A method for optimizing surface electrocatalytic hydrogen evolution reaction performance of sulfur substitutional doped rutile type ruthenium dioxide

Abstract

This invention discloses a method for optimizing the electrocatalytic hydrogen evolution reaction performance of ruthenium dioxide surfaces doped with sulfur substitution sites, belonging to the field of electrocatalysis and hydrogen energy material design technology. The method focuses on the RuO2 surface, employing S substitution doping at terminal oxygen sites. Under crystal symmetry constraints, different doping configurations are enumerated, and the doping configurations are screened based on formation energy to obtain thermodynamically feasible configurations. Simultaneously, electronic structure analysis of representative doping configurations is performed to explain the mechanistic relationship between local doping configurations and the thermodynamic performance of the hydrogen evolution reaction, verifying the rationality of the local configuration-based screening method in material design. This method features high design efficiency and strong controllability, and can be used to guide the structural and performance design of non-noble metal electrocatalysts, and is applicable to the research and screening of alkaline or acidic water electrolysis hydrogen production catalytic materials.

Description

Technical Field

[0001] This invention relates to the field of electrocatalysis and hydrogen energy material design technology, specifically to a method for optimizing the electrocatalytic hydrogen evolution reaction performance of sulfur substitution-doped ruthenium dioxide surface. Background Technology

[0002] Electrolysis of water to produce hydrogen is an important pathway to achieving green hydrogen energy, in which the hydrogen evolution reaction (HER) catalyst determines the reaction overpotential and energy efficiency. Noble metal Pt possesses near-optimal HER adsorption thermodynamics, but its high cost and limited reserves make it a potential non-noble metal electrocatalytic material. Rutile RuO2 exhibits good conductivity and stability, making it a promising non-noble metal electrocatalytic material. However, the adsorption of hydrogen intermediates by Ru sites on the RuO2 surface is often excessive, limiting hydrogen desorption and H2 generation, thus reducing intrinsic HER activity. Existing doping control methods are mostly based on empirical selection of doping concentration, lacking systematic screening of local doping configuration differences and quantitative establishment of structure-activity relationships, resulting in low material optimization efficiency and poor reproducibility. Therefore, there is an urgent need for an efficient design method that can simultaneously consider symmetry, thermodynamic stability, and key electrocatalytic descriptors at the atomic scale to achieve controllable optimization of the HER performance of RuO2-based electrocatalysts. Summary of the Invention

[0003] To address the aforementioned shortcomings of existing technologies, the present invention aims to provide a method for optimizing the electrocatalytic hydrogen evolution reaction performance of sulfur substitution-doped ruthenium dioxide surfaces. This method involves enumerating doping configurations, screening formation energies, and adjusting ΔG. H The evaluation process identifies the preferred doped local structures and corresponding active sites, and establishes the structure-activity relationship of "local configuration-electronic structure-adsorption thermodynamics," providing a general methodology for the rational design of RuO2-based non-noble metal HER catalysts.

[0004] The technical solution of this invention to solve the above-mentioned technical problems is as follows: A method for optimizing the electrocatalytic hydrogen evolution reaction performance of sulfur substitution-doped ruthenium dioxide surface is provided, comprising the following steps: (1) Construct a RuO2 surface model; (2) Enumerate the doping configurations corresponding to the rutile RuO2 surface model in step (1) under the constraint of crystal symmetry to obtain the set of symmetric non-equivalent configurations under each doping concentration. (3) Perform geometric structure optimization on the set of symmetric inequivalent configurations obtained in step (2) and calculate the formation energy, and screen the formation energy E. F Thermodynamically feasible configurations with values ​​less than zero; (4) Based on the thermodynamically feasible configurations obtained in step (3), calculate the hydrogen adsorption free energy ΔG for the coordinated unsaturated Ru sites. HFurthermore, based on the different number of S atoms in the first nearest neighbor of the coordinating unsaturated Ru site, the coordinating unsaturated Ru site is divided into different local configuration types; (5) The hydrogen adsorption free energy ΔG obtained in step (4) H As an evaluation index, when ΔG H When approaching thermal neutrality, determine the optimal doping local configuration and the corresponding hydrogen evolution active sites.

[0005] Furthermore, the RuO2 surface model in step (1) includes surface-coordinated unsaturated Ru sites and terminal oxygen sites.

[0006] Furthermore, in step (1), the RuO2 surface is the (110) crystal plane of rutile RuO2.

[0007] Furthermore, the enumeration of doped configurations in step (2) includes a process of identifying and removing equivalent configurations based on crystal symmetry.

[0008] Furthermore, in step (3), energy E is formed. F The calculation formula is as follows: E F (S-RuO2)=E total (RuO2:S) E total (RuO2) μs+μo; where E total Let μ be the total energy of the system, μ be the chemical potential, and μs and μo represent the chemical potentials of S and O, respectively.

