Design method of bent transition metal chalcogenide single-layer electrocatalyst for hydrogen evolution reaction

Abstract

The invention discloses a design method of a curved transition metal chalcogenide single-layer electrocatalyst for hydrogen evolution reaction, which comprises the following steps: constructing a curved transition metal chalcogenide TMDs MX2 single layer with uniform curvature, and judging the structural stability of a curved atom model by molecular dynamics simulation according to a first principle; constructing a hydrogen evolution reaction adsorption model of the bent transition metal chalcogenide single layer by using an explicit solvation model, calculating Gibbs free energy of hydrogen adsorption, gradually increasing the bending curvature, and screening the bent transition metal chalcogenide single layer with good electrocatalytic activity; the hydrogen adsorption Gibbs free energy of the screened WTe2 and MoTe2 single layers is reduced to be within 0.21 eV when the bending curvature exceeds # imgabs 0 #, good hydrogen evolution reaction catalytic activity is shown, and particularly, the hydrogen adsorption Gibbs free energy of the screened WTe2 and MoTe2 single layers is reduced to 0.004 eV when the bending curvature reaches # imgabs 1 #.

Description

Technical Field

[0001] The invention relates to a design method of a bent transition metal sulfide compound monolayer electrocatalyst for hydrogen evolution reaction, belonging to the technical field of chemistry and materials. Background Art

[0002] Today, the extensive use, combustion and consumption of fossil fuels and the greenhouse gas emissions generated in industrial processes have accelerated global warming, changed the earth's climate, and caused a series of serious environmental problems. The development of green and clean energy and the reduction of polluting gas emissions have received widespread attention and attention. Hydrogen energy is an ideal green and clean energy with the characteristics of pollution-free combustion and high calorific value. Water splitting to produce hydrogen is currently a major way to obtain hydrogen energy, but traditional water electrolysis methods usually consume a lot of electricity. Electrochemical catalysis (electrocatalysis) has become one of the feasible alternative ways to produce hydrogen by water splitting and reduce the cost of hydrogen production, in which water molecules dissociate into OH - and H + The subsequent hydrogen evolution reaction (HER) is an important step in hydrogen production. In electrochemical reactions, catalysts play a key role in reducing the energy barrier of water splitting and improving the ability and efficiency of hydrogen evolution reaction. Precious metal catalysts have shown excellent performance in hydrogen evolution reaction. However, precious metals and their compounds have relatively limited storage and high mining costs, resulting in high production costs, which limits their widespread application in hydrogen evolution reaction. Therefore, finding cheap, stable, and highly active catalysts and exploring ways to reduce the reaction energy barrier are of great significance to the development of clean and sustainable energy.

[0003] Two-dimensional transition metal dichalcogenides (TMDs) have excellent physical, mechanical and chemical properties due to their low bending stiffness and high specific surface area. Since the surfaces of perfect two-dimensional transition metal dichalcogenides are often inert, which limits their application in catalytic reactions, the use of perfect two-dimensional transition metal dichalcogenides without defects as catalysts is still a major challenge. The utilization and conversion of mechanical or mechanical energy is a key mechanochemical strategy to initiate chemical reactions and activate reactions. Two-dimensional transition metal dichalcogenides are usually composed of only a few layers of atoms, have low bending stiffness, and are easily deformed under compressive loads or external constraints. Therefore, two-dimensional transition metal dichalcogenides often exhibit structural corrugations and out-of-plane deformations. Bending deformation not only changes the atomic configuration and bonding structure of two-dimensional transition metal dichalcogenides, but also facilitates the anchoring of metal atoms on their surfaces, thereby enhancing the activity of their inert surfaces. Using the mechanical energy generated by bending deformation can be an effective method or stimulation to activate the chemical activity of the surface of perfect two-dimensional transition metal dichalcogenides. However, the effects of bending deformation and the subsequent stored mechanical energy on the catalytic performance of perfect 2D TMDs in hydrogen evolution reaction, especially under high bending curvature conditions, have been rarely studied and lack theoretical guidance. Summary of the invention

