Iron-embedded boron nitride nanosheet as a promising electrocatalyst for the oxygen reduction reaction (ORR): A density functional theory (DFT) study

We performed comprehensive density functional theory (DFT) calculations to explore the possibility of the Fe-embedded hexagonal boron nitride (h-BN) sheet as a novel electrocatalyst for ORR. Our results show that Fe atom can strongly bind with defective BN sheet and thus ensure its high stability. Moreover, O-2 molecule is found to be strongly chemisorbed on Fe-embedded BN sheet with the adsorption energy of -1.76 eV, which can server as precursors for ORR, followed by its hydrogenation into OOH species rather than direct breakage of the O-O bond. Further, the HOOH species in the process of OOH reduction is shown to be unstable and dissociates into two OH group, suggesting that ORR catalyzed by Fe-embedded BN sheet is a direct four-electron pathway. Finally, on the basis of the calculations on the free energy change and activate energy of each step in ORR, we expect that Fe-embedded BN sheet exhibits good catalytic activity for ORR. Our results provide an useful guidance for the design and fabrication of novel and nonprecious BN sheet-based electrocatalyst for ORR as the alternative of expensive Pt catalysts. (C) 2015 Elsevier B.V. All rights reserved.