A boronene metal mesh material and screening method and application thereof

Abstract

The application provides a boronene metal grid material and a screening method and application thereof, and belongs to the field of catalyst simulation technology.The application provides a screening method by using the first principle, calculating the lattice stability, energy stability and thermodynamic stability of a double-layer boronene metal intercalation model containing different intercalation metal types and different intercalation metal coverages, so that the boronene metal grid material has energy stability, lattice stability and thermodynamic stability, and has high stability;the boronene metal grid material has oxidation resistance and can be used at high temperature;the surface has more hydrogen atom adsorption sites, which means that multiple parallel hydrogen evolution reaction paths can exist;the boronene metal grid material has strong tensile performance, and the catalytic efficiency can be stress-regulated;the boronene metal grid material has an extremely low surface water splitting potential barrier, and is suitable for being used as a water decomposition reaction platform;the boronene metal grid material has high electrocatalytic hydrogen evolution catalytic activity and low cost, is very suitable for being used as a substitute material of a traditional noble metal platinum catalyst, and has a good application prospect in the field of electrocatalytic hydrogen evolution.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of catalyst simulation technology, in particular to a boronene metal grid material and a screening method and application thereof. BACKGROUND

[0002] After the industrial revolution, the large-scale use of fossil fuels has led to worrying environmental and climate problems, and it is necessary to find efficient and clean renewable energy. Hydrogen evolution reaction (HER) is a branch of water splitting reaction and is considered as a possible solution. The commonly used hydrogen evolution reaction catalyst is platinum catalyst, which has excellent electrocatalytic HER performance, but its cost is high. In order to reduce the cost of HER catalyst, there are mainly two means: (1) introducing other elements to reduce the content of platinum in the catalyst, and the representative HER catalysts mainly include PtSe2, PtTe2, Pt-VS2 / CP, Pt-CoS2 / CC and graphene supported Pt monatomic catalyst; (2) using inexpensive materials without platinum as HER catalyst, and such catalysts mainly include MoS2, WS2, Mo2C, MoP and FeP, etc. However, the active centers of these platinum-free HER catalysts are mostly located in defects and edges, and the effective utilization rate of catalytic active sites is low, thereby limiting their practical application.

[0003] Intercalation is a common means of controlling material performance. For example, metal intercalated graphene materials, in which graphene acts as a part of the environment supporting or covering the catalytic center or as a catalytic center, have good catalytic performance for hydrogen evolution reaction, oxygen evolution reaction, carbon dioxide reduction reaction, etc. In addition, cobalt atom intercalated phosphorene nanosheet materials and nickel atom intercalated hexagonal boron nitride also exhibit considerable catalytic performance. Therefore, it is feasible to introduce catalytic performance into materials by intercalation means. Boronene has the characteristics of multiple structures, strong tensile properties, anisotropic tensile strength, negative Poisson's ratio and light guide, and also has excellent lattice thermal conductivity and easily controllable porous surface, and can be used as a hydrogen evolution reaction catalyst. However, for the latest experimentally synthesized double-layer boronene, whether there is a metal that can remain stable in its structure has not been reported. SUMMARY

[0004] Therefore, the purpose of the present application is to provide a boronene metal grid material and a screening method and application thereof. The screening method provided by the present application obtains a boronene metal grid material which is stable in lattice, energy and thermodynamics.

[0005] In order to achieve the above-mentioned purpose of the application, the present application provides the following technical solutions:

[0006] The present application provides a screening method for a boronene metal grid material, which utilizes first principle for screening, including the following steps:

[0007] (1) constructing a plurality of double-layer boronene metal intercalation models and single metal phase models, the double-layer boronene metal intercalation models including double-layer boronene metal intercalation models of different intercalation metal species, double-layer boronene metal intercalation models of different intercalation metal coverage, and the single metal phase models being intercalation metals involved in the double-layer boronene metal intercalation models;

[0008] (2) performing ground state structure optimization on the double-layer boronene metal intercalation models and single metal phase models respectively, analyzing the lattice stability, energy stability and thermodynamic stability of the double-layer boronene metal intercalation models according to the calculation results, and screening the stable double-layer boronene metal grid model to obtain the material corresponding to the stable double-layer boronene metal grid model as the target boronene metal grid material; the lattice stability refers to that the phonon dispersion of the double-layer boronene metal intercalation model has no virtual frequency, the energy stability refers to that the formation energy is negative, and the thermodynamic stability refers to that it does not crack above 1000℃.

[0009] Preferably, the intercalation metal includes any one of the third period transition metal and the fourth period transition metal;

[0010] The ground state structure optimization is performed by using the first-principles simulation software VASP.

[0011] Preferably, the step (2) further includes simulating the kinetic behavior of the intercalation metal in the double-layer boronene metal intercalation model, including the following steps:

[0012] A surface adsorption metal model in which the intercalation metal is adsorbed on the surface of the double-layer boronene is constructed, and the intercalation metal species in the surface adsorption metal model is the same as that in the stable double-layer boronene metal grid model;

[0013] A layer intercalation site model in which the intercalation metal is located at different equivalent sites between the double-layer boronene layers is constructed under the same metal coverage;

[0014] A diffusion path of the Z-axis, X-axis and Y-axis of the intercalation metal is constructed according to the surface adsorption model and the layer intercalation site model, the transition state structure of the metal in the double-layer boronene is calculated according to the diffusion path of the Z-axis, X-axis and Y-axis respectively, the diffusion barrier is calculated according to the transition state, and the kinetic behavior result of the intercalation metal is obtained;

[0015] The diffusion path of the Z-axis takes the surface adsorption metal model as the initial state, and the model in which the intercalation metal moves from the surface to the layer intercalation site as the final state;

[0016] The diffusion path of the X-axis takes the layer intercalation site model as the initial state, and the model in which the intercalation metal moves to the nearest neighbor equivalent site along the X-axis direction as the final state;

[0017] The diffusion path of the Y axis takes an interlayer intercalation site model as an initial state, and a model in which the intercalated metal moves to the nearest neighbor equivalent site along the Y axis direction as a final state.

[0018] Preferably, the step (2) further comprises simulating a surface water splitting process of the boronene metal grid material, including the following steps:

[0019] A water molecule model is constructed, and the water molecule model is placed on the surface of the boronene metal grid material, and after a first structure optimization, the initial state model is obtained;

[0020] A model of the boronene metal grid material adsorbing one hydrogen atom and one hydroxyl group is constructed, and after a second structure optimization, the final state model is obtained;

[0021] According to the initial state model and the final state model, a water molecule splitting path is constructed, a transition state is found, and the hydrogen evolution reaction free energy is calculated according to the transition state. When the hydrogen evolution reaction free energy is -1-1eV, the boronene metal grid material is suitable as a catalyst for electrocatalytic hydrogen evolution.

[0022] Preferably, the first structure optimization, the second structure optimization and the finding of the transition state are performed by using a first-principle simulation software VASP;

[0023] The hydrogen bond in the second structure optimization process is corrected by van der Waals.

