An analytical method and system for the electrochemical oxidation performance of hydrogen on alloy catalysts.

Abstract

This invention provides a method and system for analyzing the electrochemical oxidation performance of an alloy catalyst with hydrogen. The method includes: constructing an alloy cell model (a first model), and subsequently constructing an alloy catalyst surface model (a second model); optionally, constructing an alloy catalyst surface model containing an alkaline aqueous solution layer (a third model) based on the second model; optionally, constructing structural models of reactants, intermediates, and products on the alloy catalyst surface in the third model to obtain a fourth model; optimizing the structure of the fourth model to obtain an optimal alkaline aqueous solution / alloy catalyst surface model containing reactants, intermediates, and products (a fifth model); performing oxidation potential analysis of the alloy catalyst based on the second model, and / or, performing H adsorption free energy analysis of the alloy catalyst based on the second or third model, and / or, determining the Tafel polarization curve of the alloy catalyst based on the fifth model.

Description

Technical Field

[0001] This invention pertains to the determination and characterization of the catalytic activity of electrode materials, specifically relating to an analytical method and system for the electrochemical oxidation performance of hydrogen in alloy catalysts. Background Technology

[0002] In recent decades, with social development, environmental pollution and energy shortages have become increasingly serious, making the development of new clean energy sources particularly urgent. Alkaline fuel cells (AFCs) can directly convert the chemical energy stored in H2 and O2 into electrical energy, with water as the only byproduct. They are a highly efficient, clean, and green power source, possessing advantages such as simple structure, rapid start-up, and low operating temperature. Especially in recent years, the development of alkaline anion exchange membrane technology has maintained the characteristics of alkaline electrolytes while avoiding the problem of electrolyte carbonation, making AFCs more competitive. In AFCs, the cathode oxygen reduction reaction (ORR) has a low overpotential and high reaction kinetics, and various relatively inexpensive cathode electrocatalysts, such as Ag, metal oxides, and carbon materials, have been developed. However, the AFC anode H2 oxidation reaction (HOR) rate is relatively slow, and currently, Pt-based noble metal catalysts are still used. Reports on efficient and stable non-noble metal HOR electrocatalysts are scarce. Therefore, the development of efficient and low-cost non-noble metal HOR electrocatalysts suitable for alkaline media is of great significance for the commercialization of AFC technology.

[0003] Transition metals such as Fe, Co, and Ni are abundant and inexpensive, making them ideal substitutes for Pt noble metal catalysts. However, these catalysts generally exhibit poor stability and are prone to corrosion. Compared to other non-noble metals, Ni-based catalysts demonstrate relatively high activity and corrosion resistance under alkaline conditions, indicating their potential as a class of non-noble metal HOR electrocatalysts. However, the HOR activity of these catalysts is still significantly lower than that of Pt catalysts; and oxidation still occurs when the overpotential exceeds 0.1V. In this regard, alloying nickel to adjust its oxidation resistance and HOR activity is an effective method. For example, alloying with 17.5 mg / cm³... 2 The NiW alloy used as the anode catalyst in the AFC can achieve a maximum output power of 40 mW / cm² at 60 °C. 2 (See International Journal of Hydrogen Energy 2013, 38: 16264–16268). At 4 mg / cm³ 2 Using a carbon-supported NiMo catalyst as the anode, the prepared AFC achieved a maximum output power of 120 mW / cm² at 80 °C. 2(See Journal of Materials Chemistry A 2017, 5: 24433–24443). At 4 mg / cm³ 2 Using a carbon-supported NiCu catalyst as the anode, the prepared AFC achieved a maximum output power of 350 mW / cm² at 80 °C. 2 (See Sustainable Energy Fuels, 2018, 2: 2268–2275). However, this is relative to the maximum power of a proton exchange membrane fuel cell, which is 1000 mW / cm². 2 However, the power output remains low. CN103869045A discloses a method for testing the activity of anode materials in methanol fuel cells. This method uses specific quantum chemical calculations to simulate and test the activity of the anode materials, thereby improving the accuracy of determining battery activity and efficiency. However, this method cannot analyze the structural stability of the catalyst and only analyzes activity based on the reaction energy barrier (activation energy). The characterization methods are limited, incomplete, and relatively abstract, making direct comparison and verification with electrochemical experimental results impossible.

[0004] Currently, the main method for evaluating the HOR activity of electrode catalysts under alkaline conditions is experimental. This involves first preparing the catalyst experimentally, and then conducting HOR experiments under alkaline conditions. However, alkaline electrolytes are easily carbonized in air, and H2 is a flammable and explosive substance. Therefore, the experimental operating environment is demanding, the experimental equipment is complex, and the experimental costs are high. Furthermore, due to the lack of theoretical guidance, the selection and preparation of new catalysts are somewhat arbitrary, resulting in a significant waste of time and material resources.

[0005] First-principles calculations are a method based on quantum mechanical density functional theory, using computer simulations to study the structure and properties of materials at the electronic level. In recent years, with the development of computational chemistry and the improvement of computer hardware, first-principles methods have been increasingly used to study the catalytic performance of materials and to design and search for new catalytic materials, becoming a research approach on par with experimental methods. First-principles methods only require computer simulations, eliminating the need for actual experiments. They are highly efficient, low-cost, have short computation cycles, and high accuracy, significantly saving time and material costs, and guiding the design, preparation, and application of catalysts. However, there are currently no international research cases using first-principles calculations to conduct detailed measurements and characterization of the H2 electrochemical oxidation performance of alloy catalysts. Summary of the Invention

[0006] The purpose of this invention is to provide a method and system for analyzing the H2 electrochemical oxidation performance of alloy catalysts, including nickel-based non-precious metal alloy catalysts.

[0007] To achieve the above objectives, the present invention provides a method for analyzing the electrochemical oxidation performance of an alloy catalyst under hydrogen, wherein the method includes:

[0008] First model construction steps: Construct the alloy unit cell model, i.e., the first model;

[0009] The second model construction steps are as follows: Based on the first model, construct the surface model of the alloy catalyst, i.e., the second model;

[0010] Optional third model construction step: Construct a surface model of the alloy catalyst containing an alkaline aqueous solution layer, i.e., the third model, based on the second model;

[0011] The optional fourth model construction step is to construct structural models of reactants, intermediates and products on the surface of the alloy catalyst containing the alkaline aqueous solution layer in the third model, respectively, to obtain the initial model of the alkaline aqueous solution / alloy catalyst containing reactants, intermediates and products, i.e., the fourth model.

[0012] The optional fifth model construction step is to optimize the structure of the fourth model to obtain the optimal structure of the alkaline aqueous solution / alloy catalyst surface model containing reactants, intermediates and products, which is the fifth model.

[0013] The steps for evaluating the electrochemical oxidation performance of H2 are as follows: Based on the second model, perform oxidation potential analysis of the alloy catalyst; and / or; based on the second or third model, perform H adsorption free energy analysis of the alloy catalyst; and / or; based on the fifth model, determine the Tafel polarization curve of the alloy catalyst.

[0014] In the above analytical method, preferably, the oxidation potential analysis of the alloy catalyst based on the second model includes:

[0015] Obtain the energy of the second model;

[0016] To obtain the energy after the alloy catalyst removes oxidized metal atoms;

[0017] To obtain the energy of metal atoms undergoing oxidation in the alloy catalyst when they are in an elemental state;

[0018] Obtain the standard oxidation potential of the metal that undergoes oxidation in the alloy catalyst when it is in its elemental state;

[0019] Based on the energy of the second model, the energy after the alloy catalyst removes the oxidized metal atoms, the energy of the oxidized metal atoms in the alloy catalyst in the elemental state, and the standard oxidation potential of the oxidized metal in the alloy catalyst in the elemental state, the oxidation potential of the alloy catalyst (i.e. the external potential required for the alloy to be oxidized into metal oxides or metal hydroxides) is determined.

[0020] More preferably, the oxidation potential analysis of the alloy catalyst based on the second model further includes:

[0021] The oxidation potential of alloy catalysts is used to evaluate their antioxidant properties.

[0022] More preferably, the oxidation potential of the alloy catalyst is determined by the following formula:

[0023] U ox =U ox (met1,bulk)-(E(A x B y )-E(A x B y-z )-z·E(B))÷n

[0024] In the formula, U ox V represents the oxidation potential of the alloy catalyst; U represents the oxidation potential of the catalyst. ox (met1,bulk) represents the standard oxidation potential of metal B, which undergoes oxidation in the alloy catalyst, in its elemental state; V; E(A x B y E(A) represents the energy of the second model, in eV; x B y-z E(B) represents the energy of the alloy catalyst after removing z metal B atoms that have undergone oxidation, in eV; E(B) represents the energy of the metal B atoms that have undergone oxidation in the alloy catalyst when they are in their elemental state, in eV; n represents the number of electrons e transferred during the oxidation of the alloy catalyst, in units.

[0025] In the above analytical method, preferably, the H adsorption free energy analysis of the alloy catalyst based on the second or third model includes:

[0026] The H adsorption free energy of the alloy catalyst is determined based on the second or third model.

[0027] The HOR catalytic activity of the alloy catalyst was evaluated based on the H adsorption free energy of the alloy catalyst; the closer the H adsorption free energy of the alloy catalyst is to 0.414 eV, the stronger the HOR catalytic activity of the alloy catalyst.

[0028] In the above analytical method, preferably, the determination of the Tafel polarization curve of the alloy catalyst based on the fifth model includes:

[0029] The optimal reaction pathway for the H2 electrochemical oxidation reaction on the surface of the alloy catalyst was determined based on the fifth model.

[0030] Based on the fifth model, different electrode charges are applied to the alloy catalyst unit cell in the fifth model, and the same amount of background charge is introduced to maintain the charge neutrality of the unit cell, thereby obtaining the sixth model corresponding to different charges; among them, the sixth model corresponding to the applied charge of 0 is the fifth model.

[0031] Based on the optimal reaction pathway of H2 electrochemical oxidation reaction on the surface of the alloy catalyst and the sixth model corresponding to different applied charges, the reaction energy barriers of the HOR forward and reverse reactions of the alloy catalyst under different applied charge conditions are determined.

[0032] Based on the reaction energy barriers of the HOR forward and reverse reactions of the alloy catalyst under different applied charge conditions, the reaction energy barriers of the HOR forward and reverse reactions of the alloy catalyst under different electrode potentials are determined.

[0033] Based on the reaction energy barriers of the HOR forward and reverse reactions of the alloy catalyst under different electrode potentials, the equilibrium potential of the alloy catalyst is determined.

[0034] Based on the equilibrium potential of the alloy catalyst, a given potential range is determined, and then the reaction energy barriers of the HOR forward and reverse reactions of the alloy catalyst within the given potential range are determined.

[0035] Based on the reaction energy barriers of the HOR forward and reverse reactions of the alloy catalyst within a given potential range, the kinetic current density of the alloy catalyst within the given potential range is determined, and then the polarization curve of the alloy catalyst (i.e. the curve of the kinetic current density of the alloy catalyst as a function of potential) is obtained.

[0036] More preferably, the step of applying different electrode charges to the alloy catalyst unit cell in the fifth model while introducing the same amount of background charge to maintain the charge neutrality of the unit cell, thereby obtaining a sixth model corresponding to different charges, includes:

[0037] Based on the fifth model, different electrode charges were applied to the alloy catalyst unit cell in the fifth model, and the same amount of background charge was introduced to maintain the charge neutrality of the unit cell, thus obtaining the fifth model with different electrode charges applied.

[0038] The fifth model with different electrode charges was structurally optimized to obtain the sixth model corresponding to different charges;

[0039] More preferably, the step of structurally optimizing the fifth model with different applied electrode charges to obtain the sixth model corresponding to different charges includes:

[0040] For the fifth model with different electrode charges, first-principles molecular dynamics simulations (AIMD) were performed to screen out several models with relatively stable reactants, intermediates and products. Then, the alkaline aqueous solution layer in the screened models with relatively stable reactants, intermediates and products was structurally optimized based on first-principles calculations to screen out the model with the most stable energy, which is the sixth model.

[0041] Preferably, the determination of the kinetic current density of the alloy catalyst within a given potential range, based on the reaction energy barriers of the HOR forward and reverse reactions of the alloy catalyst within a given potential range, is performed using the following formula:

[0042]

[0043] Where, j kox The oxidation kinetic current density is mA / cm². 2 ;j kred To restore the kinetic current density, mA / cm 2 A(U) is the exponential factor (usually taken as 12.0-14.0), dimensionless; R is the gas constant (usually taken as 8.3145), J / mol·K; T is the temperature, K; E a ox (U) represents the reaction energy barrier of the HOR forward reaction of the alloy catalyst at potential U, in eV; E a red (U) represents the reaction barrier of the reverse HOR reaction of the alloy catalyst at potential U, in eV; j k (U) represents the kinetic current density of the alloy catalyst at potential U, in mA / cm². 2 .

[0044] In the above analytical method, preferably, when the analytical method includes determining the Tafel polarization curve of the alloy catalyst based on the fifth model, the H2 electrochemical oxidation performance evaluation step further includes analyzing the exchange current density of the alloy catalyst based on the polarization curve of the alloy catalyst.

[0045] The analysis of the exchange current density of the alloy catalyst based on its polarization curve includes:

[0046] The exchange current density of the alloy catalyst was determined based on its polarization curve.

[0047] More preferably, the analysis of the exchange current density of the alloy catalyst based on its polarization curve further includes:

[0048] The HOR catalytic activity of the alloy catalyst was evaluated based on the exchange current density of the alloy catalyst.

