Electrocatalytic Oxygen Reduction to Hydrogen Peroxide on Graphdiyne-Based Single-Atom Catalysts: First-Principles Studies

The electrocatalytic oxygen reduction reaction (2e(-) ORR) via a two-electron process is a promising pathway for the production of hydrogen peroxide (H2O2). Here, we systematically investigated the 2e(-) ORR process on graphdiyne (GDY) supported single transition metal atoms (TM1@GDY) using density functional theory (DFT) calculations. Among the 23 TM1@GDY catalysts, Pt-1@GDY showed the best performance for the H2O2 product with an overpotential as low as 0.15 V. The electronic structure analysis, on the one hand, elucidates that the electron transfer between Pt-1@GDY and the adsorbed O-2 facilitates the activation of O-2, and, on the other hand, reveals that the high 2e(-) ORR activity of Pt-1@GDY lies in the transfer of electrons from the filled Pt-3d orbitals to the 2p antibonding orbitals of OOH*, which effectively activates the O-O bond. This work provides insights to design efficient electrocatalysts for H2O2 generation.