[0024] Preferably, the step (2) further comprises simulating a surface hydrogen evolution reaction of the boronene metal grid material, including the following steps:

[0025] A model of the boronene metal grid material adsorbing one hydrogen atom and one hydroxyl group is constructed, and after a second structure optimization, the final state model is obtained;

[0026] Preferably, the adsorption sites include the vertex sites, hole sites and bridge sites of the surface boronene and the vertex sites of the intercalated metal.

[0027] The simulation process of the hydrogen evolution reaction corrects the water solvation effect.

[0028] Preferably, the step (2) further comprises simulating the tensile properties of the boronene metal grid material, including the following steps:

[0029] A uniaxial strain is applied to the boronene metal grid material along the X axis, the energy of the strained structure is plotted to obtain a change curve of the energy with respect to the uniaxial strain, and the tensile limit is obtained according to the change curve.

[0030] The model of hydrogen atoms adsorbed on different adsorption sites of the boronene metal mesh material is constructed, uniaxial strain is applied to the hydrogen atom adsorption model within the tensile limit range, and the catalytic free energy of the hydrogen evolution reaction under different tensile stresses is calculated.

[0031] The application provides the boronene metal mesh material obtained by the screening method. x B6, wherein x is 0-1 and not 0, and M includes Co, Ni, Cu or Pd.

[0032] The application provides application of the boronene metal mesh material as a catalyst in an electrocatalytic hydrogen evolution reaction.

[0033] The application provides a screening method of a boronene metal mesh material, which is screened by using a first principle, and comprises the following steps: (1) constructing a plurality of double-layer boronene metal intercalation models and single metal phase models, the double-layer boronene metal intercalation models include double-layer boronene metal intercalation models of different intercalation metal types and double-layer boronene metal intercalation models of different intercalation metal coverages, and the single metal phase models are intercalation metals involved in the double-layer boronene metal intercalation models; (2) performing ground structure optimization on the double-layer boronene metal intercalation models and the single metal phase models respectively, analyzing lattice stability, energy stability and thermodynamic stability of the double-layer boronene metal intercalation models according to calculation results, and screening a stable double-layer boronene metal mesh model to obtain a material corresponding to the stable double-layer boronene metal mesh model as a target boronene metal mesh material; the lattice stability refers to that there is no virtual frequency in phonon dispersion of the double-layer boronene metal intercalation model, the energy stability refers to that a formation energy is a negative value, and the thermodynamic stability refers to that the double-layer boronene metal intercalation model does not crack at 1000 DEG C or above. The boronene metal mesh material with lattice stability, energy stability and thermodynamic stability can be obtained through the screening of the above steps without a complex experimental process.

[0034] Further, the boronene metal mesh material with extremely low surface water splitting potential barrier, hydrogen evolution reaction overpotential floating in ±0.01V under any metal coverage, high tensile strength and catalytic performance of the hydrogen evolution reaction equivalent to that of a traditional noble metal platinum catalyst is screened through simulation of intercalation metal kinetic behavior, surface water splitting process, hydrogen evolution reaction catalytic performance and tensile performance, and can replace the noble metal platinum catalyst.

[0035] The application provides the boronene metal mesh material obtained by the screening method. x B6, wherein x is 0-1 and not 0, and M includes Co, Ni, Cu or Pd. The boronene metal mesh material provided by the application has the following advantages:

[0036] The water dissociation reaction is easy to occur on the surface of boronene metal grid materials. The water dissociation reaction refers to the process of water molecule dissociating into a hydrogen atom and a hydroxyl group. On the surface of CoB6, the water dissociation barrier is 0.213 eV, and on the surfaces of NiB6 and CuB6, the values are 0.425 eV and 0.424 eV, respectively. PdB6 exhibits an extremely low water dissociation barrier of 0.087 eV. The surface water dissociation barrier of traditional noble metal platinum catalysts ranges from 0.44 eV on Pt(110) to 0.78 eV on Pt(111), and boronene metal grid materials M x B6(M=Co, Ni, Cu or Pd) is a good platform for water dissociation reaction compared with Pt.

[0037] The boronene metal grid material has good HER catalytic performance comparable to traditional platinum catalysts. Cu x The free energy of the hydrogen evolution reaction of the Cu x B6 system under different intercalation metal coverage, considering the solvation effect, the free energy is-0.13~0.18eV, while the reaction free energy of traditional platinum catalyst is about-0.075eV. This shows that under different metal coverage, Cu x B6 and Pd x B6 system all show extremely low hydrogen evolution reaction catalytic free energy, which is very suitable as a substitute material for traditional noble metal platinum catalysts.

[0038] The boronene metal grid material has high stability, oxidation resistance and poisoning resistance. The boronene metal grid M x B6(M=Co, Ni, Cu or Pd) is energy stable and easy to introduce intercalation metal in the system. The lattice is stable, and there is no virtual frequency in phonon dispersion. It is thermodynamically stable and can be stably used at high temperatures of 1000℃ according to molecular dynamics simulation. Since boronene itself has oxidation resistance, the intercalation metal is coated by boronene, which can prevent metal oxidation and maintain the structure for a long time without degradation.

[0039] The boronene metal grid material has excellent tensile properties, and its catalytic performance can be regulated. The boronene metal grid M x B6(M=Co, Ni, Cu or Pd) can maintain structural stability under a tensile stress of 10%, showing good tensile properties and being adaptable to complex stress conditions in practical applications. The hydrogen evolution reaction catalytic performance can be regulated by tensile stress to achieve better catalytic effect.

[0040] The cost is relatively low and economical compared with platinum. For Cu xB6 structure, which has more elements in the earth's crust than platinum, is easier to obtain, and is relatively more economical, which can reduce costs. BRIEF DESCRIPTION OF DRAWINGS

[0041] Figure 1 Flow chart for screening boronene metal mesh materials

[0042] Figure 2 Lattice structure and lattice stability of boronene metal mesh material MB6 (M = Co, Ni, Cu or Pd)

[0043] Figure 3 Boronene metal mesh material M x Energy stability and semimetal coverage structure of B6 (M = Co, Ni, Cu or Pd)

[0044] Figure 4 Thermodynamic stability of boronene metal mesh material MB6 (M = Co, Ni, Cu or Pd)

[0045] Figure 5 Boronene metal mesh material M x Diffusion path diagram and vibration frequency of intercalated metal in B6 (M = Co, Ni, Cu or Pd)

[0046] Figure 6 Schematic diagram of water splitting reaction on the surface of boronene metal mesh material MB6 (M = Co, Ni, Cu or Pd)

[0047] Figure 7 Seven possible hydrogen adsorption sites on the surface of boronene metal mesh material MB6 (M = Co, Ni, Cu or Pd) and their adsorption energy diagram

[0048] Figure 8 Boronene metal mesh material M x Diagram of the effect of the distance between the most stable hydrogen adsorption site and the metal vacancy in B6 (M = Co, Ni, Cu or Pd) on the adsorption energy

