble metal single atoms onto these sites, thereby avoiding intermetallic substitution reactions and ultimately forming a stable, integrated high-entropy single-atom electrode. The above method has the following advantages: (1) Strong universality, breaking through the limitations of carbon substrate: Through plasma doping technology, UPD technology has been successfully extended to inexpensive and inert carbon cloth substrates, no longer limited to specific TMDs crystal materials, which greatly reduces the cost of electrodes; (2) Flexible metal combinations and high degree of customization: As long as the deposition principle of "potential from positive to negative" is followed, noble metals (Ag, Pd, Pt) and non-noble metals (Fe, Co, Ni, Mn, Cu, Zn, etc.) can be arbitrarily combined according to the requirements of catalytic reaction (such as HER, OER, ORR) to construct functional high-entropy single-atom arrays.

[0052] (3) Stable process and elimination of displacement side reactions: The stepwise deposition sequence completely eliminates the possibility of "displacement reaction" from a thermodynamic point of view, ensuring that each deposition is an incremental assembly rather than destruction, thus ensuring the high yield and the integrity of the atomic-level dispersed structure.

[0053] (4) Large-size integrated: It can directly process large-size carbon cloth with high specific surface area. The product can be used directly as an electrode without coating, which is suitable for large-scale industrial applications.

[0054] The preferred features in the above embodiments can be used individually in any embodiment, or in any combination thereof, provided they do not conflict with each other. Furthermore, parts not described in detail in the embodiments can be implemented using existing technologies.

[0055] The following examples and comparative examples will be used to further illustrate this application in order to better understand the above-mentioned technical solutions. It should be understood that the following are only some examples and are not intended to limit this application.

[0056] Application Example 1: This application example provides the preparation and characterization of an O-anchored quaternary high-entropy single-atom electrode (Cu-Ni-Co-Fe-O / CC).

[0057] Using O2 plasma-treated carbon cloth as a substrate, Cu, Ni, Co, and Fe metal single atoms were sequentially deposited via stepwise UPD to prepare an integrated high-entropy electrode.

[0058] (1) Pretreatment of carbon cloth substrate and construction of oxygen anchor points Take a piece of commercial carbon cloth (size: 5 cm × 10 cm, adjustable as needed), and ultrasonically clean it sequentially in acetone, ethanol, and deionized water for 15 minutes each to remove surface organic matter and impurities. Then dry it in a vacuum drying oven at 60°C. Place the cleaned carbon cloth in the reaction chamber of an O2 plasma cleaner and treat it for 4 minutes at a power of 100 W and an O2 pressure of 50 Pa. Figure 2 As shown, this process can introduce high-density, uniformly distributed oxygen-containing functional groups (such as -COOH, -C=O, -OH) onto the surface of carbon fiber. These functional groups will serve as specific chemical anchors for subsequent metal single-atom deposition.

[0059] (2) Prepare electrolyte Prepare electrolyte A: 0.05 M CuSO4 + 0.005 M H2SO4.

[0060] Prepare electrolyte B: 0.05 M NiCl2 + 0.005 M H2SO4.

[0061] Prepare electrolyte C: 0.05 M CoCl2 + 0.005 M H2SO4.

[0062] Electrolyte D is prepared as follows: 0.05 M FeSO4 + 0.005 M H2SO4, with nitrogen purging throughout the process to prevent Fe²⁺ oxidants from forming. + Oxidation.

[0063] (3) Step-by-step underpotential deposition (UPD) All electrodeposition steps were performed at room temperature using a standard three-electrode system prepared in an H-type electrolytic cell, consisting of treated carbon cloth (as the working electrode), a graphite electrode (as the counter electrode), and an Ag / AgCl electrode (as the reference electrode).

[0064] Step 1: Cu single-atom layer deposition The plasma-treated carbon cloth was immersed in electrolyte A and purged with nitrogen for 30 minutes to remove oxygen. Cyclic voltammetry (CV, scan range: +0.3 V to -0.2 V vs. Ag / AgCl) was used to determine the UPD characteristic peak of Cu on the O-CC substrate. Subsequently, in potentiostatic mode, deposition was performed for 300 seconds at +0.1 V (vs. Ag / AgCl, this potential is within the UPD range; the underpotential deposition range on the carbon substrate was determined by cyclic voltammetry, and a potential more positive than the equilibrium potential of the most inert metal was selected for potentiostatic deposition within the underpotential deposition range). After deposition, the electrode surface was thoroughly rinsed with deionized water and dried with nitrogen. This step formed the first layer of Cu single atoms on the oxygen anchor points of the carbon cloth.

