Size dependent electrocatalytic activities of h-BN for oxygen reduction reaction to water

Electrocatalytic activities for the oxygen reduction reaction (ORR) of Au electrodes modified by as prepared and size selected (0.45-1.0, 0.22-0.45, and 0.1-0.22 µm) h-BN nanosheet (BNNS), which is an insulator, were examined in O₂ saturated 0.5M H₂SO₄ solution. The overpotential was reduced by all the BNNS modifications, and the smaller the size, the smaller the overpotential for ORR, i.e., the larger the ORR activity, in this size range. The overpotential was reduced by as much as ∼330 mV compared to a bare Au electrode by modifying the Au surface by the BNNS of the smallest size range (0.1-0.22 µm). The overpotential at this electrode was only 80 mV more than that at the Pt electrode. Both the rotation disk electrode experiments with Koutecky-Levich analysis and rotating ring disk electrode measurements showed that more than 80% of oxygen is reduced to water via the four-electron process at this electrode. These results strongly suggest and theoretical density functional theory calculations support that the ORR active sites are located at the edges of BNNS islands adsorbed on Au(111). The decrease in size of BNNS islands results in an effective increase in the number of the catalytically active sites and, hence, in the increase in the catalytic activity of the BNNS/Au(111) system for ORR.