Modeling Adsorption and Optical Properties for the Design of CO2 Photocatalytic Metal-Organic Frameworks
Abstract
:1. Introduction
2. Methods
3. Results and Discussion
3.1. IRMOF-C-BF2
3.1.1. Primitive Cell of IRMOF-C-BF2
Optical Properties of Primitive Cell of IRMOF-C-BF2 during Adsorption Process
Change in Order of the Guests’ Adsorption for Geometry Optimization in IRMOF-C-BF2
3.1.2. Unit Cell of IRMOF-C-BF2
3.2. IRMOF-C’-BF2
3.2.1. Primitive Cells of IRMOF-C-(2)-BF2 and IRMOF-C’-BF2
3.2.2. Unit Cells of IRMOF-C’-BF2
3.3. IRMOF-C-CH2BF2
Primitive Cells of IRMOF-C-CH2BF2
3.4. Further Topological Analysis of All Possible Intermolecular Hydrogen Bond
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
Sample Availability
References
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Structure | Guest | Bond a X---Y | Distance (Å) | ρ | ∇2ρ | DI(X,Y) | ΔE(X) kcal/mol | ΔN(X) |
---|---|---|---|---|---|---|---|---|
IRMOF-C-BF2-CO2 | CO2 | O---O | 3.07 | 0.00771 | 0.02996 | 0.03868 | 91.27 | −0.00446 |
O---O | 3.26 | 0.00381 | 0.01612 | 0.02143 | 92.83 | −0.02477 | ||
O---H | 2.97 | 0.00379 | 0.01349 | 0.01334 | 92.83 | −0.02477 | ||
C---O | 3.16 | 0.00528 | 0.02320 | 0.00999 | 37.41 | 0.03874 | ||
IRMOF-C-BF2-H2O | H2O | O---H | 2.32 | 0.01168 | 0.04255 | 0.04561 | 71.77 b | −0.00224 b |
IRMOF-C-BF2-H2 | H2 | H---C | 3.03 | 0.00456 | 0.01150 | 0.01614 | 12.24 | −0.00126 |
IRMOF-C-BF2-CO2 H2O | H2O | O---O | 3.01 | 0.00823 | 0.03263 | 0.04285 | 69.81 | 0.02101 |
O---O | 3.22 | 0.00593 | 0.02241 | 0.03059 | 69.81 | 0.02101 | ||
CO2 | O---O | 3.30 | 0.00348 | 0.01514 | 0.01894 | 91.68 | −0.03609 | |
O---O | 3.09 | 0.00599 | 0.02348 | 0.02581 | 89.88 | 0.01492 | ||
O---O | 3.55 | 0.00250 | 0.01147 | 0.00836 | 89.88 | 0.01492 | ||
O---H | 2.99 | 0.00373 | 0.01351 | 0.01197 | 91.68 | −0.03609 | ||
C---O | 2.95 | 0.00798 | 0.03175 | 0.01660 | 43.12 | 0.03087 | ||
C---O | 3.02 | 0.00725 | 0.03000 | 0.01374 | 43.12 | 0.03087 | ||
IRMOF-C-BF2-H2 CO2 | H2 | H---H | 2.70 | 0.00302 | 0.01053 | 0.00854 | 14.47 | −0.01376 |
CO2 | C---C | 3.26 | 0.00559 | 0.01996 | 0.00869 | 29.53 | 0.04988 | |
C---O | 3.49 | 0.00264 | 0.01230 | 0.01181 | 29.53 | 0.04988 | ||
IRMOF-C-BF2-H2 CO2 H2O | H2 | H---H | 3.14 | 0.00105 | 0.00417 | 0.00314 | 14.95 | −0.01398 |
H2O | H---O | 2.03 | 0.01879 | 0.07680 | 0.05326 | 16.71 b | −0.03286 b | |
CO2 | C---C | 3.27 | 0.00539 | 0.01927 | 0.00828 | 36.07 | 0.04204 |
Name | Guest | Angle | Distance (Å) | ρ | ∇2ρ | DI(X,Y) | ΔE(X) kcal/mol | ΔN(X) | ΔE(Y) kcal/mol | ΔN(Y) |
---|---|---|---|---|---|---|---|---|---|---|
IRMOF-C-BF2-CO2 H2O | HH2O-OCO2 | 169.24 | 2.34 | 0.00848 | 0.03246 | 0.02483 | 16.09 | −0.02908 | 89.88 | 0.01492 |
IRMOF-C-BF2-H2 CO2 | HH2-OCO2 | 164.35 | 2.90 | 0.00324 | 0.01161 | 0.01484 | 14.47 | −0.01376 | 92.89 | −0.01609 |
IRMOF-C-BF2-H2 CO2 H2O | HH2-OCO2 | 174.57 | 2.82 | 0.00372 | 0.01317 | 0.01749 | 14.95 | −0.01399 | 90.62 | 0.00061 |
Structure Name | Energy/eV | f·10−3 |