[0049] Figure 9 Boronene metal mesh material M x Hydrogen evolution reaction catalytic free energy diagram of B6 (M = Co, Ni, Cu or Pd)

[0050] Figure 10 Tensile property diagram of boronene metal mesh material MB6 (M = Co, Ni, Cu or Pd)

[0051] Figure 11 Diagram of the effect of 1-10% on the hydrogen evolution reaction catalytic performance of boronene metal mesh material MB6 (M = Co, Ni, Cu or Pd) under full metal coverage. DETAILED DESCRIPTION

[0052] The application provides a screening method of boronene metal grid material, which screens by using a first principle and comprises the following steps:

[0053] (1) constructing a plurality of double-layer boronene metal intercalation models and single metal phase models, wherein the double-layer boronene metal intercalation models comprise double-layer boronene metal intercalation models of different intercalation metal types and double-layer boronene metal intercalation models of different intercalation metal coverages, and the single metal phase models are intercalation metals involved in the double-layer boronene metal intercalation models;

[0054] (2) performing ground state structure optimization on the double-layer boronene metal intercalation models and the single metal phase models respectively, analyzing lattice stability, energy stability and thermodynamic stability of the double-layer boronene metal intercalation models according to calculation results, and screening a stable double-layer boronene metal grid model to obtain a material corresponding to the stable double-layer boronene metal grid model as a target boronene metal grid material; the lattice stability refers to that phonon dispersion of the double-layer boronene metal intercalation model has no virtual frequency, the energy stability refers to that formation energy is negative, and the thermodynamic stability refers to that the double-layer boronene metal intercalation model does not crack at above 1000 DEG C.

[0055] The application constructs a plurality of double-layer boronene metal intercalation models and single metal phase models, wherein the double-layer boronene metal intercalation models comprise double-layer boronene metal intercalation models of different intercalation metal types and double-layer boronene metal intercalation models of different intercalation metal coverages, and the single metal phase models are intercalation metals involved in the double-layer boronene metal intercalation models.

[0056] In the application, the intercalation metal preferably comprises any one of third period transition metals and fourth period transition metals; the third period transition metal preferably comprises scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper or zinc; and the fourth period transition metal preferably comprises yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver or cadmium.

[0057] In the present application, the method for constructing the double-layer boronene metal intercalation model preferably comprises: constructing a double-layer boronene metal intercalation model containing different intercalation metal species; changing the number of metal atoms in the double-layer boronene metal intercalation model containing different intercalation metal species to obtain a double-layer boronene metal intercalation model, specifically comprising the following steps: constructing a single-layer δ4 boronene, arranging two layers of δ4 boronene in parallel, placing an intercalation metal atom at the hole site between the obtained double-layer boronene model to obtain a double-layer boronene metal intercalation model; adsorbing intercalation metal atoms in all holes of the double-layer boronene model, obtaining an intercalation metal full coverage model, then subtracting any intercalation metal atom one by one, determining the most stable ground state structure under the current coverage, and determining the ground state structure of the next coverage based on the most stable ground state structure to obtain a double-layer boronene metal intercalation model. The distribution rule of intercalation metal atoms in double-layer boronene can be obtained by using the construction method provided in the present application.

[0058] In the present application, the single metal body phase model is preferably derived from the Materials Studio database, and the energy obtained after self-consistency of the single metal body phase model is used as a benchmark reference for simulation calculation of formation energy, adsorption energy, differential charge density, and state density.

[0059] In the present application, the construction of the double-layer boronene metal intercalation model and the single metal body phase model preferably uses Materials Studio software; the optimization of the ground state structure and the characterization of stability preferably use the first-principle optimization software VASP, more preferably use the VASP6.3.0 software package; the cutoff energy is preferably set to 400 eV, and the energy convergence standard is preferably that the range of change in the model structure energy is <10 -5 eV,

[0060] After obtaining the double-layer boronene metal intercalation model and the single metal body phase model, the present application optimizes the ground state structure of the double-layer boronene metal intercalation model and the single metal body phase model respectively, analyzes the lattice stability, energy stability and thermodynamic stability of the double-layer boronene metal intercalation model according to the calculation results, and screens the material corresponding to the obtained stable double-layer boronene metal grid model as a target boronene metal grid material; the lattice stability refers to that the phonon dispersion of the double-layer boronene metal intercalation model has no virtual frequency, the energy stability refers to that the formation energy is negative, and the thermodynamic stability refers to that it does not crack above 1000℃.

[0061] In the present application, the method for measuring the lattice stability preferably comprises the following steps: constructing a model and expanding the cell to make it The lattice stability is judged according to whether the phonon dispersion has a virtual frequency, and when the phonon dispersion has no virtual frequency (i.e. the phonon dispersion is less than 0), the lattice has stability. In the present application, the lattice length is obtained by comprehensively considering the calculation accuracy and calculation consumption, and the lattice length used in the present application can ensure that the atomic vibration has sufficient displacement distance, and will not cause the calculation amount to increase exponentially due to over-expansion of the cell. In the present application, the double-layer borophene metal intercalation model of cobalt, nickel, copper and palladium in the intercalated metal has no virtual frequency of phonon dispersion, and has lattice stability.

[0062] In the present application, the formation energy can be defined as: wherein E form is the formation energy, is the total energy, N B is the number of boron atoms, E B is the energy of a single boron atom in a single delta-4 borophene, N M is the number of intercalated metal atoms, E M is the energy of a single intercalated metal atom in its bulk, and the formation energy is negative, indicating energy stability. In the present application, the second-order energy difference is defined as Δ 2 E = E N+1 + 2E N-1 - 2E N wherein E N+1 is the energy of the borophene metal grid structure with N+1 intercalated metals, E N-1 is the energy of the borophene metal grid structure with N-1 intercalated metals, and E N is the energy of the borophene metal grid structure with N intercalated metals, and the second-order energy difference is positive, indicating that the double-layer borophene metal intercalation structure with N intercalated metals has higher relative stability. In the present application, the double-layer borophene metal intercalation structure of MB6 (M = Co, Ni, Cu or Pd) is screened according to energy stability, and specifically, Co x B6 is determined according to 112 structures, which has a formation energy of all negative values, indicating energy stability, and does not exhibit obvious arrangement rules at half coverage. In the present application, Ni x B6 is determined according to 77 structures, which has a formation energy of all negative values, indicating energy stability, and nickel atoms exhibit a linear distribution rule at half coverage; Cu x B6 is determined according to 134 structures, which has a formation energy of all negative values, indicating energy stability, and does not exhibit obvious arrangement rules at half coverage; and Pd x B6 is determined according to 97 structures, which has a formation energy of all negative values, indicating energy stability, and palladium atoms exhibit a diagonal distribution rule at half coverage.

