4 years ago

Consequences of Surface Oxophilicity of Ni, Ni-Co, and Co Clusters on Methane Activation

Consequences of Surface Oxophilicity of Ni, Ni-Co, and Co Clusters on Methane Activation
Weifeng Tu, Chandra Veer Singh, Mireille Ghoussoub, Ya-Huei Cathy Chin
This study describes a new C–H bond activation pathway during CH4–CO2 reactions on oxophilic Ni-Co and Co clusters, unlike those established previously on Ni clusters. The initial C–H bond activation remains as the sole kinetically relevant step on Ni-Co, Ni, and Co clusters, but their specific reaction paths vary. On Ni clusters, C–H bond activation occurs via an oxidative addition step that involves a three-center (H3C···*···H) transition state, during which a Ni-atom inserts into the C–H bond and donates its electron density into the C–H bond’s antibonding orbital. Ni-Co clusters are more oxophilic than Ni; thus, their surfaces are covered with oxygen adatoms. An oxygen adatom and a vicinal Co-atom form a metal–oxygen site-pair that cleaves the C–H bond via a σ bond metathesis reaction, during which the Co inserts into the C–H bond while the oxygen abstracts the leaving H-atom in a concerted, four-center (H3C···*···H···O*) transition state. Similarly, Co clusters also catalyze the σ bond metathesis step, but much less effectively because of their higher oxophilicities, much stronger binding to oxygen, and less effective hydrogen abstraction than Ni-Co clusters. On Ni-Co and Co clusters, the pseudo-first-order rate coefficients are single-valued functions of the CO2-to-CO ratio (or H2O-to-H2 ratio), because this ratio prescribes the oxygen chemical potentials and the relative abundances of metal–oxygen site-pairs through the water–gas shift equilibrium. The direct involvement of reactive oxygen in the kinetically relevant step leads to more effective CH4 turnovers and complete elimination of coke deposition on Ni-Co bimetallic clusters.

Publisher URL: http://dx.doi.org/10.1021/jacs.7b01632

DOI: 10.1021/jacs.7b01632

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