A method of reducing carbon dioxide graphene / low index copper catalyst

Abstract

The application discloses a method for reducing carbon dioxide graphene / low-index copper catalyst, constructs a graphene / Cu(100) structure through a Materials Studio software, uses a first principle tool VASP software tool, tests distances of graphene and a Cu(100) surface, finally, the optimal distance of the graphene / Cu(100) structure for a CO2RR reaction is established, then, the VASP software is used for structure optimization of configurations of various possible intermediates in a reaction process to obtain free energy, and it is tested that confinement can improve CO2 adsorption capacity and influence of a dimerization mechanism, through a free energy step diagram calculation method, it is found that the confinement effect can improve the eCO2RR performance of the Cu(100), and the purpose of enhancing the catalytic activity is achieved.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of electrocatalytic carbon dioxide, and particularly relates to a method for reducing carbon dioxide graphene / low-index copper catalyst. BACKGROUND

[0002] The increase in carbon dioxide (CO2) emissions and the growing demand for carbon-based materials have triggered research activities by many researchers to convert CO2 into chemicals and liquid fuels, particularly multi-carbon (C 2+ ) olefins and oxygenates, which play a crucial role in the current energy and chemical supply, such as fuel additives, plastics, disinfectants, and pharmaceuticals, etc.

[0003] In eCO2RR (electrocatalytic carbon dioxide reduction), the COOH intermediate formed after the first reaction step binds weakly for metals with higher oxygen affinity but lower hydrogen affinity than copper (such as indium, tin, mercury, and lead). Therefore, the main reduction product of CO2 reduction on these surfaces is HCOOH, and even the reaction can proceed through the O - -bound -OCHO intermediate. However, those metals with lower oxygen and hydrogen affinity (such as zinc, silver, and gold) can bind COOH more strongly than HCOO-. Thus, CO is the main product after the desorption of COOH after further hydrogenation, with CO2→COOH as the potential energy determining step (PDS). Other metals with higher oxygen affinity and hydrogen affinity than copper (including cobalt, nickel, iron, iridium, and platinum) tend to promote a competing hydrogen evolution reaction (HER), although small amounts of hydrocarbons and alcohols have been detected on these metal surfaces, only copper catalysts have been found to have a unique ability to continue to reduce CO2 into hydrocarbon products. Extensive experiments have shown that the activity and selectivity of eCO2RR can be significantly affected by the surface morphology of the copper electrode. Early experiments by Hori found that CH4 and C2H4 were the two main products on Cu(111) and Cu(100), and the C2 / C1 production ratio (0.2) of the Cu(111) surface was significantly lower than that of the Cu(100) surface under constant current conditions. However, despite various experimental and theoretical studies, the required overpotential of Cu electrocatalysts is relatively high (about 1 volt), which leads to low energy efficiency. The complexity of the electrochemical environment, high overpotential, and the inability to control product selectivity hinder the application and development of CO2 electroreduction.

[0004] In recent years, a great deal of research has been carried out to exploit the surface carbon layers formed on transition metals and to understand their role in catalytic reactions. Graphene, as a simple form of graphite deposit, has been grown on many transition surfaces by catalytic cracking of carbon-containing gases. Surface science studies have shown that gaseous molecules such as CO, O2 and H2O can easily intercalate under graphene coverings using defects in the graphene, providing channels for molecular diffusion into the graphene / metal interface. These new results have raised an interesting possibility that the space between the graphene cover and the metal substrate, through van der Waals interaction, can act as a two-dimensional container for reactions. The distance between the graphene cover and the metal surface is usually in the sub-nanometer range, and the molecules trapped inside interact directly with the graphene cover and the metal substrate. If catalytic reactions occur, they will be strongly constrained by confinement, and due to the confinement effect, extraordinary catalytic performance can occur.

[0005] Current growth of graphene on Cu surfaces has been proven to be feasible by adding cyanogen radicals to a hydrogen-methane plasma known to be able to etch copper at room temperature through plasma-enhanced chemical vapor deposition, removing the intrinsic oxide layer, and then growing graphene in neat alignment. However, there are still few catalytic reaction designs using this confined system, and the rich and complex physicochemical properties are in urgent need of theoretical research.

