High-throughput screening of hypothetical metal-organic frameworks for thermal conductivity
Source abstract
Abstract
Abstract Thermal energy management in metal-organic frameworks (MOFs) is an important, yet often neglected, challenge for many adsorption-based applications such as gas storage and separations. Despite its importance, there is insufficient understanding of the structure-property relationships governing thermal transport in MOFs. To provide a data-driven perspective into these relationships, here we perform large-scale computational screening of thermal conductivity k in MOFs, leveraging classical molecular dynamics simulations and 10,194 hypothetical MOFs created using the ToBaCCo 3.0 code. We found that high thermal conductivity in MOFs is favored by high densities (> 1.0 g cm−3), small pores (< 10 Å), and four-connected metal nodes. We also found that 36 MOFs exhibit ultra-low thermal conductivity (< 0.02 W m−1 K−1), which is primarily due to having extremely large pores (~65 Å). Furthermore, we discovered six hypothetical MOFs with very high thermal conductivity (> 10 W m−1 K−1), the structures of which we describe in additional detail.
Source: crossref · Quality: baseline
Research context
OpenAlex topics: Metal-Organic Frameworks: Synthesis and Applications · Machine Learning in Materials Science · Thermal properties of materials
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (84)
Show source-provided references
1. Kitagawa, S., Kitaura, R. & Noro, S. Functional porous coordination polymers. Angew. Chem. Int. Ed. 43, 2334–2375 (2004).10.1002/anie.200300610 ↗
2. Rowsell, J. L. C. & Yaghi, O. M. Metal–organic frameworks: a new class of porous materials. Microporous Mesoporous Mater. 73, 3–14 (2004).10.1016/j.micromeso.2004.03.034 ↗
3. Rosi, N. L. Hydrogen storage in microporous metal-organic frameworks. Science. 300, 1127–1129 (2003).10.1126/science.1083440 ↗
4. Furukawa, H., Cordova, K. E., O’Keeffe, M. & Yaghi, O. M. The chemistry and applications of metal-organic frameworks. Science. 341, 1230444 (2013).10.1126/science.1230444 ↗
5. Mason, J. A., Veenstra, M. & Long, J. R. Evaluating metal–organic frameworks for natural gas storage. Chem. Sci. 5, 32–51 (2014).10.1039/C3SC52633J ↗
6. He, Y., Zhou, W., Qian, G. & Chen, B. Methane storage in metal–organic frameworks. Chem. Soc. Rev. 43, 5657–5678 (2014).10.1039/C4CS00032C ↗
7. Sumida, K. et al. Carbon dioxide capture in metal–organic frameworks. Chem. Rev. 112, 724–781 (2012).10.1021/cr2003272 ↗
8. Matsuda, R. et al. Highly controlled acetylene accommodation in a metal–organic microporous material. Nature 436, 238–241 (2005).10.1038/nature03852 ↗
9. Li, J.-R., Kuppler, R. J. & Zhou, H.-C. Selective gas adsorption and separation in metal–organic frameworks. Chem. Soc. Rev. 38, 1477 (2009).10.1039/b802426j ↗
10. Qiu, S., Xue, M. & Zhu, G. Metal–organic framework membranes: from synthesis to separation application. Chem. Soc. Rev. 43, 6116–6140 (2014).10.1039/C4CS00159A ↗
11. Seo, J. S. et al. A homochiral metal–organic porous material for enantioselective separation and catalysis. Nature. 404, 982–986 (2000).10.1038/35010088 ↗
12. Allendorf, M. D. et al. Stress-induced chemical detection using flexible metal−organic frameworks. J. Am. Chem. Soc. 130, 14404–14405 (2008).10.1021/ja805235k ↗
