Cluster is considered as the prototypical system to gain a better understanding of active sites and the elementary steps of reaction mechanism at the atomistic level, and become one of the enduring research areas in heterogeneous catalysis. Therefore, aiming toward catalytic applications, a large data set is generated on [TMxMgyOz] +/0/− clusters (TM = Cr, Fe, Co, Ni, x + y ≤ 5) using a massively parallel cascade genetic algorithm (cGA) approach at the hybrid density functional level of theory. The low-energy isomers are further analyzed via ab initio atomistic thermodynamics to estimate their free energy of formation at a realistic temperature T and partial pressure of oxygen pO . A thermodynamic phase diagram is drawn by minimizing Gibbs free energy of formation to identify the stable phases of neutral and charged [TMxMgyOz]+/0/− clusters. From this analysis, we notice that neutral and negatively charged clusters are stable in the wide range of (T, pO ). The negatively charged clusters are more effective as a catalyst to lower the C−H bond activation barrier for oxidation of methane. We find that the nature of TM atoms toward controlling the activation barrier is less important. However, the TM gives rise to different structural motifs in the cluster, which may act as active centers for catalysis. Since Co- and Ni-based bimetallic oxide clusters favor molecular O2 adsorption, they are expected to act as a better catalyst amongst various TMxMgyOz clusters for the oxidative coupling of methane.

Unraveling the role of structure, electronic property and charge state on the catalytic activity of bimetallic clusters at realistic conditions

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.