[0006] Existing experimental and theoretical calculation studies show that the electrocatalytic reduction of carbon dioxide to C2 products on low-index copper surfaces generally requires the application of a relatively high overpotential (about 1 volt). The mechanism of the first step of eCO2RR, i.e. the activation of CO2 on Cu, is not fully clear. First, the direct activation of inert CO2 molecules is challenging, requiring electron transfer to facilitate the generation of a chemisorbed, negatively charged, bent CO2 (denoted as CO2*), and only a breakthrough in the chemisorption activation of CO2 can make large-scale utilization of CO2 a reality, so promoting the ability of CO2 to chemisorb on Cu is also one of the goals. In addition to the activation of CO2 in the first step, CO is generally considered to be the precursor of common intermediates such as CH4, CH3OH and HCHO. However, CO and its subsequent intermediates can also be reduced to C2 products such as ethylene, acetaldehyde and ethanol through C-C coupling reactions between two carbon atoms. The formation of C2 products is very complex, but the key step is the C-C coupling reaction. There are two main mechanisms that can be used to describe this process. First, the dimerization of CO and electron transfer to generate a C2O2- intermediate, which is then converted to COCOH by protonation. This intermediate can be further reduced to C2H4, CH3CHO or CH3CH2OH. Another way is that the CO intermediate is further hydrogenated to form a CHO* or COH* intermediate, which can then be converted to C2OC-CHO* and OHC-CHO* species through non-electrochemical coupling reactions. Regardless of which mechanism is used, current studies show that on different low-index copper surfaces (such as (100), (111) and (211)), the dimerization reaction faces an insurmountable dimerization barrier (about 1.00 volts). The relationship between the activation energy and the binding energy of the intermediate seriously affects the selectivity of C2 products. This requires the catalytic site to be closely associated with the key intermediate to facilitate the next C-C coupling reaction, but not too tightly bound to avoid increasing the relevant activation barrier. This is one of the main reasons why the process of generating C 2+ products on low-index copper surfaces is limited. SUMMARY

[0007] The technical problem to be solved by the present application is how to improve the selectivity of electrocatalytic reduction of carbon dioxide to C2 products.

[0008] The present application solves the above technical problems by the following technical means:

[0009] The present application provides a method for reducing carbon dioxide graphene / low-index copper catalyst, comprising the following steps:

[0010] (1) Construct a graphene / Cu(100) model: use Material Studio software to construct a graphene / Cu(100) heterojunction geometric structure;

[0011] (2) Based on the structure obtained in step (1), a CO2 molecule adsorption model is constructed in the interlayer cavity of the graphene and Cu(100) heterojunction layer, with low index copper as the adsorption side, by using Material Studio modeling software;

[0012] (3) Controlling the graphene and Cu(100) layer spacing: based on the adsorption model, different layer spacing graphene / Cu(100) structure models are established by using Materials Studio modeling software;

[0013] (4) The different structures constructed in step (3) are optimized by using VASP software to obtain reasonable adsorption configurations, and the ground state energy of the system at different layer spacings is obtained;

[0014] (5) The ground state energy obtained in step (4) is calculated by adsorption energy, and the adsorption energy change of the system at different layer spacings is obtained by the formula E ads =E CO2 / slab -E slab -E CO2 The strongest adsorption energy system, i.e. the strongest CO2 activation system, is selected as the best system for the next reaction.

[0015] (6) Theoretical calculation of electrocatalytic reduction of CO2 by VASP, comparison of reaction paths, and drawing of Gibbs free energy change reaction path diagram, and finally determining the potential energy of graphene / Cu(100) and Cu(100) step Gibbs free energy, and comparing the graphene / Cu(100) with the lowest step Gibbs free energy as the catalyst for electrocatalytic reduction of carbon dioxide.

[0016] Beneficial effects: The present application limits graphene on Cu(100) theoretically, and experiments show that the graphene limiting method reduces the eCO2RR reaction barrier and improves the C2 product generation efficiency.

[0017] Further limited, the step (1) sets the lattice constant and angle of copper and graphene.

[0018] Further limited, the lattice constant of the copper is The lattice constant of the graphene is The angle of the copper and graphene is respectively α=β=γ=90°, α=β=90°, γ=120°.

[0019] Further limited, the lattice mismatch ratio is less than 5%.