13. Kreno, L. E. et al. Metal–organic framework materials as chemical sensors. Chem. Rev. 112, 1105–1125 (2012).10.1021/cr200324t ↗
14. Hu, Z., Deibert, B. J. & Li, J. Luminescent metal–organic frameworks for chemical sensing and explosive detection. Chem. Soc. Rev. 43, 5815–5840 (2014).10.1039/C4CS00010B ↗
15. Lee, J. et al. Metal–organic framework materials as catalysts. Chem. Soc. Rev. 38, 1450 (2009).10.1039/b807080f ↗
16. Liu, J. et al. Applications of metal–organic frameworks in heterogeneous supramolecular catalysis. Chem. Soc. Rev. 43, 6011–6061 (2014).10.1039/C4CS00094C ↗
17. Zhang, T. & Lin, W. Metal–organic frameworks for artificial photosynthesis and photocatalysis. Chem. Soc. Rev. 43, 5982–5993 (2014).10.1039/C4CS00103F ↗
18. Horcajada, P. et al. Porous metal–organic-framework nanoscale carriers as a potential platform for drug delivery and imaging. Nat. Mater. 9, 172–178 (2010).10.1038/nmat2608 ↗
19. Faust, T. MOFs deliver. Nat. Chem. 7, 270–271 (2015).10.1038/nchem.2229 ↗
20. Teplensky, M. H. et al. Temperature treatment of highly porous zirconium-containing metal–organic frameworks extends drug delivery release. J. Am. Chem. Soc. 139, 7522–7532 (2017).10.1021/jacs.7b01451 ↗
21. Sun, L. et al. A microporous and naturally nanostructured thermoelectric metal-organic framework with ultralow thermal conductivity. Joule. 1, 168–177 (2017).10.1016/j.joule.2017.07.018 ↗
22. Erickson, K. J. et al. Thin film thermoelectric metal–organic framework with high seebeck coefficient and low thermal conductivity. Adv. Mater. 27, 3453–3459 (2015).10.1002/adma.201501078 ↗
23. Jin, H. et al. Hybrid organic–inorganic thermoelectric materials and devices. Angew. Chem. Int. Ed. 58, 15206–15226 (2019).10.1002/anie.201901106 ↗
24. Redel, E. & Baumgart, H. Thermoelectric porous MOF based hybrid materials. APL Mater. 8, 060902 (2020).10.1063/5.0004699 ↗
25. Fan, Y., Liu, Z. & Chen, G. Recent progress in designing thermoelectric metal–organic frameworks. Small. 17, 2100505 (2021).10.1002/smll.202100505 ↗
26. Furukawa, H. et al. Ultrahigh porosity in metal-organic frameworks. Science. 329, 424–428 (2010).10.1126/science.1192160 ↗
27. Materials Design and Discovery Group. et al. A route to high surface area, porosity and inclusion of large molecules in crystals. Nature. 427, 523–527 (2004).10.1038/nature02311 ↗
28. Zheng, Q., Hao, M., Miao, R., Schaadt, J. & Dames, C. Advances in thermal conductivity for energy applications: a review. Prog. Energy. 3, 012002 (2021).10.1088/2516-1083/abd082 ↗
29. Makal, T. A., Li, J.-R., Lu, W. & Zhou, H.-C. Methane storage in advanced porous materials. Chem. Soc. Rev. 41, 7761 (2012).10.1039/c2cs35251f ↗
30. Huang, B. L., McGaughey, A. J. H. & Kaviany, M. Thermal conductivity of metal-organic framework 5 (MOF-5): Part I. Molecular dynamics simulations. Int. J. Heat. Mass Transf. 50, 393–404 (2007).10.1016/j.ijheatmasstransfer.2006.10.002 ↗
31. Huang, B. L. et al. Thermal conductivity of a metal-organic framework (MOF-5): Part II. Measurement. Int. J. Heat. Mass Transf. 50, 405–411 (2007).10.1016/j.ijheatmasstransfer.2006.10.001 ↗
32. Liu, D. et al. MOF-5 composites exhibiting improved thermal conductivity. Int. J. Hydrog. Energy 37, 6109–6117 (2012).10.1016/j.ijhydene.2011.12.129 ↗
33. Wang, X. et al. Anisotropic Lattice Thermal Conductivity and Suppressed Acoustic Phonons in MOF-74 from First Principles. J. Phys. Chem. C. 119, 26000–26008 (2015).10.1021/acs.jpcc.5b08675 ↗
