A catalytic reaction mechanism extraction method based on enthalpy change scoring algorithm and microcosmic dynamics guidance

Abstract

The application relates to a catalytic reaction mechanism extraction method based on an enthalpy change scoring algorithm and microscopic dynamics guidance, and specifically comprises the following steps: a directed graph (i.e., a reaction network) of a catalytic reaction path is constructed by using a graph theory method, a deep-first search method is combined to obtain all reaction paths in the reaction network, an enthalpy change variance is used to score and pre-evaluate each reaction path, a reaction path with a higher score is preferentially selected for microscopic dynamics simulation, and a reaction rate and a rate-determining step of the reaction path are obtained; according to the path score, a high-score path that can replace the rate-determining step is preferentially searched in the remaining reaction network, microscopic dynamics simulation is performed again, and the optimal reaction path is found through circulation. Compared with the prior art, the application can find a globally optimal reaction path under the condition of reducing the calculation of elementary reactions, improve the speed of reaction mechanism screening, has high automation degree, does not need man-machine interaction in the process, and has a simple process and is easy to use.

Description

Technical Field

[0001] This invention relates to the field of heterogeneous catalysis theoretical simulation research, and in particular to a method for extracting catalytic reaction mechanisms based on enthalpy change scoring algorithm and microkinetic guidance. Background Technology

[0002] The elucidation of heterogeneous catalytic reaction mechanisms has always been a crucial issue in the field of catalysis. First-principles calculations can accelerate the analysis of catalytic reaction networks and have proven to play a significant role in determining reaction mechanisms. However, catalytic reaction networks are often quite complex, potentially involving thousands of reactant-to-product reaction pathways. Traditional first-principles calculations still face some challenges in their practical application to elucidating catalytic reaction mechanisms. For example, obtaining the energy information (enthalpy change and energy barrier) of elementary reactions in a catalytic reaction network relies on first-principles calculations. In particular, obtaining the energy barrier requires searching for transition states, which consumes substantial computational time and resources. Furthermore, methods that merely compare the energy information of individual reaction pathways within a complex catalytic reaction network to determine the optimal reaction mechanism contain inherent errors; the obtained optimal reaction mechanism is only the energy-optimal path, not the kinetically optimal path.

[0003] Based on first-principles calculations, microkinetic methods can map the energy information of catalytic elementary reaction processes to macroscopic catalytic reaction properties (reaction rate, coverage, rate-determining step, etc.). By comparing the reaction rates of each elementary reaction in the reaction network, the optimal catalytic reaction mechanism can be quantitatively screened from a kinetic perspective. Currently, mature microkinetic simulation programs such as CATKINAS and CatMAP provide powerful methods for solving steady-state microkinetic equations, enabling rapid acquisition of reaction rates in the catalytic elementary reaction network and extraction of the optimal catalytic reaction mechanism. However, obtaining the optimal reaction mechanism through microkinetic simulation still requires energy data (enthalpy change and energy barrier) of the complete catalytic reaction network, necessitating extensive first-principles calculations, consuming significant computational time and resources, and thus failing to achieve rapid extraction of the optimal reaction mechanism.

[0004] Therefore, with the rapid development of high-performance computers and advanced algorithms, there is an urgent need to develop a method for targeted optimization of catalytic reaction mechanisms in microscopic dynamic simulations, reduce the first-principles calculations of energy data (enthalpy change and energy barrier) of the catalytic reaction network in the early stage, and improve the computational efficiency of extracting the optimal reaction mechanism from complex catalytic reaction networks. Summary of the Invention

[0005] To overcome the shortcomings of existing methods for obtaining the optimal catalytic reaction mechanism from complex reaction networks, the present invention aims to provide a method for extracting catalytic reaction mechanisms based on free energy scoring algorithms and microkinetic guidance, which is used to establish complex reaction networks on catalyst surfaces, extract the optimal reaction, and reduce unnecessary first-principles calculations.

