Computationally-Guided Discovery of Catalytic Cobalt-Decorated Metal-Organic Framework for Ethylene Dimerization

Bernales, V.; League, A. B.; Li, Z.; Schweitzer, N. M.; Peters, A. W.; Carlson, R. K.; Hupp, J. T.; Cramer, C. J.; Farha, O. K.; Gagliardi, L.
J. Phys. Chem. C 2016, 120, 23576 (doi:10.1021/acs.jpcc.6b07362).

The catalytic performance of a cobalt(II) single-site catalyst supported on the zirconia-like nodes of the metal-organic framework (MOF) NU-1000 is herein characterized by quantum chemical methods and compared to an iso-structural analogue incorporating nickel(II) as the active transition metal. The mechanisms of atomic layer deposition (ALD) in MOFs (AIM) and of catalysis are examined using density functional theory. We compare the catalytic activity of Co and Ni installed on the zirconia-like nodes for ethylene dimerization, considering three plausible pathways. Multiconfigurational wave function theory methods are employed to further characterize the electronic structures of key transition states and intermediates. Finally, we report confirmation of Co catalytic activity for ethylene dimerization from experiments that were prompted by the computational prediction.