[0049] More preferably, the exchange current density of the alloy catalyst is determined based on its polarization curve by fitting the polarization curve using the Butler-Volmer equation, and the coefficients obtained from the fitting are the exchange current density of the alloy catalyst. Specifically, the Butler-Volmer equation is:

[0050] Where η=UU 0

[0051] In the formula, j k The kinetic current density of the alloy catalyst is mA / cm². 2 j0 represents the exchange current density of the alloy catalyst, mA / cm². 2 α is the transfer coefficient, dimensionless; F is the Faraday constant, C / mol; η is the overpotential, V; U is the j k The corresponding electric potential, V; U 0 To balance the potential, V.

[0052] In the above analytical method, preferably, the H2 electrochemical oxidation performance evaluation step further includes analyzing the formation energy of the alloy catalyst based on the first model;

[0053] The formation energy analysis of the alloy catalyst based on the first model includes:

[0054] Based on the first model, the formation energy of the alloy catalyst was determined;

[0055] The stability of alloy catalysts is determined based on their formation energy.

[0056] In the above analytical method, preferably, the H2 electrochemical oxidation performance evaluation step further includes analyzing the reaction energy barrier of the alloy catalyst based on the fifth model;

[0057] The reaction barrier analysis of the alloy catalyst based on the fifth model includes:

[0058] The optimal reaction pathway for the H2 electrochemical oxidation reaction on the surface of the alloy catalyst was determined based on the fifth model.

[0059] Based on the optimal reaction pathway of H2 electrochemical oxidation reaction on the surface of the alloy catalyst and the fifth model, the reaction energy barrier of the alloy catalyst in the HOR forward reaction is determined.

[0060] Based on the reaction energy barrier of the alloy catalyst, the catalytic activity of the alloy catalyst was determined.

[0061] In the above analysis method, preferably, the third model construction step includes:

[0062] An alkaline aqueous solution model was added to the second model to obtain an initial model of the alloy catalyst surface containing an alkaline aqueous solution layer.

[0063] First-principles molecular dynamics (AIMD) simulations were performed on the initial model of the alloy catalyst surface containing an alkaline aqueous solution layer, and several relatively stable models were selected.

[0064] The alkaline aqueous solution layer in the selected relatively stable models was structurally optimized using first-principles calculations. The model with the most stable energy was selected as the third model, which is used as the surface model of the alloy catalyst containing the alkaline aqueous solution layer.

[0065] In the above analysis method, preferably, the fourth model construction step includes:

[0066] First-principles molecular dynamics (AIMD) simulations were performed on the fourth model to screen out several models with relatively stable reactants, intermediates and products;

[0067] The alkaline aqueous solution layer in the screened models with relatively stable reactants, intermediates and products is structurally optimized based on first-principles calculations. The model with the most stable energy is selected as the fifth model, which is the surface model of the alkaline aqueous solution / alloy catalyst containing reactants, intermediates and products with the optimal structure.

[0068] In the above analysis method, preferably, the energy, displacement, and gradient convergence criteria for structural optimization calculated based on first-principles calculations are 5.442 × 10⁻⁶. -4 eV, and

[0069] In the above analytical method, preferably, the alloy is a nickel-based non-precious metal alloy; more preferably, the non-precious metal includes one or more combinations of Cr, Mn, Fe, Co, Ni, Cu and Zn.

[0070] This invention also provides an analytical system for the electrochemical oxidation performance of an alloy catalyst under hydrogen, wherein the system comprises:

[0071] First Model Construction Module: Used to construct the alloy cell model, i.e., the first model;

[0072] The second model construction module is used to construct a surface model of the alloy catalyst, i.e., the second model, based on the first model.

[0073] Optional third model building module: used to build a surface model of the alloy catalyst containing an alkaline aqueous solution layer, i.e., the third model, based on the second model;

[0074] Optional fourth model construction module: used to construct structural models of reactants, intermediates and products on the surface of the alloy catalyst containing the alkaline aqueous solution layer in the third model, respectively, to obtain the initial model of the alkaline aqueous solution / alloy catalyst containing reactants, intermediates and products, i.e. the fourth model;

[0075] Optional fifth model building module: used to optimize the structure of the fourth model to obtain the optimal structure of the alkaline aqueous solution / alloy catalyst surface model containing reactants, intermediates and products, i.e., the fifth model;

[0076] The H2 electrochemical oxidation performance evaluation module includes an oxidation potential analysis submodule, an H adsorption free energy analysis submodule, and / or a polarization curve determination submodule; among which...

[0077] The oxidation potential analysis submodule is used to perform oxidation potential analysis of alloy catalysts based on the second model;

[0078] The H adsorption free energy analysis submodule is used to perform H adsorption free energy analysis of alloy catalysts based on the second or third model.

[0079] The polarization curve determination submodule is used to determine the Tafel polarization curves of alloy catalysts based on the fifth model.

[0080] In the above analysis system, preferably, the oxidation potential analysis submodule includes:

[0081] First energy determination unit: used to obtain the energy of the second model;

[0082] Second energy determination unit: used to obtain the energy after the alloy catalyst removes the oxidized metal atoms;

[0083] The third energy determination unit is used to obtain the energy of the metal atoms undergoing oxidation in the alloy catalyst when they are in an elemental state.

[0084] Standard oxidation potential determination unit: used to obtain the standard oxidation potential of the metal undergoing oxidation in the alloy catalyst when it is in the elemental state;

[0085] Oxidation potential determination unit: used to determine the oxidation potential of the alloy catalyst (i.e. the external potential required when the alloy is oxidized to a metal oxide or metal hydroxide) based on the energy of the second model, the energy of the oxidized metal atoms in the alloy catalyst in the elemental state, and the standard oxidation potential of the oxidized metal in the alloy catalyst in the elemental state.

[0086] More preferably, the oxidation potential analysis submodule further includes:

[0087] Antioxidant performance evaluation unit: used to evaluate the antioxidant performance of alloy catalysts based on their oxidation potential;

[0088] More preferably, the oxidation potential of the alloy catalyst is determined by the following formula:

[0089] U ox =U ox (met1,bulk)-(E(A x B y )-E(A x B y-z )-z·E(B))÷n

[0090] In the formula, U ox V represents the oxidation potential of the alloy catalyst; U represents the oxidation potential of the catalyst. ox (met1,bulk) represents the standard oxidation potential of metal B, which undergoes oxidation in the alloy catalyst, in its elemental state; V; E(A x B y E(A) represents the energy of the second model, in eV; x B y-z E(B) represents the energy of the alloy catalyst after removing z metal B atoms that have undergone oxidation, in eV; E(B) represents the energy of the metal B atoms that have undergone oxidation in the alloy catalyst when they are in their elemental state, in eV; n represents the number of electrons e transferred during the oxidation of the alloy catalyst, in units.

[0091] In the above analysis system, preferably, the H adsorption free energy analysis submodule includes:

[0092] H adsorption free energy determination unit: used to determine the H adsorption free energy of the alloy catalyst based on the second or third model;

[0093] The first catalytic activity determination unit is used to evaluate the HOR catalytic activity of the alloy catalyst based on the H adsorption free energy of the alloy catalyst; wherein, the closer the H adsorption free energy of the alloy catalyst is to 0.414 eV, the stronger the HOR catalytic activity of the alloy catalyst.

[0094] In the above analysis system, preferably, the polarization curve determination submodule includes:

[0095] Optimal reaction path determination unit: used to determine the optimal reaction path for the H2 electrochemical oxidation reaction on the surface of the alloy catalyst based on the fifth model;

[0096] The sixth model determination unit is used to apply different electrode charges to the alloy catalyst unit cell in the fifth model and introduce the same amount of background charge to maintain the charge neutrality of the unit cell, thereby obtaining the sixth model corresponding to different charges; among them, the sixth model corresponding to the applied charge of 0 is the fifth model.

[0097] Unit for determining the reaction energy barrier of forward and reverse reactions under different charges: used to determine the reaction energy barrier of HOR forward and reverse reactions of alloy catalysts under different applied charges based on the optimal reaction path of H2 electrochemical oxidation reaction on the surface of alloy catalyst and the sixth model corresponding to different applied charges;

[0098] Unit for determining the reaction energy barrier of forward and reverse reactions under different potentials: Used to determine the reaction energy barrier of HOR forward and reverse reactions of alloy catalysts under different applied charge conditions, and to determine the reaction energy barrier of HOR forward and reverse reactions of alloy catalysts under different electrode potentials.

[0099] Equilibrium potential determination unit: used to determine the equilibrium potential of alloy catalyst based on the reaction energy barriers of the HOR forward and reverse reactions of alloy catalyst under different electrode potentials;

[0100] The polarization curve determination unit is used to determine a given potential range based on the equilibrium potential of the alloy catalyst, and then determine the reaction energy barriers of the HOR forward and reverse reactions of the alloy catalyst within the given potential range; based on the reaction energy barriers of the HOR forward and reverse reactions of the alloy catalyst within the given potential range, the kinetic current density of the alloy catalyst within the given potential range is determined, and then the polarization curve of the alloy catalyst (i.e., the curve of the kinetic current density of the alloy catalyst as a function of potential) is obtained.

[0101] More preferably, the sixth model determining unit includes:

[0102] Charge application sub-unit: Based on the fifth model, different electrode charges are applied to the alloy catalyst unit cell in the fifth model respectively, and the same amount of background charge is introduced to maintain the electrical neutrality of the unit cell to obtain the fifth model with different electrode charges applied;

[0103] The sixth model determines the sub-units: used to perform structural optimization on the fifth model with different electrode charges applied, so as to obtain the sixth model corresponding to different charges;

[0104] More preferably, the sixth model determines the sub-units including:

[0105] The first optimization group: used to perform first-principles molecular dynamics simulations (AIMD) on the fifth model with different electrode charges, and screen out several models with relatively stable reactants, intermediates and products;

[0106] The second optimization group is used to perform structural optimization of the alkaline aqueous solution layer in the relatively stable models of reactants, intermediates and products selected based on first-principles calculations, and to select the most energy-stable model, namely the sixth model.

[0107] Preferably, the determination of the kinetic current density of the alloy catalyst within a given potential range, based on the reaction energy barriers of the HOR forward and reverse reactions of the alloy catalyst within a given potential range, is performed using the following formula:

[0108]

[0109] Where, j kox The oxidation kinetic current density is mA / cm². 2 ;j kred To restore the kinetic current density, mA / cm 2 A(U) is the exponential factor (usually taken as 12.0-14.0), dimensionless; R is the gas constant (usually taken as 8.3145), J / mol·K; T is the temperature, K; E a ox (U) represents the reaction energy barrier of the HOR forward reaction of the alloy catalyst at potential U, in eV; E a red (U) represents the reaction barrier of the reverse HOR reaction of the alloy catalyst at potential U, in eV; j k (U) represents the kinetic current density of the alloy catalyst at potential U, in mA / cm². 2 .

[0110] In the above analysis system, preferably, when the H2 electrochemical oxidation performance evaluation module includes a polarization curve determination submodule, the H2 electrochemical oxidation performance evaluation module further includes:

[0111] Exchange current density analysis submodule: used to perform exchange current density analysis of alloy catalysts based on the polarization curves of the alloy catalysts;

[0112] The exchange current density analysis submodule includes:

[0113] Exchange current density determination unit: used to determine the exchange current density of the alloy catalyst based on the polarization curve of the alloy catalyst;

[0114] More preferably, the exchange current density analysis submodule further includes:

[0115] The second catalytic activity evaluation unit is used to evaluate the HOR catalytic activity of the alloy catalyst based on the exchange current density of the alloy catalyst.

[0116] More preferably, the exchange current density of the alloy catalyst is determined based on its polarization curve by fitting the polarization curve using the Butler-Volmer equation, and the coefficients obtained from the fitting are the exchange current density of the alloy catalyst. Specifically, the Butler-Volmer equation is:

[0117] Where η=UU 0

[0118] In the formula, j k The kinetic current density of the alloy catalyst is mA / cm². 2 j0 represents the exchange current density of the alloy catalyst, mA / cm². 2 α is the transfer coefficient, dimensionless; F is the Faraday constant, C / mol; η is the overpotential, V; U is the j k The corresponding electric potential, V; U 0 To balance the potential, V.

[0119] In the above analysis system, preferably, the H2 electrochemical oxidation performance evaluation module further includes:

[0120] Formation energy analysis submodule: used to perform formation energy analysis of alloy catalysts based on the first model;

[0121] The formation energy analysis submodule includes:

[0122] Formation energy determination unit: used to determine the formation energy of the alloy catalyst based on the first model;

[0123] Stability evaluation unit: used to determine the stability of alloy catalysts based on their formation energy.

[0124] In the above analysis system, preferably, the H2 electrochemical oxidation performance evaluation module further includes:

[0125] Reaction barrier analysis submodule: used for reaction barrier analysis of alloy catalysts based on the fifth model;

[0126] The reaction barrier analysis submodule includes:

[0127] Optimal reaction path determination unit: used to determine the optimal reaction path for the H2 electrochemical oxidation reaction on the surface of the alloy catalyst based on the fifth model;

[0128] Reaction barrier determination unit: used to determine the optimal reaction pathway of H2 electrochemical oxidation reaction based on the surface of alloy catalyst and the fifth model, and to determine the reaction barrier of alloy catalyst in the HOR forward reaction;

[0129] The third catalytic activity analysis unit is used to determine the catalytic activity of alloy catalysts based on their reaction energy barriers.

[0130] In the above analysis system, preferably, the third model construction module includes:

[0131] Initial model construction submodule: used to add an alkaline aqueous solution model to the second model to obtain an initial model of the alloy catalyst surface containing an alkaline aqueous solution layer;

[0132] The first model optimization submodule is used to perform first-principles molecular dynamics (AIMD) simulations on the initial model of the alloy catalyst surface containing an alkaline aqueous solution layer, and to screen out several relatively stable models.