[0065] Step 2: Ni monolayer deposition The electrode with deposited Cu single atoms was transferred to electrolyte B; the UPD potential window of Ni at the Cu-O / CC interface was determined by CV (scan range: -0.2 V to -0.6 V vs. Ag / AgCl). Potential constant deposition was performed at -0.55 V (vs. Ag / AgCl) for 300 seconds to control sub-monolayer coverage. The electrode was then washed and dried.

[0066] Step 3: Co monolayer deposition The electrode was transferred to electrolyte C. Potentiostatic deposition was performed at -0.58 V (vs. Ag / AgCl) for 300 seconds. After deposition, the electrode was washed and dried.

[0067] Step 4: Fe monolayer deposition The electrode was transferred to electrolyte D. A constant potential deposition was performed at -0.66 V (vs. Ag / AgCl) for 300 seconds to complete the final deposition. The resulting electrode was designated Cu-Ni-Co-Fe-O / CC and dried and stored under nitrogen protection.

[0068] In the description of the embodiments of this application, it should be understood that the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of indicated technical features. Therefore, a feature defined with "first" and "second" may explicitly or implicitly include one or more of that feature.

[0069] In the description of the embodiments in this application, "multiple" means two or more, unless otherwise explicitly specified. In this application, unless otherwise explicitly specified and limited, the terms "installed," "connected," "linked," "fixed," etc., should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; and they can refer to the internal connection of two components. Those skilled in the art can understand the specific meaning of the above terms in this application according to the specific circumstances.

[0070] The terms "comprising" and "having," and any variations thereof, in the embodiments of this application are intended to cover non-exclusive inclusion. For example, a process, method, system, product, or device that includes a series of steps or units is not limited to the steps or units listed, but may optionally include steps or units not listed, or may optionally include other steps or units inherent to such processes, methods, products, or devices.

[0071] The foregoing has described some specific embodiments of this application. It should be understood that this application is not limited to the specific embodiments described above, and those skilled in the art can make various modifications or variations within the scope of the claims, which do not affect the substantive content of this application. The above-described preferred features can be used in any combination without conflict.

Claims

1. A method for preparing an integrated high-entropy single-atom electrode, characterized in that, include: Using plasma to construct heteroatom anchor points on the surface of a carbon substrate; Preparation of electrolyte; Using the electrolyte, a stepwise underpotential deposition process is performed according to the deposition sequence of the metal to be deposited, from high to low standard reduction potential. After post-processing, an integrated high-entropy single-atom electrode is obtained.

2. The method for preparing the integrated high-entropy single-atom electrode according to claim 1, characterized in that, The method involves using plasma to construct heteroatom anchor points on the surface of a carbon substrate, wherein the heteroatom is O.

3. The method for preparing the integrated high-entropy single-atom electrode according to claim 2, characterized in that, The method involves constructing heteroatom anchor points on the surface of a carbon substrate using plasma, wherein the gas used for plasma treatment is O2.

4. The method for preparing the integrated high-entropy single-atom electrode according to claim 1, characterized in that, The method involves using plasma to construct heteroatom anchor points on the surface of a carbon substrate, wherein the heteroatom is N.

5. The method for preparing the integrated high-entropy single-atom electrode according to claim 4, characterized in that, The method involves constructing heteroatom anchor points on the surface of a carbon substrate using plasma, wherein the gas used for plasma treatment is N2 or NH3.

6. The method for preparing the integrated high-entropy single-atom electrode according to claim 1, characterized in that, The preparation of the electrolyte includes: For each deposited metal, a corresponding metal solution is prepared using a metal salt to obtain an electrolyte corresponding to each deposited metal.

7. The method for preparing the integrated high-entropy single-atom electrode according to claim 6, characterized in that, The electrolyte is prepared in the form of a solution with a concentration of 0.001-0.05 M.

8. The method for preparing the integrated high-entropy single-atom electrode according to claim 1, characterized in that, The stepwise underpotential deposition, using the electrolyte and following a deposition sequence from high to low standard reduction potential based on the metal to be deposited, includes: Based on the metal to be deposited, the metal with the most positive equilibrium potential is determined as the most inert metal. The underpotential deposition range of the metal on the carbon substrate is determined by cyclic voltammetry. In the underpotential deposition range, a potential that is more positive than the equilibrium potential of the most inert metal is selected for constant potential deposition. Following the order of standard reduction potential from high to low, the working electrodes are sequentially moved to the corresponding electrolytes for underpotential deposition.

9. The method for preparing the integrated high-entropy single-atom electrode according to claim 1, characterized in that, The underpotential deposition was performed at room temperature using a standard three-electrode system, with a carbon substrate containing heteroatom anchors as the working electrode, a graphite electrode as the counter electrode, and an Ag / AgCl electrode as the reference electrode.

10. The method for preparing the integrated high-entropy single-atom electrode according to claim 1, characterized in that, The post-processing includes: first washing with deionized water, and then drying with nitrogen or vacuum.

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