C-H Bond activation on bimetallic two-atom Co-M oxide clusters deposited on Zr-based MOF nodes: Effects of doping at the molecular level

Simons, M. C.; Ortuño, M. A.; Bernales, V.; Gaggioli, C. A.; Cramer, C. J.; Bhan, A.; Gagliardi, L.
ACS Catal. 2018, 8, 2864 (doi:10.1021/acscatal.8b00012).

Cluster-based density functional theory calculations show that energy barriers for the dissociative adsorption of propane on two-cation, doped Co-M oxide clusters supported on Zr-based nodes of NU-1000, a metal-organic framework material, can vary from 57 to 9 kcal mol^-1 based on the identity of the dopant. Systematic changes in spin density and positive partial charge on oxygen atoms bridging the two metal atoms (Co-O-M) are noted upon addition of dopants to cobalt, with increasing values of both giving lower enthalpic barriers to C-H scission. These observed correlations can be rationalized in terms of concepts applicable to bulk systems, and provide a general tool proffering target materials for synthesis.