Method for predicting catalytic activity of bimetallic supported catalyst in CO2RR reaction

Abstract

The invention discloses a method for predicting the catalytic activity of a bimetallic supported catalyst in a CO2RR reaction, and belongs to the technical field of computational material science and catalytic materials. The method comprises the following steps: constructing a spatial configuration of TMCu / W2CO2 with double metal atoms (TMCu) loaded on the surface of W2CO2; a relaxation configuration with the distance between TM atoms and Cu atoms smaller than 3.0 is screened out; calculating the adsorption energy Eads of adsorbing CO2 at different sites, and screening out a catalyst model with strong adsorption capacity on reactants; the optimal path in the reaction process is determined, the limiting potential UL of the surface of the catalyst is calculated based on the maximum value of the Gibbs free energy change delta G in the optimal path, and the UL is used for predicting the activity of different TMCu / W2CO2 surface electrocatalysis CO2RR. According to the method, screening standards taking the distance between double metal atoms, the binding energy of double metals, the adsorption energy of CO2 and the limited potential as the core are established, a low-efficiency system is rapidly eliminated, the experiment trial and error cost is reduced, and the development efficiency of the catalyst is improved.

Description

Technical Field

[0001] This invention belongs to the fields of computational materials science and catalytic materials technology, specifically relating to a method for predicting the catalytic activity of bimetallic supported catalysts in the CO2RR reaction. Background Technology

[0002] With the rapid development of the global economy and modern industry, electrocatalytic carbon dioxide reduction (CO2RR) technology has attracted much attention because it can convert CO2 into high-value-added fuels (such as methane and ethylene), and this technology is an important pathway to achieve carbon neutrality. However, the practical application of this technology is limited by low catalyst activity, poor product selectivity, and poor catalyst stability. Therefore, from the perspective of energy and economic costs, this technology faces severe challenges.

[0003] In recent years, single-atom catalysts (SACs) have shown potential by maximizing atom utilization. However, their single active sites are difficult to adapt to the adsorption requirements of different intermediates in the multi-step CO2RR reaction. Bimetallic catalysts, through the synergistic effect between the two metals, can optimize the adsorption of intermediates and have become a more promising type of catalyst. In addition, the trial-and-error method used in experimental studies has the disadvantages of long development cycles and high costs, and it cannot systematically study the relationship between catalyst structure and performance. W2CO3 has become an ideal support due to its high conductivity and tunable surface functional groups, but existing research has mostly focused on single-metal support (such as Cu / W2CO3), and there is insufficient theoretical exploration of the synergistic effect of bimetals, especially the electronic structure regulation mechanism of heteronuclear diatomic sites remains unclear.

[0004] Therefore, it is urgent to use quantum chemistry and computational chemistry methods to precisely design bimetallic active sites from a theoretical perspective, reveal the mechanism of support-bimetallic electronic interaction, and provide strong theoretical support for the design and screening of novel and efficient CO2RR catalysts. Summary of the Invention

[0005] To address the shortcomings of existing technologies, one objective of this invention is to provide a method for predicting the catalytic activity of bimetallic supported catalysts in the CO2RR reaction. A screening criterion based on the interatomic distance between bimetallic atoms, the binding energy of the bimetallic atoms, the adsorption energy of CO2, and the confinement potential has been established to quickly eliminate inefficient systems, reduce experimental trial-and-error costs, and improve catalyst development efficiency.

[0006] To achieve the above objectives, the specific technical solution of the present invention is as follows:

[0007] A method for predicting the catalytic activity of a bimetallic supported catalyst in the CO2RR reaction includes the following steps:

[0008] Based on the two-dimensional W2C configuration, an oxygen-functionalized W2CO2 monolayer configuration was constructed, and this configuration was used as the substrate material model. Based on density functional theory and VASP software, the configuration was optimized to obtain the relaxation configuration and relaxation energy.

[0009] A spatial configuration of TMCu / W2CO2 with bimetallic atoms supported on the surface of W2CO2 was constructed, and this configuration was used as a catalyst model. The relaxation configuration and relaxation energy were obtained based on density functional theory and VASP software.

[0010] Based on the obtained relaxation configurations, the interatomic spacing of the loaded bimetallic atoms was calculated, and configurations with an interatomic spacing of less than 3.0 Å between TM and Cu were selected. Based on the obtained relaxation energies, the binding energy E of TMCu on the W₂CO₂ surface was calculated. bind Screening stable TMCu / W2CO2 catalyst models;

[0011] Spatial configurations of CO2 adsorbed at different sites were constructed on the screened catalyst model, and relaxation configurations and relaxation energies were obtained based on density functional theory and VASP software.

