Catalytic activation of O molecule by transition metal atoms deposited on the outer surface of BN nanocluster.

The activation of the O molecule and yielding two separated O atoms is an essential step for the oxygen reduction reaction processes. Dissociation of the strong bond in the O often involves large activation barriers on metal particles used as catalysts. Here, the catalytic activity for the O dissociation of the transition metals (Fe, Co, Ni, Cu, Rh, Pd, Ag, Ir, Pt, and Au) deposited on the BN nanocluster have been studied theoretically using density functional theory. The following outcomes can be derived from our calculations: (1) The strong interaction between the Fe and Ni metal atoms and boron atom in BN nanocluster suggests that these transition metals deposited on BN nanocluster should be stable under high temperatures. (2) Transition metal deposition enhances the reactivity of BN nanocluster, however, it is more effective in the case of Fe-deposited on BN nanocluster. (3) Consistent with the prediction of reactivity descriptors, the maximum catalytic activity toward O dissociation is related to the Fe-deposited on BN nanoclusters. (4) The adsorption energies of the O adsorbed on the metal-deposited BN nanoclusters increase with the increase transition metals positive charges. (5) The energy barrier of the O dissociation is significantly decreased by introducing extra positive charges into the metal deposited on the BN nanocluster. Our study demonstrates that the transition metals-deposited on the BN nanoclusters can act as driving force for O dissociation. These predictions open the route for the experimental studies of catalysts that offer high activity for oxygen reduction reaction processes.