Highly Selective Metal‐Free Electrochemical Production of Hydrogen Peroxide on Functionalized Vertical Graphene Edges

Abstract Electrochemical generation of hydrogen peroxide (H 2 O 2 ) is an attractive alternative to the energy‐intensive anthraquinone oxidation process. Metal‐free carbon‐based materials such as graphene show great promise as efficient electrocatalysts in alkaline media. In particular, the graphene edges possess superior electrochemical properties than the basal plane. However, identification and enhancement of the catalytically active sites at the edges remain challenging. Furthermore, control of surface wettability to enhance gas diffusion and promote the performance in bulk electrolysis is largely unexplored. Here, a metal‐free edge‐rich vertical graphene catalyst is synthesized and exhibits a superior performance for H 2 O 2 production, with a high onset potential (0.8 V versus reversible hydrogen electrode (RHE) at 0.1 mA cm −2 ) and 100% Faradaic efficiency at various potentials. By tailoring the oxygen‐containing functional groups using various techniques of electrochemical oxidation, thermal annealing and oxygen plasma post‐treatment, the edge‐bound in‐plane ether‐type (COC) groups are revealed to account for the superior catalytic performance. To manipulate the surface wettability, a simple vacuum‐based method is developed to effectively induce material hydrophobicity by accelerating hydrocarbon adsorption. The increased hydrophobicity greatly enhances gas transfer without compromising the Faradaic efficiency, enabling a H 2 O 2 productivity of 1767 mmol g catalyst −1 h −1 at 0.4 V versus RHE.