[0006] The objective of this invention can be achieved through the following technical solutions:

[0007] This invention provides a method for extracting catalytic reaction mechanisms based on enthalpy change scoring algorithms and microkinetic guidance, comprising the following steps:

[0008] S1: Using a directed graph, intermediate species in all elementary reactions are treated as nodes, and elementary reaction processes of species transformation are treated as edges, thus establishing a complete catalytic reaction network;

[0009] S2: Optimize the structure of all intermediates in the catalytic reaction network, obtain the corresponding energy, and calculate the enthalpy change of all elementary reactions;

[0010] S3: Based on the catalytic reaction network, obtain all reaction paths, and use the enthalpy change corresponding to each reaction path obtained in S2 to calculate and score the enthalpy change deviation of each reaction path.

[0011] S4: Based on the score of each reaction path in S3, extract the path with the highest score, and use VASP software to search for the transition state of each elementary reaction in the path to obtain the energy barrier of the elementary reaction.

[0012] S5: Input the highest score path and corresponding energy information extracted in S4 into the CATKINAS software to calculate the reaction rate and rate-determining step corresponding to the path.

[0013] S6: For the rate-determining step obtained in S5, search for alternative paths in the catalytic reaction network to replace the rate-determining step, calculate the energy barrier of the replacement process, input the corresponding energy information into the CATKINAS software, and calculate the reaction rate and rate-determining step corresponding to the path again.

[0014] S7: Repeat S5 and S6 until there are no alternative paths to the rate-determining step in the catalytic reaction network. Obtain the catalytic reaction path with the maximum reaction rate, which is the optimal catalytic reaction mechanism.

[0015] Furthermore, in S1, the catalytic reaction network is constructed using graph theory to form a systematic description of the catalytic reaction pathway, specifically including:

[0016] By using catalytic reaction intermediates as nodes and corresponding elementary reactions as edges, a directional graph representing the reaction path, i.e., a directed reaction network, is constructed. When constructing the reaction network, the main reactant is used as a node to build a directed graph, and the edges are the corresponding elementary reactions.

[0017] Furthermore, in S2, the optimization of the intermediate structure is performed using VASP software;

[0018] In S2, the formula for calculating the enthalpy change is: ΔH = E FS -E IS E FS and E IS These represent the final and initial energies of the elementary reaction, respectively.

[0019] Furthermore, in S3, the reaction path is obtained using a depth-first search method;

[0020] In S3, the reaction pathway score is calculated by determining the variance of the enthalpy change of each elementary reaction in the reaction pathway. The formula for calculating the score S is as follows:

[0021]

[0022] in, x is the total enthalpy change of the reaction divided by the number of elementary reactions n in the path. i This represents the enthalpy change of each elementary reaction in the path.

[0023] Furthermore, in S3, the depth-first search algorithm recursively searches based on the nodes in the graph constructed in S1, specifically including:

[0024] Based on the provided main reactants and products, starting from the reactant node, the next reachable node is recursively searched for until the product node is reached, without returning during the recursion, and finally all possible reaction paths involved in the reaction are obtained.

[0025] Finally, the energy variance of all reaction pathways is calculated, and each reaction pathway is scored.

[0026] Furthermore, in S4, the search for the transition state is performed in VASP software, and a constrained optimization transition state search method is adopted.

[0027] In S4, the energy barrier of the elementary reaction is calculated using the following formula:

[0028] E a =E TS -E IS ,

[0029] Where E TS and E ISThese represent the transition state energy and the initial state energy of the elementary reaction, respectively.

[0030] Furthermore, S5 specifically includes:

[0031] The enthalpy change and energy barrier information of the reaction paths selected by DFT calculation in S4 are used as input to the CATKINAS software to calculate the reaction rate of the selected path and extract the rate-determining step in the corresponding path.

[0032] In S5, the rate-determining step is obtained by performing sensitivity analysis on each elementary reaction using CATKINAS software.

[0033] Furthermore, in S6, the specific process of replacing the decision-making step includes:

[0034] Using the reactants of the rate-determining step as the starting node and the products as the ending node, a scoring mechanism is used to screen reaction processes in the reaction network that can connect the starting and ending nodes, and processes with higher scores are preferentially selected to replace the rate-determining step.

[0035] Furthermore, in S6, the specific process of replacing the rate-determining step also includes: during the replacement screening, firstly, the rate-determining step to be replaced in the reaction network is removed to avoid duplicate path selection; then, reaction path segments that replace the rate-determining step are screened in the remaining reaction network to obtain new reaction paths, and these new paths are input into the CATKINAS software input file.