[0009] Furthermore, in step (4), the hydrogen adsorption free energy ΔG H The calculation formula is as follows: ΔG H =ΔE a +ΔE ZPE -TΔS; Wherein, ΔG H For the Gibbs free energy, ΔE a E is the hydrogen adsorption energy. ZPE Here, ΔS is the zero-point energy correction term, T is the temperature, and ΔS is the change in entropy.

[0010] Furthermore, ΔE a = E slab+H - E slab -1 / 2E H2 ; Among them, E slab+H and E slab E represents the energy of the structure after hydrogen adsorption and the energy of the structure before hydrogen adsorption, respectively. H2 This represents the total energy of gaseous hydrogen molecules.

[0011] Furthermore, in step (4), the coordinate unsaturated Ru sites are divided into different local configuration types according to the different number of first nearest neighbor S atoms. Specifically, in a 3×3 RuO2(110) supercell, when 1, 2, and 3 S atoms are doped respectively, all 4, 22, and 60 symmetry-inequivalent S-substituted O atoms are obtained after deduplication by surface symmetry operations. cus Local configuration.

[0012] Furthermore, when ΔG H When ≈0eV, ΔG in step (5) H Nearly thermal neutral.

[0013] Furthermore, in step (5), the optimal doping local configuration is the local configuration in which the first nearest neighbor of the coordinated unsaturated Ru site is a single S atom.

[0014] The present invention has the following beneficial effects: (1) The method of this invention takes the RuO2 surface as the object and addresses the engineering design problem of limited HER activity caused by excessive adsorption of hydrogen intermediates by Ru sites on its surface. It proposes a design strategy that considers the synergistic regulation of doping concentration and local doping configuration within a given doping concentration range: by performing S substitution doping on the terminal oxygen sites on the surface, different doping configurations are enumerated under the constraint of crystal symmetry, and the doping configurations are screened based on the formation energy to obtain thermodynamically feasible doping configurations; further, the hydrogen adsorption free energy (ΔG) is increased. H As an evaluation parameter for the thermodynamic activity of the hydrogen evolution reaction, ΔG is used for different localized doping configurations. H Numerical comparisons were performed, and ΔG was obtained through selection. H The Top-type localized configuration with the smallest absolute value and satisfying the preset threshold condition is selected as the preferred active center. The Top-type localized configuration is defined as one where the first nearest neighbor of the coordinated unsaturated Ru site is a single S atom. Simultaneously, electronic structure analysis of representative doped configurations is performed to explain the mechanistic relationship between localized doping configurations and the thermodynamic properties of the hydrogen evolution reaction, thus verifying the rationality of the localized configuration-based screening method in material design. The results show that the method of this invention has the characteristics of high design efficiency and strong controllability, and can be used to guide the structural and performance design of non-noble metal electrocatalysts, and is applicable to the research and screening of alkaline or acidic water electrolysis hydrogen production catalytic materials.

[0015] (2) Shift from “concentration-driven” to “configuration-driven”: It is clearly proposed that HER enhancement is determined by local doping configuration rather than just doping concentration, thereby improving design interpretability and transferability.

[0016] (3) High screening efficiency and strong controllability: The configuration space is narrowed by symmetric enumeration + formation energy screening, avoiding blind trial and error.

[0017] (4) Performance indicators are clearly defined: ΔG H The core descriptor is used to lock in the optimal active site, achieving adsorption thermodynamic regulation close to the Pt baseline level.

[0018] (5) Closed-loop mechanism chain: Establish a quantitative correlation between “local configuration-electronic structure-adsorption thermodynamics” to provide a general route for the rational design of catalysts. Attached Figure Description

[0019] Figure 1 To construct a rutile RuO2 surface crystal plane model; Figure 2 The formation energy distribution of S-doped RuO2(110) surface crystals at different doping concentrations is shown. Figure 3 E at different adsorption sites (Ru, S, and O) on the surface of 8% S-doped RuO(110) a and ΔG H ; Figure 4 Statistical distribution of hydrogen adsorption energy for Top / Bridge local configurations; Figure 5 The band structure is shown in the diagram. Figure 6 DOS diagram for 1S-1 structure; Figure 7 The differential charge density plot of the 1S-1 structure; Figure 8 Volcano curves for the top-type Ru sites in the 1S-1 structure. Detailed Implementation

[0020] The examples given below are for illustrative purposes only and are not intended to limit the scope of the invention. Unless otherwise specified, conditions in the examples are performed under standard conditions or as recommended by the manufacturer. Reagents or instruments whose manufacturers are not specified are all commercially available products.

