Mimicking Metalloenzyme Microenvironments in the Transition Metal‐Single Atom Catalysts for Electrochemical Hydrogen Peroxide Synthesis in an Acidic Medium
Saravanakumar Muthusamy, Palani Sabhapathy, P. Raghunath, Amr Sabbah, Yu‐Chung Chang, Vimal Krishnamoorthy, Thi-Thong Ho, J. W. Chiou, M. C. Lin, Li–Chyong Chen, Kuei‐Hsien Chen
Abstract
Abstract Electrochemical reduction of oxygen into hydrogen peroxide in an acidic medium offers an energy‐efficient and green H 2 O 2 synthesis as an alternative to the energy‐intensive anthraquinone process. Unfortunately, high overpotential, low production rates, and fierce competition from traditional four‐electron reduction limit it. In this study, a metalloenzyme‐like active structure is mimicked in carbon‐based single‐atom electrocatalysts for oxygen reduction to H 2 O 2 . Using a carbonization strategy, the primary electronic structure of the metal center with nitrogen and oxygen coordination is modulated, followed by epoxy oxygen functionalities close to the metal active sites. In an acidic medium, CoNOC active structures proceed with greater than 98% H 2 O 2 selectivity (2e − /2H + ) rather than CoNC active sites that are selective to H 2 O (4e − /4H + ). Among all MNOC (M = Fe, Co, Mn, and Ni) single‐atom electrocatalysts, the CoNOC is the most selective (> 98%) for H 2 O 2 production, with a mass activity of 10 A g −1 at 0.60 V vs. RHE. X‐ray absorption spectroscopy is used to identify the formation of unsymmetrical MNOC active structures. Experimental results are also compared to density functional theory calculations, which revealed that the structure‐activity relationship of the epoxy‐surrounded CoNOC active structure reaches optimum (ΔG *OOH ) binding energies for high selectivity.