[0036] Furthermore, in S7, when the CATKINAS software cannot solve the system of dynamic equations, an alternative path is selected.

[0037] Compared with the prior art, the present invention has the following technical advantages:

[0038] 1) This invention presents a rapid extraction method for catalytic reaction mechanisms, advancing the process of elucidating catalytic reaction pathways. The core of this method lies in minimizing reliance on traditional manual operations, reducing unnecessary elementary reaction calculations, shortening the extraction time for optimal catalytic reaction mechanisms, saving computational resources and time, and freeing researchers from arduous computational tasks.

[0039] 2) This invention can provide a powerful tool for theoretical catalysis researchers to construct complex catalytic reaction networks and explore catalytic reaction mechanisms. Attached Figure Description

[0040] Figure 1 This is a schematic flowchart of the method for extracting catalytic reaction mechanisms based on enthalpy change scoring algorithm and microkinetic guidance of the present invention.

[0041] Figure 2This is the catalytic network for the reaction in Example 1 where ZnCr2O4 catalyzes the hydrogenation of carbon monoxide to produce CH4, CH3OH, CH2CO, and HCHO. The red arrows indicate the optimal reaction pathway.

[0042] Figure 3 This is the catalytic network in Example 2 where Fe2O3 catalyzes the selective reduction of NO to N2 and H2O using NH3. The red arrow indicates the optimal reaction path. Detailed Implementation

[0043] In its overall design, this invention employs a directed graph to construct a catalytic reaction network. A depth-first search algorithm is used to obtain reaction paths, and each path is scored by calculating the enthalpy variance. The catalytic paths with higher scores are prioritized for energy barrier calculations (using the first-principles calculation software VASP) and kinetic analysis (using the CATKINAS microkinetic software) to obtain the reaction rate and rate-determining step. From the remaining paths, paths with higher scores are used to iteratively replace the rate-determining step until the reaction path with the maximum reaction rate is obtained. This process effectively reduces the number of first-principles calculations required for elementary reactions in complex catalytic reaction networks, achieving the goal of efficiently screening catalytic reaction mechanisms.

[0044] To achieve the above objectives, the specific steps of the technical solution adopted by the present invention are as follows:

[0045] Step 1: Using a directed graph, treat all intermediate species in the elementary reactions as nodes and the elementary reaction processes of species transformation as edges to establish a complete catalytic reaction network;

[0046] Step 2: Optimize all intermediates in the catalytic reaction network, obtain the corresponding energies, and calculate the enthalpy change of all elementary reactions;

[0047] Step 3: Based on the complete catalytic reaction network in Step 1, obtain all reaction pathways, and use the enthalpy change corresponding to each reaction pathway in Step 2 to calculate and score the enthalpy change deviation of each reaction pathway.

[0048] Step 4: Based on the score of each reaction path in Step 3, extract the path with the highest score, and use VASP software to search for the transition state of each elementary reaction in the path to obtain the energy barrier of the elementary reaction.

[0049] Step 5: Input the path with the highest score extracted in Step 4 and the corresponding energy information (enthalpy change, energy barrier) into CATKINAS to calculate the reaction rate and rate-determining step corresponding to the path.

[0050] Step 6: For the rate-determining step obtained in Step 5, search for replacement paths in the catalytic reaction network (prioritizing processes with high scores) to replace the rate-determining step, calculate the energy barrier of the replacement process, input the relevant energy information (enthalpy change, energy barrier) into CATKINAS, and calculate again to obtain the reaction rate and rate-determining step corresponding to the path.

[0051] Step 7: Repeat steps 5 and 6 above until there are no alternative paths to the rate-determining step in the reaction network. Obtain the catalytic reaction path corresponding to the maximum reaction rate, which is the optimal catalytic reaction mechanism.

[0052] Step 8: End.

[0053] In practice, step 1, the construction of the catalytic reaction network, utilizes graph theory to form a systematic description of the catalytic reaction pathway. Catalytic reaction intermediates are used as nodes, and their corresponding elementary reactions are used as edges, thus constructing a directional graph representing the reaction pathway, i.e., a directed reaction network. During the construction of the reaction network, the main reactants are used as nodes to build a directed graph, and the edges represent the corresponding elementary reactions.