[0020] Further limited, the different layer spacings in step (3) differ by

[0021] Further limit, the range of the different layer spacing is to

[0022] Further limit, the step (6) wherein the means of constant potential method, by examining the size of Gibbs free energy, determines the next synthesis of CO2 reduction intermediate CO* at the reaction potential.

[0023] Further limit, first by using Materials Studio modeling software to build the configuration of CO*, CHO*, COH* and OCCO*, by VESTA software, each built intermediate configuration is converted into POSCAR file, by adjusting the system electron number parameter NELECT in VASP, the constant potential condition is maintained.

[0024] Further limit, the Gibbs free energy (G=E elec +ZPE-TS) calculation is carried out by VASP software, wherein E elec represents the energy of the system ground state, ZPE represents zero point energy, S represents entropy, T represents temperature, the value is 298.15K, and the zero point energy and entropy value are obtained by vibration frequency calculation on the optimized structure.

[0025] Further limit, the reaction path of CO2 in step (6) is obtained, the activation of CO2 is through the conversion of CO2 from physical adsorption configuration to chemical adsorption configuration and then through the transfer of protons and electrons to obtain new reaction intermediates, and the ZPE and TS of each reaction intermediate are corrected, and finally the reaction path diagram of the change of Gibbs free energy of CO2 reduction to C2H4 is obtained.

[0026] Compared with the prior art, the advantages of the present application are:

[0027] The present application provides direct theoretical guidance through experimental research, compared with manual experiments, improves the screening speed, and avoids the energy, time and cost loss caused by a large number of trial and error experiments.

[0028] The present application limits graphene to Cu(100) in theory, and experiments find that the graphene limiting method reduces the eCO2RR reaction barrier and improves the C2 product generation efficiency. BRIEF DESCRIPTION OF DRAWINGS

[0029] Figure 1 is the design flow chart of the method of reducing carbon dioxide graphene / low-index copper catalyst;

[0030] Figure 2 is a structural schematic diagram of graphene / Cu(100);

[0031] Figure 3 is the energy diagram at each specific distance between graphene Cu(100) systems;

[0032] Figure 4 is the Gibbs free energy contrast diagram of further reactions of CO* at the reaction potential;

[0033] Figure 5 is the path diagram of electrochemical reduction of CO2 to generate CO*;

[0034] Figure 6 is the path diagram of electrochemical reduction of CO* to generate C2H4. DETAILED DESCRIPTION

[0035] In order to make the purposes, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be described clearly and completely below in combination with the embodiments of the present application. Obviously, the described embodiments are part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative labor fall within the scope of protection of the present application.

[0036] Embodiment 1

[0037] The method for reducing carbon dioxide graphene / low-index copper catalyst in this embodiment is specifically as follows:

[0038] Step 1, model construction

[0039] The Cu cell model in the Material project structure library is first optimized by VASP software to optimize the cell parameters and atomic positions, then the optimized cell is imported into Material Studio software, the symmetry of the cell is found through the Symmetry-Find symmetry module, and then the Cu cell is cut through the Cleave Surface module, wherein the crystal face index is set to (100) and the thickness is set to 4 layers, and then the Vacuum thickness option is set vacuum layer, and a (5*5) supercell of Cu(100) surface was constructed using Symmetry-Supercell. Then, a graphene model found in the Material project structure library was optimized using VASP, and the optimized structure was imported into Material Studio software. Afterwards, the square root surface was constructed by the Symmetry-Redefine lattice function, so that the lattice parameters in the x and y directions matched the previously constructed (5*5) Cu(100) surface. After the modeling of the above-mentioned heterojunction components, the two parts were combined by Build Layers to construct the graphene / Cu(100) heterojunction geometry. The lattice constants and angles of copper and graphene were α = β = γ = 90° and α = β = 90°, γ = 120°; after the (5*5) supercell of Cu(100) surface was constructed, the lattice mismatch ratio of the constructed heterojunction was 4.5%, which was less than 5%, meeting the conventional construction standard, as shown in Figure 2 .