[0063] In the present application, the thermodynamic stability is preferably achieved by molecular dynamics simulation, with a step length of 1 fs, within 10000 steps, the initial temperature and the final temperature are respectively from 500K, and the interval is respectively 500K, 100K and 50K, the temperature at which the structure remains stable and does not crack is determined, which is the limit temperature for the stable use of the material. In the present application, the screening result of the thermodynamic stability is preferably: the boronene metal grid structure MB6 (M=Co, Ni, Cu or Pd) has thermodynamic stability, wherein CoB6 remains stable at 1700K and cracks at 1750K; NiB6 remains stable at 1750K and cracks at 1800K; CuB6 remains stable at 1500K and cracks at 1550K; PdB6 remains stable at 1300K and cracks at 1350K.

[0064] In the present application, the chemical formula of the boronene metal grid material obtained by the screening method is M x B6, wherein M is Co, Ni, Cu or Pd.

[0065] In the present application, the step (2) preferably further comprises simulating the kinetic behavior of the intercalated metal in the double-layer boronene metal intercalation model, comprising the following steps:

[0066] A surface adsorbed metal model in which the intercalated metal is adsorbed on the surface of the double-layer boronene is constructed, and the intercalated metal species in the surface adsorbed metal model is the same as the intercalated metal species in the stable double-layer boronene metal grid model;

[0067] An interlayer intercalation site model in which the intercalated metal is located at different equivalent sites between the double-layer boronene is constructed under the same metal coverage;

[0068] According to the surface adsorbed model and the interlayer intercalation site model, diffusion paths of the intercalated metal in the Z axis, the X axis and the Y axis are constructed, and the transition state structure of the metal in the double-layer boronene is calculated according to the diffusion paths of the Z axis, the X axis and the Y axis respectively, and the diffusion barrier is calculated according to the transition state, and the diffusion path with the lowest diffusion barrier is the main diffusion path of the intercalated metal;

[0069] The diffusion path of the Z axis takes the surface adsorbed metal model as the initial state, and the model in which the intercalated metal moves from the surface to the interlayer intercalation site as the final state;

[0070] The diffusion path of the X axis takes the interlayer intercalation site model as the initial state, and the model in which the intercalated metal moves to the nearest neighbor equivalent site along the X axis direction as the final state;

[0071] The diffusion path of the Y axis takes the interlayer intercalation site model as the initial state, and the model in which the intercalated metal moves to the nearest neighbor equivalent site along the Y axis direction as the final state.

[0072] In the present application, the construction of each model in the simulation of the kinetic behavior of the intercalated metal in the double-layer boronene metal intercalation model is preferably carried out by using the Materials Studio software.

[0073] In the present application, the diffusion path of the Z-axis is along the vertical direction, diffusing from the outer layer of the double-layer boronene to the interlayer, and the two paths are diffusing to the nearest neighbor equivalent sites along the plane direction (X-axis and Y-axis) of boronene, and each diffusion path inserts eight intermediate points to find the transition state. In the present application, the finding of the transition state is preferably carried out by using the VASP6.3.0 software package.

[0074] The present application preferably further comprises converting the diffusion barrier into the average vibration frequency, by calculating the percentage of the average vibration frequency of the Z-axis, X-axis and Y-axis in the total average vibration frequency of the Z-axis, X-axis and Y-axis, respectively, and the diffusion path with the highest percentage is the main diffusion path of the intercalated metal. In the present application, the conversion of the diffusion barrier into the average vibration frequency is preferably carried out by using ν*exp(-ΔE / k B T), wherein, ν represents the pre-factor, whose value is about 10 13 Hz; ΔE is the size of the diffusion barrier; k B is the Boltzmann constant; T is the Kelvin temperature. In the present application, according to the diffusion barrier and the percentage of the average vibration frequency, it is found that the diffusion path along the Z-axis (diffusing from the outer layer of the double-layer boronene to the interlayer) is the main diffusion path of the intercalated metal, and the diffusion from the outer layer of the double-layer boronene to the interlayer is the main source of the intercalated metal in the boronene metal grid material. The present application deeply studies the formation mechanism of the boronene metal grid material and the kinetic behavior of the intercalated metal in the system, and provides technical support for the development of the material.

[0075] In the present application, the step (2) preferably further comprises simulating the surface water splitting process of the boronene metal grid material, comprising the following steps:

[0076] constructing a water molecule model, placing the water molecule model on the surface of the boronene metal grid material, and performing a first structure optimization as an initial state model;

[0077] constructing a model of the boronene metal grid material adsorbing one hydrogen atom and one hydroxyl group, and performing a second structure optimization as a final state model;

[0078] constructing a water molecule splitting path according to the initial state model and the final state model, finding a transition state, and calculating the hydrogen evolution reaction free energy according to the transition state, when the hydrogen evolution reaction free energy is-1~1eV, the boronene metal grid material is suitable as a catalyst for electrocatalytic hydrogen evolution.

[0079] In this invention, the construction of each model in the simulation of the surface water splitting process is preferably carried out using Materials Studio software.

[0080] This invention constructs a water molecule model, places the water molecule model on the surface of a boronene metal mesh material, and performs a first structural optimization as the initial state model. Preferably, this invention first optimizes the structure of individual water molecules to obtain a HO bond length of... An optimized water molecule with an HOH bond angle of 104.55° is placed in the boronene metal mesh material M. x B6 (M = Co, Ni, Cu or Pd) surface The optimization process is performed on the first structure, and the optimized structure serves as the initial state model for the water splitting reaction. In this invention, the first structure optimization is preferably performed using the first-principles simulation software VASP, and more preferably using the VASP 6.3.0 software package.

[0081] This invention constructs a model of a boronene metal mesh material adsorbing a hydrogen atom and a hydroxyl group. After a second structural optimization, this model serves as the final state model. Specifically, the hydrogen atom (-H) and the hydroxyl group (-OH) are respectively placed on two adjacent BB bonds on the surface of the boronene metal mesh material, ensuring a certain interval. The optimized structure serves as the final state model (end state) for the water splitting reaction. In this invention, the second structural optimization is preferably performed using the first-principles simulation software VASP, more preferably using the VASP 6.3.0 software package. Van der Waals correction is preferably introduced during the second structural optimization process (the input settings for the VASP software are preferably DFT-D3 BJ damping, IVDW=12). Since the introduction of H-group adsorption groups such as -H and -OH will have hydrogen bonding effects, this invention improves the accuracy of the simulation results by introducing van der Waals correction.

[0082] After obtaining the initial state model and the final state model, the application constructs a water molecule cracking path according to the initial state model and the final state model, finds a transition state, and calculates a hydrogen evolution reaction free energy according to the transition state; when the hydrogen evolution reaction free energy is-1~1eV, the boronene metal grid material is suitable as a catalyst for electrocatalytic hydrogen evolution. In the application, the finding of the transition state is preferably performed by using a first-principle simulation software VASP, and more preferably by using a VASP6.3.0 software package; and preferably eight intermediate points are inserted in the molecular cracking path to find the transition state. In the application, the simulation result of the surface water cracking process is preferably as follows: the water cracking reaction is mainly divided into two processes, the first process is that a water molecule adjusts a shape and is adsorbed on a boronene surface, changes from physical adsorption to chemical adsorption, and a H-O bond is broken to become a -H and an -OH; and the second process is that the -H diffuses on the boronene surface to a nearest neighbor hydrogen atom adsorption site. In the application, the closer the hydrogen evolution reaction free energy is to 0, the more suitable the boronene metal grid material is as a catalyst for electrocatalytic hydrogen evolution.