[0004] Purpose of the invention: The purpose of the present invention is to provide a design method for a transition metal chalcogenide monolayer electrocatalyst for hydrogen evolution reaction. Using a perfect two-dimensional transition metal chalcogenide without defects as an electrocatalyst for hydrogen evolution reaction is still a big challenge. Two-dimensional transition metal chalcogenides have low bending stiffness and are easily deformed under compressive loads or external forces, but the effect of bending deformation on their catalytic activity in hydrogen evolution reaction is unclear. This design method uses a perfect transition metal chalcogenide monolayer after bending deformation as an electrocatalyst for hydrogen evolution reaction, and enhances the catalytic ability of the transition metal chalcogenide monolayer for hydrogen evolution reaction by changing the bending curvature, so as to solve the problems existing in the prior art.

[0005] Technical solution: The design method of a bent transition metal sulfide monolayer electrocatalyst for hydrogen evolution reaction described in the present invention comprises the following steps:

[0006] (1) An atomic model of a curved 2H-phase zigzag transition metal chalcogenide TMDs MX2 monolayer with uniform curvature was constructed based on the zigzag nanotube structure and shape;

[0007] (2) performing first-principles molecular dynamics simulation on the atomic model constructed in step (1), and judging the structural stability of the atomic model based on the energy change and atomic structure of the system during the calculation time;

[0008] (3) Based on the structural stability of the atomic model, an explicit solvation model was used to construct an adsorption model for the aqueous hydrogen evolution reaction of a bent transition metal chalcogenide monolayer;

[0009] (4) The adsorption model of the aqueous hydrogen evolution reaction constructed in step (3) was optimized using the first principle method. Based on the optimized structure, the adsorption energy ΔE of hydrogen atoms in the bent transition metal sulfide monolayer was calculated. H and the hydrogen adsorption Gibbs free energy ΔG H , according to the hydrogen adsorption Gibbs free energy ΔG H Determining the catalytic activity of bent transition metal chalcogenide monolayers;

[0010] (5) increasing the curvature of the transition metal sulfide monolayer, repeating steps (1) to (4), and screening out a transition metal sulfide monolayer with good electrocatalytic activity for hydrogen evolution reaction and its corresponding curvature;

[0011] (6) By calculating the limiting potential difference U between the carbon dioxide reduction reaction and the hydrogen evolution reaction L (CO2)-U L(H2) Determine the selectivity of the bent transition metal chalcogenide monolayer for the electrochemical hydrogen evolution reaction in step (5).

[0012] Furthermore, in step (1), a single layer of transition metal chalcogenide TMDs MX2, wherein M = Mo or W, X = Te.

[0013] Furthermore, in step (1), the atomic model of a transition metal sulfide TMDs MX2 monolayer with a curved 2H phase zigzag nanotube structure and shape is constructed using Materials studio software.

[0014] Furthermore, in step (2), if the energy of the atomic model remains stable and the structure is not destroyed during the calculation time, it is determined that the atomic model structure is stable.

[0015] Furthermore, step (3) includes the following steps: constructing a curved TMDs MX2 monolayer atomic model using the atomic structure of the nanotube, and then using an explicit solvation model to add 3-4 layers of water molecules on top of the curved TMDs MX2 monolayer, and 2 layers of water molecules on both sides, and applying periodic boundary conditions on the x-axis, and setting of the vacuum layer.

[0016] Furthermore, in step (4), the adsorption energy of hydrogen atom ΔE H The following formula (1) is used for calculation:

[0017]

[0018] in, is the total energy of hydrogen atoms adsorbed on TMD+H2O, It is the energy of TMD+H2O. is the energy of gas phase molecule H2.

[0019] Further, in step (4), under the conditions of zero electrode potential and pH = 0, the hydrogen adsorption Gibbs free energy ΔG H The following formula (2) is used for calculation:

[0020] ΔG H =ΔE H +ΔE ZPE -TΔS H (2)

[0021] Where, ΔE H is the adsorption energy of the H atom, ΔE ZPE is the difference in zero-point vibration energy, T is the thermodynamic temperature, which is 298.15K, ΔS H It is the change in entropy when H atoms are adsorbed on TMD+H2O under standard atmospheric pressure.