34. Babaei, H., McGaughey, A. J. H. & Wilmer, C. E. Transient mass and thermal transport during methane adsorption into the metal–organic framework HKUST-1. ACS Appl. Mater. Interfaces 10, 2400–2406 (2018).10.1021/acsami.7b13605 ↗
35. Sezginel, K. B., Lee, S., Babaei, H. & Wilmer, C. E. Effect of flexibility on thermal transport in breathing porous crystals. J. Phys. Chem. C. 124, 18604–18608 (2020).10.1021/acs.jpcc.0c04353 ↗
36. Babaei, H. et al. Observation of reduced thermal conductivity in a metal-organic framework due to the presence of adsorbates. Nat. Commun. 11, 4010 (2020).10.1038/s41467-020-17822-0 ↗
37. Babaei, H., McGaughey, A. J. H. & Wilmer, C. E. Effect of pore size and shape on the thermal conductivity of metal-organic frameworks. Chem. Sci. 8, 583–589 (2017).10.1039/C6SC03704F ↗
38. Sezginel, K. B., Asinger, P. A., Babaei, H. & Wilmer, C. E. Thermal transport in interpenetrated metal–organic frameworks. Chem. Mater. 30, 2281–2286 (2018).10.1021/acs.chemmater.7b05015 ↗
39. Islamov, M., Babaei, H. & Wilmer, C. E. Influence of missing linker defects on the thermal conductivity of metal–organic framework HKUST-1. ACS Appl. Mater. Interfaces 12, 56172–56177 (2020).10.1021/acsami.0c16127 ↗
40. Babaei, H. & Wilmer, C. E. Mechanisms of heat transfer in porous crystals containing adsorbed gases: applications to metal-organic frameworks. Phys. Rev. Lett. 116, 025902 (2016).10.1103/PhysRevLett.116.025902 ↗
41. Babaei, H., Lee, J.-H., Dods, M. N., Wilmer, C. E. & Long, J. R. Enhanced thermal conductivity in a diamine-appended metal–organic framework as a result of cooperative CO2 adsorption. ACS Appl. Mater. Interfaces. 12, 44617–44621 (2020).10.1021/acsami.0c10233 ↗
42. Ying, P., Zhang, J., Zhang, X. & Zhong, Z. Impacts of functional group substitution and pressure on the thermal conductivity of ZIF-8. J. Phys. Chem. C. 124, 6274–6283 (2020).10.1021/acs.jpcc.0c00597 ↗
43. Wieser, S. et al. Identifying the bottleneck for heat transport in metal–organic frameworks. Adv. Theory Simul. 4, 2000211 (2021).10.1002/adts.202000211 ↗
44. Huang, J., Xia, X., Hu, X., Li, S. & Liu, K. A general method for measuring the thermal conductivity of MOF crystals. Int. J. Heat. Mass Transf. 138, 11–16 (2019).10.1016/j.ijheatmasstransfer.2019.04.018 ↗
45. Chae, J. et al. Nanophotonic atomic force microscope transducers enable chemical composition and thermal conductivity measurements at the nanoscale. Nano Lett. 17, 5587–5594 (2017).10.1021/acs.nanolett.7b02404 ↗
46. Cui, B. et al. Thermal conductivity of ZIF-8 thin-film under ambient gas pressure. ACS Appl. Mater. Interfaces 9, 28139–28143 (2017).10.1021/acsami.7b06662 ↗
47. Gunatilleke, W. D. C. B. et al. Thermal conductivity of a perovskite-type metal–organic framework crystal. Dalton Trans. 46, 13342–13344 (2017).10.1039/C7DT02927F ↗
48. Cheng, R., Li, W., Wei, W., Huang, J. & Li, S. Molecular insights into the correlation between microstructure and thermal conductivity of zeolitic imidazolate frameworks. ACS Appl. Mater. Interfaces 13, 14141–14149 (2021).10.1021/acsami.0c21220 ↗
49. Han, L., Budge, M. & Alex Greaney, P. Relationship between thermal conductivity and framework architecture in MOF-5. Comput. Mater. Sci. 94, 292–297 (2014).10.1016/j.commatsci.2014.06.008 ↗