[0083] In the application, after the step (2), the surface hydrogen evolution reaction of the boronene metal grid material is simulated, including the following steps:

[0084] The hydrogen atom model of different adsorption sites of the boronene metal grid material is constructed, and the hydrogen evolution reaction catalytic free energy of each model is determined; when the hydrogen evolution reaction free energy is-1~1eV, the boronene metal grid material is suitable as a catalyst for electrocatalytic hydrogen evolution.

[0085] In the application, the construction of each model in the simulation process of the surface hydrogen evolution reaction is preferably performed by using Materials Studio software.

[0086] In the application, the adsorption sites preferably include vertex sites (2 kinds, T1 and T2) of a surface layer boronene, hole sites (1 kind, H) of a B-B bond of the surface layer boronene, bridge sites (3 kinds, B1, B2 and B3) of the B-B bond of the surface layer boronene, and vertex sites (T3) of an intercalated metal. In the application, before the determination of the hydrogen evolution reaction catalytic free energy of each model, the hydrogen atom stable adsorption sites of each model are preferably determined, and the determination result of the hydrogen atom stable adsorption sites is that the bridge site (B1) of the B-B bond is the most stable adsorption site, three adsorption sites (B1, B2 and T2) can remain stable, and the influence of different adsorption sites on adsorption energy is about 1eV. In the application, for the boronene metal grid material with different intercalated metal coverages, the most stable adsorption site is located at the bridge site of the B-B bond related to the distance from the intercalated metal vacancy position, and each structure needs to be determined separately, and the overall performance is that the closer the distance to the defect, the weaker the adsorption is, and the M x For example, B6 (M=Co, Ni, Cu or Pd, x=0.9375), the influence of the variable on the adsorption energy is about 0.3eV.

[0087] In the present application, the water solvation effect is preferably corrected in the simulation process of the hydrogen evolution reaction, preferably by changing the source code of the VASP6.3.0 software package and recompiling to simulate the environment of water molecules around the material, preferably by adding two parameters LSOL=.TRUE. and EBK=80 in the input file INCAR when calculating with the first principle simulation software VASP, to simulate the presence of water molecules around the material.

[0088] In the present application, the free energy is defined as: ΔG=E ads +ΔE ZPE -TΔS, wherein ΔG is the free energy, E ads is the hydrogen atom adsorption energy, ΔE ZPE is the zero-point vibration energy, T is the temperature, and ΔS is the entropy change; wherein the hydrogen atom adsorption energy is defined as: E ads =E H* -E * -1 / 2E H2 , wherein E H* is the energy of the borophene metal grid material with adsorbed hydrogen atoms, E * is the energy of the borophene metal grid material, and E H2 is the energy of hydrogen.

[0089] In the present application, the step (2) further comprises simulating the tensile properties of the borophene metal grid material, comprising the following steps:

[0090] Applying uniaxial strain to the borophene metal grid material along the X axis, plotting the energy of the strained structure to obtain a curve of energy change with uniaxial strain, and obtaining the tensile limit according to the curve;

[0091] Constructing a model of adsorbed hydrogen atoms at different adsorption sites of the borophene metal grid material, applying uniaxial strain to the hydrogen atom adsorption model within the tensile limit, and calculating the hydrogen evolution reaction catalytic free energy under different tensile stresses. Within the tensile limit, the hydrogen evolution reaction free energy of the borophene metal grid material can be stress-regulated, with a slight decrease in value, but still within the range of -1 to 1.

[0092] In the present application, the construction of each model in the simulation process of the tensile properties is preferably performed using the Materials Studio software.

[0093] The present application applies uniaxial strain to the boronene metal mesh material along the X axis, plots the energy of the strained structure to obtain a curve of energy change with uniaxial strain, and obtains the tensile limit according to the curve. In the present application, the uniaxial strain is preferably stretched step by step in units of 1% of the lattice length in the X axis direction before stretching. In the present application, when the curve keeps rising, it indicates that the material remains stable at this strain, and when the curve suddenly falls, it indicates that the strain is the tensile limit of the material. In the present application, the tensile limit is preferably greater than 10%, and the material remains stable at 10% uniaxial strain, so that the material is sufficient to cope with the deformation encountered in actual material engineering applications.

[0094] After obtaining the tensile limit, the present application constructs a hydrogen atom adsorption model of different adsorption sites of the boronene metal mesh material, applies uniaxial strain to the hydrogen atom adsorption model within the tensile limit range, and calculates the free energy of the hydrogen evolution reaction catalysis under different tensile stresses. In the present application, the uniaxial strain applied to the hydrogen atom adsorption model within the tensile limit range is more preferably uniaxial strain within the 10% uniaxial strain stretching range. In the present application, the construction method of the hydrogen atom adsorption model of different adsorption sites of the boronene metal mesh material is the same as the construction method of the simulation of the surface hydrogen evolution reaction of the boronene metal mesh material, which will not be repeated here. In the present application, when the energy curves of the boronene metal mesh material are all stably rising at a certain tensile stress, it indicates that the structure has not been pulled apart and has tensile stability. In the present application, the uniaxial strain is preferably stretched step by step in units of 1% of the lattice length in the X axis direction before stretching within the tensile limit, and the calculation results of each model are analyzed to study the influence of uniaxial tensile strain on the hydrogen evolution reaction catalytic performance of the boronene metal mesh material.

[0095] The present application provides a boronene metal mesh material obtained by the screening method of the above technical solution, and the chemical formula is M x B6, wherein x is 0-1 and not 0, and M includes Co, Ni, Cu or Pd. In the present application, x is selected as 1 / 16-1.

[0096] The present application provides the application of the boronene metal mesh material as a catalyst in electrocatalytic hydrogen evolution reaction. The boronene metal mesh material provided by the present application has high stability in energy, lattice and thermodynamics; has oxidation resistance and can be used at high temperature; has more hydrogen atom adsorption sites on the surface, which means that there can be multiple parallel hydrogen evolution reaction paths; has strong tensile performance, and the catalytic efficiency can be stress-regulated; has a very low surface water splitting potential barrier, and is suitable as a water splitting reaction platform; has high electrocatalytic hydrogen evolution catalytic activity and low cost, and especially under different metal coverage, Cu x B6 and Pdx The B6 system all shows extremely low hydrogen evolution reaction catalytic free energy, is very suitable as a substitute material of traditional noble metal platinum catalyst, and has good application prospect in the field of electrocatalytic hydrogen evolution.