[0012] Based on the obtained relaxation configurations, the changes in CO bond length and the degree of distortion of the ∠OCO bond angle of CO2 after adsorption are analyzed to determine the degree of activation of the reactants; based on the obtained relaxation energies, the adsorption energy E of CO2 adsorbed at different sites is calculated. ads Catalyst models with strong adsorption capacity for reactants were screened out.

[0013] Calculate the Gibbs free energy changes ΔG for each elementary reaction in the formate and carboxylic acid pathways of the electrocatalytic CO2RR reaction on the TMCu / W2CO2 surface, determine the optimal pathway in the reaction process, and calculate the confinement potential U on the catalyst surface based on the maximum value of the Gibbs free energy change ΔG in the optimal pathway. L , with U L To predict the electrocatalytic CO2RR activity of different TMCu / W2CO2 surfaces.

[0014] This invention utilizes quantum chemistry techniques based on density functional theory. It constructs an oxygen-functionalized two-dimensional W₂CO₂ monolayer as the substrate and loads a series of bimetallic atoms (TMCu) as the catalyst model. Relaxation configurations with a distance of less than 3.0 Å between TM and Cu atoms are selected to ensure significant interactions between the bimetallic atoms, enabling synergistic effects during catalysis. The binding energy of each loading system is analyzed to preliminarily screen stable catalyst systems. The adsorption behavior of CO₂ molecules on the stable TMCu / W₂CO₂ surface is investigated. Catalysts with stable adsorption behavior are selected for further systematic research on the electrocatalytic CO₂RR mechanism. This research clarifies the relationship between the type of loaded metal atoms and catalytic activity, reveals the synergistic mechanism between the bimetals, and provides a theoretical basis for the design and development of high-performance bimetallic supported CO₂RR catalysts. Ultimately, this will promote the development of electrocatalytic CO₂ reduction processes towards higher efficiency and greener methods.

[0015] Preferably, in the TMCu / W2CO2 catalyst model, TM atoms are transition metals with 3d and 4d periods.

[0016] More preferably, the TM atom includes one of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Nb, Mo, Tc, Ru, Rh, Pd, and Ag.

[0017] Preferably, the binding energy E of the TMCu bimetallic atoms on the W2CO2 surface is... bind The calculation formula is as follows:

[0018]

[0019] In the formula, E[TMCu / W2CO2] is the total energy of the surface after loading TMCu, E[TMCu] is the energy of the bimetallic atoms of TMCu, and E[W2CO2] is the energy of the clean W2CO2 surface.

[0020] Preferably, the present invention uses a binding energy E bind A stable TMCu / W2CO2 catalyst model was selected based on a standard of < -2.51 eV.

[0021] Preferably, the adsorption energy E of the CO2 molecules on the catalyst surface is... ads The calculation formula is as follows:

[0022]

[0023] In the formula, E(CO2 / TMCu / W2CO2) is the total energy of the system after CO2 adsorption, E(TMCu / W2CO2) is the energy of the TMCu / W2CO2 surface, and E(CO2) is the energy of the CO2 molecules in the gas phase.

[0024] Preferably, the present invention uses adsorption energy E ads < -1.0 eV is the standard screening model for catalysts with strong adsorption capacity for reactants.

[0025] Preferably, the formula for calculating the Gibbs free energy change ΔG of the elementary reaction during the electrocatalytic CO2RR reaction on the TMCu / W2CO2 surface is as follows:

[0026]

[0027] In the formula, ΔE is the energy difference between the product and the reactant. ZPE ΔS and ΔG represent the zero-point energy and entropy change of the reaction, respectively, T is the room temperature (298.15 K), and ΔG is the reaction entropy change. U = -neU, where ne represents the number of electrons transferred, U is the applied electrode potential, and ΔG pH For H + The correction term for free energy, i.e., ΔG pH = k B T × ln10 × pH, where k B This is the Boltzmann constant; the default pH value in this invention is 0.

[0028] Preferably, the limiting potential U L The calculation formula is:

[0029]

[0030] In the formula, ΔG max The value of the Gibbs free energy change during the entire reaction is given by ε, where e represents the electron.

[0031] Preferably, the present invention uses |U L (CO2RR)| < |U L (HER)| is the standard screening catalyst.

[0032] To gain a deeper understanding of the structure-activity relationship (SPR) of TMCu / W₂CO₂ catalysts, specifically to comprehend the synergistic effects between the supported bimetals and the interactions between the supported metal and the support on catalytic activity from a microscopic perspective, this invention provides an analytical method for understanding the interaction mechanism between the catalytic activity of TMCu / W₂CO₂ catalysts and the type of supported bimetallic TMCu, thereby revealing the structure-activity relationship of TMCu / W₂CO₂ materials catalyzing the CO₂RR reaction. The analytical method mainly includes the following steps:

[0033] Calculate the average value of the d-band centers of bimetallic atoms and the relationship between the d-band centers of Cu atoms and the confinement potential U in different TMCu / W2CO2 materials. LThe relationship between them;

[0034] Calculate the valence state δe and confinement potential U of bimetallic atoms in different TMCu / W2CO2 materials. L The relationship between the two atoms is defined as follows: the number of electrons that will transfer from TM and Cu atoms to CO2 structural units is defined as the valence state (δe) of the bimetallic atom.