[0133] The second model optimization submodule is used to perform structural optimization based on first-principles calculations on the alkaline aqueous solution layer in the relatively stable models selected, and to select the most energy-stable model as the surface model of the alloy catalyst containing the alkaline aqueous solution layer, i.e., the third model.

[0134] In the above analysis system, preferably, the fourth model construction module includes:

[0135] The third model optimization submodule is used to perform first-principles molecular dynamics simulations (AIMD) on the fourth model and screen out several models with relatively stable reactants, intermediates and products.

[0136] The fourth model optimization submodule is used to perform first-principles calculations to optimize the structure of the alkaline aqueous solution layer in the relatively stable models of reactants, intermediates and products, and to select the most energy-stable model. The fifth model is the alkaline aqueous solution / alloy catalyst surface model containing reactants, intermediates and products with the optimal structure.

[0137] In the above analysis system, preferably, the energy, displacement, and gradient convergence criteria for structural optimization calculated based on first-principles calculations are 5.442 × 10⁻⁶. -4 eV, and

[0138] In the above analytical method, preferably, the alloy is a nickel-based non-precious metal alloy; more preferably, the non-precious metal includes one or more combinations of Cr, Mn, Fe, Co, Ni, Cu and Zn.

[0139] The technical solution provided by this invention can analyze the H2 electrochemical oxidation performance of alloy catalysts, including nickel-based non-precious metal alloy catalysts, without conducting indoor experiments. This overcomes the defects and shortcomings of existing technologies that require experimental techniques to analyze the H2 electrochemical oxidation performance of alloy catalysts. It also overcomes the problems of complex experimental equipment and corresponding operations for H2 electrochemical oxidation under alkaline conditions and the blindness in the experimental synthesis of novel alkaline H2 electrochemical oxidation catalysts, thus greatly saving time and material costs. Attached Figure Description

[0140] Figure 1 This is a schematic flowchart of the evaluation method for the electrochemical oxidation performance of the alloy catalyst H2 provided in Example 1 of the present invention.

[0141] Figure 2A This is the surface model of the Ni3Cr alloy catalyst established in Example 1 of the present invention.

[0142] Figure 2B This is the surface model of the Ni2Cr2 alloy catalyst established in Example 1 of the present invention.

[0143] Figure 2C This is the surface model of the NiCr3 alloy catalyst established in Example 1 of the present invention.

[0144] Figure 3A This is the surface model of the Ni3Cr alloy catalyst containing an alkaline aqueous solution layer established in Example 1 of the present invention.

[0145] Figure 3B This is the surface model of the Ni2Cr2 alloy catalyst containing an alkaline aqueous solution layer established in Example 1 of the present invention.

[0146] Figure 3C This is the surface model of the NiCr3 alloy catalyst containing an alkaline aqueous solution layer established in Example 1 of the present invention.

[0147] Figure 4A This is the Tafel polarization curve of the Ni3Cr alloy catalyst in Example 1 of the present invention.

[0148] Figure 4B This is the Tafel polarization curve of the Ni3Cr alloy catalyst in Example 1 of the present invention.

[0149] Figure 4C This is the Tafel polarization curve of the Ni3Cr alloy catalyst in Example 1 of the present invention. Detailed Implementation

[0150] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the protection scope of the present invention.

[0151] The principles and spirit of the present invention will be explained in detail below with reference to several representative embodiments.

[0152] A specific embodiment of the present invention provides a method for evaluating the electrochemical oxidation performance of an alloy catalyst in H2, wherein the method includes:

[0153] Step S1: Construct the alloy cell model, i.e., the first model;

[0154] Step S2: Construct a surface model of the alloy catalyst, i.e., the second model, based on the first model;

[0155] Optional step S3: Construct a surface model of the alloy catalyst containing an alkaline aqueous solution layer, i.e., a third model, based on the second model;

[0156] Optional step S4: Construct structural models of reactants, intermediates and products on the surface of the alloy catalyst containing the alkaline aqueous solution layer in the third model, respectively, to obtain the initial model of the alkaline aqueous solution / alloy catalyst containing reactants, intermediates and products, i.e., the fourth model;

[0157] Optional step S5: Optimize the structure of the fourth model to obtain the optimal structure of the alkaline aqueous solution / alloy catalyst surface model containing reactants, intermediates and products, i.e., the fifth model;

[0158] Step S6: Based on the second model, perform oxidation potential analysis of the alloy catalyst; and / or

[0159] Based on the second or third model, perform H adsorption free energy analysis of the alloy catalyst; and / or

[0160] Based on the fifth model, the Tafel polarization curves of the alloy catalyst were determined.

[0161] In some specific embodiments, the analytical method for the electrochemical oxidation performance of the alloy catalyst H2 adopts Method 1, which specifically includes:

[0162] Step S1: Construct the alloy cell model, i.e., the first model;

[0163] Step S2: Construct a surface model of the alloy catalyst, i.e., the second model, based on the first model;

[0164] Optional step S3: Construct a surface model of the alloy catalyst containing an alkaline aqueous solution layer based on the second model, i.e., the third model (belonging to the bulk alloy catalyst model);

[0165] Step S6: Based on the second or third model, perform H adsorption free energy analysis of the alloy catalyst;

[0166] Specifically, Method 1 can be implemented using either Method A or Method B:

[0167] Method A includes:

[0168] Step S1: Construct the alloy cell model, i.e., the first model;

[0169] Step S2: Construct a surface model of the alloy catalyst, i.e., the second model, based on the first model;

[0170] Step S6: Based on the second model, perform oxidation potential analysis of the alloy catalyst;

[0171] Method B includes:

[0172] Step S1: Construct the alloy cell model, i.e., the first model;

[0173] Step S2: Construct a surface model of the alloy catalyst, i.e., the second model, based on the first model;

[0174] Step S3: Construct a surface model of the alloy catalyst containing an alkaline aqueous solution layer, i.e., the third model, based on the second model;

[0175] Step S6: Based on the third model, perform oxidation potential analysis of the alloy catalyst.

[0176] In some specific embodiments, the analysis method for the electrochemical oxidation performance of the alloy catalyst H2 adopts Method 2, which specifically includes:

[0177] Step S1: Construct the alloy cell model, i.e., the first model;

[0178] Step S2: Construct a surface model of the alloy catalyst, i.e., the second model, based on the first model;

[0179] Step S3: Construct a surface model of the alloy catalyst containing an alkaline aqueous solution layer, i.e., the third model, based on the second model;

[0180] Step S6: Based on the second model, perform H adsorption free energy analysis on the alloy catalyst.

[0181] In some specific embodiments, the analysis method for the electrochemical oxidation performance of the alloy catalyst H2 adopts Method 3, which specifically includes:

[0182] Step S1: Construct the alloy cell model, i.e., the first model;

[0183] Step S2: Construct a surface model of the alloy catalyst, i.e., the second model, based on the first model;

[0184] Step S3: Construct a surface model of the alloy catalyst containing an alkaline aqueous solution layer, i.e., the third model, based on the second model;

[0185] Step S4: Construct structural models of reactants, intermediates, and products on the surface of the alloy catalyst containing the alkaline aqueous solution layer in the third model, respectively, to obtain the initial model of the alkaline aqueous solution / alloy catalyst containing reactants, intermediates, and products, i.e., the fourth model.

[0186] Step S5: Optimize the structure of the fourth model to obtain the fifth model, which is the alkaline aqueous solution / alloy catalyst surface model containing reactants, intermediates and products with the optimal structure.

[0187] Step S6: Based on the fifth model, determine the Tafel polarization curve of the alloy catalyst.

[0188] In some specific embodiments, the analysis method for the electrochemical oxidation performance of the alloy catalyst H2 is carried out in Method 4, which specifically includes at least two of Method 1, Method 2 and Method 3.

[0189] In some specific embodiments, the alloy is a nickel-based non-precious metal alloy;

[0190] Furthermore, the non-precious metals include one or more combinations of Cr, Mn, Fe, Co, Ni, Cu, and Zn.

[0191] In some specific embodiments, the oxidation potential analysis of the alloy catalyst includes:

[0192] Step S611: Obtain the energy of the second model;

[0193] Step S612: Obtain the energy after the alloy catalyst removes the oxidized metal atoms;

[0194] Step S613: Obtain the energy of the metal atoms undergoing oxidation in the alloy catalyst when they are in an elemental state;

[0195] Step S614: Obtain the standard oxidation potential of the metal that undergoes oxidation in the alloy catalyst when it is in its elemental state;

[0196] Step S615: Based on the energy of the second model, the energy after the alloy catalyst removes the oxidized metal atoms, the energy of the oxidized metal atoms in the alloy catalyst in the elemental state, and the standard oxidation potential of the oxidized metal in the alloy catalyst in the elemental state, determine the oxidation potential of the alloy catalyst (i.e. the external potential required for the alloy to be oxidized into a metal oxide or metal hydroxide).

[0197] Furthermore, the oxidation potential of the alloy catalyst is preferably determined using the following formula:

[0198] U ox =U ox (met1,bulk)-(E(Ax B y )-E(A x B y-z )-z·E(B))÷n

[0199] In the formula, U ox V represents the oxidation potential of the alloy catalyst; U represents the oxidation potential of the catalyst. ox (met1,bulk) represents the standard oxidation potential of metal B, which undergoes oxidation in the alloy catalyst, in its elemental state; V; E(A x B y E(A) represents the energy of the second model, in eV; x B y-z E(B) represents the energy of the alloy catalyst after removing z metal B atoms that have undergone oxidation, in eV; E(B) represents the energy of the metal B atoms that have undergone oxidation in the alloy catalyst when they are in their elemental state, in eV; n represents the number of electrons e transferred during the oxidation of the alloy catalyst, in units.

[0200] The energy of the second model, the energy of the alloy catalyst after removing the oxidized metal atoms, and the energy of the oxidized metal atoms in the alloy catalyst when they are in a single-element state can be obtained using conventional methods in the art, such as calculations using first-principles calculations.

[0201] The standard oxidation potential of the metal that undergoes oxidation in the alloy catalyst when it is in its elemental state can be obtained from a physicochemical handbook.

[0202] Taking NiM alloy catalyst as an example, let's assume A x B y In the alloy catalyst (corresponding to the NiM alloy catalyst), z metal B atoms underwent oxidation (because metal oxidation cannot occur all at once; it begins with partial oxidation). Using the aforementioned U... ox =U ox (met1,bulk)-(E(A x B y )-E(A x B y-z )-z·E(B))÷n calculate the oxidation potential of the NiM alloy catalyst, where E(A) x B y E(A) represents the calculated energy of the NiM alloy catalyst surface model; z represents the number of metal atoms undergoing oxidation; E(A) represents the energy of the surface model of the NiM alloy catalyst. x B y-z E represents the catalyst energy of the NiM alloy catalyst after removing z oxidized metal atoms (calculated using first-principles calculations). Bν is the energy of the atom undergoing oxidation in its elemental metallic state (obtained through first-principles calculations); n is the number of electrons e transferred during the oxidation of the NiM alloy catalyst. The standard oxidation potential of the metal undergoing oxidation in the NiM alloy catalyst when it is in its elemental state (i.e., when M (or Ni) in the NiM alloy catalyst is oxidized, then...) This represents the standard oxidation potential of M (or Ni) in its elemental crystal state. Data is available in the physical chemistry handbook; this method is based on the standard oxidation potential of metallic elements combined with first-principles calculations to obtain the oxidation potential in the alloy state;

[0203] Furthermore, the oxidation potential analysis of the alloy catalyst further includes:

[0204] Step S615: Evaluate the oxidation resistance of the alloy catalyst based on its oxidation potential;

[0205] Among them, the oxidation potential of the alloy catalyst can characterize the oxidation resistance of the alloy catalyst under alkaline conditions. If the alloy catalyst is positive, it means that the alloy can undergo oxidation reaction. The larger the oxidation potential, the easier the alloy is to be oxidized, and the worse the oxidation resistance of the alloy. If the alloy catalyst is negative, it means that the alloy is not easy to undergo oxidation reaction. The smaller the oxidation potential, the less easy the alloy is to be oxidized, and the stronger the oxidation resistance of the alloy catalyst.

[0206] In some specific embodiments, the H adsorption free energy analysis of the alloy catalyst includes:

[0207] Step S621: Determine the H adsorption free energy of the alloy catalyst based on the second or third model;

[0208] The H adsorption free energy of the alloy catalyst can be determined using conventional methods based on the second or third model. For example, first calculate the energy after H adsorbs on the surface of the alloy catalyst in the second or third model, subtract the energy of the second or third model when H is not adsorbed, and the energy of 1 / 2 H2 molecule. Then add the zero-point energy correction, entropy change correction, and pH value correction to obtain the H adsorption free energy.

[0209] Step S622: Evaluate the HOR catalytic activity of the alloy catalyst based on the H adsorption free energy of the alloy catalyst; wherein, the closer the H adsorption free energy of the alloy catalyst is to 0.414 eV, the stronger the HOR catalytic activity of the alloy catalyst.

[0210] The electrochemical oxidation of H2 on the alloy catalyst is closely related to the adsorption strength of H on the catalyst surface. If the adsorption of H on the NiM alloy surface is too weak, it is not conducive to the decomposition of H2 into H on the catalyst surface. If the adsorption of H on the alloy surface is too strong, it is not conducive to the further oxidation of the adsorbed H into water. Therefore, the H2 electrochemical oxidation performance of the alloy catalyst can be characterized by the H adsorption free energy.

[0211] Currently, when using H adsorption free energy to determine catalytic activity, it is generally believed that the closer the H adsorption free energy is to zero, the better the catalytic activity of the catalyst. However, this method is only applicable to the determination of catalytic activity under acidic conditions. After extensive research, the inventors believe that under alkaline conditions, the optimal H adsorption free energy is 0.414 eV, that is, the theoretical value of the H adsorption free energy on the surface of the most active alloy catalyst is 0.414 eV. Therefore, in the technical solution of this invention, the closer the H adsorption free energy is to 0.414 eV, the stronger the HOR activity of the alloy catalyst.