[0022] Furthermore, in step (4), the hydrogen adsorption Gibbs free energy ΔG H The closer it is to 0 eV, the better the electrocatalytic activity for hydrogen evolution reaction.

[0023] Furthermore, in step (5), the curvature of the selected transition metal sulfide monolayer is

[0024] Furthermore, in step (6), the curved WTe2 monolayer selected in step (5) has a curvature of The carbon dioxide reduction reaction (CO2RR) adsorption model was constructed on the atomic model at , and the binding energy and Gibbs free energy of the reaction intermediates COOH* and CO* were calculated; the binding energy of the intermediates COOH* and CO* was calculated by formulas (3) and (4):

[0025]

[0026] in, is the binding energy of the intermediate COOH*, is the energy of WTe2+H2O, is the total energy of the intermediate COOH* adsorbed on WTe2+H2O, is the binding energy of the intermediate CO*, is the total energy of the intermediate CO* adsorbed on WTe2+H2O, is the energy of gas phase molecule CO2, is the energy of gas phase molecule H2, It is the energy of liquid molecules H2O.

[0027] Furthermore, under the conditions of zero electrode potential and pH = 0, the Gibbs free energy of adsorption of intermediates COOH* and CO* is calculated by equations (5) and (6), respectively:

[0028]

[0029]

[0030] in, is the Gibbs free energy of the intermediate COOH*, is the Gibbs free energy of the intermediate CO*, It is the intermediate COOH * The binding energy, is the binding energy of the intermediate CO*, ΔE ZPE is the difference in zero-point vibration energy, T is the thermodynamic temperature, which is 298.15K, It is the change of the intermediate entropy when the intermediate COOH* is adsorbed on WTe2+H2O at a standard atmospheric pressure; It is the change in the entropy of the intermediate CO* when it is adsorbed on WTe2+H2O under standard atmospheric pressure.

[0031] Furthermore, for each elementary reaction step, the difference in Gibbs free energy ΔG i , i = 1, 2, 3, respectively calculated by the following formulas (7), (8) and (9):

[0032]

[0033]

[0034]

[0035] in, is the Gibbs free energy of the intermediate COOH*, is the Gibbs free energy of the intermediate CO*. In CO2RR, when the main product is CO, at a thermodynamic temperature of 298.15K and an atmospheric pressure of 101.325 kPa, the potential of the reversible hydrogen electrode RHE is set to zero, and the standard reduction potential of the reaction is U = -0.12 V.

[0036] When the side reaction CO2RR affects the selectivity of HER, the thermodynamic limiting potential U L (U L (CO2) or U L (H2)) is calculated using formula (10):

[0037]

[0038] in, It is the difference in Gibbs free energy of the carbon dioxide reduction reaction at U = 0 V or the Gibbs free energy of the hydrogen evolution reaction.

[0039] Furthermore, in step (6), the limit potential difference U L (CO2)-U L (H2) are all negative, indicating that HER tends to occur, whereas CO2RR tends to occur.

[0040] The present invention is based on the calculation method of the first principles. The technical route is to use the curved TMDs MX2 monolayer as an electrocatalyst for HER, and explain the influence of the curvature on the catalytic performance of the TMDs MX2 monolayer. A stable and efficient HER catalyst that suppresses the side reaction CO2RR was screened out. The present invention reveals the reaction mechanism, provides theoretical guidance for experimental preparation, and promotes the research of new HER electrocatalysts.

[0041] The present invention constructs a curved transition metal sulfide TMDs MX2 monolayer with uniform curvature, and uses first-principles molecular dynamics simulation to determine the structural stability of the curved atomic model; uses an explicit solvation model to construct a hydrogen evolution reaction adsorption model for the curved transition metal sulfide monolayer, calculates the Gibbs free energy of hydrogen adsorption, and gradually increases the curvature to screen the curved transition metal sulfide monolayer with good electrocatalytic activity; the screened WTe2 and MoTe2 monolayers have good electrocatalytic activity when the curvature exceeds When the hydrogen adsorption Gibbs free energy is reduced to less than 0.21 eV, it shows good catalytic activity for hydrogen evolution reaction, especially when the WTe2 monolayer reaches the bending curvature of When , its hydrogen adsorption Gibbs free energy decreases to 0.004eV.