50. Anderson, R. & Gómez-Gualdrón, D. A. Increasing topological diversity during computational “synthesis” of porous crystals: how and why. Cryst. Eng. Comm. 21, 1653–1665 (2019).10.1039/C8CE01637B ↗
51. Anderson, R. & Gómez-Gualdrón, D. A. Large-scale free energy calculations on a computational metal–organic frameworks database: toward synthetic likelihood predictions. Chem. Mater. 32, 8106–8119 (2020).10.1021/acs.chemmater.0c00744 ↗
52. Wieme, J. et al. Thermal engineering of metal–organic frameworks for adsorption applications: a molecular simulation perspective. ACS Appl. Mater. Interfaces 11, 38697–38707 (2019).10.1021/acsami.9b12533 ↗
53. Chen, Z. et al. Balancing volumetric and gravimetric uptake in highly porous materials for clean energy. Science. 368, 297–303 (2020).10.1126/science.aaz8881 ↗
54. Graebner, J. E. Thermal conductivity of diamond. In Diamond: Electronic Properties and Applications (eds. Pan, L. S. & Kania, D. R.) 285–318 (Springer US, 1995).10.1007/978-1-4615-2257-7_7 ↗
55. Kang, J. S., Li, M., Wu, H., Nguyen, H. & Hu, Y. Experimental observation of high thermal conductivity in boron arsenide. Science. 361, 575–578 (2018).10.1126/science.aat5522 ↗
56. Qian, X., Zhou, J. & Chen, G. Phonon-engineered extreme thermal conductivity materials. Nat. Mater. 20, 1188–1202 (2021).10.1038/s41563-021-00918-3 ↗
57. Duda, J. C., Hopkins, P. E., Shen, Y. & Gupta, M. C. Exceptionally low thermal conductivities of films of the fullerene derivative PCBM. Phys. Rev. Lett. 110, 015902 (2013).10.1103/PhysRevLett.110.015902 ↗
58. Moghadam, P. Z. et al. Structure-mechanical stability relations of metal-organic frameworks via. Mach. Learn. Matter. 1, 219–234 (2019).
59. Goodson, K. E. Ordering up the minimum thermal conductivity of solids. Science. 315, 342–343 (2007).10.1126/science.1138067 ↗
60. Blakemore, J. S. Semiconducting and other major properties of gallium arsenide. J. Appl. Phys. 53, R123–R181 (1982).10.1063/1.331665 ↗
61. Ma, H., Aamer, Z. & Tian, Z. Ultrahigh thermal conductivity in three-dimensional covalent organic frameworks. Mater. Today Phys. 21, 100536 (2021).10.1016/j.mtphys.2021.100536 ↗
62. Giri, A., Dionne, C. J. & Hopkins, P. E. Atomic coordination dictates vibrational characteristics and thermal conductivity in amorphous carbon. npj Comput. Mater. 8, 55 (2022).10.1038/s41524-022-00741-7 ↗
63. Henry, A. & Chen, G. High thermal conductivity of single polyethylene chains using molecular dynamics simulations. Phys. Rev. Lett. 101, 235502 (2008).10.1103/PhysRevLett.101.235502 ↗
64. Shen, S., Henry, A., Tong, J., Zheng, R. & Chen, G. Polyethylene nanofibres with very high thermal conductivities. Nat. Nanotechnol. 5, 251–255 (2010).10.1038/nnano.2010.27 ↗
65. Morelli, D. T., Heremans, J., Sakamoto, M. & Uher, C. Anisotropic heat conduction in diacetylenes. Phys. Rev. Lett. 57, 869–872 (1986).10.1103/PhysRevLett.57.869 ↗
66. Wilmer, C. E. et al. Large-scale screening of hypothetical metal–organic frameworks. Nat. Chem. 4, 83–89 (2012).10.1038/nchem.1192 ↗
67. Addicoat, M. A., Coupry, D. E. & Heine, T. AuToGraFS: automatic topological generator for framework structures. J. Phys. Chem. A 118, 9607–9614 (2014).10.1021/jp507643v ↗
68. Boyd, P. G. & Woo, T. K. A generalized method for constructing hypothetical nanoporous materials of any net topology from graph theory. Cryst. Eng. Comm. 18, 3777–3792 (2016).10.1039/C6CE00407E ↗