[0212] In some specific embodiments, the determination of the polarization curve of the alloy catalyst includes:

[0213] Step S631: Determine the optimal reaction pathway for the H2 electrochemical oxidation reaction on the surface of the alloy catalyst based on the fifth model (see step S661 below);

[0214] Step S632: Based on the fifth model, different electrode charges are applied to the alloy catalyst unit cell in the fifth model and the same amount of background charge is introduced to maintain the charge neutrality of the unit cell, thereby obtaining the sixth model corresponding to different charges; among them, the sixth model corresponding to the applied charge of 0 is the fifth model.

[0215] Step S633: Based on the optimal reaction pathway of H2 electrochemical oxidation reaction on the surface of the alloy catalyst and the sixth model corresponding to different applied charges, determine the reaction energy barriers of the HOR forward and reverse reactions of the alloy catalyst under different applied charge conditions.

[0216] Step S634: Based on the reaction energy barriers of the HOR forward and reverse reactions of the alloy catalyst under different applied charge conditions, determine the reaction energy barriers of the HOR forward and reverse reactions of the alloy catalyst under different electrode potentials.

[0217] Step S635: Determine the equilibrium potential of the alloy catalyst based on the reaction energy barriers of the HOR forward and reverse reactions under different electrode potentials.

[0218] Step S636: Based on the equilibrium potential of the alloy catalyst, determine the given potential range, and then determine the reaction energy barriers of the HOR forward and reverse reactions of the alloy catalyst within the given potential range;

[0219] Step S637: Based on the reaction energy barriers of the HOR forward and reverse reactions of the alloy catalyst within a given potential range, determine the kinetic current density of the alloy catalyst within the given potential range, and then obtain the polarization curve of the alloy catalyst (i.e., the curve of the kinetic current density of the alloy catalyst changing with the potential).

[0220] Further, step S632 includes:

[0221] Step S6321: Based on the fifth model, different electrode charges are applied to the alloy catalyst cell in the fifth model respectively, and the same amount of background charge is introduced to maintain the electrical neutrality of the cell to obtain the fifth model with different electrode charges applied.

[0222] Step S6322: Optimize the structure of the fifth model with different applied electrode charges to obtain the sixth model corresponding to different charges; wherein, the sixth model corresponding to the applied charge of 0 is the fifth model.

[0223] Furthermore: Step S6322 includes:

[0224] For the fifth model with different electrode charges, first-principles molecular dynamics simulations (AIMD) were performed to screen out several models with relatively stable reactants, intermediates and products. Then, the alkaline aqueous solution layer in the screened models with relatively stable reactants, intermediates and products was structurally optimized based on first-principles calculations to screen out the model with the most stable energy, which is the sixth model.

[0225] Furthermore: Based on the reaction energy barriers of the HOR forward and reverse reactions of the alloy catalyst within a given potential range, the kinetic current density of the alloy catalyst within a given potential range is determined by the following formula:

[0226]

[0227] Where, j kox The oxidation kinetic current density is mA / cm². 2 ;j kred To restore the kinetic current density, mA / cm 2 A(U) is the exponential factor (usually taken as 12.0-14.0), dimensionless; R is the gas constant (usually taken as 8.3145), J / mol·K; T is the temperature, K; E a ox (U) represents the reaction energy barrier of the HOR forward reaction of the alloy catalyst at potential U, in eV; E a red (U) represents the reaction barrier of the reverse HOR reaction of the alloy catalyst at potential U, in eV; j k(U) represents the kinetic current density of the alloy catalyst at potential U, in mA / cm². 2 ;

[0228] Taking NiM alloy catalyst as an example, a dual-reference electrode model is used to simulate the catalyst / solution interface. Specifically, the electrode is simulated by a fifth model, using the charge on the alloy catalyst unit cell to simulate the electrode charge q. An equal amount of counter-charge is introduced as background charge to maintain the unit cell's electroneutrality. During calculation, a certain amount of charge q (i.e., electrode charge) is applied to the alloy catalyst model, and then the reaction energy barriers for the HOR forward reaction (oxidation) and reverse reaction (reduction) on the alloy catalyst are calculated under this charge. By changing the applied charge amount, the reaction energy barrier values ​​for the HOR forward reaction (oxidation) and reverse reaction (reduction) on the alloy catalyst under different applied charge amounts q are calculated, thus obtaining two curves showing the HOR forward and reverse reaction energy barriers as a function of electrode charge q.

[0229] The electrode charge q is related to the work function W and the electrode potential U; after applying a certain amount of electrode charge, the work function W of the alloy catalyst model under charge q can be calculated; then, according to the formula U = W ÷ eU NHE (W is the work function; UNHE is the standard hydrogen electrode potential), the electrode potential U on the alloy catalyst model is calculated under a given electrode charge q, thus transforming the two curves of the HOR forward reaction energy barrier and reverse reaction energy barrier as a function of electrode charge q into curves of the HOR forward reaction energy barrier and reverse reaction energy barrier as a function of electrode potential U.

[0230] When the curves of the HOR forward and reverse reaction energy barriers as a function of the electrode potential U intersect, the corresponding electrode potential is the reversible electrode potential, i.e., the equilibrium potential.

[0231] By controlling the potential within the region near the equilibrium potential, the forward and reverse reaction energy barriers of HOR at a given electrode potential value are determined, and further utilization... Determine the HOR kinetic current density for a given electrode potential; where j kox j is the oxidation kinetic current density; kred The current density is the reduction kinetic current density; A(U) is the pre-exponential factor; R is the gas constant; T is the temperature; E a ox (U) represents the reaction energy barrier of the HOR forward reaction of the alloy catalyst at potential U; E a red (U) represents the reaction energy barrier of the HOR reverse reaction of the alloy catalyst at potential U; j k (U) represents the kinetic current density of the alloy catalyst at potential U.

[0232] In some specific embodiments, when the analytical method includes determining the Tafel polarization curve of the alloy catalyst based on the fifth model, the H2 electrochemical oxidation performance evaluation step further includes analyzing the exchange current density of the alloy catalyst based on the polarization curve of the alloy catalyst.

[0233] The analysis of the exchange current density of the alloy catalyst based on its polarization curve includes:

[0234] Step S641: Determine the exchange current density of the alloy catalyst based on the polarization curve of the alloy catalyst.

[0235] Furthermore, based on the polarization curve of the alloy catalyst, the exchange current density of the alloy catalyst is determined as follows: the polarization curve is fitted using the Butler-Volmer equation, and the coefficients obtained from the fitting are the exchange current density of the alloy catalyst; specifically, the Butler-Volmer equation is:

[0236] Where η=UU 0

[0237] In the formula, j k The kinetic current density of the alloy catalyst is mA / cm². 2 j0 represents the exchange current density of the alloy catalyst, mA / cm². 2 α is the transfer coefficient, dimensionless; F is the Faraday constant, C / mol; η is the overpotential, V; U is the j k The corresponding electric potential, V; U 0 To balance the potential, V.

[0238] Furthermore, the analysis of the exchange current density of the alloy catalyst based on its polarization curve further includes:

[0239] Step S642: Evaluate the HOR catalytic activity of the alloy catalyst based on the exchange current density of the alloy catalyst;

[0240] Among them, the higher the exchange current density of H2 electrochemical oxidation, the stronger the catalytic activity of the alloy catalyst; the lower the exchange current density, the weaker the catalytic activity of the alloy catalyst.

[0241] In some specific embodiments, step S6 further includes formation energy analysis of the alloy catalyst, specifically including:

[0242] Step S651: Based on the first model, determine the formation energy of the alloy catalyst;

[0243] The formation energy of the alloy catalyst can be determined using conventional methods. For example, the formation energy of the alloy catalyst can be obtained by subtracting the energy of the corresponding elemental metal from the energy of the alloy catalyst (determined using the first model).

[0244] Taking NiM alloy catalyst as an example, the formation energy of NiM alloy catalyst can be obtained by subtracting the energy of the corresponding elemental Ni and M from the energy of alloy NiM (determined using the first model).

[0245] Furthermore, the formation energy analysis of the alloy catalyst further includes:

[0246] Step S652: Determine the stability of the alloy catalyst based on its formation energy;

[0247] The formation energy of the alloy catalyst can characterize the feasibility of the corresponding metal forming an alloy. If the calculated formation energy is negative, the alloy catalyst can be formed, and the smaller the formation energy, the more stable the alloy catalyst structure. If the calculated formation energy is positive, the alloy catalyst cannot be formed.

[0248] Taking NiM alloy catalyst as an example, the formation energy of NiM alloy catalyst characterizes the feasibility of Ni and M forming an alloy. If the formation energy of NiM alloy catalyst is negative, Ni and M can form an alloy, and the smaller the formation energy of NiM alloy catalyst, the more stable the structure of NiM alloy catalyst. If the formation energy of NiM alloy catalyst is positive, Ni and M will each form an independent phase and cannot form an alloy catalyst.

[0249] In some specific embodiments, step S6 further includes reaction barrier analysis of the alloy catalyst, specifically including:

[0250] Step S661: Determine the optimal reaction pathway for the H2 electrochemical oxidation reaction on the surface of the alloy catalyst based on the fifth model;

[0251] Step S662: Based on the optimal reaction pathway of H2 electrochemical oxidation reaction on the surface of the alloy catalyst and the fifth model, determine the reaction energy barrier of the alloy catalyst in the HOR forward reaction;

[0252] The reaction energy barrier of the alloy catalyst in the HOR forward reaction can be determined using any conventional method. For example, firstly, the initial and final states of each elementary reaction in the fifth model are geometrically optimized to obtain stable structures for the initial and final states. Then, starting from the stable structures of the initial and final states, the corresponding transition states are searched using the linear synchronous transition / secondary synchronous transition (LST / QST) method, and the correctness of the transition states is verified by frequency calculation. Finally, the reaction energy between the initial and final states and the reaction energy barrier between the initial and transition states are calculated. Based on the magnitude of the reaction energy barrier, the optimal reaction path on the surface of the alloy catalyst is determined, and the rate-controlling step in the reaction process on the surface of the alloy catalyst is determined. The reaction energy barrier corresponding to the rate-controlling step in the reaction process on the surface of the alloy catalyst is the reaction energy barrier of the alloy catalyst in the HOR forward reaction.

[0253] Taking NiM alloy catalyst as an example, under alkaline conditions, the calculation of the H2 electrochemical oxidation reaction pathway in the fifth model involves the initial, final, and transition states of three elementary reactions: Tafel, Heyrovsky, and Volmer. First, the geometric structure of the initial and final states of each elementary reaction in the fifth model is optimized to obtain stable structures. Then, starting from the stable structures of the initial and final states, the corresponding transition states are searched using the linear simultaneous transition / secondary simultaneous transition (LST / QST) method, and the correctness of the transition states is verified by frequency calculation. Finally, the reaction energy between the initial and final states and the reaction energy barrier between the initial and transition states are calculated. Based on the magnitude of the reaction energy barrier, the optimal reaction pathway on the surface of the NiM alloy catalyst is determined, and the rate-controlling step in the reaction process on the surface of the NiM alloy catalyst is identified. The reaction energy barrier corresponding to the rate-controlling step in the reaction process on the surface of the NiM alloy catalyst is the reaction energy barrier of the NiM alloy catalyst in the HOR forward reaction.

[0254] Furthermore, the analysis of the reaction energy barrier of the alloy catalyst further includes:

[0255] Step S663: Determine the catalytic activity of the alloy catalyst based on the reaction energy barrier of the alloy catalyst in the HOR forward reaction;

[0256] Among them, the reaction energy barrier of the alloy catalyst in the HOR forward reaction can characterize the catalytic activity of the alloy catalyst. The lower the reaction energy barrier of the alloy catalyst in the HOR forward reaction, the stronger the catalytic activity of the alloy catalyst.

[0257] In some specific implementations, step S1 constructs the first model based on existing alloy structure data;

[0258] Taking NiM alloy catalyst as an example, a Ni unit cell model is established based on existing nickel crystal structure data. Then, a Ni alloy unit cell model is established by proportionally replacing some Ni atoms with non-precious metal atoms M. The Ni unit cell model can be established using the Visualizer module in the Materials Studio software package. Furthermore, the Ni alloy unit cell model can be established by proportionally replacing some Ni atoms with non-precious metal atoms Cr, Mn, Fe, Co, Ni, Cu, or Zn.

[0259] In some specific implementations, step S2 constructs the second model by cutting out the corresponding alloy surface based on the alloy cell model;

[0260] Taking NiM alloy catalyst as an example, the corresponding NiM surface is cut out based on the NiM alloy unit cell model to obtain the NiM alloy catalyst surface model.

[0261] In some specific embodiments, step S3 includes:

[0262] Step S31: Based on the second model, add an alkaline aqueous solution model to obtain an initial model of the alloy catalyst surface containing an alkaline aqueous solution layer;

[0263] Step S32: Perform first-principles molecular dynamics simulation (AIMD) on the initial model of the alloy catalyst surface containing the alkaline aqueous solution layer, and screen out several relatively stable models;

[0264] Step S33: Perform structural optimization based on first-principles calculations on the alkaline aqueous solution layer in the selected relatively stable models, and select the model with the most stable energy as the surface model of the alloy catalyst containing the alkaline aqueous solution layer, i.e., the third model.

[0265] In this embodiment, the initial model is structurally optimized by first-principles molecular dynamics simulation followed by first-principles calculation, resulting in higher accuracy.

[0266] Further, step S31 includes:

[0267] A vacuum layer is set on the alloy surface of the second model; an alkaline aqueous solution model is added into the vacuum layer to obtain an initial model of the alloy catalyst surface containing an alkaline aqueous solution layer.