[0040] Step 2, test the interlayer distance and construct the most stable structure

[0041] The adsorption configuration of chemisorbed CO2 was constructed in the above structure using Materials Studio modeling software, and the interlayer distance between Cu(100) and graphene was controlled in to with intervals. The change in adsorption energy of CO2 on graphene / Cu(100) was tested by using VASP software. When using VASP for calculation, the input files required for calculation (input files containing POSCAR, INCAR, KPOINTS, POTCAR and running script) need to be set. POTCAR is realized by vaspkit 103 block; KPOINTS: Gamma grid method is selected to calculate the integral in the Brillouin zone, and the K point is set to 2*2*1. INCAR: the interaction between electrons is described by BEEF-VDW functional under generalized gradient approximation, the valence band electron wave function is described by projected augmented plane wave pseudopotential basis, the energy convergence standard is 1*10 5 eV, the force convergence is not more than 0.01 eV, the cutoff energy is 450 eV, and the other parameters are the program default values. After the calculation, the corresponding CONTCAR is obtained, and the structure information can be visualized by importing the CONTCAR file into VESTA and Material Studio, and the energy information is extracted from the OSZICAR file by VASP calculation. Then, according to the energy criterion (E ads = ECO2 / slab -E slab -E CO2 ), select the structure with the strongest CO2 adsorption energy, i.e. as the final configuration, and fix this distance as the value of the graphene-Cu(100) distance throughout the eCO2RR reaction, as shown in Figure 3

[0042] Step 3, CO2 reduction to CO * Reaction path (compared to Cu(100))

[0043] Modeling was performed by Materials Studio and VESTA, and VASP was used to calculate each intermediate to analyze the effect of confinement on CO2 activation.

[0044] It was determined that adsorbed CO is an important intermediate in the eCO2RR, from which the reaction pathways lead to different products. Therefore, we began our mechanistic analysis by comparing the formation of CO from CO2 reduction in the eCO2RR on Cu(100) and graphene / Cu(100). * First, is the activation of CO2, which involves the transfer of electrons and the transformation of CO2 from a physisorbed configuration to a chemisorbed configuration. It was found that CO2 activation was significantly enhanced by confinement, with the Gibbs free energy change of CO2→CO2* changing from 0.94 eV on Cu(100) to 0.76 eV on graphene / Cu(100). After activation, the electrochemical hydrogenation of CO2 is experienced, where COOH was found to be the first electrochemical intermediate in the eCO2RR on Cu(100) and graphene / Cu(100). The results showed that the adsorption of COOH * was enhanced after confinement. Finally, COOH* was further reduced to CO* and a water molecule. In the eCO2RR process from CO2→CO*, we can find that confinement has a significant impact on the activation of CO2, effectively lowering the activation barrier of CO2 and accelerating the reaction rate of CO2→CO*, as shown in Figure 4

[0045] Step 4, comparison of the Gibbs free energy of the further hydrogenation of CO at the reaction potential

[0046] Various reaction intermediates were constructed using Materials Studio and VESTA, converted to POSCAR files. Free energy calculations were performed by VASP to determine that CO is more inclined to direct hydrogenation at the working potential of eCO2RR.

[0047] ​​CO as the key intermediate of the reaction determines the way of dimerization and the final product of eCO2RR to some extent, so it is necessary to investigate whether CO is first hydrogenated (CHO*, COH*) or first dimerized (OCCO*) at the reaction potential. We investigated the next step Gibbs of CO at the reaction potential by constant potential method. First, we constructed the configurations of CO, CHO*, COH* and OCCO* by using Materials Studio modeling software, and then converted each constructed intermediate configuration into a POSCAR file by VESTA software. It is worth noting that in order to maintain the constant potential condition, the charge number of the reactant intermediate needs to be adjusted, which can be achieved by setting the number of electrons in VASP. Then, we calculated the Gibbs free energy (G = E elec + ZPE-TS) by VASP software, where E elec represents the energy of the ground state of the system, ZPE represents the zero-point energy, S represents the entropy, and T represents the temperature, which is 298.15 K. The zero-point energy and entropy values are obtained by calculating the vibration frequency of the optimized structure. Since the eCO2RR reaction potential is usually carried out at -0.6 V vs. RHE and below, according to the reaction free energy curves of CO*→CHO*, CO*→COH* and CO*→OCCO* with increasing negative potential, at the working potential of eCO2RR, CO* tends to hydrogenate on C, i.e. form CHO* reaction intermediate, which has the most negative reaction free energy; on the contrary, hydrogenation on O is not dominant from the thermodynamic point of view. The reaction free energy of the other, direct dimerization of two CO*, is the largest, which has a reaction free energy of 0.55 eV at 0.6 V vs. RHE, and when the negative voltage continues to increase, the reaction Gibbs free energy does not reverse compared with the free energy of direct hydrogenation, and it can be obtained that for the graphene / Cu(100) system, CO tends to be directly hydrogenated rather than CO* direct dimerization, as shown in Figure 5 .

