A computational method for the preparation of formic acid by hydration reaction

Abstract

The application provides a calculation method for preparing formic acid through hydration reaction, comprising the following steps: constructing an adduct model of a carbonyl and a hydroxyl associated functional group added to a surface of a silver-loaded magnesia material; and in the presence of water molecules, analyzing a reaction process of obtaining formic acid from the surface of the silver-loaded magnesia material to which the carbonyl and the hydroxyl associated functional group are added, and predicting a reaction path of generating formic acid. The calculation method for preparing formic acid through hydration reaction provided by the application predicts the reaction path of generating formic acid by constructing the adduct model of the carbonyl and the hydroxyl associated functional group added to the surface of the silver-loaded magnesia material and calculating the reaction path of preparing formic acid through hydration reaction of the constructed model, thereby laying a theoretical foundation for related experimental exploration of preparing formic acid through hydration reaction of CO molecules on the surface of an oxide thin film composite material.

Description

Technical Field

[0001] This invention relates to the field of computational chemistry, and more specifically, to a computational method for preparing formic acid via a hydration reaction. Background Technology

[0002] When formic acid is transported in plastic pipes, it slowly decomposes into carbon monoxide and water at room temperature. The resulting carbon monoxide byproducts pose a significant safety hazard. How to treat and utilize carbon monoxide, and convert it back into formic acid, is an important research topic.

[0003] There are four traditional processes for producing formic acid: the formamide method, the butane (light oil) liquid-phase oxidation method to produce formic acid as a byproduct of acetic acid, the formate method, and the methyl formate hydrolysis method. Currently, due to advancements in technology and technological development, the formamide method and the butane (light oil) liquid-phase oxidation method have been phased out in industrial formic acid production. The current traditional formic acid production processes are mainly based on two main routes: the formate method and the methyl formate hydrolysis method. Among these, the methyl formate hydrolysis method dominates the global industrial production of formic acid.

[0004] The hydrolysis of methyl formate to methanol and formic acid has been commercialized by various companies, primarily developing four economically viable processes: the Kemira-Leonard process, the SD-Bethlehem process, the BASF process, and the USSR process. Methyl formate hydrolysis has been industrially practiced since the early 1980s, using CO as a raw material, and the reaction conditions for the first-stage carbonylation step of methanol with carbon monoxide in the liquid phase are largely similar.

[0005] Existing formic acid preparation processes have low atom utilization, require high reaction temperatures or harsh separation conditions, and produce byproducts that are difficult to separate. Furthermore, there is no theoretical route for producing formic acid using hydration reactions in traditional methods, nor are there corresponding calculation and prediction methods. Summary of the Invention

[0006] In view of this, the present invention provides a calculation method for the preparation of formic acid by hydration reaction, comprising:

[0007] An adduct model was constructed for the addition of carbonyl and hydroxyl-related functional groups to the surface of silver-supported magnesium oxide material; wherein, the hydroxyl and carbonyl groups in the carbonyl and hydroxyl-related functional groups have a weak correlation relationship, and each of the carbonyl and hydroxyl groups has an adsorption site;

[0008] With the assistance of water molecules, the reaction process of obtaining formic acid from the surface of silver-supported magnesium oxide material by the addition of carbonyl and hydroxyl related functional groups was analyzed according to the adduct model, and the reaction pathway for the formation of formic acid was predicted.

[0009] Preferably, the construction of the adduct model for the addition of carbonyl and hydroxyl related functional groups to the surface of silver-supported magnesium oxide material includes:

[0010] Surface supercell models of different magnesium oxide crystal planes and silver surfaces were constructed using Visual Molecular Dynamics and VESTA software; wherein the vacuum layer thickness of the surface supercell model is not less than

[0011] The surface supercell model was optimized using the Vienna Ab Initio Simulation Package to make CO molecules adsorb perpendicular to the magnesium surface, thus forming the optimized adduct model.

[0012] Preferably, after constructing the adduct model of carbonyl and hydroxyl related functional groups added to the surface of silver-supported magnesium oxide material, the method further includes:

[0013] Based on the adduct model, charge layout analysis is performed on the adduct on the surface of the silver-supported magnesium oxide material composed of carbonyl and hydroxyl related functional groups; and reaction pathways for generating the adduct are predicted; and local and electronic density of states analysis is performed on the adduct.

[0014] Preferably, the charge layout analysis of the adducts on the surface of the silver-supported magnesium oxide material composed of carbonyl and hydroxyl-related functional groups includes:

[0015] Charge calculations were performed on the surface supercell model using the Bader program to obtain the charge calculation results;

[0016] The differential charge density of the surface supercell model was calculated and analyzed using Visual Molecular Dynamics software.

[0017] The Bader program is used to calculate the charge of magnesium at the adsorption site, the atomic volume of CO, the charge of the silver substrate, and the negative charges of surface hydroxyl and hydrohydroxyl groups.

[0018] Preferably, the predicted reaction pathway for generating the adduct includes:

[0019] The reaction pathway for generating the adduct was calculated using density functional theory using the climbing elastic band method, and the reaction pathway was obtained.

[0020] Preferably, after performing density functional theory calculations on the reaction pathway for generating the adduct using the climbing elastic band method to obtain the reaction pathway, the method further includes:

[0021] Based on the climbing elastic band method, the transition state configuration structure characteristics were calculated using VTST software; and the activation energy barrier of CO and water molecules combining to form the adduct in the reaction pathway was analyzed using VTST software.

[0022] Preferably, the local and electronic density of states analysis of the adduct includes:

[0023] Electronic density of states analysis was performed using the p4vasp program to determine the interaction between CO and the water hydroxyl groups obtained from dissociation.

[0024] The local density of states of the hydroxyl group and the projected electronic density of states of the silver and oxygen atoms at the interface were calculated using the p4vasp program.

[0025] Preferably, the process of obtaining formic acid from the surface of silver-supported magnesium oxide material by the addition of carbonyl and hydroxyl related functional groups under the assistance of water molecules, according to the adduct model analysis, and the prediction of the reaction pathway for the formation of formic acid, includes:

[0026] The process of obtaining formic acid products on the surface of silver-supported magnesium oxide material was simulated with the assistance of water molecules.

[0027] Based on the process simulation, the charge mechanism in the process of obtaining formic acid products was analyzed;

[0028] Based on the intermediate with a carboxyl-related functional group obtained from the adduct, the reaction pathway for the formation of formic acid from the intermediate with the carboxyl-related functional group is predicted. The carboxyl-related functional group has two adsorption sites.

[0029] Preferably, the process of obtaining formic acid products on the surface of silver-supported magnesium oxide material with the assistance of water molecules includes:

[0030] A simulation model incorporating surface water molecules was constructed using Visual Molecular Dynamics software.