[0268] Taking NiM alloy catalyst as an example, a vacuum layer is set on the NiM surface of the NiM alloy catalyst surface model; an alkaline aqueous solution model is added to the vacuum layer near the NiM surface to obtain the initial NiM alloy catalyst surface model containing the alkaline aqueous solution layer, i.e., the third model; wherein, the set vacuum layer height can be... Among them, the alkaline aqueous solution model can be composed of water molecules and K + OH - Ionic composition.

[0269] In some specific embodiments, step S4 includes:

[0270] Step S41: Perform first-principles molecular dynamics simulations (AIMD) on the fourth model to screen out several models with relatively stable reactants, intermediates and products;

[0271] Step S42: Perform structural optimization based on first-principles calculations on the alkaline aqueous solution layer in the relatively stable models of reactants, intermediates and products, and screen out the most energy stable model. The alkaline aqueous solution / alloy catalyst surface model containing reactants, intermediates and products with the optimal structure is the fifth model.

[0272] In this embodiment, the initial model is structurally optimized by first-principles molecular dynamics simulation followed by first-principles calculation, resulting in higher accuracy.

[0273] In some specific implementations, the energy, displacement, and gradient convergence criteria for structural optimization calculated based on first-principles calculations are 5.442 × 10⁻⁶. -4 eV, and

[0274] In some specific implementations, the structure optimization process based on first-principles calculations employs a spin-unrestricted calculation method, calculates PBE functionals using the generalized gradient approximation, calculates long-range dispersion forces using Grimme's PBE-D2 method, describes the ion nuclei of metal atoms using density functional theory half-nuclear pseudopotentials, and uses a dual-numerical polarization (DNP) basis set for valence electron functions.

[0275] This invention also provides an analysis system for the electrochemical oxidation performance of alloy catalysts in H2. Preferably, this system is used to implement the above-described method embodiments.

[0276] The system includes:

[0277] First Model Construction Module: Used to construct the alloy cell model, i.e., the first model;

[0278] The second model construction module is used to construct a surface model of the alloy catalyst, i.e., the second model, based on the first model.

[0279] Optional third model building module: used to build a surface model of the alloy catalyst containing an alkaline aqueous solution layer, i.e., the third model, based on the second model;

[0280] Optional fourth model construction module: used to construct structural models of reactants, intermediates and products on the surface of the alloy catalyst containing the alkaline aqueous solution layer in the third model, respectively, to obtain the initial model of the alkaline aqueous solution / alloy catalyst containing reactants, intermediates and products, i.e. the fourth model;

[0281] Optional fifth model building module: used to optimize the structure of the fourth model to obtain the optimal structure of the alkaline aqueous solution / alloy catalyst surface model containing reactants, intermediates and products, i.e., the fifth model;

[0282] The H2 electrochemical oxidation performance evaluation module includes an oxidation potential analysis submodule, an H adsorption free energy analysis submodule, and / or a polarization curve determination submodule; among which...

[0283] The oxidation potential analysis submodule is used to perform oxidation potential analysis of alloy catalysts based on the second model;

[0284] The H adsorption free energy analysis submodule is used to perform H adsorption free energy analysis of alloy catalysts based on the second or third model.

[0285] The polarization curve determination submodule is used to determine the Tafel polarization curves of alloy catalysts based on the fifth model.

[0286] In some specific embodiments, the oxidation potential analysis submodule includes:

[0287] First energy determination unit: used to obtain the energy of the second model;

[0288] Second energy determination unit: used to obtain the energy after the alloy catalyst removes the oxidized metal atoms;

[0289] The third energy determination unit is used to obtain the energy of the metal atoms undergoing oxidation in the alloy catalyst when they are in an elemental state.

[0290] Standard oxidation potential determination unit: used to obtain the standard oxidation potential of the metal undergoing oxidation in the alloy catalyst when it is in the elemental state;

[0291] Oxidation potential determination unit: used to determine the oxidation potential of the alloy catalyst (i.e. the external potential required when the alloy is oxidized to a metal oxide or metal hydroxide) based on the energy of the second model, the energy of the oxidized metal atoms in the alloy catalyst in the elemental state, and the standard oxidation potential of the oxidized metal in the alloy catalyst in the elemental state.

[0292] Furthermore, the oxidation potential analysis submodule further includes:

[0293] Antioxidant performance evaluation unit: used to evaluate the antioxidant performance of alloy catalysts based on their oxidation potential;

[0294] Furthermore, the oxidation potential of the alloy catalyst is preferably determined using the following formula:

[0295] U ox =U ox (met1,bulk)-(E(A x B y )-E(A x B y-z )-z·E(B))÷n

[0296] In the formula, U ox V represents the oxidation potential of the alloy catalyst; U represents the oxidation potential of the catalyst. ox (met1,bulk) represents the standard oxidation potential of metal B, which undergoes oxidation in the alloy catalyst, in its elemental state; V; E(A x B y E(A) represents the energy of the second model, in eV; x B y-z E(B) represents the energy of the alloy catalyst after removing z metal B atoms that have undergone oxidation, in eV; E(B) represents the energy of the metal B atoms that have undergone oxidation in the alloy catalyst when they are in their elemental state, in eV; n represents the number of electrons e transferred during the oxidation of the alloy catalyst, in units.

[0297] In some specific embodiments, the H adsorption free energy analysis submodule includes:

[0298] H adsorption free energy determination unit: used to determine the H adsorption free energy of the alloy catalyst based on the second or third model;

[0299] The first catalytic activity determination unit is used to evaluate the HOR catalytic activity of the alloy catalyst based on the H adsorption free energy of the alloy catalyst; wherein, the closer the H adsorption free energy of the alloy catalyst is to 0.414 eV, the stronger the HOR catalytic activity of the alloy catalyst.

[0300] In some specific embodiments, the polarization curve determination submodule includes:

[0301] Optimal reaction path determination unit: used to determine the optimal reaction path for the H2 electrochemical oxidation reaction on the surface of the alloy catalyst based on the fifth model;

[0302] The sixth model determination unit is used to apply different electrode charges to the alloy catalyst unit cell in the fifth model and introduce the same amount of background charge to maintain the charge neutrality of the unit cell, thereby obtaining the sixth model corresponding to different charges; among them, the sixth model corresponding to the applied charge of 0 is the fifth model.

[0303] Unit for determining the reaction energy barrier of forward and reverse reactions under different charges: used to determine the reaction energy barrier of HOR forward and reverse reactions of alloy catalysts under different applied charges based on the optimal reaction path of H2 electrochemical oxidation reaction on the surface of alloy catalyst and the sixth model corresponding to different applied charges;

[0304] Unit for determining the reaction energy barrier of forward and reverse reactions under different potentials: Used to determine the reaction energy barrier of HOR forward and reverse reactions of alloy catalysts under different applied charge conditions, and to determine the reaction energy barrier of HOR forward and reverse reactions of alloy catalysts under different electrode potentials.

[0305] Equilibrium potential determination unit: used to determine the equilibrium potential of alloy catalyst based on the reaction energy barriers of the HOR forward and reverse reactions of alloy catalyst under different electrode potentials;

[0306] The polarization curve determination unit is used to determine a given potential range based on the equilibrium potential of the alloy catalyst, and then determine the reaction energy barriers of the HOR forward and reverse reactions of the alloy catalyst within the given potential range; based on the reaction energy barriers of the HOR forward and reverse reactions of the alloy catalyst within the given potential range, the kinetic current density of the alloy catalyst within the given potential range is determined, and then the polarization curve of the alloy catalyst (i.e., the curve of the kinetic current density of the alloy catalyst as a function of potential) is obtained.

[0307] Furthermore, the sixth model determining unit includes:

[0308] Charge application sub-unit: Based on the fifth model, different electrode charges are applied to the alloy catalyst unit cell in the fifth model respectively, and the same amount of background charge is introduced to maintain the electrical neutrality of the unit cell to obtain the fifth model with different electrode charges applied;

[0309] The sixth model determines the sub-units: used to perform structural optimization on the fifth model with different electrode charges applied, so as to obtain the sixth model corresponding to different charges;

[0310] Furthermore, the sixth model identifies the sub-units as including:

[0311] The first optimization group: used to perform first-principles molecular dynamics simulations (AIMD) on the fifth model with different electrode charges, and screen out several models with relatively stable reactants, intermediates and products;

[0312] The second optimization group is used to perform structural optimization of the alkaline aqueous solution layer in the relatively stable models of reactants, intermediates and products selected based on first-principles calculations, and to select the most energy-stable model, namely the sixth model.

[0313] Furthermore, the kinetic current density of the alloy catalyst within a given potential range is determined by the following formula, based on the reaction energy barriers of the HOR forward and reverse reactions of the alloy catalyst within a given potential range:

[0314]

[0315] Where, j kox The oxidation kinetic current density is mA / cm². 2 ;j kred To restore the kinetic current density, mA / cm 2 A(U) is the exponential factor (usually taken as 12.0-14.0), dimensionless; R is the gas constant (usually taken as 8.3145), J / mol·K; T is the temperature, K; E a ox (U) represents the reaction energy barrier of the HOR forward reaction of the alloy catalyst at potential U, in eV; E a red (U) represents the reaction barrier of the reverse HOR reaction of the alloy catalyst at potential U, in eV; j k (U) represents the kinetic current density of the alloy catalyst at potential U, in mA / cm². 2 .

[0316] In some specific embodiments, when the H2 electrochemical oxidation performance evaluation module includes a polarization curve determination submodule, the H2 electrochemical oxidation performance evaluation module further includes:

[0317] Exchange current density analysis submodule: used to perform exchange current density analysis of alloy catalysts based on the polarization curves of the alloy catalysts;

[0318] The exchange current density analysis submodule includes:

[0319] Exchange current density determination unit: used to determine the exchange current density of the alloy catalyst based on the polarization curve of the alloy catalyst;

[0320] Furthermore, the exchange current density analysis submodule further includes:

[0321] The second catalytic activity evaluation unit is used to evaluate the HOR catalytic activity of the alloy catalyst based on the exchange current density of the alloy catalyst.

[0322] Furthermore, based on the polarization curve of the alloy catalyst, the exchange current density of the alloy catalyst is determined as follows: the polarization curve is fitted using the Butler-Volmer equation, and the coefficients obtained from the fitting are the exchange current density of the alloy catalyst; specifically, the Butler-Volmer equation is:

[0323] Where η=UU 0

[0324] In the formula, j k The kinetic current density of the alloy catalyst is mA / cm². 2 j0 represents the exchange current density of the alloy catalyst, mA / cm². 2 α is the transfer coefficient, dimensionless; F is the Faraday constant, C / mol; η is the overpotential, V; U is the j k The corresponding electric potential, V; U 0 To balance the potential, V.

[0325] In some specific embodiments, the H2 electrochemical oxidation performance evaluation module further includes:

[0326] Formation energy analysis submodule: used to perform formation energy analysis of alloy catalysts based on the first model;

[0327] Furthermore, the energy analysis submodule includes:

[0328] Formation energy determination unit: used to determine the formation energy of the alloy catalyst based on the first model;

[0329] Stability evaluation unit: used to determine the stability of alloy catalysts based on their formation energy.

[0330] In some specific embodiments, the H2 electrochemical oxidation performance evaluation module further includes:

[0331] Reaction barrier analysis submodule: used for reaction barrier analysis of alloy catalysts based on the fifth model;

[0332] Furthermore, the reaction barrier analysis submodule includes:

[0333] Optimal reaction path determination unit: used to determine the optimal reaction path for the H2 electrochemical oxidation reaction on the surface of the alloy catalyst based on the fifth model;

[0334] Reaction barrier determination unit: used to determine the optimal reaction pathway of H2 electrochemical oxidation reaction based on the surface of alloy catalyst and the fifth model, and to determine the reaction barrier of alloy catalyst in the HOR forward reaction;

[0335] The third catalytic activity analysis unit is used to determine the catalytic activity of alloy catalysts based on their reaction energy barriers.

[0336] In some specific embodiments, the third model building module includes:

[0337] Initial model construction submodule: used to add an alkaline aqueous solution model to the second model to obtain an initial model of the alloy catalyst surface containing an alkaline aqueous solution layer;

[0338] The first model optimization submodule is used to perform first-principles molecular dynamics (AIMD) simulations on the initial model of the alloy catalyst surface containing an alkaline aqueous solution layer, and to screen out several relatively stable models.

[0339] The second model optimization submodule is used to perform structural optimization based on first-principles calculations on the alkaline aqueous solution layer in the relatively stable models selected, and to select the most energy-stable model as the surface model of the alloy catalyst containing the alkaline aqueous solution layer, i.e., the third model.

[0340] In some specific embodiments, the fourth model building module includes:

[0341] The third model optimization submodule is used to perform first-principles molecular dynamics simulations (AIMD) on the fourth model and screen out several models with relatively stable reactants, intermediates and products.

[0342] The fourth model optimization submodule is used to perform first-principles calculations to optimize the structure of the alkaline aqueous solution layer in the relatively stable models of reactants, intermediates and products, and to select the most energy-stable model. The fifth model is the alkaline aqueous solution / alloy catalyst surface model containing reactants, intermediates and products with the optimal structure.

[0343] In some specific embodiments, the energy, displacement, and gradient convergence criteria for structural optimization calculated based on first-principles calculations are 5.442 × 10⁻⁶. -4 eV, and

[0344] In some specific embodiments, the alloy is a nickel-based non-precious metal alloy;

[0345] Furthermore, the non-precious metals include one or more combinations of Cr, Mn, Fe, Co, Ni, Cu, and Zn.

[0346] Example 1

[0347] This embodiment provides a method for evaluating the electrochemical oxidation performance of NiCr alloy catalysts in H2.