[0042] Beneficial effects: Compared with the prior art, the present invention has the following significant advantages:

[0043] (1) The present invention utilizes curved TMDs MX2 monolayer as HER electrocatalyst.

[0044] (2) The WTe2 and MoTe2 catalysts selected in the present invention are free of defects, undoped with metal atoms, and are environmentally friendly.

[0045] (3) The curved WTe2 and MoTe2 monolayers selected by the present invention have a curvature of When , the hydrogen adsorption Gibbs free energy is 0.09 eV and 0.21 eV, respectively, showing good HER catalytic performance.

[0046] (4) The present invention selects the curved WTe2 monolayer, and the curvature is When , the Gibbs free energy of hydrogen adsorption can be reduced to 0.004eV, and the catalytic performance reaches the best.

[0047] (5) The present invention provides direct theoretical guidance for experiments. Compared with manual experiments, it can avoid a lot of trial and error, reduce the loss of time and cost, and provide a new way to design electrocatalysts for hydrogen evolution reaction by combining bending deformation with TMDs monolayer. BRIEF DESCRIPTION OF THE DRAWINGS

[0048] Figure 1 This is the energy diagram of a single-layer TMDs MX2 nanotube calculated by molecular dynamics simulation within 5ps at 300K;

[0049] Figure 2 is a plane and has a curvature of Schematic diagram of the atomic structure model of WTe2 monolayer adsorbed H atoms;

[0050] Figure 3 is a plane (solid green line) with a curvature of (solid blue line) and the curvature is (Red solid line) Radar plot of the hydrogen adsorption Gibbs free energy of TMDs MX2 monolayer. DETAILED DESCRIPTION

[0051] The technical solution of the present invention will be further described below in conjunction with the accompanying drawings.

[0052] Example 1

[0053] S1: Constructing nanotubes and calculating their stability

[0054] In the Materials studio software, 2H phase zigzag single-walled TMDs MX2 nanotubes were constructed, including 2H phase zigzag WTe2, MoTe2, WSe2, MoSe2, WS2, MoS2, WTe2, and 2H phase armchair bent WTe2 nanotubes. The corresponding CIF files were exported and converted into the required POSCAR files through VASP software. First-principles molecular dynamics simulation was used in VASP for calculations, and the calculations were run for 5ps at a temperature of 300K. Figure 1 As shown, the energy of the single-layer TMDs MX2 nanotube remains stable within 5ps and the structure is not damaged, indicating that the nanotube is stable.

[0055] S2: Construction of atomic model of curved TMDs MX2 monolayer

[0056] The unit cell atomic model of the planar TMDs MX2 monolayer is constructed in Materials studio software. The length of the unit cell in the x-axis and y-axis directions is greater than According to the explicit solvation model, 3-4 layers of water molecules were added above the planar TMDs MX2 monolayer, and periodic boundary conditions were applied in the x- and y-axis directions, and the z-axis direction was set The vacuum layer was used to obtain the flat TMDs MX2 single-layer atomic model for comparison.

[0057] Based on the stability of the TMDs MX2 monolayer nanotube in step S1, the bent TMDs MX2 monolayer atomic model was constructed using the atomic structure of the nanotube according to the explicit solvation model. 3-4 layers of water molecules were added on top and 2 layers of water molecules were added on both sides. Periodic boundary conditions were applied on the x-axis and the y and z directions were set. The vacuum layer is used to obtain the curved TMDsMX2 monolayer atomic model.

[0058] The numbers of M, X atoms and H2O molecules in the corresponding TMDs MX2 monolayer atomic model are shown in Table 1, and the corresponding lattice lengths are shown in Table 2. The corresponding CIF files were exported and converted into the required POSCAR files using VASP software.