---|---|---|
IRMOF-1 | 4.2 | 0.57 |
IRMOF-C-BF2 | 5.4 | 8.4 |
C-BF2 | 4.0 | 210 |
IRMOF-C’-BF2 | 5.4 | 6.3 |
C’-BF2 | 3.0 | 305 |
IRMOF-C-CH2BF2 | 2.5 | 5.02 |
C-CH2BF2 | 4.0 | 331 |
Structure Name | Guest Molecule(s) | Relative Energy/eV |
---|---|---|
IRMOF-C-BF2 | - | 0.000 |
IRMOF-C-BF2-CO2 | CO2 | −22.912 |
IRMOF-C-BF2-H2 | H2 | −6.803 |
IRMOF-C-BF2-H2O | H2O | −14.096 |
IRMOF-C-BF2-CO2-H2 | CO2 + H2 | −29.661 |
IRMOF-C-BF2-CO2-H2O | CO2 + H2O | −37.117 |
Guest Molecules | IRMOF-C-BF2 | IRMOF-1 | ||
---|---|---|---|---|
Energy/eV | f·103 | Energy/eV | f·10−3 | |
- | 2.7 | 8.3 | 4.1 | 0.64 |
CO2 | 2.7 | 5.6 | 4.1 | 0.42 |
H2 | 2.7 | 8.3 | 4.1 | 0.69 |
H2O | 2.7 | 8.3 | 4.2 | 0.56 |
CO2 H2 | 2.7 | 8.4 | 4.2 | 0.57 |
CO2 H2O | 2.5 | 4.3 | 4.2 | 0.43 |
Name | Guest | Bond a X---Y | Distance (Å) | ρ | ∇2ρ | DI(X,Y) | ΔE(X) kcal/mol | ΔN(X) |
---|---|---|---|---|---|---|---|---|
IRMOF-C-BF2---CO2 H2 | H2 | H--C | 2.92 | 0.00624 | 0.01902 | 0.01642 | 7.96 | 0.01584 |
CO2 | C---O | 3.16 | 0.00526 | 0.02315 | 0.00998 | 37.96 | 0.03723 | |
O---H | 2.97 | 0.00378 | 0.01325 | 0.01322 | 1.34 b | −0.00624 | ||
O---O | 3.26 | 0.00379 | 0.01606 | 0.02123 | 92.68 | −0.02581 | ||
O---O | 3.08 | 0.00768 | 0.02994 | 0.03838 | 91.29 | −0.00058 |
Name | Guest | Angle | Distance (Å) | ρ | ∇2ρ | DI(X,Y) | ΔE(X) kcal/mol | ΔN(X) | ΔE(Y) kcal/mol | ΔN(Y) |
---|---|---|---|---|---|---|---|---|---|---|
IRMOF-C-BF2---CO2 H2 | HH2O-OCO2 | 157.24 | 3.16 | 0.00163 | 0.00708 | 0.00766 | 15.89 | −0.01790 | 91.29 | −0.00058 |
Structure | Guest Molecules | Band Gap/eV | Valence Electrons | Valence Band Index | Conduction Band Index | Bottom of Valence Band/eV | Top of Conduction Band/eV |
---|---|---|---|---|---|---|---|
IRMOF-1 | - | 3.4 | - | - | - | - | - |
IRMOF-C-BF2 | - | 0.403 | 548 | 274 | 275 | −4.789 | −4.408 |
IRMOF-C-BF2 | CO2 | 0.378 | 570 | 285 | 286 | −4.789 | −4.408 |
IRMOF-C-BF2 | CO2, H2 | 0.714 | 572 | 286 | - | −5.089 | −4.354 |
IRMOF-C’-BF2 | - | 2.413 | 548 | 274 | - | −6.476 | −4.082 |
Structure | Guest | Bond a X---Y | Distance (Å) | ρ | ∇2ρ | DI(X,Y) | ΔE(X) kcal/mol | ΔN(X) |
---|---|---|---|---|---|---|---|---|
IRMOF-C-BF2 unit cell CO2 | CO2 | O---C | 3.62 | 0.00282 | 0.01015 | 0.01167 | 98.13 | −0.02345 |
O---O | 3.67 | 0.00118 | 0.00666 | 0.00844 | 101.69 | −0.04197 | ||
O---O | 4.78 | 0.00014 | 0.00068 | 0.00149 | 98.13 | −0.02345 | ||
IRMOF-C-BF2 unit cell CO2 H2 | CO2 | O---C | 4.91 | 0.0001 | 0.00043 | 0.00033 | 76.99 | −0.02534 |
O---H | 2.93 | 0.00298 | 0.01232 | 0.00889 | 76.99 | −0.02534 | ||
H2 | H---O | 2.93 | 0.00283 | 0.01044 | 0.01512 | 18.43 b | −0.02876 b | |
H---O | 3.43 | 0.00137 | 0.00639 | 0.00569 | 6.65 b | 0.02471 b | ||
H---C | 3.42 | 0.00177 | 0.00538 | 0.00534 | 6.65 | 0.02471 |
Name | Guest | Angle | Distance (Å) | ρ | ∇2ρ | DI(X,Y) | ΔE(X) kcal/mol | ΔN(X) | ΔE(Y) kcal/mol | ΔN(Y) |
---|---|---|---|---|---|---|---|---|---|---|
