Comprehensive performance scoring method for high-throughput screening of MOFs adsorption separation material

Abstract

The invention discloses a comprehensive performance scoring method for high-throughput screening of MOFs adsorption separation materials. The comprehensive performance scoring method comprises the steps that the Henry constant ratio or the adsorption heat ratio of molecules of two species of a binary mixture in a binary mixture adsorption system of multiple MOFs materials is obtained; the multiple MOFs materials are sorted from large to small, and the MOFs materials ranked in the top are screened out; calculating the performance of the top-ranked MOFs material on the binary mixture in the binary mixture system; ranking the performance of the binary mixture in the binary mixture system from large to small for the MOFs material ranked in the top and scoring; and finally, carrying out weight summation on the performance scores of the binary mixture in the binary mixture system by the MOFs materials ranked in the top to obtain a comprehensive score. According to the method, the research and synthesis process of the MOFs material can be accelerated, blindness of trial and error of a traditional experiment is avoided, the screening accuracy and reliability of the MOFs material are improved, and industrial application of a new material can be accelerated.

Description

Technical Field

[0001] The present invention relates to the technical field of MOFs simulation calculation and performance evaluation, and in particular to a comprehensive performance scoring method for high-throughput screening of MOFs adsorption and separation materials. Background Art

[0002] MOFs (Metal-organic frameworks) materials have shown potential for wide application in gas adsorption, energy storage, separation and catalysis due to their unique structure and excellent adsorption properties. These materials have highly controllable pore structure, surface area and chemical activity, making them ideal for solving problems such as separation, storage and catalysis. However, traditional MOFs material research methods mainly rely on trial and error, which is not only expensive but also inefficient, limiting their promotion in practical application fields. In recent years, the rapid development of computational simulation and high-throughput computing has brought new opportunities for material research and development.

[0003] High-throughput computational methods can quickly perform high-throughput calculations on large batches of materials, but they usually only focus on a single performance parameter. However, in practical applications, multiple performance parameters of materials need to be considered comprehensively. Taking methane adsorption performance as an example, it is not enough to rely solely on the evaluation of a single performance parameter, because some MOFs materials may show good adsorption performance for multiple gases such as methane and sulfur-containing impurities. This single performance indicator evaluation method has limitations in comprehensive performance evaluation. Practical industrial applications require not only that the material has high adsorption performance, but also a series of performance parameters such as the material's selectivity, recyclability, diffusion coefficient and chemical stability. Therefore, the comprehensive performance of materials as an evaluation indicator has become increasingly important. Summary of the invention

[0004] The purpose of the present invention is to overcome the shortcomings of the prior art and provide a comprehensive performance scoring method for high-throughput screening of MOFs adsorption and separation materials. This method can overcome the problem of insufficient performance evaluation of MOFs materials in the prior art, efficiently predict the adsorption and separation performance of MOFs materials for different binary mixtures in a binary mixed system, and provide a comprehensive score for them.

[0005] To achieve the above purpose, the technical solution provided by the present invention is:

[0006] A comprehensive performance scoring method for high-throughput screening of MOFs adsorption and separation materials, including:

[0007] S1. Use Widom algorithm to obtain the ratio of Henry constants or adsorption heat of two species molecules in binary mixtures of various MOFs materials adsorbed in binary mixture systems;

[0008] S2. According to the values ​​of the data obtained in S1, various MOFs materials are sorted from large to small, and the top-ranked MOFs materials are selected;

[0009] S3. Based on real application conditions, simulation methods are used to calculate the performance of the top-ranked MOFs materials for binary mixtures in binary mixed systems;

[0010] S4. Sort and score the performance of the binary mixture in the binary mixture system by the top-ranked MOFs materials from large to small. The larger the performance value, the higher the score.

[0011] S5. According to the actual application needs, the scores of the top-ranked MOFs materials on the performance of the binary mixture in the binary mixture system are weighted and summed to obtain a comprehensive score. MOFs materials with higher comprehensive scores are considered to be more promising for use in binary mixture systems.

[0012] Further, step S1 includes:

[0013] The Widom algorithm is used to obtain the Henry constant or adsorption heat corresponding to the two species molecules in the binary mixture of various MOFs materials adsorbed in the binary mixture system;

[0014] Determine the ratio of the Henry constants or the ratio of the heats of adsorption of the two species in a binary mixture.

