Carbon-Supported Single Fe/Co/Ni Atom Catalysts for Water Oxidation: Unveiling the Dynamic Active Sites.

Extensive research has been conducted on carbon-supported single-atom catalysts (SACs) for electrochemical applications, owing to their outstanding conductivity and high metal atom utilization. The atomic dispersion of active sites provides an ideal platform to investigate the structure-performance correlations. Despite this, the development of straightforward and scalable synthesis methods, along with the tracking of the dynamic active sites under catalytic conditions, remains a significant challenge. Herein, we introduce a biomass-inspired coordination confinement strategy to construct a series of carbon-supported SACs, incorporating various metal elements, such as Fe, Co, and Ni. We have systematically characterized their electronic and geometric structure using various spectroscopic and microscopic techniques. Through in situ X-ray absorption spectroscopy (XAS), atomic scanning transmission electron microscopy (STEM), and electron paramagnetic resonance (EPR) analyses, it is demonstrated that the single atoms undergo structural rearrangement to form amorphous (oxy)hydroxide clusters during oxygen evolution reaction (OER), where the newly formed oxygen-bridged dual metal M─O─M or M─O─M' (M/M' = Fe, Co, Ni) moieties within these clusters play key role in the OER performance. This work provides essential insights into tracking the actual active sites of SACs during electrochemical OER.