[0031] Based on the simulation model, calculate the total energy and structure of the first transition state;

[0032] The charge of the OC…OH adduct at the first transition state was calculated using the Bader program;

[0033] By examining the simulation model in the first transition state using the VESTA program, the double bond distance of carbonyl C=O and the single bond distance of CO can be determined to establish the bonding relationship between CO and the water hydroxyl group.

[0034] By examining the C=O double bond distance and CO single bond distance in the intermediate state of the simulation model using the VESTA program, the bonding between the carbonyl carbon atom and the hydrogen in water can be determined.

[0035] The total energy of the second transition state was calculated using the VESTA program; and the interactions of each chemical bond during the formation of formic acid were determined in the second transition state.

[0036] Preferably, the step of analyzing the charge mechanism in the process of obtaining formic acid products based on the process simulation includes:

[0037] Based on the process simulation, the charge reduction and charge accumulation of hydrogen and carbonyl oxygen molecules in the initial state were obtained using Visual Molecular Dynamics software, and the charge distribution of the first transition state, the intermediate state, and the second transition state were analyzed using Visual Molecular Dynamics software.

[0038] Preferably, predicting the reaction pathway for the formation of formic acid from the carboxyl-related functional group based on the carboxyl-related functional group obtained from the adduct includes:

[0039] The adsorption structure of the adduct was determined by density functional optimization calculations with dispersion correction performed using the Vienna Ab Initio Simulation Package software.

[0040] Based on the adsorption structure, the reaction mechanism is predicted using the climbing elastic band method.

[0041] The VESTA program was used to obtain the formation of O-Mg and C-Mg bonds in the carbonyl group;

[0042] The activation energy barrier for the transition state of the carboxyl-related functional group to form formic acid was calculated using the VTST program.

[0043] The charge layout of the transition state configuration of formic acid generated by the carboxyl-associated functional group was calculated using the Bader program.

[0044] Preferably, after analyzing the reaction process of obtaining formic acid from the surface of silver-supported magnesium oxide material by the addition of the carbonyl and hydroxyl related functional groups according to the adduct model with the assistance of water molecules, and predicting the reaction pathway for the formation of formic acid, the method further includes:

[0045] The influence mechanism of surface defects on formic acid formation was analyzed separately; and the influence mechanism of oxygen-magnesium co-defect surfaces on formic acid formation was analyzed separately.

[0046] Preferably, the analysis of the influence mechanism of the surface defects on the formation of formic acid includes:

[0047] On a magnesium-containing defect surface, the activation energy barrier for the conversion of carbon-oxygen bonds and hydroxyl bonds in the adduct to carboxyl groups is calculated and used as the first activation energy barrier;

[0048] On the oxygen-magnesium co-defect surface, the activation energy barrier for the conversion of carbon-oxygen bonds and hydroxyl bonds in the adduct to carboxyl groups is calculated and used as the second activation energy barrier;

[0049] The activation barrier for converting carbon-oxygen bonds and hydroxyl bonds in the adduct on a defect-free surface into carboxyl groups is used as the third activation barrier; and the first and second activation barriers are compared with the third activation barrier to determine the effect of the surface defects on the formation of formic acid.

[0050] Preferably, the analysis of the influence mechanism of the oxygen-magnesium co-defect surface on the formation of formic acid includes:

[0051] The activation energy barrier for the formation of formic acid was calculated using the VTST program;

[0052] Optimization calculations using the Vienna Ab Initio Simulation Package software show the O-Mg distance between the water hydroxyl group and the surface magnesium.

[0053] The charges carried by the oxygen and hydrogen in the hydroxyl group, as well as the charges of the carbon and oxygen in the carbonyl group, were calculated using the Bader program.

[0054] Hamiltonian crystal orbital layout of the major chemical bonds at active sites was calculated using the LOBSTER program.

[0055] This invention provides a computational method for preparing formic acid via a hydration reaction, comprising: constructing an adduct model of carbonyl and hydroxyl-related functional groups adducting onto the surface of a silver-supported magnesium oxide material; wherein, the hydroxyl and carbonyl groups in the carbonyl and hydroxyl-related functional groups have a weak correlation, and each of the carbonyl and hydroxyl groups has an adsorption site; with the assistance of water molecules, analyzing the reaction process of obtaining formic acid from the surface of the silver-supported magnesium oxide material by the adducting of the carbonyl and hydroxyl-related functional groups according to the adduct model, and predicting the reaction pathway for the formation of formic acid. The calculation method for preparing formic acid by hydration reaction provided by this invention constructs an adduct model of carbonyl and hydroxyl functional groups added to the surface of silver-supported magnesium oxide material, and calculates the reaction path for the preparation of formic acid by hydration reaction using the constructed model. The reaction path for preparing formic acid by hydration reaction calculated by the method provided by this invention has 100% atom utilization, does not produce difficult-to-separate or highly toxic byproducts, and has a low reaction energy barrier. It points the way for novel experimental preparation process of formic acid by hydration reaction and lays the theoretical foundation for related experimental exploration of the preparation of formic acid by hydration reaction of CO molecules on the surface of oxide thin film composite materials. Attached Figure Description

[0056] Figure 1 This is a schematic flowchart of the calculation method for preparing formic acid by hydration reaction according to the present invention in the first embodiment;

[0057] Figure 1a This is a detailed flowchart of step S100 in the first embodiment of the calculation method for preparing formic acid by hydration reaction of the present invention.

[0058] Figure 1b , 1c 1d represents the construction and analysis of the adduct model in the first embodiment of the calculation method for the preparation of formic acid by hydration reaction of the present invention; including:

[0059] Figure 1b This is a differential charge density image of CO and water co-adsorbed on the surface of the composite material, with the charge density isosurface at 0.002e Bohr. -3 ;

[0060] Figure 1c Potential energy curves for the reaction of CO with water molecules to form adducts;

[0061] Figure 1d This is a local density of states analysis diagram of the adduct in the adduct model;

[0062] Figure 2 This is a schematic diagram of the process after step S200 (S300-S500) in the second embodiment of the calculation method for preparing formic acid by hydration reaction of the present invention.

[0063] Figure 2a This is a detailed flowchart of step S300 in the second embodiment of the calculation method for preparing formic acid by hydration reaction of the present invention.

[0064] Figure 2b This is a detailed flowchart of step S400 in the second embodiment of the calculation method for preparing formic acid by hydration reaction of the present invention.

[0065] Figure 2c This is a detailed flowchart of step S500 in the second embodiment of the calculation method for preparing formic acid by hydration reaction of the present invention.

[0066] Figure 3 This is a detailed flowchart of step S200 in the third embodiment of the calculation method for preparing formic acid by hydration reaction of the present invention.

[0067] Figure 3a The reaction potential energy curve of formic acid production by hydration reaction in the third embodiment of the calculation method for preparing formic acid by hydration reaction of the present invention is shown.