[0059] Table 1 Plane and curvature and The number of M, X atoms and H2O molecules in the atomic model of the TMDs MX2 monolayer

[0060]

[0061] Table 2 Plane and curvature and The atomic model of the TMDs MX2 monolayer corresponds to the lattice length

[0062]

[0063] S3: Atomic structure optimization

[0064] Set up the required calculation files in VASP (the required calculation files are POSCAR, INCAR, KPOINTS, POTCAR and the submission script). All calculations are performed based on density functional theory (DFT) using the Perdew-Burke-Ernzerhof (PBE) exchange-correlation functional with the projected augmented wave method and the generalized gradient approximation (GGA). Van der Waals interaction corrections from DFT-D3 are considered and applied. The whole system is structurally optimized using the conjugate gradient algorithm until the forces on each atom are less than After the structure is optimized and the calculation is completed, the energy information can be obtained in the output file OUTCAR, and the structural information of the output file CONTCAR can be obtained through software such as VASTA.

[0065] S4: Construct hydrogen adsorption model and calculate hydrogen atom adsorption energy and Gibbs free energy

[0066] Convert the CONTCAR calculated after the structural optimization in step S3 into CIF format and import it into Materialsstudio. Place an H atom above the six rings of the planar TMDs MX2 monolayer and above the metal atom of the curved TMDs MX2 monolayer, and repeat step S3. After the structural optimization is completed, the frequency calculation is performed, and the Gibbs free energy is calculated by the hydrogen adsorption Gibbs free energy formula. Based on the results of the convergence test, the plane wave cutoff energy is set to 500 eV, and the 3×3×1 and 3×1×1 k-point grids centered on the Gamma point are used to calculate the planar and curved TMDs MX2 monolayer atomic models, respectively.

[0067] Planar and curved curvature The structure of hydrogen adsorption atoms constructed on the TMDs MX2 monolayer is shown in the figure. Figure 2 As shown. The blue, orange, green, red and white atoms are W, Te, H*, O and H atoms respectively.

[0068] The binding energy of adsorbed H atoms is calculated by formula (1):

[0069]

[0070] in, is the total energy of H atoms adsorbed on TMD+H2O, It is the energy of TMD+H2O. is the energy of gas phase molecule H2.

[0071] Furthermore, the hydrogen adsorption Gibbs free energy ΔG H The following formula (2) is used for calculation:

[0072] ΔG H =ΔE H +ΔE ZPE -TΔS H (2)

[0073] Where, ΔE H is the adsorption energy of the H atom, ΔE ZPE is the difference in zero-point vibration energy, T is the thermodynamic temperature, which is 298.15K, ΔS H is the entropy change of H atoms adsorbed on a TMDs MX2 monolayer at standard atmospheric pressure. The Gibbs free energy of hydrogen adsorption ΔG H The closer it is to 0 eV, the better the electrocatalytic activity.

[0074] Figure 3 is a plane (solid green line) with a curvature of (solid blue line) and the curvature is (Red solid line) Radar plot of the hydrogen adsorption Gibbs free energy of TMDs MX2 monolayer. Figure 3 As shown in Table 3, WTe2 and MoTe2 monolayers have better catalytic performance for HER at the same curvature, and the Gibbs free energy of hydrogen adsorption decreases with the increase of curvature. When , the Gibbs free energy of hydrogen adsorption in WTe2 and MoTe2 monolayers is 0.09 eV and 0.21 eV, respectively.

[0075] Table 3 Plane and curvature are and Gibbs free energy of hydrogen adsorption on TMD MX2 monolayer

[0076]

[0077] S5: Construct curvature The CO2RR adsorption model of the curved WTe2 monolayer is calculated by calculating the limiting potential difference U between the CO2 reduction reaction and the hydrogen evolution reaction. L (CO2)-U L (H2) Determine the curved WTe2 monolayer with a curvature of Selectivity of electrochemical hydrogen evolution reaction

[0078] The curvature calculated and output in step S3 is The CONTCAR of the WTe2 single layer was converted into CIF format and imported into Materials Studio. Figure 2 Similar to the atomic model in , COOH groups and CO groups were placed above the metal atoms of the bent WTe2 monolayer, and the frequency calculation was performed after structural optimization. The binding energy and Gibbs free energy formula of the adsorbed intermediates were used to calculate the binding energy and Gibbs free energy of the intermediates COOH* and CO*.