69. Gómez-Gualdrón, D. A. et al. Evaluating topologically diverse metal–organic frameworks for cryo-adsorbed hydrogen storage. Energy Environ. Sci. 9, 3279–3289 (2016).10.1039/C6EE02104B ↗
70. Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. The Cambridge Structural Database. Acta Crystallogr. B. Struct. Sci. Cryst. Eng. Mater. 72, 171–179 (2016).10.1107/S2052520616003954 ↗
71. Boyd, P. G. et al. Data-driven design of metal–organic frameworks for wet flue gas CO2 capture. Nature. 576, 253–256 (2019).10.1038/s41586-019-1798-7 ↗
72. Colón, Y. J., Gómez-Gualdrón, D. A. & Snurr, R. Q. Topologically guided, automated construction of metal–organic frameworks and their evaluation for energy-related applications. Cryst. Growth Des. 17, 5801–5810 (2017).10.1021/acs.cgd.7b00848 ↗
73. O’Keeffe, M., Peskov, M. A., Ramsden, S. J. & Yaghi, O. M. The reticular chemistry structure resource (RCSR) database of, and symbols for, crystal nets. Acc. Chem. Res. 41, 1782–1789 (2008).10.1021/ar800124u ↗
74. Anderson, R., Rodgers, J., Argueta, E., Biong, A. & Gómez-Gualdrón, D. A. Role of pore chemistry and topology in the CO 2 capture capabilities of MOFs: from molecular simulation to machine learning. Chem. Mater. 30, 6325–6337 (2018).10.1021/acs.chemmater.8b02257 ↗
75. Anderson, R., Biong, A. & Gómez-Gualdrón, D. A. Adsorption isotherm predictions for multiple molecules in MOFs using the same deep learning model. J. Chem. Theory Comput. 16, 1271–1283 (2020).10.1021/acs.jctc.9b00940 ↗
76. Sellan, D. P., Landry, E. S., Turney, J. E., McGaughey, A. J. H. & Amon, C. H. Size effects in molecular dynamics thermal conductivity predictions. Phys. Rev. B 81, 214305 (2010).10.1103/PhysRevB.81.214305 ↗
77. Babaei, H., Keblinski, P. & Khodadadi, J. M. Equilibrium molecular dynamics determination of thermal conductivity for multi-component systems. J. Appl. Phys. 112, 054310 (2012).10.1063/1.4749265 ↗
78. Plimpton, S. Fast parallel algorithms for short-range molecular dynamics. J. Comput. Phys. 117, 1–19 (1995).10.1006/jcph.1995.1039 ↗
79. Boone, P., Babaei, H. & Wilmer, C. E. Heat flux for many-body interactions: corrections to LAMMPS. J. Chem. Theory Comput. 15, 5579–5587 (2019).10.1021/acs.jctc.9b00252 ↗
80. Rappe, A. K., Casewit, C. J., Colwell, K. S., Goddard, W. A. & Skiff, W. M. UFF, a full periodic table force field for molecular mechanics and molecular dynamics simulations. J. Am. Chem. Soc. 114, 10024–10035 (1992).10.1021/ja00051a040 ↗
81. Coupry, D. E., Addicoat, M. A. & Heine, T. Extension of the universal force field for metal–organic frameworks. J. Chem. Theory Comput. 12, 5215–5225 (2016).10.1021/acs.jctc.6b00664 ↗
82. Gómez-Gualdrón, D. A., Moghadam, P. Z., Hupp, J. T., Farha, O. K. & Snurr, R. Q. Application of consistency criteria to calculate BET areas of micro- and mesoporous metal–organic frameworks. J. Am. Chem. Soc. 138, 215–224 (2016).10.1021/jacs.5b10266 ↗
83. Talu, O. & Myers, A. L. Molecular simulation of adsorption: gibbs dividing surface and comparison with experiment. AIChE J. 47, 1160–1168 (2001).10.1002/aic.690470521 ↗
84. Willems, T. F., Rycroft, C. H., Kazi, M., Meza, J. C. & Haranczyk, M. Algorithms and tools for high-throughput geometry-based analysis of crystalline porous materials. Microporous Mesoporous Mater. 149, 134–141 (2012).10.1016/j.micromeso.2011.08.020 ↗