[0048] Step 5, CO * Continued reduction to C2H4 reaction path (compared with Cu(100))

[0049] By constructing the reaction intermediates by Materials Studio and VESTA, calculating the free energy of each intermediate by VASP, drawing the reaction path diagram of the change of Gibbs free energy, and analyzing the difference between graphene / Cu(100) and Cu(100).

[0050] After establishing the reaction path of CO2 reduction to CO and the influence of confinement on the overall performance, the next step is to continue to reduce CO* to C 2+The research and exploration of the product. In the process, we first model the potential reaction configurations of various reaction intermediates through Material Studio and VESTA software, then calculate each reaction intermediate through VASP, finally obtain the most stable reaction configuration in the reaction path, and correct the ZPE and TS of each reaction intermediate through frequency calculation, and finally obtain the reaction path diagram of the Gibbs free energy change of CO* reduction to C2H4. For the graphene / Cu(100) model, the first step is a proton-electron transfer process, forming CHO*, with a free energy change of 0.64 eV, which is an endothermic reaction; in the second step, two CHO* couple to form the OHCCHO* intermediate, with a reaction free energy of -0.33 eV, which is an exothermic reaction; the coupled OHCCHO* continues to be hydrogenated in the third step, which is a proton-electron transfer process, forming the OHCCHOH* intermediate, with a reaction free energy of 0.64 eV, which is an endothermic reaction; in the fourth step, the proton and electron continue to attack the O in OHCCHOH*, which is finally reduced to OHCCH* and a water molecule, with a reaction free energy of -1.17 eV, which is an exothermic reaction; in the fifth step, OHCCH* is hydrogenated, which is a proton-electron transfer process, generating the OHCCH2* intermediate, with a reaction free energy of -0.36 eV, which is an exothermic reaction; in the sixth step, the OHCCH2* intermediate is hydrogenated at the C end to generate CH2CH2O*, with a reaction free energy of 0.70 eV, which is an endothermic reaction and is also the potential determining step of this reaction, i.e., the maximum value of the Gibbs free energy change. The seventh step is a proton-electron transfer process in which the CH2CH2O* intermediate is hydrogenated at the O end to form the CH2CH2OH* intermediate, which is a weak endothermic process with a reaction free energy of 0.10 eV; finally, CH2CH2OH* is hydrogenated at the O end to generate water and C2H4 molecules, releasing 0.97 eV of heat, and the eCO2RR reaction is complete. Compared with Cu(100), the potential determining step changes from CO*CHO* to OHCCH2*CH2CH2O*, the maximum energy required for the reaction changes from 0.81 eV to 0.70 eV, and the effect of confinement is also obvious, effectively improving the conversion of Cu(100) to C 2+ The yield of the product, as shown in Figure 6 .

[0051] The present application provides a design method for significantly improving the selectivity of electrocatalytic carbon dioxide reduction reaction by limiting low-index copper with graphene confinement means. Compared with the prior art, we successfully enhanced the chemical adsorption capacity of CO2 on the copper surface. This enhanced adsorption is crucial for directly activating inert CO2 molecules and converting them into negatively charged chemisorbed bent CO2. In addition, for the key C-C coupling reaction, the presence of graphene confinement significantly reduces the potential barrier required for the reaction, thereby providing an effective route for the generation of C2 products such as ethylene. By optimizing the distance between graphene and the low-index Cu(100) surface, and through fine exploration of the optimal distance between graphene and the Cu(100) structure, the present application provides a method with high universality and controllability, which will have a profound impact on the further research and practical application of electrocatalytic carbon dioxide reduction.

[0052] In summary, by introducing graphene confinement, the present application not only optimizes the adsorption and activation process of CO2, but also promotes the generation of higher selective C2 products, thereby providing a highly efficient and industrially applicable method for large-scale utilization of CO2 from theoretical calculations.

[0053] Due to the constraints of experimental conditions and costs, the reaction mechanism of electrocatalytic reduction of CO2 on low-index copper is not fully disclosed, which leads to a lack of systematic theoretical guidance for the design of low-index copper catalysts. Therefore, how to improve the generation of C2 products from CO2 reduction cannot be predicted.