[0079] The binding energy of the intermediates COOH* and CO* is calculated by equations (3) and (4):

[0080]

[0081] in, is the binding energy of the intermediate COOH*, is the energy of WTe2+H2O, is the total energy of the intermediate COOH* adsorbed on WTe2+H2O, is the binding energy of the intermediate CO*, is the total energy of the intermediate CO* adsorbed on WTe2+H2O, is the energy of gas phase molecule CO2, is the energy of gas phase molecule H2, It is the energy of liquid molecules H2O.

[0082] Furthermore, under the conditions of zero electrode potential and pH = 0, the Gibbs free energy of adsorption of intermediates COOH* and CO* is calculated by equations (5) and (6), respectively:

[0083]

[0084]

[0085] in, is the Gibbs free energy of the intermediate COOH*, is the Gibbs free energy of the intermediate CO*, is the binding energy of the intermediate COOH*, is the binding energy of the intermediate CO*, ΔE ZPE is the difference in zero-point vibration energy, T is the thermodynamic temperature, which is 298.15K, It is the change in entropy of the intermediate COOH* adsorbed on WTe2+H2O at a standard atmospheric pressure. It is the change in the entropy of the intermediate CO* when it is adsorbed on WTe2+H2O under standard atmospheric pressure.

[0086] After obtaining the Gibbs free energy of the adsorption intermediates COOH* and CO*, for each elementary reaction step, the difference in Gibbs free energy ΔG i , i = 1, 2, 3, respectively calculated by the following formulas (7), (8) and (9):

[0087]

[0088]

[0089]

[0090] in, is the Gibbs free energy of the intermediate COOH*, is the Gibbs free energy of the intermediate CO*. In CO2RR, when the main product is CO, at a thermodynamic temperature of 298.15K and an atmospheric pressure of 101.325 kPa, the potential of the reversible hydrogen electrode RHE is set to zero, and the standard reduction potential of the reaction is U = -0.12 V.

[0091] S6: The curvature calculated by the Gibbs free energy obtained in steps S4 and S5 is The difference in limiting potentials between CO2RR and HER in WTe2 monolayer

[0092] The side reaction CO2RR will affect the selectivity of WTe2 for HER, and the thermodynamic limiting potential (U L ) is used to describe the competition between CO2RR and HER, as shown in formula (10):

[0093]

[0094] in, It is the difference in Gibbs free energy at U = 0V.

[0095] Further, the curvature is calculated from the hydrogen adsorption Gibbs free energy obtained in steps S4 and S5 and the Gibbs free energy of the intermediates COOH* and CO*. The difference between the limiting potential of the CO2 reduction reaction and the limiting potential of the hydrogen evolution reaction of WTe2 monolayer is U L (CO2)-U L (H2) is -0.62 V, which is a negative value, proving that the catalytic activity of the bent WTe2 monolayer in the electrochemical reaction tends to be HER with clear selectivity.

[0096] S7: Calculate the curvature Gibbs free energy of hydrogen adsorption in a bent WTe2 monolayer

[0097] Repeat steps S1-S4, the curvature is The molecular dynamics simulation results of WTe2 nanotubes are shown in Figure 1 As shown in (a), its energy is stable and the structure is not damaged within 5ps. The curvature is calculated by VASP software. The hydrogen adsorption Gibbs free energy of the curved WTe2 monolayer is 0.004 eV. When , its hydrogen adsorption Gibbs free energy is closer to 0 eV, indicating that bending the WTe2 monolayer achieves the optimal curvature for HER catalytic effect.

[0098] S8: HER electrocatalytic performance of 2H phase armchair-shaped WTe2 monolayer

[0099] The curvature is constructed to and Repeat steps S1-S4 to obtain 2H-phase armchair single-walled WTe2 nanotubes. Figure 1 As shown in (g), the curvature within 5ps is The armchair WTe2 nanotube is energetically stable and structurally intact. The calculated curvature is and The hydrogen adsorption Gibbs free energy of the armchair WTe2 monolayer is 0.58 eV and 0.26 eV, respectively. As the curvature increases, the hydrogen adsorption Gibbs free energy decreases. The catalytic performance for HER increases with the increase of curvature, but is weaker than the HER electrocatalytic ability of the zigzag curved WTe2 monolayer.

