A full understanding of oxygen reduction reaction mechanism on Au(1 1 1) surface.

Oxygen reduction and hydrogen peroxide reduction are technologically important reactions in energy-conversion devices. In this work, a full understanding of oxygen reduction reaction (ORR) mechanism on Au(1 1 1) surface is investigated by density functional theory (DFT) calculations, including the reaction mechanisms of O dissociation, OOH dissociation, and HO dissociation. Among these ORR mechanisms on Au(1 1 1), the activation energy of [Formula: see text] hydrogenation reaction is much lower than that of [Formula: see text] dissociation, indicating that [Formula: see text] hydrogenation reaction is more appropriate at the first step than [Formula: see text] dissociation. In the following, HO can be formed with the lower activation energy compared with the OOH dissociation reaction, and finally HO could be generated as a detectable product due to the high activation energy of HO dissociation reaction. Furthermore, the potential dependent free energy study suggests that the HO formation is thermodynamically favorable up to 0.4 V on Au(1 1 1), reducing the overpotential for 2e ORR process. And the elementary step of first HO formation becomes non-spontaneous at 0.4 V, indicating the difficulty of 4e reduction pathway. Our DFT calculations show that HO can be generated on Au(1 1 1) and the first electron transfer is the rate determining step. Our results show that gold surface could be used as a good catalyst for small-scale manufacture and on-site production of HO.