IRMOF-C-BF2 unit cell CO2 H2 | HH2-OCO2 | 89.14 | 3.40 | 0.00171 | 0.00742 | 0.00738 | 18.43 | −0.02876 | 76.99 | −0.02534 |
Structure Name | Energy/eV | f·103 |
---|---|---|
IRMOF-C-BF2 | 2.7 | 8.4 |
IRMOF-C-(2)-BF2 | 1.96 | 2.5 |
IRMOF-C-BF2 | 3.0 | 6.3 |
Structure | Guest | Bond a X---Y | Distance (Å) | ρ | ∇2ρ | DI(X,Y) | ΔE(X) kcal/mol | ΔN(X) |
---|---|---|---|---|---|---|---|---|
IRMOF-C-(2)-BF2 | H2 | H---C | 3.07 | 0.00529 | 0.01608 | 0.01332 | 13.98 | −0.01306 |
CO2 | O---C | 3.36 | 0.00443 | 0.01573 | 0.01788 | 87.19 | −0.01574 | |
O---C | 3.18 | 0.00481 | 0.02022 | 0.01158 | 84.24 | −0.00994 | ||
C---O | 3.01 | 0.00703 | 0.02939 | 0.01498 | 34.01 | 0.03829 | ||
IRMOF-C’-BF2 | H2 | H---O | 2.71 | 0.00524 | 0.01680 | 0.02629 | 19.67 b | −0.03312 b |
CO2 | H---C | 3.07 | 0.00393 | 0.01011 | 0.01476 | 5.33 | 0.02927 | |
O---O | 3.12 | 0.00610 | 0.02394 | 0.02616 | 86.48 | −0.01103 | ||
O---O | 3.03 | 0.00700 | 0.02624 | 0.03210 | 87.84 | −0.01642 |
Name | Guest | Angle | Distance (Å) | ρ | ∇2ρ | DI(X,Y) | ΔE(X) kcal/mol | ΔN(X) | ΔE(X) kcal/mol | ΔN(Y) | |
---|---|---|---|---|---|---|---|---|---|---|---|
IRMOF-C-(2)-BF2 | HH2-OCO2 | 141.45 | 2.81 | 0.00429 | 0.01474 | 0.02012 | 13.98 | −0.01306 | 84.24 | −0.00994 | |
IRMOF-C’-BF2 | HH2-OCO2 | 112.87 | 3.12 | 0.00270 | 0.01030 | 0.01307 | 5.33 | 0.02927 | 86.48 | −0.01103 |
Structure | Guest | Bond a X---Y | Distance (Å) | ρ | ∇2ρ | DI(X,Y) | ΔE(X) kcal/mol | ΔN(X) |
---|---|---|---|---|---|---|---|---|
IRMOF-C-CH2BF2-H2 CO2 | H2 | H---O | 3.13 | 0.00216 | 0.00855 | 0.01077 | 13.40 b | −0.00557 b |
H2 | H---O | 2.92 | 0.00432 | 0.01430 | 0.01754 | 11.98 | −0.00067 | |
H2 | H---O | 3.47 | 0.00128 | 0.00549 | 0.00566 | 11.98 | −0.00067 | |
CO2 | O---O | 3.19 | 0.00516 | 0.01941 | 0.02875 | 92.17 | −0.01350 | |
CO2 | O---C | 3.43 | 0.00477 | 0.01459 | 0.01971 | 91.03 | −0.01823 |
Name | Guest | Angle | Distance (Å) | ρ | ∇2ρ | DI(X,Y) | ΔE(X) kcal/mol | ΔN(X) | ΔE(Y) kcal/mol | ΔN(Y) |
---|---|---|---|---|---|---|---|---|---|---|
IRMOF-C-CH2 BF2 H2 CO2 | HH2---OCO2 | 90.48 | 3.32 | 0.00204 | 0.00855 | 0.00873 | 13.40 | −0.00557 | 91.03 | −0.01823 |
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Chacón, P.; Hernández-Lima, J.G.; Bazán-Jiménez, A.; García-Revilla, M.A. Modeling Adsorption and Optical Properties for the Design of CO2 Photocatalytic Metal-Organic Frameworks. Molecules 2021, 26, 3060. https://doi.org/10.3390/molecules26103060
Chacón P, Hernández-Lima JG, Bazán-Jiménez A, García-Revilla MA. Modeling Adsorption and Optical Properties for the Design of CO2 Photocatalytic Metal-Organic Frameworks. Molecules. 2021; 26(10):3060. https://doi.org/10.3390/molecules26103060
Chicago/Turabian StyleChacón, Priscila, Joseelyne G. Hernández-Lima, Adán Bazán-Jiménez, and Marco A. García-Revilla. 2021. "Modeling Adsorption and Optical Properties for the Design of CO2 Photocatalytic Metal-Organic Frameworks" Molecules 26, no. 10: 3060. https://doi.org/10.3390/molecules26103060