[0068] Figure 3b Differential charge density diagram of formic acid generation reaction on the surface of magnesium oxide composite material in the third embodiment of the calculation method for preparing formic acid by hydration reaction of the present invention;

[0069] Figure 3cThe third embodiment of the calculation method for preparing formic acid by hydration reaction of the present invention shows the reaction energy barrier, transition state and potential energy curve of the conversion of the adduct into the intermediate (carboxyl-related functional group) (a) and the generation of formic acid from the intermediate (b).

[0070] Figure 4 This is a schematic flowchart of the fourth embodiment of the calculation method for preparing formic acid by hydration reaction according to the present invention;

[0071] Figure 4a This is a flowchart illustrating the refinement of step S600 (S610-S630) in the fourth embodiment of the calculation method for preparing formic acid by hydration reaction of the present invention.

[0072] Figure 4b This is a flowchart illustrating the refinement of step S600 (S640-S670) in the fourth embodiment of the calculation method for preparing formic acid by hydration reaction of the present invention.

[0073] Figure 4c This is a schematic diagram of the geometric structure and charge layout of formic acid formation on the surface of a magnesium oxide thin film composite material with magnesium defects in the fourth embodiment of the calculation method for preparing formic acid by hydration reaction of the present invention.

[0074] Figure 4d This is a schematic diagram of the reaction mechanism for the generation of formic acid on the surface of a magnesium oxide film with magnesium defects in the fourth embodiment of the calculation method for preparing formic acid by hydration reaction of the present invention.

[0075] Figure 4e This is a schematic diagram of the formic acid generation reaction path on the surface of a magnesium oxide thin film composite material with oxygen-magnesium co-defects in the fourth embodiment of the calculation method for preparing formic acid by hydration reaction of the present invention.

[0076] Figure 4f This is a schematic diagram of COHP bonding in the formic acid generation reaction on the surface of a magnesium oxide thin film composite material with magnesium-oxygen co-defects, as described in the fourth embodiment of the calculation method for preparing formic acid by hydration reaction of the present invention.

[0077] The realization of the objective, functional features and advantages of the present invention will be further explained in conjunction with the embodiments and with reference to the accompanying drawings. Detailed Implementation

[0078] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. 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.

[0079] Unless otherwise defined below, all technical and scientific terms used in the specific embodiments of this invention are intended to have the same meaning as commonly understood by those skilled in the art. While it is believed that the following terms will be well understood by those skilled in the art, the following definitions are set forth to better explain the invention.

[0080] As used in this invention, the terms “comprising,” “including,” “having,” “containing,” or “involving” are inclusive or open-ended and do not exclude other unlisted elements or method steps. The term “consisting of” is considered a preferred embodiment of the term “comprising.” If a group is defined below as comprising at least a certain number of embodiments, this should also be understood to disclose a group that preferably consists only of those embodiments.

[0081] When referring to a singular noun, the indefinite or definite article used, such as "a" or "a kind of," "the," includes the plural form of the noun.

[0082] The term "approximately" in this invention refers to an accuracy range that, as would be understood by those skilled in the art, still guarantees the technical effects of the features in question. This term typically indicates a deviation from the indicated value of ±10%, preferably ±5%.

[0083] Furthermore, the terms first, second, third, (a), (b), (c), and similar terms used in the specification and claims are for distinguishing similar elements and are not necessary for the order of description or chronological sequence. It should be understood that such terms are interchangeable in appropriate contexts, and the embodiments described in this invention can be implemented in a different order than that described or illustrated in this invention.

[0084] The following is provided merely to aid in understanding the invention. These definitions should not be construed as having a scope less than that understood by those skilled in the art.

[0085] The technical solution of the present invention will be further described in detail below with reference to specific embodiments, but this does not constitute any limitation on the present invention. Any limited modifications made by any person within the scope of the claims of the present invention are still within the scope of the claims of the present invention.

[0086] Example 1:

[0087] Reference Figure 1 The first embodiment of the present invention provides a calculation method for the preparation of formic acid by hydration reaction, comprising:

[0088] Step S100: Construct an adduct model of carbonyl and hydroxyl related functional groups adducting onto the surface of silver-supported magnesium oxide material; wherein, the hydroxyl and carbonyl groups in the carbonyl and hydroxyl related functional groups have a weak correlation relationship, and each of the carbonyl and hydroxyl groups has an adsorption site.

[0089] The carbonyl and hydroxyl related functional groups mentioned above can be represented as *O=C…*OH, where “…” indicates a weak correlation, and the “*” before the carbonyl O=C and hydroxyl OH are adsorption sites.

[0090] The adduct model described above is a surface supercell model with magnesium oxide silver crystal faces and a silver surface, wherein the surface is equipped with *O=C…*OH functional groups. The adduct model is referenced in the appendix. Figure 1b For the analysis of this adduct model, the potential energy curve of the reaction between CO and water molecules to form the adduct is attached. Figure 1c The local density of states analysis of the surface *O=C…*OH adduct of its composite structure is shown in the attached reference. Figure 1d .

[0091] In step S200, with the assistance of water molecules, the reaction process of obtaining formic acid from the surface of silver-supported magnesium oxide material by the addition of carbonyl and hydroxyl related functional groups is analyzed according to the adduct model, and the reaction pathway for the formation of formic acid is predicted.

[0092] The above-described reaction process is the process by which formic acid is generated on the surface of silver-supported magnesium oxide material, which is composed of carbonyl and hydroxyl functional groups, through a hydration reaction.

[0093] The hydration reaction, also known as water hydration, is a chemical reaction in inorganic chemistry that occurs when a substance dissolves in water. It generally refers to the process by which solute molecules (or ions) react with water molecules to form hydrated molecules (or hydrated ions). The hydration reaction of this invention can be represented as follows:

[0094]

[0095] The reaction catalyst is a MgO / Ag composite material.

[0096] Further reference Figure 1a Step S100, constructing an adduct model of carbonyl and hydroxyl related functional groups on the surface of silver-supported magnesium oxide material, includes:

[0097] Step S110: Construct surface supercell models of different magnesium oxide crystal planes and silver surfaces using Visual Molecular Dynamics and VESTA software; wherein the vacuum layer thickness of the surface supercell model is not less than...

[0098] It should be noted that Visual Molecular Dynamics (VDM) is a molecular graphics software specifically designed for modeling, visualizing, and analyzing biological macromolecules (such as proteins and nucleic acids). It can read and display PDB files, offers various analysis and visualization options and rendering methods, and can also process and analyze trajectories from molecular dynamics (MD) simulations.

[0099] It should be noted that VESTA (Visualization for Electronic and Structural Analysis) is a professional software for visualizing crystal and electronic structures. VESTA can easily perform a range of functions, including crystal structure modeling, viewing structural information, adjusting crystal structure parameters, displaying appearance, outputting images, and converting data formats.