[0054] Based on first-principles calculations, the present application develops a method for screening catalysts with high selectivity for the generation of C2 products from carbon dioxide reduction, providing necessary theoretical guidance for experimental preparation and verification, promoting the research progress of new catalysts, and verifying the next step reaction of intermediate CO*, revealing the catalytic reaction mechanism.

[0055] For electrocatalytic materials, the present application designs graphene / Cu(100) with different interlayer distances, combines first-principles calculations, uses CO2 molecule adsorption model as the basis for judging material thermodynamic stability, and then uses first-principles calculation method to study the reaction mechanism of graphene / Cu(100) that meets the stability standard for electrocatalytic reduction of carbon dioxide, and screens out catalysts with high selectivity for carbon dioxide reduction performance.

[0056] The above examples are only used to illustrate the technical solutions of the present application, but not to limit it; although the present application has been described in detail with reference to the foregoing examples, those skilled in the art should understand that they can modify the technical solutions recorded in the foregoing examples, or make equivalent substitutions for part of the technical features; and these modifications or substitutions do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present application.

Claims

1. A method for constructing a graphene / low-index copper catalyst for reducing carbon dioxide, characterized in that, Includes the following steps: (1) Constructing a graphene / Cu(100) model: The graphene / Cu(100) heterojunction geometry was constructed using Material Studio software; the lattice constants and angles of copper and graphene were set; the lattice constant of copper was... The lattice constant of graphene is The angles of copper and graphene are α=β=γ=90°, α=β=90°, and γ=120°, respectively, and the lattice mismatch ratio is set to be less than 5%. (2) Based on the structure obtained in step (1), an adsorption model of CO2 molecules is constructed in the cavity between the graphene and Cu(100) heterojunction layers, with low-index surface copper as the adsorption side, using Material Studio modeling software. (3) Controlling the interlayer spacing between graphene and Cu(100): Based on the adsorption model, graphene / Cu(100) structure models with different interlayer spacings were established using Materials Studio modeling software; the differences between the different interlayer spacings were as follows: The range of different interlayer spacing is arrive (4) Use VASP software to optimize the different structures constructed in step (3) to obtain reasonable adsorption configurations and obtain the ground state energy of different interlayer spacings of the system; (5) Calculate the adsorption energy from the ground state energy obtained in step (4), using E ads =E CO2 / slab -E slab -E CO2 The formula yields the change in adsorption energy of the system under different interlayer spacings. The system with the strongest adsorption energy is selected as the optimal system for the subsequent reaction. (6) Using VASP, theoretical calculations were performed on the electrocatalytic reduction of CO2. The reaction pathways were compared, and a reaction pathway diagram showing the change in Gibbs free energy was drawn. Finally, the potential energy of graphene / Cu(100) and Cu(100) was compared, and graphene / Cu(100), with its lower Gibbs free energy, was selected as the catalyst for the electrocatalytic reduction of carbon dioxide. The free energy G=E was calculated using VASP software. elec +ZPE-TS calculation, where E elec The energy represents the ground state of the system, ZPE represents the zero-point energy, S represents the entropy, and T represents the temperature, with a value of 298.15 K. The zero-point energy and entropy values ​​are obtained by calculating the vibrational frequency of the optimized structure. The reaction pathway of CO2 is derived. The activation of CO2 is achieved through the transformation of CO2 from a physical adsorption configuration to a chemical adsorption configuration, followed by the transfer of protons and electrons to obtain new reaction intermediates. The ZPE and TS values ​​are corrected for each reaction intermediate to finally obtain the reaction pathway diagram of the Gibbs free energy change of CO2 reduction to C2H4.

2. The construction method according to claim 1, characterized in that, In step (6), the COOH* and CO* configurations are constructed using Materials Studio modeling software to perform VASP calculations and analyze the mechanism of CO* formation from CO2 reduction within the confinement domain.

3. The construction method according to claim 1, characterized in that, First, the configurations of CO*, CHO*, COH*, and OCCO* were constructed using Materials Studio modeling software. Then, each constructed intermediate configuration was converted into a POSCAR file using VESTA software. By adjusting the system electron number parameter NELECT in VASP, a constant potential condition was maintained.

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