[0035] For bimetallic atom catalysts, the synergistic effect between adjacent metals will affect the d-band center of the system and the valence state of the bimetallic atoms, thereby affecting their catalytic activity.

[0036] In the method proposed in this invention, four general "descriptors" are selected for screening bimetallic supported catalysts (TMCu / W2CO2 type catalysts) formed by supporting bimetallic atoms TMCu on W2CO2 material:

[0037] (1) The distance (d) between the loaded bimetallic atoms, that is, the appropriate distance between TM and Cu atoms should be maintained. If the distance is too far, it means that TMCu / W2CO2 is equivalent to a single-atom catalyst loaded with isolated TM and Cu atoms, and cannot give full play to the synergistic effect of bimetallic atoms in the catalytic process.

[0038] (2) Binding energy (E) of TMCu bimetallic atoms on the W2CO2 surface bind According to E bind The numerical value is used to determine the stability of the load configuration. That is, E bind The more negative the value, the stronger the bond between TMCu and the support, and the more thermodynamically stable the load configuration.

[0039] (3) Adsorption energy of CO2 molecules (E) ads According to E ads The numerical value is used to determine the stability of reactant adsorption on the catalyst surface. That is, E ads The more negative the value, the more thermodynamically stable the adsorption configuration of CO2 molecules.

[0040] (4) Limiting potential (U) in the electrocatalytic CO2RR reaction process L According to U L The value of U measures the electrocatalytic performance of a catalyst. L As a standard, the ease of CO2RR and HER on the TMCu / W2CO2 surface is judged. When the limitation potential of CO2RR is lower than that of HER, the material is considered to be a high-performance CO2RR electrocatalyst.

[0041] Compared with the prior art, the advantages of the present invention are:

[0042] (1) This invention uses density functional theory calculations to reveal the effects of bimetallic loading on the electronic structure of W2CO2 surface, CO2 adsorption activation and reaction pathway at the atomic scale, providing clear theoretical guidance for experimental synthesis.

[0043] (2) This invention establishes a screening standard based on the interatomic distance of bimetals, the binding energy of bimetals, the adsorption energy of CO2 and the limiting potential, which can quickly eliminate inefficient systems, reduce experimental trial and error costs and improve the development efficiency of catalysts.

[0044] (3) This invention proposes the regulation of catalytic activity by electron transfer and coordination environment between bimetallic atoms, reveals the synergistic mechanism between bimetals, and improves catalytic activity by optimizing the d-band center, providing ideas for the design of novel bifunctional catalysts and having certain universality. Attached Figure Description

[0045] Figure 1 Flowchart for screening bimetallic supported catalyst TMCu / W2CO2 for electrocatalytic CO2RR reaction;

[0046] Figure 2 This is a top view of the surface configuration of W2CO2, where gray and red spheres represent W and O atoms, respectively.

[0047] Figure 3 The calculated binding energy is for the most stable loading configuration of the TMCu / W2CO2 system.

[0048] Figure 4 Five possible chemisorption configurations of CO2 on the TMCu / W2CO2 surface;

[0049] Figure 5 A side view of the most stable adsorption configuration of CO2 on the TMCu / W2CO2 surface;

[0050] Figure 6 The possible reaction pathways for CO2RR are shown, with red and blue representing the carboxylic acid pathway and the formate pathway, respectively.

[0051] Figure 7 Correlation diagram of the limiting potentials of H2 and CH4 generated on the TMCu / W2CO2 surface;

[0052] Figure 8 The limiting potential (U) for the formation of methane products on the TMCu / W2CO2 surface L Correlation plot between the average value of the bimetallic d-band center;

[0053] Figure 9 The limiting potential (U) for the formation of methane products on the TMCu / W2CO2 surface LCorrelation diagram with the d-band center of Cu atoms;

[0054] Figure 10 The limiting potential (U) for the formation of methane products on the TMCu / W2CO2 surface L The correlation diagram between the valence state (δe) of bimetallic atoms and the valence state (δe). Detailed Implementation

[0055] The technical solution of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0056] Example 1

[0057] This embodiment uses heteronuclear bimetallic atoms V and Cu atoms supported on the surface of W2CO2 to form a VCu / W2CO2 catalyst. The activity and selectivity of this catalyst for the electrocatalytic CO2RR reaction are studied. Figure 1 As shown, the specific model and detailed research process are as follows:

[0058] (1) The spatial configuration card of the W2C surface was obtained through the Material Project website. Its cell parameters are a=b=2.85Å, c=5.66 Å, α=β=90°, γ=120°.