[0100] Step S120: The surface supercell model is optimized using the Vienna Ab Initio Simulation Package to make CO molecules adsorb perpendicular to the magnesium surface, forming the optimized adduct model.

[0101] Supercell models of different magnesium oxide crystal planes and silver surfaces were constructed using Visual Molecular Dynamics and VESTA software, where the vacuum layer thickness was not less than [missing information]. After optimization using the Vienna Ab Initio SimulationPackage, in the initial state, CO molecules adsorb perpendicularly to the magnesium surface, and the distance between the C-Mg bonds is... The distance between C-Ow bonds is

[0102] The calculation method for preparing formic acid by hydration reaction provided in this embodiment constructs an adduct model of carbonyl and hydroxyl related functional groups added to the surface of silver-supported magnesium oxide material, and calculates the reaction path for the preparation of formic acid by hydration reaction using the constructed model, predicting the reaction path for the formation of formic acid. This lays a theoretical foundation for related experimental explorations on the preparation of formic acid by hydration reaction of CO molecules on the surface of oxide thin film composite materials.

[0103] Example 2:

[0104] refer to Figure 2 Based on Example 1, the second embodiment of the present invention provides a calculation method for the preparation of formic acid by hydration reaction, wherein, after constructing the adduct model of carbonyl and hydroxyl related functional groups on the surface of silver-supported magnesium oxide material in step S100, the method further includes:

[0105] Step S300: Based on the adduct model, perform charge layout analysis on the adduct on the surface of the silver-supported magnesium oxide material composed of carbonyl and hydroxyl related functional groups; and Step S400: Predict the reaction pathway for generating the adduct; and Step S500: Perform local and electronic density of states analysis on the adduct.

[0106] The order of steps S300, S400, and S500 described above can be performed simultaneously, or any one step can be performed first. The execution order shown in the accompanying drawings is only to illustrate one implementation method.

[0107] refer to Figure 2a Step S300, the charge layout analysis of the adducts on the surface of the silver-supported magnesium oxide material composed of carbonyl and hydroxyl related functional groups, includes:

[0108] Step S310: Perform charge calculation on the surface supercell model using the Bader program to obtain the charge calculation results;

[0109] Based on Bader charge calculations, the calculated charge result is that CO carries a negative charge of 0.072|e|. From this charge calculation, it can be concluded that due to the induction of strongly electron-withdrawing groups, O... w A large area around H (water hydroxyl group, w represents water, the same below) exhibits an electron aggregation phenomenon.

[0110] Step S320: Perform differential charge density calculation and analysis on the surface supercell model using Visual Molecular Dynamics software;

[0111] Differential charge density was calculated and analyzed using VMD software. Due to hydrogen bonding, surface oxygen O2 at the reaction sites... s (s represents surface, the same below) The electron-withdrawing ability of surface magnesium and interfacial silver is reduced, O s Electron reduction occurs around H (surface hydroxyl group) and below silver atoms.

[0112] Step S330: Calculate the charge of magnesium at the adsorption site, the atomic volume of CO, the charge of the silver substrate, and the negative charges of surface hydroxyl and hydrohydroxyl groups using the Bader program.

[0113] Calculations using the Bader program show that the magnesium at the adsorption site is positively charged with +1.671|e|. The Bader program also calculates that due to adsorption, the atomic volume of CO decreases to [value missing]. Calculations using the Bader program show that the silver substrate carries a negative charge of -1.087|e|, which can be considered as an electron storage device. The surface hydroxyl groups (O) were calculated using the Bader program.s The negative charge of H (-0.829|e|) is significantly less than that of the water hydroxyl group O. w The H (-0.906|e|) indicates that the surface hydroxyl group is more reactive and may be able to abstract more electrons from neighboring adsorbates. The surface hydroxyl group in the transition state exhibits a lower charge value of -0.666|e|, indicating high reactivity.

[0114] Step S400, predicting the reaction pathway for generating the adduct, includes:

[0115] Step S410: Density functional theory calculations are performed on the reaction path for generating the adduct using the climbing elastic band method to obtain the reaction path.

[0116] Density functional theory calculations were performed to investigate the adduct formation pathway of carbonyl and hydroxyl-related functional groups on the surface of silver-supported magnesium oxide material using the climbing image nudged elastic band (CI-NEB) technique.

[0117] As mentioned above, density functional theory (DFT) is a quantum mechanical method for studying the electronic structure of multi-electron systems. DFT has wide applications in physics and chemistry, particularly in studying the properties of molecules and condensed matter physics, and is one of the most commonly used methods in condensed matter physics and computational chemistry.

[0118] Further reference Figure 2b In step S410, after performing density functional theory calculations on the reaction pathway for generating the adduct using the climbing elastic band method to obtain the reaction pathway, the method further includes:

[0119] Step S420: Based on the climbing elastic band method, the transition state configuration structural characteristics are calculated using VTST software; and the activation energy barrier of CO and water molecules combining to form the adduct in the reaction pathway is analyzed using VTST software.

[0120] The above analysis using VTST software to calculate the transition state configuration characteristics reveals that it exhibits a shorter CO2... w distance The C-Mg and carbonyl CO bond lengths were extended to and Furthermore, analysis using VTST software revealed that the activation barrier of the adduct formed by the combination of carbon monoxide and water molecules to form *O=C…*OH (carbonyl and hydroxyl related functional groups) was 0.29 eV.

[0121] In this embodiment, density functional theory calculations were performed using VTST software and climbing image nudged elastic band (CI-NEB) technology to analyze the reaction pathway of the adduct (an adduct of carbonyl and hydroxyl related functional groups on the surface of silver-supported magnesium oxide material). The activation barrier for the combination of carbon monoxide and water molecules to form the adduct is 0.29 eV. Figure 1c The calculated transition state configuration exhibits a shorter CO2 length. w distance The C-Mg and carbonyl CO bond lengths were extended to and

[0122] Further reference Figure 2c Step S500 involves performing local and electronic density of states analysis on the adduct, including:

[0123] Step S510: Perform electronic density of states analysis using the p4vasp program to determine the interaction between CO and the water hydroxyl groups obtained from dissociation;

[0124] As mentioned above, p4vasp is a graphical processing software that can be used to draw and adjust band density of states diagrams, view electronic structure DOS, surface electrostatic potential output, STM surface output, K-point, and dynamic data output, etc.

[0125] Electronic density of states analysis using the p4vasp program reveals the interaction between CO and the water hydroxyl groups (O2) that have dissociated from CO. w There are many coincidence density peaks between H), and coincidence density peaks also appear at a position above the Fermi level of 2.30 eV, which proves that CO and O w There is an interaction between H.

[0126] In step S520, the local density of states of the hydroxyl group and the projected electronic density of states of the silver and oxygen atoms at the interface are calculated using the p4vasp program.