[0054] In practice, in step 2, the intermediate structure optimization is completed by VASP software.

[0055] In practice, the enthalpy change in step 2 is calculated using the formula: ΔH=E FS -E IS E FS and E IS These represent the final and initial energies of the elementary reaction, respectively.

[0056] In practice, the reaction path acquisition in step 3 adopts a depth-first search method, which can quickly extract the reaction paths in the reaction network utilization.

[0057] In practice, the reaction path scoring in step 3 is performed by calculating the variance of the enthalpy change of each elementary reaction in the reaction path (S), as shown in the following formula: in, x is the total enthalpy change of the reaction divided by the number of elementary reactions n in the path. i This represents the enthalpy change of each elementary reaction in the path.

[0058] In specific implementation, in step 3, the depth-first search algorithm is only used to recursively search for nodes in the graph built in step 1. Based on the provided main reactants and products, starting from the reactant nodes, new reachable nodes are used as new starting points to continue recursively searching for the next node until the product node is reached. "Backtracking" is not allowed during the recursive process, ultimately obtaining all possible reaction paths involved in the reaction. Finally, the energy variance of all reaction paths is calculated, and each reaction path is scored.

[0059] In practice, the transition state search in step 4 is performed in VASP software, using a constrained optimization transition state search method. The energy barrier is further calculated using the following formula: E a =E TS -E IS E TS and E IS These represent the transition state energy and the initial state energy of the elementary reaction, respectively.

[0060] In practice, step 5 uses the enthalpy change and energy barrier information of the reaction paths selected by DFT calculation as input to the CATKINAS software to calculate the reaction rate of the selected path and extract the rate-determining step in the corresponding path.

[0061] In practice, the rate-determining step in step 5 is obtained by performing sensitivity analysis on each elementary reaction using CATKINAS.

[0062] In practice, the replacement of the rate-determining step in step 6 is carried out by taking the reactants of the rate-determining step as the starting node and the products as the ending node. A scoring mechanism is used to screen the reaction processes in the reaction network that can connect the starting node and the ending node, and the process with the higher score is selected to replace the rate-determining step.

[0063] In practice, during the rate-determining step replacement screening in step 6, the rate-determining steps to be replaced in the reaction network are first removed to avoid duplicate path selection. Then, reaction path fragments that replace the rate-determining steps are screened in the remaining reaction networks to obtain new reaction paths, which are then input into the CATKINAS software input file.

[0064] In practice, if CATKINAS is unable to solve the dynamic equations during the automated loop process in step 7, the program will automatically select another alternative path and perform the above loop operation.

[0065] In specific implementation, in steps 3 and 6, based on the reaction network established in step 1 (excluding the elementary reactions corresponding to byproducts), the corresponding main product reaction paths are selected. All elementary reactions corresponding to byproducts are combined with the main product reaction paths, with the elementary reaction formulas as rows and each different intermediate as a column. Reactants in the elementary reaction formulas are positive, and products are negative, creating a matrix. In the matrix, the initial reactant and the final product correspond to a value of 0, and the values ​​of the remaining intermediates correspond to the reaction coefficients of each elementary reaction formula. After obtaining the matrix, the null space is solved, and vector solutions with non-zero columns corresponding to the main product reaction paths in the null space are selected. At this point, the elementary reactions corresponding to the vector solutions can constitute a complete reaction path.

[0066] In practice, if CATKINAS is unable to solve the dynamic equations during the automated loop process in step 7, the program will automatically select another alternative path and perform the above loop operation.

[0067] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments. Component models, material names, connection structures, control methods, algorithms, and other features not explicitly described in this technical solution are considered common technical features disclosed in the prior art.

[0068] Example 1

[0069] The optimal catalytic reaction mechanism for the ZnCr2O4-catalyzed hydrogenation of carbon monoxide to produce CH4, CH3OH, CH2CO, and HCHO is extracted. Figure 1 This is a schematic flowchart of the method for extracting catalytic reaction mechanisms based on enthalpy change scoring algorithm and microkinetic guidance of the present invention.