[0059] (2) The configuration of oxygen-functionalized W2C surface (i.e., W2CO2) was constructed using Material Studio software, and the initial unit cell was expanded to 4 × 4 using a repeating plate model. The thickness of the repeating plate model was 5 atomic layers. The resulting configuration contained a total of 32 W, 16 C, and 32 O atoms. Using this configuration as the substrate material model, the configuration of the W2CO2 substrate material was optimized based on density functional theory and VASP calculations. The optimized configuration is shown below. Figure 2 As shown.

[0060] (3) Based on the relaxation configuration of the obtained W2CO2 substrate material, the spatial configuration of VCu / W2CO2 loaded with bimetallic atoms (VCu) on the W2CO2 surface was constructed, and this configuration was used as the catalyst model. The spatial configuration of bimetallic V and Cu atoms loaded on the W2CO2 surface was also constructed using Material Studio software. The creation of the surface configuration required the addition of a 13 Å vacuum layer along the normal direction to eliminate the interaction between the periodic layer interfaces.

[0061] The possible binding sites of TMCu bimetallic loading on the W2CO2 surface are mainly the following four possible positions: hole site (H) on the W2CO2 surface, position above oxygen atom (OT), bridge site between two adjacent O atoms (OB), and position above W atom (WT).

[0062] After the above configuration file is constructed, use VESTA software to convert it from a CIF file type to a POSCAR file type required for calculation.

[0063] (4) The structure of the above-constructed configuration was optimized using VASP software based on first principles. During the configuration optimization process of W2CO2 and VCu / W2CO2 surfaces, the three layers of atoms at the bottom of the plate were fixed, while the two layers of atoms near the top surface were relaxed. The purpose of optimization was to obtain the relaxed configuration and relaxation energy.

[0064] (5) The relaxed configuration obtained after configuration optimization has a distance of 2.53 Å between the loaded bimetallic atoms V and Cu, which is less than 3.0 Å, indicating that there is a significant interaction between V and Cu atoms, which is beneficial to exert the synergistic effect between the two metals.

[0065] The synergistic effect between bimetals was evaluated by the distance (d) between the loaded bimetallic atoms, with d < 3.0 Å as the initial condition for screening catalysts.

[0066] (6) The relaxation energy obtained after configuration optimization is based on the binding energy (E) of TMCu bimetallic atoms on the W2CO2 surface. bind The formula for calculating E is used to calculate E. bind The results are as follows Figure 3 As shown, the binding energy of the VCu bimetallic element is -4.99 eV. bind The calculation method is as follows:

[0067]

[0068] Where E[TMCu / W2CO2] is the total energy of the surface after loading TMCu, E[TMCu] is the energy of the TMCu bimetallic atoms, and E[W2CO2] is the energy of the clean W2CO2 surface.

[0069] The stability of bimetallic atoms loaded on the W₂CO₂ surface is evaluated using binding energy, with the binding energy (E) of homonuclear Cu₂ / W₂CO₂ as the primary measure. bind = -2.51 eV) as the standard, E bind < -2.51 eV is used as the second "descriptor" for screening catalysts.

[0070] (7) Based on the relaxed configuration of the stable VCu / W2CO2 after the above screening, construct spatial configurations of CO2 adsorbed at different sites in the configuration; according to the five possible chemisorption configurations of CO2 on the TMCu / W2CO2 surface, such as Figure 4 As shown, after constructing the structure using Material Studio software, VASP software is used for structural optimization to obtain the most stable relaxation configuration and relaxation energy.

[0071] (8) Based on the side view of the most stable adsorption configuration of CO2 on the optimized VCu / W2CO2 surface (e.g.) Figure 5 As shown in the figure, the most stable adsorption mechanism of CO2 on the VCu / W2CO2 surface is as follows: C atoms are connected to Cu atoms through Cu-C bonds, and O atoms are connected to V atoms through VO bonds. After adsorption, the CO bonds in CO2 undergo a certain degree of stretching, and their structure is significantly deformed. Specifically, the two CO bonds are stretched from 1.17 Å in the gas phase to 1.32 Å and 1.23 Å, respectively. At the same time, CO2 also changes from a linear configuration to a V-shaped configuration, with a ∠OCO bond angle of 125.8°. These results indicate that CO2 is significantly activated after adsorption on the VCu / W2CO2 surface.