[0127] In this embodiment, the local state density of hydroxyl groups is obtained using the p4vasp program. Compared to O w H, O s The H electronic state density appears at low energy levels, indicating that O s H exhibits high chemical stability, making it difficult for the hydroxyl group to undergo dehydrogenation reactions. Furthermore, the projected electronic density of states of the interfacial silver and oxygen atoms, obtained using the p4vasp program, shows hybridization, resulting in a significant occupation of the 2p electron state by the oxygen atom near the Fermi level. "OC…OH", CO, OwH, and Mgs show hybridization density of states peaks at energy levels of -2 eV, -2.9 eV, -4.8 eV, -5.3 eV, -6.6 eV, -7.3 eV, and -9 eV.

[0128] Example 3:

[0129] Reference Figure 3 Based on Example 2, the third embodiment of the present invention provides a calculation method for preparing formic acid by hydration reaction. In step 200, with the assistance of water molecules, the reaction process of obtaining formic acid from the surface of silver-supported magnesium oxide material by the addition of the carbonyl and hydroxyl related functional groups is analyzed according to the adduct model, and the reaction pathway for the formation of formic acid is predicted, including:

[0130] Step 210: With the assistance of water molecules, process simulation is performed to obtain formic acid products on the surface of silver-supported magnesium oxide material;

[0131] To activate surface hydrogen and catalyze further strong bonding between CO and water hydroxyl groups, in this embodiment, another water molecule was introduced via a VMD procedure (see reference). Figure 3a Water molecules can react with surface hydroxyl groups (O). s H forms hydrogen bonds.

[0132] Step 220: Based on the process simulation, analyze the charge mechanism in the process of obtaining formic acid products;

[0133] Step 230: Based on the intermediate with a carboxyl-related functional group obtained from the adduct, predict the reaction pathway for the formation of formic acid from the intermediate with the carboxyl-related functional group. The carboxyl-related functional group has two adsorption sites.

[0134] Step 210, simulating the process of obtaining formic acid products on the surface of silver-supported magnesium oxide material with the assistance of water molecules, includes:

[0135] Step 211: Construct a simulation model of surface water molecules using Visual Molecular Dynamics software;

[0136] To activate surface hydrogen and catalyze further strong bonding between CO and water hydroxyl groups, surface water molecules were introduced by constructing a model using a VMD program.

[0137] Calculations using the Vienna Ab Initio Package software showed that water molecules can form hydrogen bonds with surface hydroxyl groups OsH, and the initial O w The distance between -Mg bonds is

[0138] Step 212: Calculate the total energy and structure of the first transition state based on the simulation model;

[0139] The first transition state is TS1.

[0140] Step 213: Calculate the charge of the OC…OH adduct at the first transition state using the Bader program;

[0141] The charge of the OC…OH adduct in the first transition state (TS1) was calculated to be -0.833|e| using the Bader program.

[0142] Step 214: Use the VESTA program to view the double bond distance of carbonyl C=O and the single bond distance of CO in the first transition state of the simulation model to determine the bonding effect between CO and the water hydroxyl group;

[0143] Using the VESTA program, the distance between the C=O double bonds in the TS1 state is [value missing]. The distance between CO and CO is much longer. This indicates that there is a partial bond between CO and the hydroxyl group in water.

[0144] Step 215: Use the VESTA program to check the double bond distance of C=O and the single bond distance of CO in the intermediate state of the simulation model to determine the bonding between the carbonyl carbon atom and the hydrogen in water.

[0145] Using the VESTA program, the carbonyl C=O distance in the intermediate state (IM) is [value missing]. The distance between CO bonds is It is not much different from the transition state. However, the carbon atom of the carbonyl group reacts with water and hydrogen (H) w (and bind with surface oxygen) approach each other, CH w The distance from Reduce to For CH w This laid the foundation for further bonding interactions.

[0146] Step 216: Calculate the total energy of the second transition state using the VESTA program; and determine the interaction of each chemical bond during the formation of formic acid in the second transition state.

[0147] As shown above, the VTST program can be used to calculate and analyze that the second transition state is TS2, with an energy 0.188 eV higher than the initial state. Here, the initial state is IS relative to the initial state preceding TS1.

[0148] As described above, under the second transition state TS2 obtained through the VESTA program, CH w The distance has been further shortened to When formic acid is generated on a magnesium oxide film, the hydroxyl groups of formic acid react with the O-Mg bonds on the surface (at a distance of...). The interaction between the hydroxyl groups promotes the desorption of formic acid from the magnesium oxide surface. In the final state, the hydrohydroxyl groups form strengthened O-Mg bonds, and the distance between the O-Mg bonds is shortened. The interaction between hydrogen formate and the water hydroxyl group changes from a strong covalent bond to a weak hydrogen bond (CH…OH), with a hydrogen bond distance of [missing value].

[0149] In this embodiment, to activate surface hydrogen, another water molecule is introduced to catalyze further strong bonding between CO and water hydroxyl groups. The water molecule can react with surface hydroxyl groups O. s H forms hydrogen bonds, initially O w The distance between -Mg bonds is The first transition state (TS1) exhibits a total energy and structure close to the initial state, while the charge of the OC…OH adduct (-0.833|e|) at TS1 is almost identical to that of the initial state. In the TS1 state, the C=O double bond distance is... The distance between CO and CO is much longer. This indicates a partial bonding relationship between CO and the hydroquinone group. In the intermediate state (IM), the carbonyl C=O distance is... The distance between CO bonds is It is not much different from the transition state. However, the carbon atom of the carbonyl group reacts with water and hydrogen (H) w (and bind with surface oxygen) approach each other, CH w The distance from Reduce to For CH w Further bonding interactions are established. The energy of TS2 is 0.188 eV higher than that of the initial state. In the TS2 state, the C-Hw distance is further shortened to... When formic acid is generated on a magnesium oxide film, the hydroxyl groups of formic acid react with the O-Mg bonds on the surface (at a distance of...). The interaction between the formic acid and the hydroxyl group facilitates the desorption of formic acid from the magnesium oxide surface. Furthermore, in the final state, the hydrohydroxyl group forms a strengthened O-Mg bond, the distance between the O-Mg bonds shortens, and the interaction between the hydrogen formic acid and the hydrohydroxyl group changes from a strong covalent bond to a weak hydrogen bond (CH…OH).

[0150] Furthermore, step 220, based on the process simulation, analyzes the charge mechanism in the process of obtaining formic acid products, including:

[0151] Step 221: Based on the process simulation, the charge reduction and charge accumulation of hydrogen and carbonyl oxygen in the initial state of water molecules are obtained by using Visual Molecular Dynamics software, and the charge distribution of the first transition state, the intermediate state and the second transition state are analyzed by using Visual Molecular Dynamics software.