[0097] The technical solutions in the present application will be clearly and completely described below in combination with the embodiments in the present application. Obviously, the described embodiments are only some of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the present application.

[0098] In the following embodiments, the models are built by using Materials Studio software; the optimization of the ground state structure, the characterization of stability, the search for the transition state, the simulation and evaluation of the performance of the material are carried out by using VASP6.3.0 software package; the truncation energy is set to 400eV, and the energy convergence standard is that the range of the energy change of the model structure is <10 -5 eV,

[0099] Embodiment 1

[0100] The screening is carried out by using the flowchart shown in the figure, and the specific steps are as follows: Figure 1

[0101] (1) Construction of double-layer boronene metal intercalation model and stability characterization

[0102] A single-layer δ4 boronene is constructed, two layers of δ4 boronene are arranged in parallel, an intercalation metal atom is placed in the hole site of the obtained double-layer boronene model, and a double-layer boronene metal intercalation model is obtained; all hole intercalation metal atoms in the double-layer boronene model are adsorbed to obtain an intercalation metal full coverage model, then any intercalation metal atom is removed one by one to determine the most stable ground state structure under the current coverage, and the ground state structure of the next coverage is determined based on the most stable ground state structure, thereby obtaining a double-layer boronene metal intercalation model containing different intercalation metal types and different intercalation metal coverages and the distribution rule of intercalation metal atoms in the double-layer boronene. The intercalation metal is any one of the third period transition metal (scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper and zinc) and the fourth period transition metal (yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver and cadmium).

[0103] According to the single metal body phase model of the intercalation metal in the construction of the double-layer boronene metal intercalation model based on the Materials Studio database, the self-consistent energy is obtained for the simulation and calculation of the formation energy, adsorption energy, differential charge density and state density.

[0104] ​The base state structure of the double-layer boronene metal intercalation model and the single metal body phase model is optimized respectively, the lattice stability, energy stability and thermodynamic stability of the double-layer boronene metal intercalation model are analyzed according to the calculation results, and the material corresponding to the stable double-layer boronene metal grid model screened is a boronene metal grid material; the double-layer boronene metal intercalation model has lattice stability when the phonon dispersion has no virtual frequency, has energy stability when the formation energy is negative, and has specific thermodynamic stability when it does not crack at 1000 DEG C.

[0105] Among them, the lattice stability is determined by constructing a model to expand the cell to make it The lattice stability is determined by whether the phonon dispersion has a virtual frequency. Figure 2 The lattice structure and lattice stability of the boronene metal grid structure MB6 (M = Co, Ni, Cu or Pd) are determined according to Figure 2 It can be seen that when the intercalated metal is cobalt, nickel, copper and palladium, there is no virtual frequency and the lattice is stable. For the third period transition metal and the fourth period transition metal element except the cobalt, nickel, copper and palladium intercalation system, the phonon spectrum calculation of the double-layer boronene metal intercalation grid structure contains a virtual frequency, indicating that the phonon oscillation is strong and the lattice is unstable, so there is no subsequent research.

[0106] Energy stability: according to 112 structures, the formation energy of Co x B6 under different cobalt metal coverage, the formation energy is all negative, showing energy stability, and no obvious arrangement rule is shown when half covered. According to 77 structures, the structure of Ni x B6 under different nickel metal coverage, the formation energy is all negative, showing energy stability, and the nickel atoms obviously show a linear distribution rule when half covered. According to 134 structures, the structure of Cu x B6 under different copper metal coverage, the formation energy is all negative, showing energy stability, and no obvious arrangement rule is shown when half covered. According to 97 structures, the structure of Pd x B6 under different palladium metal coverage, the formation energy is all negative, showing energy stability, and the palladium atoms obviously show a diagonal distribution rule when half covered. Figure 3 The energy stability of the boronene metal grid structure M x B6 (M = Co, Ni, Cu or Pd) and the half-metal coverage structure diagram, the negative formation energy indicates energy stability, and the positive value in the second-order energy difference indicates that the corresponding structure has greater relative stability.

[0107] Kinetic stability: molecular dynamics simulation with 1 fs step, within 10000 steps, the starting temperature and the ending temperature are from 500K, respectively, with 500K, 100K and 50K as intervals. Figure 4Thermodynamic stability of the boronene metal mesh structure MB6 (M = Co, Ni, Cu, or Pd); by Figure 4 It can be seen that CoB6 remains stable at 1700K and decomposes at 1750K; NiB6 remains stable at 1750K and decomposes at 1800K; CuB6 remains stable at 1500K and decomposes at 1550K; PdB6 remains stable at 1300K and decomposes at 1350K; and the MB6 structure can maintain thermodynamic stability at the temperatures shown in the figure.

[0108] (2) Simulation of the dynamic behavior of intercalated metals

[0109] A surface adsorption model of intercalated metals adsorbed on the surface of a borane bilayer was constructed, wherein the intercalated metals were Co, Ni, Cu or Pd; Al was used as a control.

[0110] Interlayer intercalation site models were constructed with intercalated metals located at different equivalent sites between the layers of bilayer borene, under the same metal coverage.

[0111] Based on the surface adsorption model and the intercalation site model, diffusion paths for the intercalated metal along the Z, X, and Y axes are constructed. Eight intermediate points are inserted into each of the diffusion paths along the Z, X, and Y axes to find transition states. The diffusion barrier is calculated based on the transition states to obtain the dynamic behavior of the intercalated metal. Specifically, the diffusion path along the Z axis uses the surface adsorption metal model as the initial state, and the model of the intercalated metal moving from the surface to the intercalation site as the final state. The diffusion path along the X axis (positive direction) uses the intercalation site model as the initial state, and the model of the intercalated metal moving along the X-axis to the nearest neighbor equivalent site as the final state. The diffusion path along the Y axis (positive direction) uses the intercalation site model as the initial state, and the model of the intercalated metal moving along the Y-axis to the nearest neighbor equivalent site as the final state. x B6 (M = Co, Ni, Cu or Pd) and Al x The diffusion barrier results for B6 are shown in Table 1. Further analysis of the calculated results can be performed from the perspective of molecular vibrations, using ν*exp(-ΔE / k B T) The potential barrier is converted into an average vibrational frequency (in Hertz), and the proportion of the vibrational frequency diffusing along the Z-axis in the vibrational frequencies of the X, Y, and Z axes is calculated. The diffusion path of the intercalated metal is obtained based on this proportion. A schematic diagram of the diffusion path and vibrational frequencies of the intercalated metal is shown below. Figure 5 As shown.

[0112] Table 1 M x B6 (M = Co, Ni, Cu or Pd) and Al x B6 diffusion barrier results

[0113]

[0114] From Table 1 and Figure 5 It can be seen that the boronene metal mesh structure M x The intercalated metal in B6(M = Co, Ni, Cu or Pd) shows the lowest diffusion barrier along the Z-axis diffusion path, and by converting into molecular average vibration frequency, the vibration frequency in the Z-axis direction accounts for more than 99% of the total vibration frequency, indicating that the Z-axis diffusion path (i.e. diffusion from the double boronene layer to the interlayer) occupies a dominant position, and the diffusion of the intercalated metal from the double boronene layer to the interlayer is the main source of the intercalated metal.