[0100] The above description is only an example of the present invention and does not limit the scope of this patent. All equivalent structures and methods made using the contents of this invention and the drawings are also included in the patent protection scope of the present invention.

Claims

1. A design method for a bent transition metal chalcogenide monolayer electrocatalyst for hydrogen evolution reaction, characterized in that: The following steps are involved: (1) An atomic model of a curved 2H-phase zigzag transition metal chalcogenide TMDs MX2 monolayer with uniform curvature was constructed based on the zigzag nanotube structure and shape; (2) performing first-principles molecular dynamics simulation on the atomic model constructed in step (1), and judging the structural stability of the atomic model based on the energy change and atomic structure of the system during the calculation time; (3) Based on the structural stability of the atomic model, an explicit solvation model was used to construct an adsorption model for aqueous hydrogen evolution reaction in a bent transition metal chalcogenide monolayer; (4) The adsorption model of the aqueous hydrogen evolution reaction constructed in step (3) was optimized using the first principle method. Based on the optimized structure, the adsorption energy ΔE of hydrogen atoms in the bent transition metal sulfide monolayer was calculated. H and the hydrogen adsorption Gibbs free energy ΔG H , according to the hydrogen adsorption Gibbs free energy ΔG H Determining the catalytic activity of bent transition metal chalcogenide monolayers; (5) increasing the curvature of the transition metal sulfide monolayer, repeating steps (1) to (4), and screening out a transition metal sulfide monolayer with good electrocatalytic activity for hydrogen evolution reaction and its corresponding curvature; (6) By calculating the limiting potential difference U between the carbon dioxide reduction reaction and the hydrogen evolution reaction L (CO2)-U L (H2) Determine the selectivity of the bent transition metal chalcogenide monolayer for the electrochemical hydrogen evolution reaction in step (5).

2. The design method according to claim 1, characterized in that: In step (1), in the monolayer transition metal chalcogenide TMDs MX2, M=Mo or W, and X=Te.

3. The design method according to claim 1, characterized in that: In step (1), the atomic model of the transition metal sulfide TMDs MX2 monolayer with a curved 2H phase zigzag nanotube structure and shape is constructed using Materials studio software.

4. The design method according to claim 1, characterized in that: In step (2), if the energy of the atomic model remains stable and the structure is not destroyed during the calculation time, the atomic model structure is judged to be stable.

5. The design method according to claim 1, characterized in that: Step (3) includes the following steps: constructing a curved TMDs MX2 monolayer atomic model using the atomic structure of the nanotube, and then using an explicit solvation model to add 3-4 layers of water molecules on top of the curved TMDs MX2 monolayer, and 2 layers of water molecules on both sides, and applying periodic boundary conditions on the x-axis, and setting of vacuum layer.

6. The design method according to claim 1, characterized in that: In step (4), the adsorption energy of hydrogen atom ΔE H The following formula (1) is used for calculation: in, is the total energy of hydrogen atoms adsorbed on TMD+H2O, It is the energy of TMD+H2O. is the energy of gas phase molecule H2.

7. The design method according to claim 1, characterized in that: In step (4), under the conditions of zero electrode potential and pH = 0, the hydrogen adsorption Gibbs free energy ΔG H The following formula (2) is used for calculation: ΔG H =ΔE H +ΔE ZPE -TΔS H (2) Where, ΔE H is the adsorption energy of the H atom, ΔE ZPE is the difference in zero-point vibration energy, T is the thermodynamic temperature, which is 298.15K, ΔS H It is the change in entropy when H atoms are adsorbed on TMD+H2O under standard atmospheric pressure.

8. The design method according to claim 1, characterized in that: In step (4), the hydrogen adsorption Gibbs free energy ΔG H The closer it is to 0 eV, the better the electrocatalytic activity for hydrogen evolution reaction.

9. The design method according to claim 1, characterized in that: In step (5), the curvature of the selected transition metal sulfide monolayer is 10. The design method according to claim 1, characterized in that: In step (6), U L (CO2) and U L (H2) is calculated using the following formula (10): in, It is the difference in Gibbs free energy of the carbon dioxide reduction reaction at U = 0 V or the Gibbs free energy of the hydrogen evolution reaction.

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