[0348] like Figure 1 As shown, the method includes:

[0349] Step 1, Model Building, including:

[0350] Step 1.1, Ni unit cell model establishment: based on the lattice parameters as follows The nickel crystal structure was determined by using the Visualizer module in the MaterialsStudio software package to build a 4×4 Ni unit cell model.

[0351] Step 1.2, Establishment of NiCr alloy unit cell models: Based on the 4×4 Ni unit cell model, according to the Ni / Cr atomic ratios of 3:1, 2:2, and 1:3, some Ni atoms were uniformly replaced with Cr atoms to establish Ni3Cr, Ni2Cr2, and NiCr3 alloy unit cell models, which are the first models of Ni3Cr, Ni2Cr2, and NiCr3 alloy catalysts; the parameters of the Ni3Cr, Ni2Cr2, and NiCr3 alloy unit cell models are shown in Table 1.

[0352] Table 1. Lattice parameters of NiCr alloy

[0353]

[0354] Step 1.2, Construction of NiCr alloy catalyst surface models: Based on the Ni3Cr, Ni2Cr2, and NiCr3 alloy cell models, the surfaces of Ni3Cr(111), Ni2Cr2(111), and NiCr3(111) are cut out to obtain the surface models of Ni3Cr, Ni2Cr, and NiCr3 alloy catalysts, i.e., the second models of Ni3Cr, Ni2Cr2, and NiCr3 alloy catalysts. The alloy thickness is 4 layers, and the height is set to [missing information]. Vacuum layer, the corresponding structure is as follows Figures 2A-2C As shown.

[0355] Step 1.3: Construction of the NiCr alloy catalyst surface model containing an alkaline aqueous solution layer: 13 water molecules and 2 K+ molecules are added near the surface of the alloy catalyst in a vacuum layer. + / OH - An alkaline solution layer model was established using ions to obtain surface models of Ni3Cr, Ni2Cr, and NiCr3 alloy catalysts containing an alkaline aqueous solution layer. This is the third model for Ni3Cr, Ni2Cr2, and NiCr3 alloy catalysts. The results are as follows: Figures 3A-3C As shown.

[0356] Step 1.4, Fourth Model Construction: On the surface models of Ni3Cr, Ni2Cr2, and NiCr3 alloy catalysts containing alkaline aqueous solution layers, structural models of reactants, intermediates, and products are further constructed respectively, to obtain the initial models of alkaline aqueous solution / Ni3Cr alloy catalysts containing reactants, intermediates, and products, the initial models of alkaline aqueous solution / Ni2Cr2 alloy catalysts containing reactants, intermediates, and products, and the initial models of alkaline aqueous solution / NiCr3 alloy catalysts containing reactants, intermediates, and products, i.e., the fourth models of Ni3Cr, Ni2Cr2, and NiCr3 alloy catalysts.

[0357] Step 1.5, Construction of the fifth model: The fourth model is structurally optimized to obtain the optimal structure of the alkaline aqueous solution / alloy catalyst surface model containing reactants, intermediates and products, which is the fifth model;

[0358] Specifically, first-principles molecular dynamics (AIMD) simulations were performed on the fourth model of the Ni3Cr alloy catalyst to screen out several models with relatively stable reactants, intermediates and products. First-principles density functional theory was used to optimize and calculate the structure of reactants, intermediates and products in the three elementary reaction processes on the Ni3Cr(111) surface of the screened models, and the most energy-stable model was selected as the fifth model of the Ni3Cr alloy catalyst, which is the alkaline aqueous solution / Ni3Cr alloy catalyst surface model containing reactants, intermediates and products.

[0359] First-principles molecular dynamics (AIMD) simulations were performed on the fourth model of the Ni2Cr2 alloy catalyst to screen out several models with relatively stable reactants, intermediates and products. First-principles density functional theory was used to optimize and calculate the reactants, intermediates and products in the three elementary reaction processes on the Ni2Cr2(111) surface of the screened models, and the most energy-stable model was selected. The alkaline aqueous solution / Ni2Cr2 alloy catalyst surface model containing reactants, intermediates and products with the optimal structure is the fifth model of the Ni2Cr2 alloy catalyst.

[0360] First-principles molecular dynamics (AIMD) simulations were performed on the fourth model of the NiCr3 alloy catalyst to screen out several models with relatively stable reactants, intermediates and products. First-principles density functional theory was used to optimize and calculate the reactants, intermediates and products in the three elementary reaction processes on the surface of NiCr3(111) of the screened models, and the most energy-stable model was selected as the fifth model of NiCr3 alloy catalyst, which is the alkaline aqueous solution / NiCr3 alloy catalyst surface model containing reactants, intermediates and products.

[0361] The structural optimization employed spin-unrestricted calculations using a PBE functional approximation with a generalized gradient. Long-range dispersion forces were calculated using Grimme's PBE-D2 method. The ionic nuclei of metal atoms were described using density functional theory seminuclear pseudopotentials, and the valence electron functions were derived using a dual numerical polarization (DNP) basis set. The energy, displacement, and gradient convergence criteria in the structural optimization were 5.442 × 10⁻⁶. -4 eV, and

[0362] Step 2: Obtaining parameters for evaluating the electrochemical oxidation performance of H2, including:

[0363] Step 2.1: Determine the formation energy of the alloy catalysts: Based on the Ni3Cr alloy cell model, determine the energy of the Ni3Cr alloy, and then subtract the energies of elemental Ni and Cr to obtain the formation energy of the Ni3Cr alloying agent; based on the Ni2Cr2 alloy cell model, determine the energy of the Ni2Cr2 alloy, and then subtract the energies of elemental Ni and Cr to obtain the formation energy of the Ni3Cr alloying agent; based on the NiCr3 alloy cell model, determine the energy of the NiCr3 alloy, and then subtract the energies of elemental Ni and Cr to obtain the formation energy of the Ni3Cr alloying agent; the formation energies of the Ni3Cr, Ni2Cr2, and NiCr3 alloy catalysts are determined to be -2.76 eV, -2.53 eV, and -2.34 eV, respectively.

[0364] Step 2.2: Determine the oxidation potential of the alloy catalyst:

[0365] When Ni in Ni3Cr(111), Ni2Cr2(111), and NiCr3(111) is oxidized to Ni(OH)2, the energy of the surface model of the Ni3Cr, Ni2Cr2, and NiCr3 alloy catalysts is obtained respectively; the energy of the Ni3Cr, Ni2Cr2, and NiCr3 alloy catalysts after removing the oxidized Ni metal atoms is obtained respectively; the energy of Ni metal atoms in the elemental state is obtained; the standard oxidation potential of Ni metal in the elemental state is obtained; and then the oxidation potential of Ni in Ni3Cr(111), Ni2Cr2(111), and NiCr3(111) when Ni is oxidized to Ni(OH)2 is determined by the following formula:

[0366] U ox =U ox (met1,bulk)-(E(A x B y )-E(A x B y-z )-z·E(B))÷n

[0367] In the formula, U ox V represents the oxidation potential of the alloy catalyst; U represents the oxidation potential of the catalyst. ox (met1,bulk) represents the standard oxidation potential of metal B, which undergoes oxidation in the alloy catalyst, in its elemental state; V; E(A x B y E(A) represents the energy of the second model, in eV; x B y-z E(B) represents the energy of the alloy catalyst after removing z metal B atoms that have undergone oxidation, in eV; E(B) represents the energy of the metal B atoms that have undergone oxidation in the alloy catalyst when they are in their elemental state, in eV; n represents the number of electrons e transferred during the oxidation of the alloy catalyst, in units.

[0368] When Cr in Ni3Cr(111), Ni2Cr2(111), and NiCr3(111) is oxidized to Cr(OH)3, the energy of the surface model of the Ni3Cr, Ni2Cr2, and NiCr3 alloy catalysts is obtained respectively; the energy of the Ni3Cr, Ni2Cr2, and NiCr3 alloy catalysts after removing the oxidized Cr metal atoms is obtained respectively; the energy of Cr metal atoms in the elemental state is obtained; the standard oxidation potential of Cr metal in the elemental state is obtained; and then, the oxidation potential of Cr in Ni3Cr(111), Ni2Cr2(111), and NiCr3(111) when Cr is oxidized to Cr(OH)3 is determined by the above formula.

[0369] Specifically, the oxidation potentials of Ni to Ni(OH)2 in Ni3Cr(111), Ni2Cr2(111), and NiCr3(111) are 0.68V, 0.50V, and 0.47V, respectively; and the oxidation potentials of Cr to Cr(OH)3 in Ni3Cr(111), Ni2Cr2(111), and NiCr3(111) are 1.27V, 1.14V, and 1.03V, respectively.

[0370] Step 2.3: Determine the reaction energy barrier for alloy catalysis:

[0371] Under alkaline conditions, the electrochemical oxidation of H2 mainly involves three elementary reactions: the Tafel reaction, the Heyrovsky reaction, and the Volmer reaction. The Tafel reaction refers to the direct decomposition of H2 molecules into two adsorbed H atoms on the catalyst surface; the Heyrovsky reaction refers to the reaction of H2 molecules with alkaline anions (OH-). - The Volmer reaction is a process in which adsorbed H+ and H2O are generated and an electron is released; the Volmer reaction refers to the reaction of adsorbed H+ with the basic anion OH-. - The reaction produces H2O and releases an electron; therefore, the electrochemical oxidation of H2 can proceed via the Tafel-Volmer process or the Heyrovsky-Volmer process.

[0372] Under alkaline conditions, the calculation of the H2 electrochemical oxidation reaction pathway on the fifth model of Ni3Cr, Ni2Cr2, and NiCr3 alloy catalysts involves the initial, final, and transition states of three elementary reactions: Tafel, Heyrovsky, and Volmer. First, the geometric structure of the initial and final states of each elementary reaction on the fifth model is optimized to obtain stable structures. Then, starting from the stable structures of the initial and final states, the corresponding transition states are searched using the linear simultaneous transition / secondary simultaneous transition (LST / QST) method, and the correctness of the transition states is verified by frequency calculation. Finally, the reaction energy between the initial and final states and the reaction energy barrier between the initial and transition states are calculated. Based on the magnitude of the reaction energy barrier, the optimal reaction pathway on the surface of the NiM alloy catalyst is determined, and the rate-controlling step in the reaction process on the surface of the NiM alloy catalyst is identified. The reaction energy barrier corresponding to the rate-controlling step in the reaction process on the surface of the NiM alloy catalyst is the reaction energy barrier of the NiM alloy catalyst in the HOR forward reaction.

[0373] Table 2 shows the reaction barriers of Tafel, Heyrovsky, and Volmer reactions on the surfaces of Ni3Cr(111), Ni2Cr2(111), and NiCr3(111) at pH=13. As can be seen from Table 2, the Tafel reaction barrier is significantly lower than that of Heyrovsky. Therefore, the optimal reaction pathway for H2 electrochemical oxidation on the surface of NiCr catalyst is Tafel-Volmer. Compared with the Tafel reaction, the Volmer reaction barrier is significantly higher. Therefore, the Volmer step is the rate-controlling step of the entire H2 electrochemical oxidation. Thus, the reaction barriers of the rate-controlling steps on Ni3Cr(111), Ni2Cr2(111), and NiCr3(111) (i.e., the reaction barriers of Ni3Cr, Ni2Cr2, and NiCr3 alloy catalysts in the HOR forward reaction) are 0.67 eV, 2.20 eV, and 1.08 eV, respectively.

[0374] Table 2. Energy barriers for Tafel, Heyrovsky, and Volmer reactions on NiCr alloy catalysts at pH = 13.

[0375] catalyst Tafel(eV) Heyrovsky (eV) Volmer(eV) <![CDATA[Ni3Cr]]> 0.15 0.53 0.67 <![CDATA[Ni2Cr2]]> 0.17 0.50 2.20 <![CDATA[NiCr3]]> 0.24 0.34 1.08

[0376] Step 2.4: Determine the H adsorption free energy of the alloy catalysis:

[0377] H may adsorb at the top of a metal atom on the catalyst surface, i.e., the top site; it may also adsorb at the position between two metal atoms on the catalyst surface, i.e., the bridge site; or it may adsorb at the position between three metal atoms on the catalyst surface, i.e., the vacancy. The most stable H adsorption site on the NiCr alloy surface is the vacancy. When H is initially placed at the top site and the bridge site on the NiCr alloy surface, H will automatically move to the vacancy during the geometric optimization process.

[0378] The energy of H adsorption on the surface of the second model of Ni3Cr alloy catalyst after H adsorption is calculated, and the energy of the second model of Ni3Cr alloy catalyst when H is not adsorbed and the energy of 1 / 2 H2 molecule are subtracted. Then, the zero-point energy correction, entropy change correction and pH value correction are added to obtain the H adsorption free energy.

[0379] The energy of H adsorption on the surface of the second model of Ni2Cr2 alloy catalyst is calculated by subtracting the energy of the second model of Ni2Cr2 alloy catalyst when H is not adsorbed and the energy of 1 / 2 H2 molecule, and then adding the zero-point energy correction, entropy change correction and pH value correction to obtain the H adsorption free energy.

[0380] The energy of H adsorption on the surface of the second model of NiCr3 alloy catalyst is calculated by subtracting the energy of the second model of NiCr3 alloy catalyst when H is not adsorbed and the energy of 1 / 2 H2 molecule, and then adding the zero-point energy correction, entropy change correction and pH value correction to obtain the H adsorption free energy.

[0381] Under alkaline conditions at pH=13, the H adsorption free energies on the Ni3Cr(111) surface of the Ni3Cr alloy catalyst, the Ni2Cr2(111) surface of the Ni2Cr2 alloy catalyst, and the NiCr3(111) surface of the NiCr3 alloy catalyst are 0.494 eV, 0.699 eV, and 0.238 eV, respectively.