[0115] (3) Simulation of the surface water splitting process of boronene metal mesh material

[0116] First, the structure of a single water molecule is optimized to obtain the H-O bond length H-O-H bond angle 104.55°, and then it is placed on the surface of the boronene metal mesh material (M x B6, M = Co, Ni, Cu or Pd, with Al as a control) for optimization, and the optimized structure is used as the initial state model of the water splitting reaction.

[0117] A model of boronene metal mesh material adsorbing one hydrogen atom and one hydroxyl group is constructed, and the hydrogen atom-H and the hydroxyl group-OH are respectively placed on two adjacent B-B bonds on the surface of the boronene metal mesh material, ensuring a certain interval, and the optimized structure is used as the final state model of the water splitting reaction. Due to the introduction of H-based adsorption groups such as -H and -OH, the hydrogen bond interaction needs to be considered, so the van der Waals correction (DFT-D3 BJ damping, IVDW = 12) is added when calculating.

[0118] According to the initial state model and the final state model, the water molecule splitting path is constructed, eight intermediate points are inserted to find the transition state, and the hydrogen evolution reaction free energy is calculated according to the transition state; when the hydrogen evolution reaction free energy is -1-1eV, the boronene metal mesh material is suitable as a catalyst for electrocatalytic hydrogen evolution.

[0119] Figure 6 A schematic diagram of the surface water splitting reaction of boronene metal mesh structure MB6(M = Co, Ni, Cu or Pd) is shown in Table 2, and the energy results of the water splitting reaction are shown in Table 2.

[0120] Table 2 Energy results of water splitting reaction

[0121]

[0122] From Figure 6 and Table 2, it can be seen that among the four boronene metal mesh materials M x ​Among B6(M=Co, Ni, Cu or Pd), NiB6 and CuB6 exhibit water dissociation barriers of 0.425 eV and 0.424 eV, which are comparable to the value of 0.44 eV for the traditional noble metal platinum catalyst Pt(110). The water dissociation barrier of CoB6 is 0.213 eV, while the PdB6 surface exhibits an extremely low water dissociation barrier of 0.087 eV, which is much better than the value of 0.78 eV for Pt(111). It is shown that the boronene metal mesh material M x B6(M=Co, Ni, Cu or Pd) is a good platform for water dissociation reaction.

[0123] (4) Simulation of hydrogen evolution reaction of boronene metal mesh material

[0124] A model of double-layer boronene metal intercalation structure for hydrogen atom adsorption is constructed, and possible hydrogen atom adsorption sites (hole site H of surface B-B bond, 3 bridge sites B1, B2 and B3 of surface B-B bond, 2 vertex sites T1 and T2 of surface boron atom, and vertex site T3 of interlayer metal) are determined;

[0125] The most stable adsorption site of hydrogen atom for each model is determined, and which adsorption sites can remain stable. Among them, the bridge site B1 of B-B bond is the most stable adsorption site, and three adsorption sites can remain stable. The influence of different adsorption sites on adsorption energy is about 1 eV (such as Figure 7 ); for boronene metal mesh materials with different interlayer metal coverage, the most stable adsorption site of B-B bond bridge site is related to the distance from the interlayer metal vacancy position, and each structure needs to be determined separately. The overall performance is that the closer the distance to the defect, the weaker the adsorption, and this variable affects the adsorption energy by about 0.3 eV (such as Figure 8 );

[0126] The free energy of hydrogen evolution reaction of each model is determined, and when the free energy of hydrogen evolution reaction is -1-1 eV, the boronene metal mesh material is suitable as a catalyst for electrocatalytic hydrogen evolution.

[0127] Based on the fact that actual electrocatalytic process is generally carried out in solution environment, the water solvation effect is corrected. The correction of water solvation effect is realized by changing the source code of VASP6.3.0 software package and recompiling. When calculating by using the first principle simulation software VASP, two parameters LSOL=.TRUE. and EB_K=80 are added in the input file INCAR to simulate the existence of water molecules around the structure. The free energy ΔG=E ads +ΔE ZPE -TΔS, wherein ΔG is the free energy, E ads is the hydrogen atom adsorption energy, ΔE ZPE is the zero-point vibration energy, T is the temperature, and ΔS is the entropy change, wherein the hydrogen atom adsorption energy is defined as: E ads =EH* -E * -1 / 2E H2 , of which E H* For the energy of boronene metal mesh materials that adsorb hydrogen atoms, E * For the energy of boronene metal mesh material, E H2 It uses hydrogen as its energy source.

[0128] Figure 7 M is a boronene metal mesh material x The catalytic free energy of the hydrogen evolution reaction of B6 (M = Co, Ni, Cu, or Pd); the closer the free energy ΔG is to zero, the lower the overpotential required for the experimental electrolysis of water to split it into hydrogen and oxygen, and the better the effect. Figure 9 It can be seen that among the four highly stable boronene metal mesh materials (M... x In B6, M = Co, Ni, Cu or Pd, Cu x The B6 system, considering solvation effects, exhibits a free energy ranging from -0.16 to 0.18 eV under different intercalation metal coverages. (Pd) x The B6 system exhibits a free energy ranging from -0.13 to 0.18 eV, considering the solvation effect, under different intercalation metal coverage rates, while the reaction free energy of conventional platinum catalysts is approximately -0.075 eV. This indicates that the intercalation of any number of Cu or Pd metals into the interlayer of the bilayer borone allows this borone metal mesh material to possess hydrogen evolution reaction catalysts comparable to platinum.

[0129] (5) Simulation of the tensile properties of boronene metal mesh material

[0130] The boronene metal mesh material was subjected to uniaxial strain (gradually stretched in units of 1% of the lattice length in the X-axis direction when unstretched) to obtain the tensile limit;

[0131] A model of hydrogen atom adsorption at different adsorption sites of boronene metal mesh material was constructed. Uniaxial strain was applied to the hydrogen atom adsorption model within the tensile limit range (gradual stretching in units of 1% of the lattice length in the X-axis direction when unstretched). The catalytic free energy of hydrogen evolution reaction under different tensile stresses was calculated. When the free energy of hydrogen evolution reaction is -1 to 1 eV, the boronene metal mesh material has stable tensile properties.

[0132] Figure 10 The tensile properties of the boronene metal mesh material MB6 (M = Co, Ni, Cu, or Pd) are shown in the diagram. Figure 10 It can be seen that MB6 maintains structural stability under uniaxial tensile strain of 1% to 10% along the X-axis. The energy curve of the boronene metal mesh structure under 10% tensile stress along the X-axis rises steadily, indicating that its structure is not broken and remains stable. It has high tensile strength and can adapt to complex stress conditions in practical applications.

