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 2 dissociation, OOH dissociation, and H 2 O 2 dissociation. Among these ORR mechanisms on Au(1 1 1), the activation energy of O 2 ∗ hydrogenation reaction is much lower than that of O 2 ∗ dissociation, indicating that O 2 ∗ hydrogenation reaction is more appropriate at the first step than O 2 ∗ dissociation. In the following, H 2 O 2 can be formed with the lower activation energy compared with the OOH dissociation reaction, and finally H 2 O 2 could be generated as a detectable product due to the high activation energy of H 2 O 2 dissociation reaction. Furthermore, the potential dependent free energy study suggests that the H 2 O 2 formation is thermodynamically favorable up to 0.4 V on Au(1 1 1), reducing the overpotential for 2 e − ORR process. And the elementary step of first H 2 O formation becomes non-spontaneous at 0.4 V, indicating the difficulty of 4 e − reduction pathway. Our DFT calculations show that H 2 O 2 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 H 2 O 2 .