[0152] As described above, the VMD program revealed that in the initial state, hydrogen and carbonyl oxygen molecules in water molecules exhibited charge reduction and charge accumulation, respectively. Surface hydrohydroxyl groups also showed charge reduction.

[0153] Analysis of the transition state charge distribution using the VMD program revealed a significant charge accumulation effect on the carbonyl carbon in the transition state structure. This is attributed to the strong interaction between hydrogen atoms in the water molecule and the carbon atom. Compared to the initial state, the atom interacting with hydrogen atoms in the transition state is now a carbon atom (initially an oxygen atom). The electron affinity of carbon atoms is lower than that of oxygen, resulting in less charge transfer between the water molecule and the carbonyl group, weakening the interaction, and increasing the system energy.

[0154] Analysis of intermediate charge distribution using VMD program: In intermediate configuration, CH w The connection reveals a more pronounced charge accumulation pattern. Analysis of the TS2 transition state charge distribution using VMD software shows that the water molecule structure is distorted, with hydrogen atoms forming chemical bonds with carbonyl groups, while the OH bonds within the water molecule itself are broken. In the product configuration, significant charge reduction occurs around the hydrogen atoms of the HCOO- group, and CH bonds are formed. The differential charge density of the formic acid formation reaction on the magnesium oxide composite surface is shown in the attached reference. Figure 3b .

[0155] Step 230, based on the carboxyl-related functional group obtained from the adduct, predicts the reaction pathway for the formation of formic acid from the carboxyl-related functional group, including:

[0156] Step 231: Perform density functional optimization calculations with dispersion correction using the Vienna Ab Initio Simulation Package software to determine the adsorption structure of the adduct;

[0157] The above-mentioned density functional optimization calculations with dispersion correction were carried out using the Vienna Ab Initio Simulation Package software. The adduct (*CO…*OH) with carbonyl and hydroxyl related functional groups has an adsorption structure in which carbon and hydroxyl oxygen are adsorbed on the magnesium surface.

[0158] Step 232: Based on the adsorption structure, predict the reaction mechanism using the climbing elastic band method;

[0159] The reaction mechanism was predicted using CI-NEB technology, and it was found that the structure can be transferred to the carboxyl-related functional group (**O=C-OH, where * represents the adsorption site), and carbon and carbonyl oxygen are adsorbed on the magnesium surface.

[0160] Step 233: Using the VESTA program, O-Mg and C-Mg bonds are formed on the carbonyl group;

[0161] Using the VESTA program, it was found that the carbonyl group forms O-Mg and C-Mg bonds, with distances of respectively. and

[0162] Step 234: Calculate the activation barrier of the transition state of the carboxyl-related functional group to form formic acid using the VTST program;

[0163] Calculations using the VTST program show that the reaction to generate formic acid via the carboxyl-related functional group (**O=C-OH) configuration proceeds through a transition state with an activation barrier of 1.133 eV.

[0164] Step 235: Calculate the charge layout of the transition state configuration of the carboxyl-related functional group to form formic acid using the Bader program.

[0165] Charge distribution calculations were performed on the transition state configuration for formic acid production using the Bader program: Hydrogen atoms are covalently bonded to two oxygen atoms, with a charge value of 0.526|e|. The HCOO- group carries a negative charge of 0.861|e|, and the oxygen atom carries a negative charge of -1.237|e|. The oxygen atom furthest from the surface carries a negative charge of -1.170|e|, indicating a sudden change in charge state on the magnesium surface (the bond length of the adsorbed CO bond is...). The change in the charge state of the carboxyl group laid the foundation for the transformation of the CO single bond to the C=O double bond on the oxide surface. In the product configuration, the formyl oxygen adsorbed on the magnesium surface carries a negative charge of -1.311|e|, while the oxygen farther from the magnesium surface carries an even smaller negative charge of -1.146|e|, indicating that the adsorbed CO bond is a double bond. The other CO bond perpendicular to the magnesium surface is a single bond. The reaction involves the formation of a carboxyl-related functional group from a carbonyl and hydroxyl group, followed by the formation of formic acid from the carboxyl-related functional group. The reaction energy barrier, transition state, and potential energy curves are shown in the attached diagram. Figure 3c .

[0166] Example 4:

[0167] Reference Figure 4 Based on Example 1, the fourth embodiment of the present invention provides a calculation method for preparing formic acid by hydration reaction. Specifically, step 200, after analyzing the reaction process of obtaining formic acid from the surface of silver-supported magnesium oxide material by the addition of the carbonyl and hydroxyl functional groups according to the adduct model with the assistance of water molecules, and predicting the reaction pathway for the formation of formic acid, further includes:

[0168] Step 600 involves analyzing the influence mechanism of surface defects on formic acid formation, and analyzing the influence mechanism of oxygen-magnesium co-defect surfaces on formic acid formation.

[0169] After predicting the reaction pathway for formic acid formation and analyzing the reaction process, we considered whether surface defects would affect formic acid formation. To address this, we conducted separate analyses of the influence mechanisms of surface defects on formic acid formation and the influence mechanisms of oxygen-magnesium co-defect surfaces on formic acid formation.

[0170] Further reference Figure 4a In step 600, the analysis of the influence mechanism of surface defects on the formation of formic acid includes:

[0171] Step 610: On the magnesium-containing defect surface, calculate the activation energy barrier for the conversion of carbon-oxygen bonds and hydroxyl bonds in the adduct into carboxyl groups, and use it as the first activation energy barrier;

[0172] Step 620: On the oxygen-magnesium co-defect surface, calculate the activation energy barrier for the conversion of carbon-oxygen bonds and hydroxyl bonds in the adduct to carboxyl groups, as the second activation energy barrier;

[0173] Step 630: The activation barrier for converting carbon-oxygen bonds and hydroxyl bonds in the adduct on the defect-free surface into carboxyl groups is taken as the third activation barrier; and the first activation barrier and the second activation barrier are compared with the third activation barrier to determine the effect of the surface defects on the formation of formic acid.

[0174] Considering the influence of surface defects on the formation of carboxyl-related functional groups (**O=C-OH), on surfaces containing magnesium defects, the adducts *CO…*OH can be converted into carboxyl groups (**O=C-OH). Using CI-NEB technology, the activation barrier is 1.158 eV, which is 25 meV higher than that of perfect magnesium oxide (001) films.

[0175] refer to Figure 4c and Figure 4d The effects of surface defects and dual defects on the formation of **O=C-OH were considered using the VTST program. The reaction potential energy curves of surfaces with magnesium-oxygen co-defects were calculated using CI-NEB technology: the activation energy barrier of the phase transition reaction was 49 meV higher than that of perfect magnesium oxide (001) films. Therefore, surface defects do not increase the reactivity for formic acid formation, while CO on the surface of perfect defect-free magnesium oxide films can generate formic acid through hydration under the promotion of water molecules, with a very low reaction barrier. Therefore, it is not necessary to introduce surface magnesium defects in the formic acid preparation process. In plastic pipes used for storing and transporting formic acid, formic acid decomposes slowly, shifting the formic acid decomposition equilibrium to the left. Incorporating oxide films and silver nanoparticles into the pipe material can inhibit formic acid decomposition and promote the regeneration of formic acid from CO.