[0015] Furthermore, the formula for calculating the Henry constant of two species molecules in a binary mixture system is as follows:

[0016]

[0017] Among them, K H is Henry's constant, T is temperature, R is the ideal gas constant, ρf is the density of MOFs material, <w>is the Rosenbluth specific gravity of the molecule in adsorption state, <W IG > is the ideal Rosenbluth density of the molecule.

[0018] Furthermore, the adsorption heat corresponding to the two species molecules of the binary mixture in the binary mixture system is the adsorption heat under infinite dilution state, and the calculation formula is as follows:

[0019]

[0020] Where ΔH is the heat of adsorption, K H is Henry's constant, β = 1 / k B T is the temperature related parameter, k B is the Boltzmann constant.

[0021] Furthermore, the properties of binary mixtures include adsorption capacity, selectivity, and structural stability of the material itself;

[0022] When calculating the adsorption amount, the MOFs material interacts with the two species of the binary mixture, taking into account the van der Waals force and electrostatic force interaction, and performing iterative insertion calculations under the consideration of the mass ratio of the two species, temperature and external pressure; each iteration includes the translation, flipping, stretching, twisting and regeneration of the molecule, and then retains or discards the attempt based on whether the force error is less than a given accuracy threshold; the iterative calculation is repeated for no less than 1×10 5 times to ensure the energy stability of the system, and then repeat for no less than 1×10 5 Iterations are used to calculate the adsorption results.

[0023] Furthermore, the selectivity of MOFs materials for binary mixtures was calculated based on the adsorption amounts of the two species in the binary mixture. The calculation formula is as follows:

[0024]

[0025] Among them, the two species in the binary mixture include the target species and water, S represents the separation selectivity of the target species relative to water, x1 is the molar fraction of the target species in the adsorbent, x2 is the molar fraction of water in the adsorbent, y2 is the molar fraction of water in the liquid phase, and y1 is the molar fraction of the target species in the liquid phase.

[0026] Compared with the existing technology, the principle and advantages of this solution are as follows:

[0027] This scheme uses the Widom algorithm to obtain the ratio of Henry constants or adsorption heats of two species of molecules in a binary mixture in a binary mixed system adsorbed by various MOFs materials; then, according to the numerical values ​​of the obtained data, the various MOFs materials are sorted from large to small, and the top-ranked MOFs materials are screened out; then, based on the actual application conditions, a simulation method is used to calculate the performance of the top-ranked MOFs materials on the binary mixture in the binary mixed system; and the performance of the top-ranked MOFs materials on the binary mixture in the binary mixed system is sorted from large to small and scored, and the larger the performance value, the higher the score; finally, according to the actual application needs, the scores of the performance of the top-ranked MOFs materials on the binary mixture in the binary mixed system are weighted and summed to obtain a comprehensive score, and MOFs materials with higher comprehensive scores are considered to be more promising for use in binary mixed systems.

[0028] This scheme can not only predict the adsorption and separation performance of MOFs materials for different binary mixtures in binary mixed systems, but also comprehensively consider multiple performance indicators, including adsorption capacity, selectivity, etc., providing researchers with a more comprehensive material evaluation tool. In addition, the calculation method of this scheme can more realistically simulate the performance changes of MOFs materials under different conditions, thereby improving the accuracy and reliability of MOFs material screening, which will help accelerate the industrial application of new materials.

[0029] In addition, this scheme can accelerate the research and synthesis process of MOFs materials and avoid the blindness of traditional experimental trial and error. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the services required for use in the embodiments or the prior art descriptions are briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0031] Figure 1 This is a principle flow chart of the comprehensive performance scoring method for high-throughput screening of MOFs adsorption and separation materials according to Example 1 of the present invention;

[0032] Figure 2 A bubble chart showing the comprehensive performance scores of the adsorption capacity, selectivity and structural stability of the MOFs material for the furfural-water binary mixture;

[0033] Figure 3 A bubble chart showing the comprehensive performance scores of the adsorption capacity, selectivity and structural stability of MOFs materials for ethanol-water binary mixtures;

[0034] Figure 4 Comparison diagram of adsorption heat of MOFs materials on xylose-water binary mixture and acetic acid-water binary mixture;

[0035] Figure 5 Schematic diagram of the adsorption capacity (abscissa), selectivity (ordinate) and comprehensive score (bubble size) of MOFs materials on xylose-water binary mixture;

