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Recent advances in experimental thermodynamics of metal–organic frameworks

  • Hui Sun (a1) (a2) and Di Wu (a3) (a4) (a5) (a6)


This mini review summarizes recent advances in experimental thermodynamics of metal–organic frameworks (MOFs). Taking advantage of the development in mechanochemistry, near-room temperature solution calorimetry, and low-temperature heat capacity measurements, the energetic landscape, entropy trends, and Gibbs free energy evolutions of MOFs with true polymorphism [Zn(MeIm)2, Zn(EtIm)2, and Zn(CF3Im)2] as framework topology varies were thoroughly explored by integrated calorimetric and computational methodologies. In addition, the formation enthalpies of MOFs with ultrahigh porosity (MOF-177 and UMCM-1) and the simplest structure (metal formates) have been determined. The studies summarized below highlight the complex interplays among interrelated compositional, chemical, and topological (structural) factors in the determination of the thermodynamic parameters of MOFs.


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Akimbekov, Z. and Navrotsky, A. (2016). “Little thermodynamic penalty for the synthesis of ultraporous metal organic frameworks,” Chem. Phys. Chem. 17, 468470.
Akimbekov, Z., Katsenis, A. D., Nagabhushana, G. P., Ayoub, G., Arhangelskis, M., Morris, A. J., Friščić, T., and Navrotsky, A. (2017). “Experimental and theoretical evaluation of the stability of true MOF polymorphs explains their mechanochemical interconversions,” J. Am. Chem. Soc. 139, 79527957.
Arhangelskis, M., Katsenis, A. D., Novendra, N., Akimbekov, Z., Gandrath, D., Marrett, J. M., Ayoub, G., Morris, A. J., Farha, O. K., Friščić, T., and Navrotsky, A. (2019). “Theoretical prediction and experimental evaluation of topological landscape and thermodynamic stability of a fluorinated zeolitic imidazolate framework,” Chem. Mater. 31, 37773783.
Calvin, J. J., Asplund, M., Akimbekov, Z., Ayoub, G., Katsenis, A. D., Navrotsky, A., Friščić, T., and Woodfield, B. F. (2018). “Heat capacity and thermodynamic functions of crystalline and amorphous forms of the metal organic framework zinc 2-ethylimidazolate, Zn(EtIm)2,” J. Chem. Thermodyn. 116, 341351.
Cook, T. R., Zheng, Y. R., and Stang, P. J. (2013). “Metal-organic frameworks and self-assembled supramolecular coordination complexes: comparing and contrasting the design, synthesis, and functionality of metal-organic materials,” Chem. Rev. 113, 734777.
Furukawa, H., Cordova, K. E., O'Keeffe, M., and Yaghi, O. M. (2013). “The chemistry and applications of metal-organic frameworks,” Science. 341, 1230444.
Li, G., Sun, H., Xu, H., Guo, X., and Wu, D. (2017). “Probing the energetics of molecule-material interactions at interfaces and in nanopores,” J. Phys. Chem. C. 121, 2614126154.
Nagabhushana, G. P., Shivaramaiah, R., and Navrotsky, A. (2018). “Thermochemistry of the simplest metal organic frameworks: formates [M(HCOO)2]·xH2O (M = Li, Mg, Mn, Co, Ni, and Zn),” J. Chem. Thermodyn. 118, 325330.
Rosen, P. F., Calvin, J. J., Dickson, M. S., Katsenis, A. D., Friščić, T., Navrotsky, A., Ross, N. L., Kolesnikov, A. I., and Woodfield, B. F. (2019). “Heat capacity and thermodynamic functions of crystalline forms of the metal-organic framework zinc 2-methylimidazolate, Zn(MeIm)2,” J. Chem. Thermodyn. 136, 160169.
Sun, H., Jiang, H., Kong, R., Ren, D., Wang, D., Tan, J., Wu, D., Zhu, W., and Shen, B. (2019a). “Tuning n-alkane adsorption on mixed-linker ZIF-8-90 via controllable ligand hybridization: insight into the confinement from an energetics perspective.Ind. Eng. Chem. Res. 58, 1327413283.
Sun, H., Ren, D., Kong, R., Wang, D., Jiang, H., Tan, J., Wu, D., Chen, S., and Shen, B. (2019b). “Tuning 1-hexene/n-hexane adsorption on MOF-74 via constructing Co-Mg bimetallic frameworks,” Microporous Mesoporous Mater. 284, 151160.
Wu, D. and Navrotsky, A. (2015). “Thermodynamics of metal-organic frameworks,” J. Solid State Chem. 223, 5358.


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Recent advances in experimental thermodynamics of metal–organic frameworks

  • Hui Sun (a1) (a2) and Di Wu (a3) (a4) (a5) (a6)


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