[0176] Further reference Figure 4b In step 600, the analysis of the influence mechanism of the oxygen-magnesium co-defect surface on the formation of formic acid includes:

[0177] Step 640: Calculate the activation energy barrier for the generation of formic acid using the VTST program;

[0178] The above is for reference only. Figure 4e The influence of magnesium and oxygen co-defect surfaces on formic acid formation was investigated based on density functional theory. The dual defects of cations and anions induce unsaturated bonds in the O-Mg lattice, thereby enhancing the chemical activity of the magnesium oxide film. In the absence of additional water molecules, the activation energy barrier for formic acid formation was calculated to be 0.648 eV using the VTST program.

[0179] Step 650: The Vienna Ab Initio Simulation Package software was used to optimize the calculations and show the O-Mg distance between the water hydroxyl group and the surface magnesium.

[0180] Optimization calculations using the Vienna Ab Initio Simulation Package show that the O-Mg distance between the water hydroxyl group and the surface magnesium is...

[0181] Step 660: Calculate the charges carried by the oxygen and hydrogen in the hydroxyl group, and the charges of the carbon and oxygen in the carbonyl group, using the Bader program.

[0182] Calculations using the Bader program showed that the hydroxyl oxygen and hydrogen carry charges of -1.222|e| and 0.562|e|, respectively. The hydrogen adsorbed on the oxygen surface carries a charge of 0.606|e|, greater than that of the hydrogen adsorbed on the water hydroxyl group. The O-Mg bond around the adsorbed hydroxyl group exhibits the largest bond distance. The O-Mg bond distance around the oxygen-magnesium double defect is... and The distance between them indicates that the adsorption interaction does not lead to severe surface distortion or reconstruction. The distance between the carbonyl carbon and the surface magnesium is... The C-Mg bond. The CO distance of the carbonyl group is...

[0183] Calculations using the Bader program yielded carbon and oxygen charges of 0.988|e| and -1.191|e|, respectively. The average negative charge of the top layer silver atoms was -0.078|e|, while the average positive charge of the second layer silver atoms was 0.014|e|. The average charge of all silver atoms in the substrate model was -0.017|e|, indicating that the substrate can act as an electron pool, and the top layer silver plays a crucial role in charge transfer and electron storage.

[0184] Step 670: Calculate the Hamiltonian layout of the crystal orbitals of the major chemical bonds at the active sites using the LOBSTER program.

[0185] To further investigate the reaction mechanism, the Hamiltonian layout of the crystal orbitals of the major chemical bonds at the active sites was calculated using the LOBSTER program (see reference). Figure 4f The bonding effect between carbonyl oxygen and carbon is relatively strong, with some COHP curves showing negative peaks in the -10 eV to -3 eV energy range. Compared to the occupied antibonding orbitals of the IS and TS states between -3 eV and -1 eV, the lower-energy antibonding orbitals of the FS carbonyl group are unoccupied electrons. Two weak bonding interactions exist in the CO bond of IS near -9.2 eV and -7 eV. Near the Fermi level, TS exhibits a significant antibonding interaction, making the CO bond unstable and prone to transfer to the final product. In contrast, the CO bond of FS exhibits a strong bonding interaction and three distinct antibonding peaks far from the Fermi level. The absolute values ​​of overall COHP(Ow-Mgs) and COHP(C-Mgs) decrease significantly during the reaction, indicating a weaker bond between formic acid and magnesium oxide (compared to the bonding between the hydrohydroxyl group and magnesium oxide). The formation of formic acid slightly weakens the C=O bond of carbon monoxide. The absolute value of the overall COHP of C-Ow increased from 2.33 (IS) and 8.151 (TS) to 12.027 (FS), indicating that the C-Ow bond gradually strengthened. The absolute value of the overall COHP of CH bond increased from 0.006 (IS) and 3.468 (TS) to 7.445 (FS) (accompanied by a decrease in the overall COHP (H-Os) value).

[0186] In summary, this invention, through theoretical calculations of the reaction pathway for the preparation of formic acid by hydration reaction using the constructed model using numerical calculation software such as Vienna Ab Initio Simulation Package, lays a theoretical foundation for related experimental explorations of the preparation of formic acid by CO molecules on the surface of oxide thin film composites via hydration reaction.

[0187] The sequence numbers of the above embodiments of the present invention are for descriptive purposes only and do not represent the superiority or inferiority of the embodiments.

[0188] Through the above description of the embodiments, those skilled in the art can clearly understand that the methods of the above embodiments can be implemented by means of software plus necessary general-purpose hardware platforms. Of course, they can also be implemented by hardware, but in many cases the former is a better implementation method. Based on this understanding, the technical solution of the present invention, or the part that contributes to the prior art, can be embodied in the form of a software product. This computer software product is stored in a storage medium (such as ROM / RAM, magnetic disk, optical disk) as described above, and includes several instructions to cause a terminal device (which may be a mobile phone, computer, server, or network device, etc.) to execute the methods described in the various embodiments of the present invention. The above are only preferred embodiments of the present invention and do not limit the patent scope of the present invention. Any equivalent structural or procedural transformations made based on the content of the present invention specification and drawings, or direct or indirect applications in other related technical fields, are similarly included within the patent protection scope of the present invention.

Claims

1. A calculation method for the preparation of formic acid via hydration reaction, characterized in that, include: An adduct model was constructed for the addition of carbonyl and hydroxyl-related functional groups to the surface of silver-supported magnesium oxide material; wherein, the hydroxyl and carbonyl groups in the carbonyl and hydroxyl-related functional groups have a weak correlation relationship, and each of the carbonyl and hydroxyl groups has an adsorption site; With the assistance of water molecules, the reaction process of obtaining formic acid from the surface of silver-supported magnesium oxide material by the adduct of the carbonyl and hydroxyl related functional groups is analyzed according to the adduct model, and the reaction pathway for the formation of formic acid is predicted. Specifically, the process of obtaining formic acid products from the surface of silver-supported magnesium oxide material is simulated with the assistance of water molecules; the charge mechanism in the process of obtaining formic acid products is analyzed according to the process simulation; and the reaction pathway for the formation of formic acid from the intermediate of the carboxyl related functional group obtained by the adduct is predicted according to the intermediate of the carboxyl related functional group; wherein, the carboxyl related functional group has two adsorption sites. The prediction of the reaction pathway for the formation of formic acid from the carboxyl-related functional group obtained from the adduct includes: The adsorption structure of the adduct was determined by density functional optimization calculations with dispersion correction performed using the Vienna Ab Initio Simulation Package software. Based on the adsorption structure, the reaction mechanism is predicted using the climbing elastic band method. The VESTA program was used to obtain the formation of O-Mg and C-Mg bonds in the carbonyl group; The activation energy barrier for the transition state of the carboxyl-related functional group to form formic acid was calculated using the VTST program. The charge layout of the transition state configuration of formic acid generated by the carboxyl-associated functional group was calculated using the Bader program.