[0070] Reaction conditions: The partial pressures of CO and H2 were 7.143 and 17.857 atm, respectively, and the reaction temperature was 673 K. The reaction pathway, reaction energy barrier, and reaction enthalpy change are shown in Table 1.

[0071] The total number of elementary reactions examined manually was 49, while the total number of elementary reactions examined in this invention was 28. The optimal reaction path selected by this invention is consistent with the optimal reaction path extracted manually (the bold text indicates the optimal path in the current method, see Table 1); this invention can reduce the number of elementary reactions examined by 21, greatly reducing first-principles calculations. #1 and #2 represent oxygen vacancy sites and Cr sites, respectively, and O#1 represents a lattice oxygen site. See the table below for details:

[0072] Table 1

[0073]

[0074]

[0075] Table 1 compares the elementary reactions artificially investigated in Example 1 (ZnCr2O4 catalyzing the hydrogenation of carbon monoxide to produce CH4, CH3OH, CH2CO, and HCHO) with the elementary reactions used in this invention. Bold text in the table indicates the current optimal path.

[0076] The specific steps are as follows:

[0077] Step 1: Classify all elementary reactions in the reaction network, categorizing them into reversible and irreversible reactions, main product elementary reactions (those containing carbon), and byproduct elementary reactions based on their properties. Use intermediates containing carbon as nodes and corresponding elementary reactions as edges to construct a directional map representing the reaction pathway, such as... Figure 2 As shown;

[0078] Step 2: Use VASP software to perform structural analysis on all intermediates in the input file, and calculate the enthalpy change using the formula ΔH = E. FS -E IS Obtain the enthalpy change of each elementary reaction in the reaction network;

[0079] Step 3: Based on the reaction network established in Step 1, use the deep search algorithm to obtain all possible reaction paths, and score each reaction path by calculating the variance of the enthalpy change of each elementary reaction in each reaction path.

[0080] Step 4: For the highest-scoring path obtained in Step 3, use VASP software to perform a transition state search for the elementary reactions in that path, and calculate the energy barrier using the formula: E a =E TS -E IS Obtain the corresponding elementary reaction energy barrier and input both its energy barrier and enthalpy change into the CATKINAS input file;

[0081] Step 5: Based on the CATKINAS input file obtained in Step 4, perform microkinetic simulation on the selected reaction path using CATKINAS to calculate the reaction rate and rate-determining step corresponding to the path.

[0082] Step 6: Based on the rate-determining step obtained in Step 5, using the reactant intermediate as the starting node and the product intermediate as the ending node, delete the reaction network corresponding to the rate-determining step from the reaction network constructed in Step 1, and search for corresponding replacement reaction paths. Select the path segment with the highest score for replacement, calculate the energy barrier of the replacement path, and supplement the relevant energy barrier and enthalpy change into the CATKINAS input file. Calculate the corresponding reaction rate and rate-determining step again. For the newly obtained reaction rate and path, if the new reaction rate is lower than the old optimal reaction rate, reselect a path that can replace the rate-determining step; if the new reaction rate is higher than the old reaction rate, back up the current reaction rate and extract the new rate-determining step.

[0083] Step 7: Repeat steps 5 and 6 until there is no alternative rate-determining step in the reaction network, obtain the fastest reaction rate, and the corresponding reaction path is the optimal reaction path.

[0084] Step 8: End.

[0085] Example 2

[0086] Fe2O3 catalyzes the selective reduction of NO by NH3 to produce N2 and H2O reaction network. Figure 1 This is a schematic flowchart of the method for extracting catalytic reaction mechanisms based on enthalpy change scoring algorithm and microkinetic guidance of the present invention.

[0087] Reaction conditions: The partial pressures of NH3, NO, O2, H2O, and N2 were 0.0005 atm, 0.0005 atm, 0.03 atm, 0.05 atm, and 0.8 atm, respectively; the reaction temperature was 500 K; and the reaction mechanism, reaction energy barrier, and reaction enthalpy change are shown in Table 2.