[0382] Step 2.5: Determine the polarization curve and exchange current density of the alloy catalysis.

[0383] The fifth model is used to simulate the electrode charge q by using the charge carried by the unit cell of the alloy catalyst. The electroneutrality of the unit cell is maintained by introducing an opposite charge of the same amount as a background charge. During the calculation, a certain amount of charge q (i.e., electrode charge) is applied to the alloy catalyst model, and then the reaction energy barriers of the HOR forward reaction (i.e., oxidation) and reverse reaction (i.e., reduction) on the alloy catalyst are calculated under this charge. By changing the amount of applied charge, the reaction energy barrier values ​​of the HOR forward reaction (i.e., oxidation) and reverse reaction (i.e., reduction) on the alloy catalyst under different applied charge amounts q are calculated, thus obtaining two curves showing the change of the HOR forward reaction energy barrier and the reverse reaction energy barrier with the electrode charge q, respectively.

[0384] The electrode charge q is related to the work function W and the electrode potential U; after applying a certain amount of electrode charge, the work function W of the alloy catalyst model under charge q can be calculated; then, according to the formula U = W ÷ eU NHE (W is the work function; UNHE is the standard hydrogen electrode potential), the electrode potential U on the alloy catalyst model is calculated under a given electrode charge q, thus transforming the two curves of the HOR forward reaction energy barrier and reverse reaction energy barrier as a function of electrode charge q into curves of the HOR forward reaction energy barrier and reverse reaction energy barrier as a function of electrode potential U.

[0385] When the curves of the HOR forward reaction energy barrier and the reverse reaction energy barrier change with the electrode potential U intersect, the corresponding electrode potential is the reversible electrode potential, i.e. the equilibrium potential.

[0386] By controlling the potential within the region near the equilibrium potential, the forward and reverse reaction energy barriers of HOR at a given electrode potential value are determined, and further utilization... The HOR kinetic current density at a given electrode potential is determined to obtain the Tafel polarization curve of the alloy catalyst; where j kox j is the oxidation kinetic current density;kred The current density is the reduction kinetic current density; A(U) is the pre-exponential factor; R is the gas constant; T is the temperature; E a ox (U) represents the reaction energy barrier of the HOR forward reaction of the alloy catalyst at potential U; E a red (U) represents the reaction energy barrier of the HOR reverse reaction of the alloy catalyst at potential U; j k (U) represents the kinetic current density of the alloy catalyst at potential U;

[0387] The polarization curve of the alloy catalyst was fitted using the Butler-Volmer equation, and the coefficients obtained from the fitting represent the exchange current density of the alloy catalyst. The Butler-Volmer equation is as follows:

[0388] Where η=UU 0

[0389] In the formula, j k The kinetic current density of the alloy catalyst is mA / cm². 2 j0 represents the exchange current density of the alloy catalyst, mA / cm². 2 α is the transfer coefficient, dimensionless; F is the Faraday constant, C / mol; η is the overpotential, V; U is the j k The corresponding electric potential, V; U 0 To balance the potential, V.

[0390] The Tafel polarization curves of Ni3Cr, Ni2Cr2, and NiCr3 alloy catalysts were determined according to the above method, and the results are as follows: Figures 4A-4C As shown in Table 3, the exchange current densities of Ni3Cr, Ni2Cr2, and NiCr3 alloy catalysts were determined according to the above method. Table 3 shows that the exchange current densities for H2 electrochemical oxidation of Ni3Cr, Ni2Cr2, and NiCr3 alloy catalysts are 0.82 mA / cm². 2 7.78×10 -15 mA / cm 2 and 2.31×10 -7 mA / cm 2 .

[0391] Table 3 Calculation of H adsorption free energy and exchange current density on NiCr alloy catalyst at pH=13.

[0392]

[0393] Step 3, Evaluation of H2 electrochemical oxidation performance, including:

[0394] Step 3.1: Determine the stability of the alloy catalyst based on its formation energy.

[0395] The formation energy of an alloy catalyst can characterize the feasibility of forming an alloy with the corresponding metal. If the calculated formation energy is negative, an alloy catalyst can be formed, and the smaller the formation energy, the more stable the structure of the alloy catalyst. If the calculated formation energy is positive, an alloy catalyst cannot be formed.

[0396] Specifically, the formation energies of Ni3Cr, Ni2Cr2, and NiCr3 alloy catalysts are -2.76 eV, -2.53 eV, and -2.34 eV, respectively; the calculated formation energies are all negative, indicating that Ni and Cr can form stable Ni3Cr, Ni2Cr2, and NiCr3 alloys.

[0397] Step 3.2: Evaluate the oxidation resistance of the alloy catalyst based on its oxidation potential.

[0398] The oxidation potential of an alloy catalyst can characterize its antioxidant capacity under alkaline conditions. A positive value indicates that the alloy can undergo oxidation. The higher the oxidation potential, the easier the alloy is to be oxidized, and the worse its antioxidant capacity. A negative value indicates that the alloy is not easily oxidized. The lower the oxidation potential, the less easily the alloy is oxidized, and the stronger its antioxidant capacity.

[0399] Specifically, the oxidation potentials of Ni to Ni(OH)2 in Ni3Cr, Ni2Cr2, and NiCr3 alloy catalysts are 0.68V, 0.50V, and 0.47V, respectively, all lower than the oxidation potential of pure Ni (0.72V). Similarly, the oxidation potentials of Cr to Cr(OH)3 in Ni3Cr, Ni2Cr2, and NiCr3 are 1.27V, 1.14V, and 1.03V, respectively, also lower than the oxidation potential of pure Cr (1.48V). This indicates that the oxidation potential of Ni and Cr alloys is lower than that of their respective elemental forms, suggesting a significant improvement in oxidation resistance after NiCr alloying.

[0400] Step 3.3: Evaluate the HOR catalytic activity of the alloy catalyst based on the H adsorption free energy of the alloy catalyst;

[0401] The closer the H adsorption free energy of the alloy catalyst is to 0.414 eV, the stronger the HOR catalytic activity of the alloy catalyst.

[0402] Specifically, the H adsorption free energies of Ni3Cr, Ni2Cr2, and NiCr3 alloy catalysts are 0.494 eV, 0.699 eV, and 0.238 eV, respectively. The absolute values ​​of their differences from the optimal H adsorption free energy of 0.414 eV are 0.08 eV, 0.285 eV, and 0.176 eV, respectively. This indicates that the Ni3Cr alloy catalyst has the closest H adsorption free energy to the optimal H adsorption free energy of 0.414 eV and has the highest H2 electrochemical oxidation activity. The NiCr3 alloy catalyst has the second highest H2 electrochemical oxidation activity, while the Ni2Cr2 alloy catalyst has the worst H2 electrochemical oxidation activity.

[0403] Step 3.4: Determine the catalytic activity of the alloy catalyst based on the reaction energy barrier of the alloy catalyst in the HOR forward reaction;

[0404] The reaction energy barrier of the alloy catalyst in the HOR forward reaction can characterize the catalytic activity of the alloy catalyst. The lower the reaction energy barrier of the alloy catalyst in the HOR forward reaction, the stronger the catalytic activity of the alloy catalyst.

[0405] Specifically, the reaction barriers of Ni3Cr, Ni2Cr2, and NiCr3 alloy catalysts in the HOR forward reaction are 0.67 eV, 2.20 eV, and 1.08 eV, respectively, indicating that the Ni3Cr alloy catalyst has the highest H2 electrochemical oxidation activity, followed by the NiCr3 alloy catalyst, while the Ni2Cr2 alloy catalyst has the worst H2 electrochemical oxidation activity.

[0406] Step 3.5: Evaluate the HOR catalytic activity of the alloy catalyst based on the exchange current density of the alloy catalyst;

[0407] The higher the exchange current density of H2 electrochemical oxidation, the stronger the catalytic activity of the alloy catalyst; the lower the exchange current density, the weaker the catalytic activity of the alloy catalyst.

[0408] Specifically, the H2 electrochemical oxidation exchange current densities of Ni3Cr, Ni2Cr2, and NiCr3 alloy catalysts are 0.82 mA / cm², respectively. 2 7.78×10 -15 mA / cm 2 and 2.31×10 -7 mA / cm 2 This indicates that the order of H2 electrochemical oxidation activity is Ni3Cr>NiCr3>Ni2Cr2.

[0409] Specific embodiments have been used to illustrate the principles and implementation methods of this invention. The descriptions of the embodiments above are only for the purpose of helping to understand the method and core ideas of this invention. At the same time, for those skilled in the art, there will be changes in the specific implementation methods and application scope based on the ideas of this invention. Therefore, the content of this specification should not be construed as a limitation of this invention.

Claims

1. A method for analyzing the performance of an alloy catalyst for the electrochemical oxidation of hydrogen, wherein, The method comprises: A first model construction step: constructing an alloy unit cell model, i.e., a first model; A second model construction step: constructing an alloy catalyst surface model, i.e., a second model, based on the first model; A third model construction step: constructing an alloy catalyst surface model containing an alkaline aqueous solution layer, i.e., a third model, based on the second model; A fourth model construction step: constructing structure models of reactants, intermediates, and products in the alloy catalyst surface containing the alkaline aqueous solution layer in the third model, respectively, to obtain an initial model of the alkaline aqueous solution / alloy catalyst containing the reactants, intermediates, and products, i.e., a fourth model; A fifth model construction step: performing structure optimization on the fourth model to obtain an optimal structure of the alkaline aqueous solution / alloy catalyst surface model containing the reactants, intermediates, and products, i.e., a fifth model; An H2 electrochemical oxidation performance evaluation step: based on the fifth model, performing Tafel polarization curve determination of the alloy catalyst; The Tafel polarization curve determination of the alloy catalyst based on the fifth model comprises: determining an optimal reaction path of the H2 electrochemical oxidation reaction on the surface of the alloy catalyst based on the fifth model; on the basis of the fifth model, applying different electrode charges to the alloy catalyst unit cell in the fifth model and introducing background charges of the same amount to maintain the electrical neutrality of the unit cell, thereby obtaining a sixth model corresponding to different charges; wherein, when the applied charge is 0, the corresponding sixth model is the fifth model; based on the optimal reaction path of the H2 electrochemical oxidation reaction on the surface of the alloy catalyst and the sixth model corresponding to different applied charges, determining the reaction energy barrier of the HOR forward reaction and reverse reaction of the alloy catalyst under different applied charges; based on the reaction energy barrier of the HOR forward reaction and reverse reaction of the alloy catalyst under different applied charges, determining the reaction energy barrier of the HOR forward reaction and reverse reaction of the alloy catalyst under different electrode potentials; based on the reaction energy barrier of the HOR forward reaction and reverse reaction of the alloy catalyst under different electrode potentials, determining the equilibrium potential of the alloy catalyst; based on the equilibrium potential of the alloy catalyst, determining a given potential range, and further determining the reaction energy barrier of the HOR forward reaction and reverse reaction of the alloy catalyst in the given potential range; based on the reaction energy barrier of the HOR forward reaction and reverse reaction of the alloy catalyst in the given potential range, determining the kinetic current density of the alloy catalyst in the given potential range, and further obtaining the polarization curve of the alloy catalyst.

2. The method of claim 1, wherein, The H2 electrochemical oxidation performance evaluation step further comprises: based on the second model, performing oxidation potential analysis of the alloy catalyst; The oxidation potential analysis of the alloy catalyst based on the second model comprises: obtaining the energy of the second model; obtaining the energy of the alloy catalyst after removing the metal atoms that undergo oxidation; obtaining the energy of the metal atoms that undergo oxidation in the alloy catalyst when in the elemental state; obtaining the standard oxidation potential of the metal that undergoes oxidation in the alloy catalyst when in the elemental state; The oxidation potential of the alloy catalyst is determined based on the second model, the energy of the alloy catalyst, the energy of the metal atom after oxidation of the alloy catalyst, the energy of the metal atom in the alloy catalyst in the elemental state, and the standard oxidation potential of the metal in the alloy catalyst in the elemental state.

3. The method of claim 2, wherein, The oxidation potential analysis of the alloy catalyst based on the second model further comprises: The oxidation resistance of the alloy catalyst is evaluated based on the oxidation potential of the alloy catalyst.

4. The method of claim 2, wherein, The oxidation potential of the alloy catalyst is determined by the following formula: U ox = U ox (met1,bulk)-(E(A x B y )-E(A x B y-z )-z·E(B))÷n wherein U ox is the oxidation potential of the alloy catalyst, V; U ox (met1,bulk) is the standard oxidation potential of the metal B that undergoes oxidation in the alloy catalyst in the elemental state, V; E(A x B y ) is the energy of the second model, eV; E(A x B y-z ) is the energy of the alloy catalyst after removal of z atoms of the metal B that undergoes oxidation, eV; E(B) is the energy of an atom of the metal B that undergoes oxidation in the alloy catalyst in the elemental state, eV; and n is the number of electrons e transferred during oxidation of the alloy catalyst, number.

5. The method of claim 1, wherein, The H2 electrochemical oxidation performance evaluation step further comprises: based on the second model or the third model, analyzing the H adsorption free energy of the alloy catalyst; Wherein, wherein, based on the second model or the third model, analyzing the H adsorption free energy of the alloy catalyst comprises: Based on the second model or the third model, the H adsorption free energy of the alloy catalyst is determined; Based on the H adsorption free energy of the alloy catalyst, the HOR catalytic activity of the alloy catalyst is evaluated; wherein, the closer the H adsorption free energy of the alloy catalyst to 0.414eV, the stronger the HOR catalytic activity of the alloy catalyst.