[0021] Example: A method for optimizing the electrocatalytic hydrogen evolution reaction performance of sulfur substitution-doped ruthenium dioxide surface includes the following steps: (1) Construct a crystal plane model of rutile RuO2 surface (preferably RuO2(110)), including surface-coordinated unsaturated Ru sites (Ru cus ) and terminal oxygen site (O cus Typical surface sites, such as Figure 1 As shown, Figure 1 (a) shows a side view of the structure of a rutile RuO2(110) surface; Figure 1(b) shows schematic adsorption sites of hydrogen atoms at different surface sites, including Ru sites, S sites and O sites; Figure 1 (c)~ Figure 1 (e) shows schematic adsorption configurations of hydrogen atoms at the different surface sites described above; Figure 1 (f) shows a schematic diagram of the classification of Ru sites by local configuration based on the different number of first nearest neighbor S atoms of the coordinated unsaturated Ru site, including top configuration and bridging configuration, which is used to illustrate the basis for the classification of local configuration and determination of active sites in this invention.

[0022] (2) RuO2 surface model establishment and S-doped configuration generation: Rutile RuO2 surface (preferably RuO2(110)) was selected as the model system, and a model was constructed containing surface-coordinated unsaturated Ru sites (Ru cus ) and terminal oxygen site (O cus Supercell models of surface sites (see) Figure 1 Among them, (a) is a side view of the rutile RuO2(110) surface; (b) shows the adsorption sites of H atoms at sites ①Ru, ②S, and ③O; (c)–(e) show the optimized adsorption configurations of H atoms at sites ①Ru, ②S, and ③O; (f) shows the top-type and bridge-type Ru adsorption sites. A 3×3 supercell structure (96 atoms in total) is adopted, with the bottom layer fixed to simulate bulk phase constraint. The surface O... cus The sites are candidate doping sites. One, two, and three O→S substitution doping sites are set respectively. Based on crystal symmetry, configuration enumeration and symmetry deduplication are performed to obtain a set of symmetric non-equivalent doping configurations.

[0023] (3) Formation energy screening of thermodynamically stable configurations: structural optimization is performed on all obtained symmetric inequivalent configurations and the formation energy E is calculated. F The calculation formula is as follows: E F (S-RuO2)=E total (RuO2:S) E total (RuO2) μs+μo; where E total Let E be the total energy of the system, μ be the chemical potential, and μs and μo represent the chemical potentials of S and O, respectively. F <0 was used as the criterion to determine the thermodynamically stable configuration and to exclude thermodynamically unfavorable structures caused by excessive doping. The formation energy distribution diagrams of S-doped RuO2(110) surface crystals at different doping concentrations are shown in [reference needed]. Figure 2 .Depend on Figure 2 It can be seen that the formation energy under different S doping concentrations is affected by different doping configurations, and the higher the doping concentration, the more unstable the structure.

[0024] (4) ΔG H Evaluation and Determination of Optimal Local Configuration: Among the thermodynamically stable configurations obtained through screening, the optimal local configuration for Ru is determined. cus The hydrogen adsorption energy was calculated from the site, S site, and surface oxygen site, and then converted to obtain ΔG. H Further differentiation of Top-type and Bridge-type sites based on local environment was performed on the stable configuration at a doping level of 17%. The results showed that Top-type Ru... cus ΔG corresponding to the site H The absolute value is significantly smaller than other local configurations, and satisfies |ΔG H The screening condition of ≤0.1 eV exhibits superior hydrogen evolution thermodynamic characteristics (see Figure 3-4 ). Figure 3 E represents the energy at different adsorption sites (Ru, S, and O) on the surface of 8% S-doped RuO(110). a and ΔG H It can be seen that the adsorption energy and Gibbs free energy at the Ru site are better than those at the O and S sites; Figure 4 The statistical distribution of hydrogen adsorption energy corresponding to the Top / Bridge local configurations is shown, and it is clear that the adsorption energy of the Top adsorption configuration is in a more ideal range.

[0025] (5) Establishment of electronic structure mechanism and structure-property relationship: Electronic structure calculations were performed on the optimal configuration and the control system, including band and density of states analysis, d-band center calculation, and differential charge density analysis. The results show that S substitution doping causes a redistribution of local electronic states at Ru sites, accompanied by a downward shift of the d-band center position, thereby regulating the hydrogen adsorption free energy and making the adsorption interface charge more delocalized, thus weakening the excessive interaction between hydrogen and Ru sites and reducing the ΔG of the corresponding configuration. H The absolute value was adjusted to within the preset threshold range (see the relevant control electronic structure diagram). Figure 5-8 ). Figure 5-6 The band structure and DOS diagram of the 1S-1 structure are shown, and the surface spin degenerate electronic structure is more conducive to adsorption energy. Figure 7 Differential charge density maps show that the positions of electron-rich and deficient regions have changed, which can effectively control the electron redistribution behavior of materials; Figure 8 The graph shows the volcano curve of the "top" type Ru site, indicating that the Gibbs free energy of the S-doped partial structure is superior to that of Pt, the traditional best HER catalyst, thus verifying the catalytic activity of RuO2 material.