[0133] Figure 11 The influence of uniaxial 1-10% tensile strain along X-axis direction on the catalytic performance of boronene metal grid structure MB6 (M=Co, Ni, Cu or Pd) for hydrogen evolution reaction under full metal coverage. Figure 11 It can be seen that the four kinds of boronene metal grid structure M x The free energy of hydrogen evolution reaction of B6 (M=Co, Ni, Cu or Pd) is shifted from positive to negative with the increase of tensile strain. For example, under full metal coverage, the free energy of CoB6 decreases from-0.73 eV to-0.96 eV under 10% tensile strain, the free energy of NiB6 decreases from-0.23 eV to-0.48 eV under 10% tensile strain, the free energy of CuB6 decreases from-0.04 eV to-0.25 eV under 10% tensile strain, and the free energy of PdB6 decreases from 0.08 eV to-0.32 eV under 10% tensile strain. According to this rule, the structure with part of positive free energy can be adjusted to be closer to 0 by a certain tensile strain, which means that the overvoltage in the experiment is lower. It is shown that the tensile stress can adjust the catalytic performance, and the boronene metal grid structure M x B6 (M=Co, Ni, Cu or Pd) is suitable for the platform of electrocatalytic hydrogen evolution reaction as a catalyst.

[0134] The above only describes the preferred embodiments of the present application, and it should be noted that for ordinary skilled in the art, without departing from the principles of the present application, a number of improvements and refinements can be made, and these improvements and refinements should be considered as the protection scope of the present application.

Claims

1. A method for screening boronene metal mesh materials, utilizing first-principles calculations, comprising the following steps: (1) Construct multiple bilayer boronene metal intercalation models and single-metal bulk phase models. The bilayer boronene metal intercalation models include bilayer boronene metal intercalation models with different intercalation metal types and bilayer boronene metal intercalation models with different intercalation metal coverage. The single-metal bulk phase model is the intercalation metal involved in the bilayer boronene metal intercalation model. (2) Ground-state structure optimization was performed on the bilayer boronene metal intercalation model and the single-metal bulk phase model, respectively. Based on the calculation results, the lattice stability, energy stability, and thermodynamic stability of the bilayer boronene metal intercalation model were analyzed. The material corresponding to the stable bilayer boronene metal mesh model was selected as the target boronene metal mesh material. The lattice stability refers to the absence of imaginary frequencies in the phonon dispersion of the bilayer boronene metal intercalation model; the energy stability refers to a negative formation energy; and the thermodynamic stability refers to no decomposition above 1000℃. The formation energy is defined as: Among them, E form In order to form energy, For the total energy, N B E represents the number of boron atoms. B For the energy of a boron atom in a single δ4-boronene, N M E represents the number of intercalated metal atoms. M The energy of a single intercalated metal atom in its bulk.

2. The screening method according to claim 1, characterized in that, The intercalation metal includes any one of the third-period transition metal and the fourth-period transition metal; The ground-state structure optimization was performed using the first-principles simulation software VASP.

3. The screening method according to claim 1, characterized in that, Step (2) is followed by simulating the dynamic behavior of the intercalated metal in the bilayer boronene metal intercalation model, including the following steps: A surface adsorption metal model is constructed in which intercalated metals are adsorbed on the surface of a bilayer boronene, wherein the types of intercalated metals in the surface adsorption metal model are the same as the types of intercalated metals in the stable bilayer boronene metal mesh model; Interlayer intercalation site models were constructed with intercalated metals located at different equivalent sites between the layers of bilayer borene, under the same metal coverage. Based on the surface adsorption model and the intercalation site model, the diffusion paths of the intercalated metal along the Z-axis, X-axis and Y-axis are constructed. The transition state structure of the metal in the bilayer borene is calculated based on the diffusion paths along the Z-axis, X-axis and Y-axis, respectively. The diffusion barrier is calculated based on the transition state to obtain the kinetic behavior results of the intercalated metal. The diffusion path along the Z-axis takes the surface-adsorbed metal model as the initial state and the model of the intercalated metal moving from the surface to the intercalation site as the final state. The diffusion path along the X-axis takes the interlayer intercalation site model as the initial state and the model of the intercalated metal moving along the X-axis to the nearest equivalent site as the final state. The diffusion path along the Y-axis uses the interlayer intercalation site model as the initial state and the model of the intercalated metal moving along the Y-axis to the nearest equivalent site as the final state.

4. The screening method according to claim 1 or 3, characterized in that, Step (2) is followed by simulating the surface water splitting process of the boronene metal mesh material, including the following steps: A water molecule model is constructed, and the water molecule model is placed on the surface of a boronene metal mesh material. After the first structural optimization, it is used as the initial state model. A model was constructed to adsorb one hydrogen atom and one hydroxyl group into a boronene metal mesh material, and the result of the second structural optimization was used as the final state model. Based on the initial state model and the final state model, a water molecule splitting pathway is constructed, a transition state is found, and the hydrogen evolution reaction free energy is calculated based on the transition state. When the hydrogen evolution reaction free energy is -1 to 1 eV, the boronene metal mesh material is suitable as a catalyst for electrocatalytic hydrogen evolution.

5. The screening method according to claim 4, characterized in that, The first structural optimization, the second structural optimization, and the search for the transition state were performed using the first-principles simulation software VASP. The hydrogen bonds in the second structure optimization process are modified by van der Waals.

6. The screening method according to claim 1 or 3, characterized in that, Step (2) is followed by simulating the surface hydrogen evolution reaction of the boronene metal mesh material, including the following steps: A model of hydrogen atom adsorption at different adsorption sites of boronene metal mesh material was constructed, and the catalytic free energy of hydrogen evolution reaction for each model was determined. When the free energy of hydrogen evolution reaction is -1 to 1 eV, boronene metal mesh material is suitable as a catalyst for electrocatalytic hydrogen evolution.

7. The screening method according to claim 6, characterized in that, The adsorption sites include the apex sites, pore sites, and bridge sites of the surface borene, as well as the apex sites of the intercalated metal. The simulation of the hydrogen evolution reaction corrected for the water solubilization effect.

8. The screening method according to claim 1 or 3, characterized in that, Step (2) is followed by simulation of the tensile properties of the boronene metal mesh material, including the following steps: A uniaxial strain is applied to the boronene metal mesh material along the X-axis, and the energy of the strained structure is plotted to obtain the energy change curve with uniaxial strain. The tensile limit is obtained based on the change curve. A model of hydrogen atom adsorption at different adsorption sites in a boronene metal mesh material was constructed. Uniaxial strain was applied to the hydrogen atom adsorption model within the tensile limit range, and the catalytic free energy of hydrogen evolution reaction under different tensile stresses was calculated.

9. The boronene metal mesh material obtained by the screening method according to any one of claims 1 to 8, having the chemical formula M x B6, of which x is 0 to 1 and not 0, and M includes Co, Ni, Cu or Pd.

10. The application of the boronene metal mesh material according to claim 9 as a catalyst in the electrocatalytic hydrogen evolution reaction.

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