6. The method of claim 1, wherein, The fifth model is based on the fifth model, and different electrode charges are applied to the alloy catalyst unit cell in the fifth model, and background charges of the same electric quantity are introduced to maintain the electrical neutrality of the unit cell, thereby obtaining the sixth model corresponding to different charges. The fifth model is based on the fifth model, and different electrode charges are applied to the alloy catalyst unit cell in the fifth model, and background charges of the same electric quantity are introduced to maintain the electrical neutrality of the unit cell, thereby obtaining the fifth model with different electrode charges. The structure of the fifth model with different electrode charges is optimized respectively to obtain the sixth model corresponding to different charges.

7. The method of claim 6, wherein, The structure of the fifth model with different electrode charges is optimized respectively to obtain the sixth model corresponding to different charges. For the fifth model with different electrode charges, first-principle molecular dynamics simulation is performed respectively, and a number of relatively stable models of reactants, intermediates and products are screened out; Further, the alkaline aqueous solution layer in the screened out relatively stable models of reactants, intermediates and products is optimized based on first-principle calculation, and the most stable model, i.e. the sixth model, is screened out.

8. The method of claim 1, wherein, Based on the reaction energy barrier of the HOR forward reaction and reverse reaction of the alloy catalyst in a given potential range, the kinetic current density of the alloy catalyst in the given potential range is determined by the following formula: where j kox is the oxidation kinetic current density, mA / cm 2 ; j kred is the reduction kinetic current density, mA / cm 2 ; A(U) is the pre-exponential factor, dimensionless; R is the gas constant, J / mol-K; T is the temperature, K; E a ox (U) is the reaction energy barrier for the HOR forward reaction of the alloy catalyst at U potential, eV; E a red (U) is the reaction energy barrier for the HOR reverse reaction of the alloy catalyst at U potential, eV; j k (U) is the kinetic current density of the alloy catalyst at U potential, mA / cm 2 .

9. The method of claim 1, wherein, When the Tafel polarization curve of the alloy catalyst is determined based on the fifth model, the H2 electrochemical oxidation performance evaluation step further comprises: based on the polarization curve of the alloy catalyst, analyzing the exchange current density of the alloy catalyst; Wherein, the exchange current density of the alloy catalyst is determined based on the polarization curve of the alloy catalyst.

10. The method of claim 9, wherein, Based on the polarization curve of the alloy catalyst, the exchange current density of the alloy catalyst is analyzed further comprising: based on the exchange current density of the alloy catalyst, the HOR catalytic activity of the alloy catalyst is evaluated.

11. The method of claim 9, wherein, The exchange current density of the alloy catalyst is determined based on the polarization curve of the alloy catalyst, by fitting the polarization curve using the Bulter-Volmer equation, and the fitting coefficient is the exchange current density of the alloy catalyst.

12. The method of claim 1, wherein, The H2 electrochemical oxidation performance evaluation step further includes forming energy analysis of the alloy catalyst based on the first model; The forming energy analysis of the alloy catalyst based on the first model includes: The forming energy of the alloy catalyst is determined based on the first model; The stability of the alloy catalyst is determined based on the forming energy of the alloy catalyst.

13. The method of claim 1, wherein, The H2 electrochemical oxidation performance evaluation step further includes reaction energy barrier analysis of the alloy catalyst based on the fifth model; The reaction energy barrier analysis of the alloy catalyst based on the fifth model includes: The optimal reaction path of the H2 electrochemical oxidation reaction on the surface of the alloy catalyst is determined based on the fifth model; The reaction energy barrier of the HOR forward reaction of the alloy catalyst is determined based on the optimal reaction path of the H2 electrochemical oxidation reaction on the surface of the alloy catalyst and the fifth model; The catalytic activity of the alloy catalyst is determined based on the reaction energy barrier of the alloy catalyst.

14. The method of claim 1, wherein, The third model construction step includes: An alkaline aqueous solution model is added to the second model to obtain an initial model of the alloy catalyst surface containing an alkaline aqueous solution layer; First-principles molecular dynamics simulation is performed on the initial model of the alloy catalyst surface containing the alkaline aqueous solution layer to screen out several relatively stable models; The alkaline aqueous solution layer in the screened relatively stable models is optimized based on first-principles calculation to screen out the most stable energy model as the alloy catalyst surface model containing the alkaline aqueous solution layer, i.e. the third model.

15. The method of claim 1, wherein, The fourth model construction step includes: First-principles molecular dynamics simulation is performed on the fourth model to screen out several relatively stable models of reactants, intermediates and products; The alkaline aqueous solution layer in the screened relatively stable models of reactants, intermediates and products is optimized based on first-principles calculation to screen out the most stable energy model as the optimal structure of the alkaline aqueous solution / alloy catalyst surface model containing reactants, intermediates and products, i.e. the fifth model.

16. The method of claim 1, wherein, The alloy is a nickel-based non-noble metal alloy.

17. The method of claim 16, wherein, The non-noble metal includes one or a combination of two or more of Cr, Mn, Fe, Co, Ni, Cu and Zn.

18. An analytical system for the hydrogen electrochemical oxidation performance of an alloy catalyst, wherein, The system includes: A first model construction module for constructing an alloy unit cell model, i.e. a first model; A second model construction module for constructing an alloy catalyst surface model based on the first model, i.e. a second model; A third model construction module for constructing an alloy catalyst surface model containing an alkaline aqueous solution layer based on the second model, i.e. a third model; A fourth model construction module for constructing a structure model of reactants, intermediates and products in the alloy catalyst surface containing the alkaline aqueous solution layer in the third model to obtain an initial model of the alkaline aqueous solution / alloy catalyst containing reactants, intermediates and products, i.e. a fourth model; A fifth model construction module for constructing an optimal structure model of the alkaline aqueous solution / alloy catalyst containing reactants, intermediates and products based on the fourth model, i.e. a fifth model; The fifth model construction module is configured to perform structural optimization on the fourth model to obtain an optimal-structure alkaline aqueous solution / alloy catalyst surface model containing reactants, intermediates and products, i.e., a fifth model; The H2 electrochemical oxidation performance evaluation module includes a polarization curve determination submodule; wherein the polarization curve determination submodule is configured to determine a Tafel polarization curve of the alloy catalyst based on the fifth model; The polarization curve determination submodule includes: The optimal reaction path determination unit is configured to determine an optimal reaction path of the H2 electrochemical oxidation reaction on the surface of the alloy catalyst based on the fifth model; The sixth model determination unit is configured to apply different electrode charges to the alloy catalyst unit cell in the fifth model and introduce background charges of the same electric quantity to maintain the electrical neutrality of the unit cell, thereby obtaining sixth models corresponding to different charges; wherein the sixth model corresponding to the charge of 0 is the fifth model; The reaction energy barrier determination unit for the forward and reverse reactions under different charges is configured to determine the reaction energy barriers of the HOR forward and reverse reactions of the alloy catalyst under different applied charges based on the optimal reaction path of the H2 electrochemical oxidation reaction on the surface of the alloy catalyst and the sixth models corresponding to different applied charges; The reaction energy barrier determination unit for the forward and reverse reactions under different potentials is configured to determine the reaction energy barriers of the HOR forward and reverse reactions of the alloy catalyst under different electrode potentials based on the reaction energy barriers of the HOR forward and reverse reactions of the alloy catalyst under different applied charges; The equilibrium potential determination unit is configured to determine the equilibrium potential of the alloy catalyst based on the reaction energy barriers of the HOR forward and reverse reactions of the alloy catalyst under different electrode potentials; The polarization curve determination unit is configured to determine a given potential range based on the equilibrium potential of the alloy catalyst, and further determine the reaction energy barriers of the HOR forward and reverse reactions of the alloy catalyst in the given potential range; and determine the kinetic current density of the alloy catalyst in the given potential range based on the reaction energy barriers of the HOR forward and reverse reactions of the alloy catalyst in the given potential range, and further obtain the polarization curve of the alloy catalyst.

19. The system of claim 18, wherein, The H2 electrochemical oxidation performance evaluation module includes an oxidation potential analysis submodule; wherein the oxidation potential analysis submodule is configured to perform oxidation potential analysis on the alloy catalyst based on the second model; The oxidation potential analysis submodule includes: The first energy determination unit is configured to obtain the energy of the second model; The second energy determination unit is configured to obtain the energy of the alloy catalyst after removing the metal atoms that undergo oxidation; The third energy determination unit is configured to obtain the energy of the metal atoms that undergo oxidation in the alloy catalyst when in the elemental state; The standard oxidation potential determination unit is configured to obtain the standard oxidation potential of the metal that undergoes oxidation in the alloy catalyst when in the elemental state; The oxidation potential determination unit is configured to determine the oxidation potential of the alloy catalyst based on the energy of the second model, the energy of the alloy catalyst after removing the metal atoms that undergo oxidation, the energy of the metal atoms that undergo oxidation in the alloy catalyst when in the elemental state, and the standard oxidation potential of the metal that undergoes oxidation in the alloy catalyst when in the elemental state.

20. The system of claim 19, wherein, The oxidation potential analysis submodule further comprises: The oxidation resistance performance evaluation unit is configured to evaluate the oxidation resistance performance of the alloy catalyst based on the oxidation potential of the alloy catalyst.

21. The system of claim 19, wherein, The oxidation potential of the alloy catalyst is determined by the following formula: U ox = U ox (met1,bulk)-(E(A x B y )-E(A x B y-z )-z·E(B))÷n wherein U ox is the oxidation potential of the alloy catalyst, V; U ox (met1,bulk) is the standard oxidation potential of the oxidized metal B in the alloy catalyst in the elemental state, V; E(A x B y ) is the energy of the second model, eV; E(A x B y-z ) is the energy of the alloy catalyst after removal of z atoms of the oxidized metal B, eV; E(B) is the energy of the oxidized metal B atom in the alloy catalyst in the elemental state, eV; and n is the number of electrons e transferred during oxidation of the alloy catalyst, e.

22. The system of claim 18, wherein, The H2 electrochemical oxidation performance evaluation module comprises an H adsorption free energy analysis submodule, wherein the H adsorption free energy analysis submodule is configured to analyze the H adsorption free energy of the alloy catalyst based on the second model or the third model; The H adsorption free energy analysis submodule comprises: The H adsorption free energy determination unit is configured to determine the H adsorption free energy of the alloy catalyst based on the second model or the third model; The first catalytic activity determination unit is configured to evaluate the HOR catalytic activity of the alloy catalyst based on the H adsorption free energy of the alloy catalyst; the closer the H adsorption free energy of the alloy catalyst is to 0.414 eV, the stronger the HOR catalytic activity of the alloy catalyst is.

23. The system of claim 18, wherein, The H2 electrochemical oxidation performance evaluation module further comprises: The exchange current density analysis submodule is configured to analyze the exchange current density of the alloy catalyst based on the polarization curve of the alloy catalyst; The exchange current density analysis submodule comprises: The exchange current density determination unit is configured to determine the exchange current density of the alloy catalyst based on the polarization curve of the alloy catalyst.

24. The system of claim 23, wherein, The exchange current density analysis submodule further comprises: The second catalytic activity evaluation unit is configured to evaluate the HOR catalytic activity of the alloy catalyst based on the exchange current density of the alloy catalyst.

25. The system of claim 18, wherein, The H2 electrochemical oxidation performance evaluation module further comprises: The formation energy analysis submodule is configured to analyze the formation energy of the alloy catalyst based on the first model; The formation energy analysis submodule comprises: The formation energy determination unit is configured to determine the formation energy of the alloy catalyst based on the first model; The stability evaluation unit is configured to determine the stability of the alloy catalyst based on the formation energy of the alloy catalyst.

26. The system of claim 18, wherein, The H2 electrochemical oxidation performance evaluation module further comprises: The reaction energy barrier analysis submodule is configured to analyze the reaction energy barrier of the alloy catalyst based on the fifth model; The reaction energy barrier analysis submodule comprises: The optimal reaction path determination unit is configured to determine the optimal reaction path of the H2 electrochemical oxidation reaction on the surface of the alloy catalyst based on the fifth model; The reaction energy barrier determination unit is configured to determine the reaction energy barrier of the HOR forward reaction of the alloy catalyst based on the optimal reaction path of the H2 electrochemical oxidation reaction on the surface of the alloy catalyst and the fifth model; The third catalytic activity analysis unit is configured to determine the catalytic activity of the alloy catalyst based on the reaction energy barrier of the alloy catalyst.

27. The system of claim 18, wherein, The third model construction module comprises: The initial model construction submodule is configured to add a basic aqueous solution model to the second model to obtain an initial model of the surface of the alloy catalyst containing a basic aqueous solution layer; The first model optimization submodule is configured to perform first-principle molecular dynamics simulation on the initial model of the surface of the alloy catalyst containing the basic aqueous solution layer, and screen out a plurality of relatively stable models; The second model optimization submodule is configured to perform structure optimization on the alkaline aqueous solution layer in the screened relatively stable model based on first-principle calculation, and screen out a model with the most stable energy as the alloy catalyst surface model containing the alkaline aqueous solution layer, i.e., a third model.

28. The system of claim 18, wherein, The fourth model construction module comprises: The third model optimization submodule is configured to perform first-principle molecular dynamics simulation on the fourth model, and screen out a plurality of relatively stable models of reactants, intermediates and products; The fourth model optimization submodule is configured to perform structure optimization on the alkaline aqueous solution layer in the screened relatively stable model of the reactants, intermediates and products based on first-principle calculation, and screen out a model with the most stable energy as the alkaline aqueous solution / alloy catalyst surface model containing the reactants, intermediates and products with the optimal structure, i.e., a fifth model.

29. The system of claim 18, wherein, The alloy is a nickel-based non-noble metal alloy.

30. The system of claim 29, wherein, The non-noble metal includes one or a combination of two or more of Cr, Mn, Fe, Co, Ni, Cu and Zn.

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