[0072] (9) The relaxation energy of the most stable adsorption configuration of CO2 on the VCu / W2CO2 surface after optimization, based on the adsorption energy E ads The calculation formula, the calculated E ads The result is -1.76 eV, indicating that the adsorption of CO2 on the VCu / W2CO2 surface is thermodynamically stable. ads The calculation method is as follows:

[0073]

[0074] Where E(CO2 / TMCu / W2CO2) is the total energy of the system after CO2 adsorption, E(TMCu / W2CO2) is the energy of the TMCu / W2CO2 surface, and E(CO2) is the energy of the CO2 molecules in the gas phase.

[0075] With E ads To evaluate the stability of reactant adsorption on catalyst surface, E ads < -1.0 eV is used as the third "descriptor" for screening catalysts.

[0076] (10) Based on the above-screened adsorption configurations, namely the adsorption configurations that show significant activation of reactant molecules and are thermodynamically stable, these configurations are used as the initial configurations in the subsequent electrocatalytic CO2RR reaction process to study the CO2RR reaction mechanism. In each protonation step of CO2RR, H…+ It can not only attack C atoms, but also bond with O atoms. Considering the diversity of reaction intermediate structures and the complexity of the CO2RR mechanism, intermediates are screened by comparing the Gibbs free energy changes (ΔG) of each elementary reaction. Then, the corresponding configuration is selected as the reactant for the next proton-electron pair bonding process, thereby determining the optimal path and final product of CO2RR on different TMCu / W2CO2 surfaces.

[0077] The TMCu / W2CO2 surface selected in the previous steps was used as a catalyst for further electrocatalytic CO2RR reaction. Based on the different initial protonation steps in the CO2RR reaction, two reaction pathways can be identified, such as... Figure 6 As shown, the first pathway is the formate pathway with HCOO* as the key reaction intermediate (CO2* + H). + + e - → HCOO*); the second is the carboxylic acid pathway with COOH* as the key intermediate (CO2* + H). + + e - → COOH*).

[0078] Based on the two reaction pathways, calculate the Gibbs free energy change ΔG in the elementary steps of each pathway, and determine the optimal pathway and the Gibbs free energy change ΔG in the rate-determining step of the reaction process. max On the VCu / W2CO2 surface, the optimal pathway for the CO2RR reaction is: CO2* → COOH* → CO* → CHO* → CHOH* → CH2OH* → CH2* → CH3* → CH4(g), where the rate-determining step is the final elementary reaction, CH3* → CH4(g), and its ΔG max It is 0.62 eV.

[0079] The method for calculating the Gibbs free energy change ΔG is as follows:

[0080]

[0081] Where ΔE is the energy difference between the product and the reactant, ΔE ZPE ΔS and ΔG represent the zero-point energy and entropy change of the reaction, respectively, T is the room temperature (298.15 K), and ΔG is the reaction entropy change. U = -neU, where ne represents the number of electrons transferred, U is the applied electrode potential (here U is set to zero), ΔG pH For H + The correction term for free energy, i.e., ΔG pH = k B T × ln10 × pH, where kB Let be the Boltzmann constant. This project assumes the reaction takes place at pH = 0. The zero-point energy ΔE of the reaction intermediate is also given. ZPE The entropy of gas phase molecules is obtained through vibrational frequency calculation. In the frequency calculation, the positions of atoms belonging to the W2CO2 substrate are fixed, while the positions of adsorbed reactant molecules and bimetallic atoms are released, i.e., the vibrational contribution of the support is ignored.

[0082] (11) Based on the Gibbs free energy ΔG of the velocity-determining step max Determine the limiting potential U of the CO2RR reaction L Because a competing reaction occurs in CO2RR: the hydrogen evolution reaction (HER, H... + + e - →1 / 2 H2, E 0 = 0 V), as a high-performance CO2RR electrocatalyst, the absolute value of the CO2RR confinement potential should be lower than that of HER. The correlation diagram of the confinement potentials of H2 and CH4 generation on different TMCu / W2CO2 surfaces is shown below. Figure 7 As shown.

[0083] The |U| of VCu / W2CO2 was calculated. L The result for (CO2RR) is 0.62 V, while |U L The value of (HER)| is 1.20 V, indicating that the system with V TM atoms has good selectivity for CO2RR.

[0084] Limiting potential U L The calculation method is as follows:

[0085]

[0086] Where ΔG max The value of the Gibbs free energy change during the entire reaction is given by ε, where e represents the electron.

[0087] Take U L To evaluate the selectivity of electrocatalytic CO2RR reduction on the catalyst surface, |U L (CO2RR)| < |U L (HER)| serves as the fourth "descriptor" for screening catalysts.