[0088] The total number of elementary reactions examined manually was 50, while the total number of elementary reactions examined in this invention was 33. The optimal reaction path selected by this invention is consistent with the optimal reaction path extracted manually (the bold text indicates the optimal path using the current method, see Table 1); this invention can reduce the number of elementary reactions examined by 17, greatly reducing first-principles calculations. #1 represents the [Fe-O] site. See the table below for details:

[0089] Table 2

[0090]

[0091]

[0092] Table 2 compares the elementary reactions artificially investigated in Example 2 (Fe2O3-catalyzed selective reduction of NO to N2 and H2O using NH3) with the elementary reactions used in this invention. The bolded text in the table indicates the current optimal path.

[0093] The specific steps are as follows:

[0094] Step 1: Classify all elementary reactions in the reaction network, categorizing them into reversible and irreversible reactions, main product elementary reactions (those containing nitrogen), and byproduct elementary reactions based on their properties. Use intermediates containing nitrogen as nodes and corresponding elementary reactions as edges to construct a directional map representing the reaction pathway, such as... Figure 3 As shown;

[0095] Step 2: Use VASP software to perform structural analysis on all intermediates in the input file, and calculate the enthalpy change using the formula ΔH = E. FS -E IS Obtain the enthalpy change of each elementary reaction in the reaction network;

[0096] Step 3: Based on the reaction network established in Step 1, use the deep search algorithm to obtain all possible reaction paths, and score each reaction path by calculating the variance of the enthalpy change of each elementary reaction in each reaction path.

[0097] Step 4: For the highest-scoring path obtained in Step 3, use VASP software to perform a transition state search for the elementary reactions in that path, and calculate the energy barrier using the formula: E a =E TS -EIS Obtain the corresponding elementary reaction energy barrier and input both its energy barrier and enthalpy change into the CATKINAS input file;

[0098] Step 5: Based on the CATKINAS input file obtained in Step 4, perform microkinetic simulation on the selected reaction path using CATKINAS to calculate the reaction rate and rate-determining step corresponding to the path.

[0099] Step 6: Based on the rate-determining step obtained in Step 5, using the reactant intermediate as the starting node and the product intermediate as the ending node, delete the reaction network corresponding to the rate-determining step from the reaction network constructed in Step 1, and search for corresponding replacement reaction paths. Select the path segment with the highest score for replacement, calculate the energy barrier of the replacement path, and supplement the relevant energy barrier and enthalpy change into the CATKINAS input file. Calculate the corresponding reaction rate and rate-determining step again. For the newly obtained reaction rate and path, if the new reaction rate is lower than the old optimal reaction rate, reselect a path that can replace the rate-determining step; if the new reaction rate is higher than the old reaction rate, back up the current reaction rate and extract the new rate-determining step.

[0100] Step 7: Repeat steps 5 and 6 until there is no alternative rate-determining step in the reaction network, obtain the fastest reaction rate, and the corresponding reaction path is the optimal reaction path.

[0101] Step 8: End.

[0102] The above description of the embodiments is provided to enable those skilled in the art to understand and use the invention. It will be apparent to those skilled in the art that various modifications can be made to these embodiments, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, the present invention is not limited to the above embodiments, and any improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the invention should be within the protection scope of the present invention.

Claims

1. A method for extracting catalytic reaction mechanisms based on enthalpy change scoring algorithm and microkinetic guidance, characterized in that, Includes the following steps: S1: Using a directed graph, intermediate species in all elementary reactions are treated as nodes, and elementary reaction processes of species transformation are treated as edges, thus establishing a complete catalytic reaction network; S2: Optimize the structure of all intermediates in the catalytic reaction network, obtain the corresponding energy, and calculate the enthalpy change of all elementary reactions; S3: Based on the catalytic reaction network, obtain all reaction pathways, and use the enthalpy change corresponding to each reaction pathway obtained in S2 to calculate the enthalpy change variance of each reaction pathway and score it. S4: Based on the score of each reaction path in S3, extract the path with the highest score, and use VASP software to search for the transition state of each elementary reaction in the path to obtain the energy barrier of the elementary reaction. S5: Input the highest score path and corresponding energy information extracted in S4 into the CATKINAS software to calculate the reaction rate and rate-determining step corresponding to the path. S6: For the rate-determining step obtained in S5, search for alternative paths in the catalytic reaction network to replace the rate-determining step, calculate the energy barrier of the replacement process, input the corresponding energy information into the CATKINAS software, and calculate again to obtain the reaction rate and rate-determining step corresponding to the path. S7: Repeat S5 and S6 until there are no alternative paths to the rate-determining step in the catalytic reaction network. Obtain the catalytic reaction path with the maximum reaction rate, which is the optimal catalytic reaction mechanism.