[0036] Figure 6 Schematic diagram of the adsorption amount (abscissa), selectivity (ordinate) and comprehensive score (bubble size) of MOFs materials for acetic acid-water binary mixture;

[0037] Figure 7 Schematic diagram of the adsorption capacity (abscissa), selectivity (ordinate) and comprehensive score (bubble size) of the molecular sieve for the binary mixture of xylose-water and the binary mixture of acetic acid-water. DETAILED DESCRIPTION

[0038] The present invention will be further described below in conjunction with two specific embodiments:

[0039] Example 1 (for furfural-water binary mixture)

[0040] like Figure 1 As shown, the comprehensive performance scoring method for high-throughput screening of MOFs adsorption and separation materials described in this embodiment includes:

[0041] S1. Use Widom algorithm to obtain the ratio of Henry constants of two species molecules in binary mixtures of various MOFs materials adsorbed in binary mixture systems;

[0042] In this step,

[0043] MOFs materials are from the CoRE MOF database (2020 edition), which contains the structural information of 10,143 experimentally synthesized MOFs materials;

[0044] The binary mixture in the binary mixture system is a furfural-water binary mixture, and furfural and water are two corresponding species;

[0045] The calculation formula of Henry's constant corresponding to the adsorption of furfural and water molecules by MOFs materials is as follows:

[0046]

[0047] Among them, K H is Henry's constant, T is temperature, R is the ideal gas constant, ρf is the density of MOFs material, <w>is the Rosenbluth specific gravity of the molecule in adsorption state, <W IG > is the ideal Rosenbluth density of the molecule.

[0048] After obtaining the Henry constants corresponding to furfural and water molecules, the two are compared to obtain the ratio of the Henry constants of furfural and water molecules.

[0049] S2. According to the ratio of the Henry constants of furfural and water molecules obtained in step S1, a plurality of MOFs materials are sorted from large to small, and the top 100 MOFs materials are screened out;

[0050] S3. Based on real application conditions, the GCMC (Grand Canonical Monte Carlo) simulation method was used to calculate the performance of the top 100 MOFs materials on the furfural-water binary mixture in the binary mixture system;

[0051] Among them, the performance includes adsorption capacity, selectivity, and the stability of the material's own structure;

[0052] When calculating the adsorption amount, MOFs interact with the two species of furfural and water in the furfural-water binary mixture, taking into account the van der Waals force and electrostatic force interaction, and performing iterative insertion calculations under the consideration of the mass ratio of furfural to water (3%), temperature (298K) and external pressure (1bar); each iteration includes the translation, flipping, stretching, twisting and regeneration of the molecule, and then the force error is less than the given accuracy threshold of 1×10 -6 K is used to retain or discard the attempts; the iterative calculation is repeated for no less than 1×10 5 times to ensure the energy stability of the system, and then repeat for no less than 1×10 5 Iterations are used to calculate the adsorption results.

[0053] Next, the selectivity of MOFs materials for the binary mixture was calculated based on the adsorption of furfural and water species in the furfural-water binary mixture. The calculation formula is as follows:

[0054]

[0055] Among them, the two species of the furfural-water binary mixture include the target species (furfural) and water, S represents the separation selectivity of the target species (furfural) relative to water, x1 is the molar fraction of the target species (furfural) in the adsorbent, x2 is the molar fraction of water in the adsorbent, y2 is the molar fraction of water in the liquid phase, and y1 is the molar fraction of the target species (furfural) in the liquid phase.

[0056] It should be noted that since there are currently no force field parameters for furfural molecules, the adsorption amount calculated by simulation may deviate from the experimental value. However, this deviation exists for all MOFs, so when comparing the relative size of adsorption amount and selectivity between different materials, the calculated results are still of reference value, see Figure 2 .

[0057] S4. The performance of the top 100 MOFs materials on the furfural-water binary mixture in the binary mixture system is ranked from large to small and scored. The larger the performance value, the higher the score;

[0058] The scoring process is:

[0059] MOFs materials are ranked from large to small according to their adsorption capacity, with the largest adsorption capacity scoring 100 points, and the smallest adsorption capacity scoring 1 point. Similar rankings and scores are also performed on properties such as selectivity and the stability of the material's own structure.