[0088] (12) To understand the influence of the synergistic effect between the supported bimetals on catalytic activity from a microscopic perspective, the average values ​​of the central energy levels of the bimetallic d orbitals in four types of TMCu / W2CO2 with TM atoms of V, Ni, Tc, and Pd were calculated. Figure 8 and 9As shown, the average value of the d-band center and the relationship between the d-band center of Cu atoms and U atoms are presented in different TM-Cu combinations. L The relationship diagram shows that U L There is a clear linear relationship between the average value of the d-band centers of bimetallic atoms and the d-band centers of Cu atoms. That is, the closer the d-band center is to the Fermi level, the smaller the absolute value of the confinement potential. Furthermore... Figure 10 U is given L The correlation diagram between U and the valence state δe (defined as the number of electrons transferred from TM and Cu atoms to the CO2 structural unit) shows that U L A clear linear relationship is also observed between δe and catalytic activity. That is, the fewer electrons transferred from the metal atom to CO2, the better the catalytic activity of the system.

[0089] Therefore, for bimetallic catalysts, the synergistic effect between adjacent metals affects the catalytic activity by influencing the d-band center and the valence state of the bimetallic atoms.

[0090] Example 2

[0091] In this embodiment, Ni and Cu were selected as heteronuclear bimetallic atoms to explore the activity and selectivity of the NiCu / W2CO2 electrocatalytic CO2RR reaction. The specific process and calculation software were basically the same as in Example 1.

[0092] In this embodiment, following the method of step (5) of Example 1, the distance between the loaded bimetallic atoms Ni and Cu is 2.48 Å. The distance (d) between the loaded bimetallic atoms is used to evaluate whether the bimetals can play a synergistic role, and d < 3.0 Å is used as the initial condition for screening catalysts.

[0093] In this embodiment, the method of step (6) of embodiment 1 is followed, such as Figure 3 As shown, the calculated binding energy of the NiCu bimetal is -3.33 eV. Similarly, the binding energy of the homonuclear Cu2 / W2CO2 (E...) is... bind = -2.51 eV) was used as a standard to measure the stability of the heteronuclear TMCu bimetallic atom-supported configuration. E bind < -2.51 eV was used as the second "descriptor" for screening catalysts, indicating that NiCu / W2CO2 is a thermodynamically stable catalyst surface.

[0094] In this embodiment, following the method of step (8) in Example 1, the side view of the most stable adsorption configuration of CO2 on the NiCu / W2CO2 surface is optimized (e.g., Figure 5As shown in the figure, on the NiCu / W2CO2 surface, CO2 forms Ni-C, Ni-O and Cu-O adsorption bonds with the catalyst surface, with bond lengths of 1.82, 1.97 and 1.90 Å, respectively.

[0095] In this embodiment, following the method in step (9) of Example 1, the adsorption energy of the most stable adsorption configuration of CO2 on the NiCu / W2CO2 surface was calculated to be -1.22 eV. Similarly, using E... ads < -1.0 eV is used as the third "descriptor" for screening catalysts.

[0096] In this embodiment, following the method of step (10) in Example 1, the optimal path for the CO2RR reaction on the NiCu / W2CO2 surface was calculated as: CO2* → COOH* → HCOOH* → CHO* → CH2O* → CH2OH* → CH2* → CH3* → CH4(g). The potential-determining rate step is CO2 → COOH* (ΔGmax = 0.28 eV).

[0097] In this embodiment, following the method of step (11) in Example 1, the absolute values ​​of the limiting potentials during the CO2RR and HER reactions on the NiCu / W2CO2 surface were calculated to be 0.28 V and 0.90 V, respectively. Similarly, using U... L To evaluate the selectivity of electrocatalytic CO2RR reduction on the catalyst surface, |U L (CO2RR)| < |U L (HER)| serves as the fourth "descriptor" for screening catalysts.

[0098] Example 3

[0099] In this embodiment, Tc and Cu were selected as heteronuclear bimetallic atoms to explore the activity and selectivity of the TcCu / W2CO2 electrocatalytic CO2RR reaction. The specific process and calculation software were basically the same as in Example 1.

[0100] In this embodiment, following the method of step (5) of Example 1, the distance between the loaded bimetallic atoms Tc and Cu atoms is 2.32 Å. The distance (d) between the loaded bimetallic atoms is used to evaluate whether the bimetals can play a synergistic role, and d < 3.0 Å is used as the initial condition for screening catalysts.

[0101] In this embodiment, the method of step (6) of embodiment 1 is followed, such as Figure 3 As shown, the calculated binding energy of the TcCu bimetal is -3.35 eV. Similarly, the binding energy of the homonuclear Cu2 / W2CO2 (E...) is... bind= -2.51 eV) was used as a standard to measure the stability of the heteronuclear TMCu bimetallic atom-supported configuration. E bind < -2.51 eV was used as the second "descriptor" for screening catalysts, indicating that TcCu / W2CO2 is a thermodynamically stable catalyst surface.