2. The method for extracting catalytic reaction mechanisms based on enthalpy change scoring algorithm and microkinetic guidance according to claim 1, characterized in that, In S1, the catalytic reaction network is constructed using graph theory to form a systematic description of the catalytic reaction pathway, specifically including: By using catalytic reaction intermediates as nodes and corresponding elementary reactions as edges, a directional graph representing the reaction path, i.e., a directed reaction network, is constructed. When constructing the reaction network, the main reactant is used as a node to build a directed graph, and the edges are the corresponding elementary reactions.

3. The method for extracting catalytic reaction mechanisms based on enthalpy change scoring algorithm and microkinetic guidance according to claim 1, characterized in that, In S2, the optimization of the intermediate structure is performed using VASP software; In S2, the formula for calculating the enthalpy change is: Δ H = E FS - E IS ,in E FS and E IS These represent the final and initial energies of the elementary reaction, respectively.

4. The method for extracting catalytic reaction mechanisms based on enthalpy change scoring algorithm and microkinetic guidance according to claim 1, characterized in that, In S3, the reaction path is obtained using a depth-first search method; In S3, the reaction pathway is scored by calculating the variance of the enthalpy change of each elementary reaction in the reaction pathway, and the score is calculated accordingly. S The calculation formula is as follows: ； in, The total enthalpy change is calculated by dividing the total enthalpy change by the number of elementary reactions in the pathway. n , This represents the enthalpy change of each elementary reaction in the path.

5. The method for extracting catalytic reaction mechanisms based on enthalpy change scoring algorithm and microkinetic guidance according to claim 4, characterized in that, In S3, the depth-first search algorithm recursively searches based on the nodes in the graph constructed in S1, specifically including: Based on the provided reactants and products, starting from the reactant node, the next reachable node is recursively searched for until the product node is reached, without returning during the recursion, and finally all possible reaction paths involved in the reaction are obtained. Finally, the energy variance of all reaction pathways is calculated, and each reaction pathway is scored.

6. The method for extracting catalytic reaction mechanisms based on enthalpy change scoring algorithm and microkinetic guidance according to claim 1, characterized in that, In S4, the search for the transition state is performed in VASP software, and a constrained optimization transition state search method is used. In S4, the energy barrier of the elementary reaction is calculated using the following formula: E a = E TS - E IS ， in E TS and E IS These represent the transition state energy and the initial state energy of the elementary reaction, respectively.

7. The method for extracting catalytic reaction mechanisms based on enthalpy change scoring algorithm and microkinetic guidance according to claim 1, characterized in that, S5 specifically includes: The enthalpy change and energy barrier information of the reaction paths selected by DFT calculation in S4 are used as input to the CATKINAS software to calculate the reaction rate of the selected path and extract the rate-determining step in the corresponding path. In S5, the rate-determining step is obtained by performing sensitivity analysis on each elementary reaction using CATKINAS software.

8. The method for extracting catalytic reaction mechanisms based on enthalpy change scoring algorithm and microkinetic guidance according to claim 1, characterized in that, In S6, the specific process of replacing the speed determination step includes: Using the reactants of the rate-determining step as the starting node and the products as the ending node, a scoring mechanism is used to screen reaction processes in the reaction network that can connect the starting and ending nodes, and processes with higher scores are preferentially selected to replace the rate-determining step.

9. The method for extracting catalytic reaction mechanisms based on enthalpy change scoring algorithm and microkinetic guidance according to claim 8, characterized in that, In S6, the specific process of replacing the rate-determining step further includes: during the replacement screening, firstly, the rate-determining step to be replaced in the reaction network is removed to avoid repeated path selection; then, reaction path segments that replace the rate-determining step are screened in the remaining reaction network to obtain new reaction paths, and these new paths are input into the CATKINAS software input file.

10. The method for extracting catalytic reaction mechanisms based on enthalpy change scoring algorithm and microkinetic guidance according to claim 8, characterized in that, In S7, when the CATKINAS software cannot solve the system of dynamic equations, an alternative path is selected.

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