[0026] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for optimizing the electrocatalytic hydrogen evolution reaction performance of sulfur substitution-doped ruthenium dioxide surface, characterized in that, Includes the following steps: (1) Construct a RuO2 surface model; (2) Enumerate the doping configurations corresponding to the rutile RuO2 surface model in step (1) under the constraint of crystal symmetry to obtain the set of symmetric non-equivalent configurations under each doping concentration. (3) Perform geometric structure optimization on the set of symmetric inequivalent configurations obtained in step (2) and calculate the formation energy, and screen the formation energy E. F Thermodynamically feasible configurations with values ​​less than zero; (4) Based on the thermodynamically feasible configurations obtained in step (3), calculate the hydrogen adsorption free energy ΔG for the coordinated unsaturated Ru sites. H Furthermore, based on the different number of S atoms in the first nearest neighbor of the coordinating unsaturated Ru site, the coordinating unsaturated Ru site is divided into different local configuration types; (5) The hydrogen adsorption free energy ΔG obtained in step (4) H As an evaluation index, when ΔG H When approaching thermal neutrality, determine the optimal doping local configuration and the corresponding hydrogen evolution active sites.

2. The method for optimizing the electrocatalytic hydrogen evolution reaction performance of sulfur substitution-doped ruthenium dioxide surface according to claim 1, characterized in that, The RuO2 surface model described in step (1) includes surface-coordinated unsaturated Ru sites and terminal oxygen sites.

3. The method for optimizing the electrocatalytic hydrogen evolution reaction performance of sulfur substitution-doped ruthenium dioxide surface according to claim 1, characterized in that, The RuO2 surface mentioned in step (1) is the (110) crystal plane of rutile RuO2.

4. The method for optimizing the electrocatalytic hydrogen evolution reaction performance of sulfur substitution-doped ruthenium dioxide surface according to claim 1, characterized in that, The enumeration of doped configurations in step (2) includes a process of identifying and removing equivalent configurations based on crystal symmetry.

5. The method for optimizing the electrocatalytic hydrogen evolution reaction performance of sulfur substitution-doped ruthenium dioxide surface according to claim 1, characterized in that, The formation energy E described in step (3) F The calculation formula is as follows: E F (S-RuO2)=E total (RuO2:S) E total (RuO2) μs+μo; where E total Let μ be the total energy of the system, μ be the chemical potential, and μs and μo represent the chemical potentials of S and O, respectively.

6. The method for optimizing the electrocatalytic hydrogen evolution reaction performance of sulfur substitution-doped ruthenium dioxide surface according to claim 1, characterized in that, The hydrogen adsorption free energy ΔG mentioned in step (4) H The calculation formula is as follows: ΔG H =ΔE a +ΔE ZPE -TΔS; Wherein, ΔG H For the Gibbs free energy, ΔE a E is the hydrogen adsorption energy. ZPE Here, ΔS is the zero-point energy correction term, T is the temperature, and ΔS is the change in entropy.

7. The method for optimizing the electrocatalytic hydrogen evolution reaction performance of sulfur substitution-doped ruthenium dioxide surface according to claim 6, characterized in that, The ΔE a = E slab+H - E slab -1 / 2E H2 ; Among them, E slab+H and E slab E represents the energy of the structure after hydrogen adsorption and the energy of the structure before hydrogen adsorption, respectively. H2 This represents the total energy of gaseous hydrogen molecules.

8. The method for optimizing the electrocatalytic hydrogen evolution reaction performance of sulfur substitution-doped ruthenium dioxide surface according to claim 1, characterized in that, Step (4) describes classifying the coordinating unsaturated Ru sites into different local configuration types based on the different numbers of the first nearest neighbor S atoms. Specifically, in a 3×3 RuO2(110) supercell, when 1, 2, and 3 S atoms are doped respectively, all 4, 22, and 60 symmetry-inequivalent S-substituted O atoms are obtained after deduplication through surface symmetry operations. cus Local configuration.

9. The method for optimizing the electrocatalytic hydrogen evolution reaction performance of sulfur substitution-doped ruthenium dioxide surface according to claim 1, characterized in that, When ΔG H When ≈0eV, the ΔG mentioned in step (5) H Nearly thermal neutral.

10. The method for optimizing the electrocatalytic hydrogen evolution reaction performance of sulfur substitution-doped ruthenium dioxide surface according to claim 1, characterized in that, The optimal doping local configuration described in step (5) is a local configuration in which the first nearest neighbor of the coordinated unsaturated Ru site is a single S atom.

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