[0102] In this embodiment, following the method of step (8) in Example 1, the side view of the most stable adsorption configuration of CO2 on the TcCu / W2CO2 surface is optimized (e.g., Figure 5 As shown in the figure, on the TcCu / W2CO2 surface, CO2 forms adsorption bonds Cu-C and Tc-O with the catalyst surface, with bond lengths of 1.95 and 2.00 Å, respectively.

[0103] In this embodiment, following the method in step (9) of Example 1, the adsorption energy of the most stable adsorption configuration of CO2 on the TcCu / W2CO2 surface was calculated to be -2.51 eV. Similarly, using E... ads < -1.0 eV is used as the third "descriptor" for screening catalysts.

[0104] In this embodiment, following the method of step (10) in Example 1, the optimal path for the CO2RR reaction on the TcCu / W2CO2 surface was calculated as: CO2* → COOH* → CO* → CHO* → CHOH* → CH* → CH2* → CH3* → CH4(g). The potential-determining rate step is CO* → CHO* (ΔGmax = 0.74 eV).

[0105] In this embodiment, following the method of step (11) in Example 1, the absolute values ​​of the limiting potentials during the CO2RR and HER reactions on the TcCu / W2CO2 surface were calculated to be 0.74 V and 1.80 V, respectively. Similarly, using U... L To evaluate the selectivity of electrocatalytic CO2RR reduction on the catalyst surface, |U L (CO2RR)| < |U L (HER)| serves as the fourth "descriptor" for screening catalysts.

[0106] Example 4

[0107] In this embodiment, Pd and Cu were selected as heteronuclear bimetallic atoms to explore the activity and selectivity of the PdCu / W2CO2 electrocatalytic CO2RR reaction. The specific process and calculation software were basically the same as in Example 1.

[0108] In this embodiment, following the method of step (5) of Example 1, the distance between the loaded bimetallic atoms Pd and Cu atoms is 2.43 Å. The distance (d) between the loaded bimetallic atoms is used to evaluate whether the bimetals can play a synergistic role, and d < 3.0 Å is used as the initial condition for screening catalysts.

[0109] In this embodiment, the method of step (6) of embodiment 1 is followed, such as Figure 3 As shown, the calculated binding energy of the PdCu bimetal is -2.90 eV. Similarly, the binding energy of the homonuclear Cu2 / W2CO2 (E...) is... bind = -2.51 eV) was used as a standard to measure the stability of the heteronuclear TMCu bimetallic atom-supported configuration. E bind < -2.51 eV was used as the second "descriptor" for screening catalysts, indicating that PdCu / W2CO2 is a thermodynamically stable catalyst surface.

[0110] In this embodiment, following the method of step (8) in Example 1, the side view of the most stable adsorption configuration of CO2 on the PdCu / W2CO2 surface is optimized (e.g., Figure 5 As shown in the figure, on the PdCu / W2CO2 surface, CO2 forms adsorption bonds Pd-C, Pd-O and Cu-O with the catalyst surface, with bond lengths of 1.93, 2.27 and 1.87 Å, respectively.

[0111] In this embodiment, following the method in step (9) of Example 1, the adsorption energy of the most stable adsorption configuration of CO2 on the PdCu / W2CO2 surface was calculated to be -1.31 eV. Similarly, using E... ads < -1.0 eV is used as the third "descriptor" for screening catalysts.

[0112] In this embodiment, following the method of step (10) in Example 1, the optimal path of the CO2RR reaction process on the PdCu / W2CO2 surface was calculated as: CO2* → HCOO* → HCOOH* → CHO* → CH2O* → CH2OH* → CH2* → CH3* → CH4(g), where the potential rate-determining step is CH2O* → CH2OH* (ΔGmax = 0.22 eV).

[0113] In this embodiment, following the method of step (11) in Example 1, the absolute values ​​of the limiting potentials during the CO2RR and HER reactions on the PdCu / W2CO2 surface were calculated to be 0.22 and 0.42 V, respectively. Similarly, using U... L To evaluate the selectivity of electrocatalytic CO2RR reduction on the catalyst surface, |U L (CO2RR)| < |UL (HER)| serves as the fourth "descriptor" for screening catalysts.

[0114] Based on the analysis of Examples 1-4 above, we can see that the surfaces of bimetallic atoms with TM atoms of V, Ni, Tc, and Pd are not only thermodynamically stable catalytic surfaces, but also possess good catalytic performance and exhibit high selectivity for the CO2RR reaction. Furthermore, for the four TMCu / W2CO2 materials mentioned above, there is a clear linear relationship between the confinement potential and the average position of the bimetallic d-band center, as well as the d-band center of Cu atoms. When the valence state (δe) of the bimetallic atom is used as the descriptor, a good linear relationship also exists between the confinement potential and δe.