[0060] S5. According to the actual application needs, the scores of the top 100 MOFs materials on the performance of furfural-water binary mixture in the binary mixture system (adsorption capacity, selectivity, and material's own structural stability) are weighted and summed to obtain a comprehensive score. MOFs materials with higher comprehensive scores are considered to be more promising for use in binary mixture systems.

[0061] In addition to the furfural-water binary mixture, the above method can also be used to obtain the comprehensive score of MOFs materials for ethanol-water binary mixtures. For ethanol-water binary mixtures, due to the relatively mature force field parameters, the calculated results are close to the experimental results. For example, for the MOFs material ZIF-8, the experimental value of the adsorption of ethanol is about 150 mg / g, while the calculated value is about 146 mg / g, which is basically consistent. For details, see Figure 3 , which proves the rationality of high-throughput screening and comprehensive scoring methods.

[0062] Example 2 (for xylose-water binary mixture)

[0063] The comprehensive performance scoring method for high-throughput screening of MOFs adsorption and separation materials described in this embodiment includes:

[0064] S1. Use Widom algorithm to obtain the ratio of adsorption heat of xylose and water molecules in the xylose-water binary mixture in the binary mixture system of various MOFs materials;

[0065] In this step,

[0066] The adsorption heat corresponding to the adsorption of xylose and water molecules by MOFs materials is the adsorption heat under infinite dilution state, and the calculation formula is as follows:

[0067]

[0068] Where ΔH is the heat of adsorption, K H is Henry's constant, β = 1 / k B T is the temperature related parameter, k B is the Boltzmann constant.

[0069] After obtaining the adsorption heat corresponding to xylose and water molecules, the two are compared to obtain the ratio of the adsorption heat of xylose and water molecules.

[0070] It should be noted that the larger the adsorption heat value, the stronger the adsorption capacity of the MOFs material for the adsorbate (xylose and water). The detailed results can be seen Figure 4 .

[0071] S2. According to the ratio of the adsorption heat of the two species of xylose and water in the obtained xylose-water binary mixture, a variety of MOFs materials are sorted from large to small, and the top 100 MOFs materials are screened out;

[0072] S3. Based on real application conditions, the GCMC (Grand Canonical Monte Carlo) simulation method was used to calculate the performance of the top 100 MOFs materials on the xylose-water binary mixture in the binary mixture system;

[0073] When calculating the adsorption amount, the MOFs material interacts with the two species of xylose and water in the xylose-water binary mixture, taking into account the van der Waals force and electrostatic force interaction, and performing iterative insertion calculations under the consideration of the mass ratio of xylose to water (5%), temperature (298K) and external pressure (1bar); each iteration includes the translation, flipping, stretching, twisting and regeneration of the molecule, and then the force error is less than the given accuracy threshold of 1×10 -6 K is used to retain or discard the attempts; the iterative calculation is repeated for no less than 1×10 5 times to ensure the energy stability of the system, and then repeat for no less than 1×10 5 Iterations are used to calculate the adsorption results.

[0074] The principle of selective determination is consistent with that of Example 1.

[0075] S4. The performance of the top 100 MOFs materials on the xylose-water binary mixture in the binary mixture system is ranked from large to small and scored. The larger the performance value, the higher the score;

[0076] S5. According to the actual application needs, the scores of the top 100 MOFs materials on the performance of xylose-water binary mixture in the binary mixture system (adsorption capacity, selectivity, and material structural stability) were weighted and summed to obtain a comprehensive score. The results are as follows: Figure 5 shown.

[0077] In addition to the xylose-water binary mixture, the above method can also be used to obtain the comprehensive score of MOFs materials for the acetic acid-water binary mixture. The results are as follows Figure 6 shown.

[0078] In addition to the MOFs database, the present invention also systematically studies the molecular sieve database (IZIF database, containing about 200 molecular sieves) to evaluate its adsorption and separation performance in xylose-water binary mixtures and acetic acid-water binary mixtures. Given that the molecular sieve database is relatively small (only about 200 molecular sieves), high-precision GCMC calculations can be performed on the entire database to obtain the adsorption and selectivity data of molecular sieves for xylose and acetic acid, and the comprehensive performance scores are obtained by combining these data. The results are as follows: Figure 7 As shown. For the binary mixture of acetic acid and water, the results are similar to those of the binary mixture of xylose and water. The molecular sieve with the largest adsorption capacity is not among the top three, and the adsorption capacity is about 120 mg / g, and the selectivity is about 100. However, the molecular sieves with the best comprehensive performance have similar adsorption capacities, about 90 mg / g, but there is a significant gap in acetic acid selectivity. The selectivity of the top three can reach more than 200, while the remaining two molecular sieves are about 150. Through systematic high-throughput screening and comprehensive scoring methods, the best zeolite materials suitable for binary mixtures of xylose and water and binary mixtures of acetic acid and water in the IZIF database are selected, which shows that the comprehensive scoring method of the present invention also shows good versatility on the molecular sieve database.