2. The calculation method for preparing formic acid by hydration reaction as described in claim 1, characterized in that, The model for constructing adducts of carbonyl and hydroxyl-related functional groups on the surface of silver-supported magnesium oxide materials includes: Surface supercell models of different magnesium oxide crystal planes and silver surfaces were constructed using Visual Molecular Dynamics and VESTA software; wherein the vacuum layer thickness of the surface supercell model is not less than 18 Å. The surface supercell model was optimized using the Vienna Ab Initio Simulation Package to make CO molecules adsorb perpendicular to the magnesium surface, thus forming the optimized adduct model.

3. The calculation method for preparing formic acid by hydration reaction as described in claim 2, characterized in that, Following the construction of the adduct model of carbonyl and hydroxyl related functional groups added to the surface of silver-supported magnesium oxide material, the following is also included: Based on the adduct model, a charge distribution analysis was performed on the adducts on the surface of the silver-supported magnesium oxide material composed of carbonyl and hydroxyl-related functional groups; and, Predict the reaction pathway that generates the adduct; and, The local electronic density of states of the adduct was analyzed.

4. The calculation method for preparing formic acid by hydration reaction as described in claim 3, characterized in that, The charge layout analysis of the adducts on the surface of the silver-supported magnesium oxide material composed of carbonyl and hydroxyl-related functional groups includes: Charge calculations were performed on the surface supercell model using the Bader program to obtain the charge calculation results; The differential charge density of the surface supercell model was calculated and analyzed using Visual Molecular Dynamics software. The Bader program is used to calculate the charge of magnesium at the adsorption site, the atomic volume of CO, the charge of the silver substrate, and the negative charges of surface hydroxyl and hydrohydroxyl groups.

5. The calculation method for preparing formic acid by hydration reaction as described in claim 3, characterized in that, The predicted reaction pathway for generating the adduct includes: The reaction pathway for generating the adduct was calculated using density functional theory using the climbing elastic band method, and the reaction pathway was obtained.

6. The calculation method for preparing formic acid by hydration reaction as described in claim 5, characterized in that, After calculating the reaction pathway for generating the adduct using density functional theory using the climbing elastic band method, the method further includes: Based on the climbing elastic band method, the transition state configuration structure characteristics were calculated using VTST software; and the activation energy barrier of CO and water molecules combining to form the adduct in the reaction pathway was analyzed using VTST software.

7. The calculation method for preparing formic acid by hydration reaction as described in claim 3, characterized in that, The local and electronic density of states analysis of the adduct includes: Electronic density of states analysis was performed using the p4vasp program to determine the interaction between CO and the water hydroxyl groups obtained from dissociation. The local density of states of the hydroxyl group and the projected electronic density of states of the silver and oxygen atoms at the interface were calculated using the p4vasp program.

8. The calculation method for preparing formic acid by hydration reaction as described in claim 1, characterized in that, The process of obtaining formic acid products on the surface of silver-supported magnesium oxide material with the assistance of water molecules is simulated, including: A simulation model incorporating surface water molecules was constructed using Visual Molecular Dynamics software. Based on the simulation model, calculate the total energy and structure of the first transition state; Calculate OC using the Bader program The charge amount of the OH adduct at the first transition state; in the OC In OH adducts, OC OH represents the carbonyl and hydroxyl functional group. Represents a weak association; By examining the simulation model in the first transition state using the VESTA program, the double bond distance of carbonyl C=O and the single bond distance of CO can be determined to establish the bonding relationship between CO and the water hydroxyl group. By examining the C=O double bond distance and CO single bond distance in the intermediate state of the simulation model using the VESTA program, the bonding between the carbonyl carbon atom and the hydrogen in water can be determined. The total energy of the second transition state was calculated using the VESTA program; and the interactions of each chemical bond during the formation of formic acid were determined in the second transition state.

9. The calculation method for preparing formic acid by hydration reaction as described in claim 8, characterized in that, The process of simulating and analyzing the charge mechanism in obtaining formic acid products, based on the aforementioned process simulation, includes: Based on the process simulation, the charge reduction and charge accumulation of hydrogen and carbonyl oxygen in the initial state of water molecules were obtained using Visual Molecular Dynamics software, and the charge distribution of the first transition state, the intermediate state, and the second transition state were analyzed using Visual Molecular Dynamics software.

10. The calculation method for preparing formic acid by hydration reaction as described in claim 1, characterized in that, The process of obtaining formic acid from the surface of silver-supported magnesium oxide material by the addition of carbonyl and hydroxyl functional groups under the assistance of water molecules, based on the adduct model analysis, and the prediction of the reaction pathway for formic acid formation, further includes: The influence mechanism of surface defects on formic acid formation was analyzed separately; and the influence mechanism of oxygen-magnesium co-defect surfaces on formic acid formation was analyzed separately.

11. The calculation method for preparing formic acid by hydration reaction as described in claim 10, characterized in that, The analysis of the influence mechanism of surface defects on formic acid formation includes: On a magnesium-containing defect surface, the activation energy barrier for the conversion of carbon-oxygen bonds and hydroxyl bonds in the adduct to carboxyl groups is calculated and used as the first activation energy barrier; On the oxygen-magnesium co-defect surface, the activation energy barrier for the conversion of carbon-oxygen bonds and hydroxyl bonds in the adduct to carboxyl groups is calculated and used as the second activation energy barrier; The activation barrier for converting carbon-oxygen bonds and hydroxyl bonds in the adduct on a defect-free surface into carboxyl groups is defined as the third activation barrier; and the first and second activation barriers are compared with the third activation barrier to determine the effect of the surface defects on the formation of formic acid.

12. The calculation method for preparing formic acid by hydration reaction as described in claim 11, characterized in that, The analysis of the influence mechanism of the oxygen-magnesium co-defect surface on the formation of formic acid includes: The activation energy barrier for the formation of formic acid was calculated using the VTST program; Optimization calculations using the Vienna Ab Initio Simulation Package software show the O-Mg distance between the water hydroxyl group and the surface magnesium. The charges carried by the oxygen and hydrogen in the hydroxyl group, as well as the charges of the carbon and oxygen in the carbonyl group, were calculated using the Bader program. Hamiltonian crystal orbital layout of the major chemical bonds at active sites was calculated using the LOBSTER program.

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