(504c) Computational Screening of Metal-Organic Frameworks for Direct Methane to Methanol Conversion

In the United Sates, the demand for natural gas as a chemical feedstock is currently high and predicted to continue to rise in the future.¹ However, the industrial method for transforming methane, the main constituent of natural gas, to valuable chemicals such as methanol is inefficient and can only be carried out on a large scale. In contrast, biomimetic catalyst design strategies employing supported iron or copper oxide nanoclusters allow for direct conversion of methane to methanol under mild temperature and pressure conditions.² Recent experimental and computational work has investigated a variety of approaches for generating iron and copper oxide nanoclusters, for example on zeolites,³ metal-organic framework (MOF) nodes,⁴ and porphyrin linkers in MOFs.⁵ Here, we explore a new possibility where copper oxide nodes in MOFs may be used directly as the active sites for the reaction of interest. By means of Density Functional Theory calculations, MOFs with relevant copper node motifs were evaluated for important reaction steps such as methane activation and methanol desorption. Our goal is to identify potential candidates for further experimental verification and derive key activity descriptors that can provide insights into structure-property relations of active catalysts for direct methane to methanol conversion.

(1) Energy Information Administration. Annual Energy Review; U.S. Department of Energy, 2018.
(2) Groothaert, M. H.; Smeets, P. J.; Sels, P. F.; Jacobs, P. A.; Schoonheydt, R. A. J. Am. Chem. Soc. 2005, 127, 1304-1395.
(3) Mahyuddin, M. H.; Staykov, A; Shiota, Y; Miyanishi, M; Yoshizawa, K. ACS Catal. 2017, 7, 3741–3751.
(4) Ikuno, T; Zheng, J; Vjunov, A; Sanchez-Sanchez, M; Ortuno, M. A.; Pahls, D.; Fulton, J. L.; Camaioni, D. M.; Li, Z; Ray, D.; Mehdi, B. L.; Browning, N. D.; Farha, O. K.; Hupp, J. T.; Cramer, C. J.; Gagliardi, L.; Lercher, J. A. J. Am. Chem. Soc. 2017, 139, 10294–10301.
(5) Doan, H. A.; Li, Z.; Farha, O. K.; Hupp, J. T.; Snurr, R. Q. Catal. Today 2018. Advance Online Publication. https://doi.org/10.1016/j.cattod.2018.03.063.