[0079] The embodiments described above are only preferred embodiments of the present invention and are not intended to limit the scope of implementation of the present invention. Therefore, all changes made according to the shape and principle of the present invention should be included in the protection scope of the present invention.< / w> < / w>

Claims

1. A comprehensive performance scoring method for high-throughput screening of MOFs adsorption and separation materials, characterized in that: include: S1. Use Widom algorithm to obtain the ratio of Henry constants or adsorption heat of two species molecules in binary mixtures of various MOFs materials adsorbed in binary mixture systems; S2. According to the values ​​of the data obtained in S1, various MOFs materials are sorted from large to small, and the top-ranked MOFs materials are selected; S3. Based on real application conditions, simulation methods are used to calculate the performance of the top-ranked MOFs materials for binary mixtures in binary mixed systems; S4. Sort and score the performance of the binary mixture in the binary mixture system by the top-ranked MOFs materials from large to small. The larger the performance value, the higher the score. S5. According to the actual application needs, the scores of the top-ranked MOFs materials on the performance of the binary mixture in the binary mixture system are weighted and summed to obtain a comprehensive score.

2. The comprehensive performance scoring method for high-throughput screening of MOFs adsorption and separation materials according to claim 1, characterized in that: Step S1 includes: The Widom algorithm is used to obtain the Henry constant or adsorption heat corresponding to the two species molecules in the binary mixture of various MOFs materials adsorbed in the binary mixture system; Determine the ratio of the Henry constants or the ratio of the heats of adsorption of the two species in a binary mixture.

3. The comprehensive performance scoring method for high-throughput screening of MOFs adsorption and separation materials according to claim 2, characterized in that: The formula for calculating the Henry constant for the two species of molecules in a binary mixture is as follows: Among them, K H is Henry's constant, T is temperature, R is the ideal gas constant, ρf is the density of MOFs material, <w>is the Rosenbluth specific gravity of the molecule in adsorption state, <W IG > is the ideal Rosenbluth density of the molecule.< / w> 4. The comprehensive performance scoring method for high-throughput screening of MOFs adsorption and separation materials according to claim 2, characterized in that: The adsorption heat corresponding to the two species molecules in the binary mixture in the binary mixture system is the adsorption heat under infinite dilution state, and the calculation formula is as follows: Where ΔH is the heat of adsorption, K H is Henry's constant, β = 1 / k B T is the temperature related parameter, k B is the Boltzmann constant.

5. The comprehensive performance scoring method for high-throughput screening of MOFs adsorption and separation materials according to claim 1, characterized in that: The properties of binary mixtures include adsorption capacity, selectivity, and structural stability of the material itself; When calculating the adsorption amount, the MOFs material interacts with the two species of the binary mixture, taking into account the van der Waals force and electrostatic force interaction, and performing iterative insertion calculations under the consideration of the mass ratio of the two species, temperature and external pressure; each iteration includes the translation, flipping, stretching, twisting and regeneration of the molecule, and then retains or discards the attempt based on whether the force error is less than a given accuracy threshold; the iterative calculation is repeated for no less than 1×10 5 times to ensure the energy stability of the system, and then repeat for no less than 1×10 5 Iterations are used to calculate the adsorption results.

6. The comprehensive performance scoring method for high-throughput screening of MOFs adsorption and separation materials according to claim 5, characterized in that: The selectivity of MOFs materials for binary mixtures was calculated based on the adsorption of the two species in the binary mixture. The calculation formula is as follows: Among them, the two species in the binary mixture include the target species and water, S represents the separation selectivity of the target species relative to water, x1 is the molar fraction of the target species in the adsorbent, x2 is the molar fraction of water in the adsorbent, y2 is the molar fraction of water in the liquid phase, and y1 is the molar fraction of the target species in the liquid phase.

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