[0115] Therefore, the four general "descriptors" proposed in this invention can be applied to the screening of various bimetallic supported electrocatalysts for CO2RR reactions on other two-dimensional MXene materials (such as Ti2CO2 and Mo2CO2). Furthermore, this invention clarifies the regulatory mechanism of synergistic effects between bimetals on catalytic activity, enabling the prediction of the catalytic activity of other bimetallic supported catalysts in the CO2RR reaction. This reduces the high operating costs associated with experimental equipment and materials, saving researchers significant time and providing strong theoretical support for subsequent experiments.

[0116] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A method for predicting the catalytic activity of a bimetallic supported catalyst in the CO2RR reaction, characterized in that, Includes the following steps: Based on the two-dimensional W2C configuration, an oxygen-functionalized W2CO2 monolayer configuration was constructed, and this configuration was used as the substrate material model. Based on density functional theory and VASP software, the configuration was optimized to obtain the relaxation configuration and relaxation energy. A spatial configuration of TMCu / W2CO2 with bimetallic atoms supported on the surface of W2CO2 was constructed, and this configuration was used as a catalyst model. The relaxation configuration and relaxation energy were obtained based on density functional theory and VASP software. Based on the obtained relaxation configurations, the interatomic spacing of the loaded bimetallic atoms was calculated, and configurations with an interatomic spacing of less than 3.0 Å between TM and Cu were selected. Based on the obtained relaxation energies, the binding energy E of TMCu on the W₂CO₂ surface was calculated. bind Screening stable TMCu / W2CO2 catalyst models; Spatial configurations of CO2 adsorbed at different sites were constructed on the screened catalyst model, and relaxation configurations and relaxation energies were obtained based on density functional theory and VASP software. Based on the obtained relaxation configurations, the changes in CO bond length and the degree of distortion of the ∠OCO bond angle of CO2 after adsorption are analyzed to determine the degree of activation of the reactants; based on the obtained relaxation energies, the adsorption energy E of CO2 adsorbed at different sites is calculated. ads Catalyst models with strong adsorption capacity for reactants were screened out. Calculate the Gibbs free energy changes ΔG for each elementary reaction in the formate and carboxylic acid pathways of the electrocatalytic CO2RR reaction on the TMCu / W2CO2 surface, determine the optimal pathway in the reaction process, and calculate the confinement potential U on the catalyst surface based on the maximum value of the Gibbs free energy change ΔG in the optimal pathway. L , with U L To predict the electrocatalytic CO2RR activity of different TMCu / W2CO2 surfaces.

2. The method according to claim 1, characterized in that, In the TMCu / W2CO2 catalyst model, TM atoms are transition metals with 3d and 4d periods.

3. The method according to claim 2, characterized in that, The TM atom includes one of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Nb, Mo, Tc, Ru, Rh, Pd, and Ag.

4. The method according to claim 1, characterized in that, The binding energy E of the TMCu bimetallic atoms on the W2CO2 surface bind The calculation formula is as follows: In the formula, E[TMCu / W2CO2] is the total energy of the surface after loading TMCu, E[TMCu] is the energy of the bimetallic atoms of TMCu, and E[W2CO2] is the energy of the clean W2CO2 surface.

5. The method according to claim 1, characterized in that, With binding energy E bind < -2.51 eV is the standard screening model for stable TMCu / W2CO2 catalysts.

6. The method according to claim 1, characterized in that, The adsorption energy E of the CO2 molecules on the catalyst surface ads The calculation formula is as follows: In the formula, E(CO2 / TMCu / W2CO2) is the total energy of the system after CO2 adsorption, E(TMCu / W2CO2) is the energy of the TMCu / W2CO2 surface, and E(CO2) is the energy of the CO2 molecules in the gas phase.

7. The method according to claim 1, characterized in that, With adsorption energy E ads < -1.0 eV is the standard screening model for catalysts with strong adsorption capacity for reactants.

8. The method according to claim 1, characterized in that, The formula for calculating the Gibbs free energy change ΔG of the elementary reaction during the electrocatalytic CO2RR reaction on the TMCu / W2CO2 surface is as follows: In the formula, ΔE is the energy difference between the product and the reactant. ZPE ΔS and ΔG represent the zero-point energy and entropy change of the reaction, respectively, T is the room temperature (298.15 K), and ΔG is the reaction entropy change. U = -neU, where ne represents the number of electrons transferred, U is the applied electrode potential, and ΔG pH For H + The correction term for free energy, i.e., ΔG pH = k B T × ln10 × pH, where k B is the Boltzmann constant.

9. The method according to claim 1, characterized in that, The limiting potential U L The calculation formula is: In the formula, ΔG max The value of the Gibbs free energy change during the entire reaction is given by ε, where e represents the electron.

10. The method according to claim 1, characterized in that, Take |U L (CO2RR)| < |U L (HER)| is the standard screening catalyst.

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