Isolated Metal Centers Activate Small Molecule Electrooxidation: Mechanisms and Applications

Abstract Electrochemical oxidation of small molecules shows great promise to substitute oxygen evolution reaction (OER) or hydrogen oxidation reaction (HOR) to enhance reaction kinetics and reduce energy consumption, as well as produce high‐valued chemicals or serve as fuels. For these oxidation reactions, high‐valence metal sites generated at oxidative potentials are typically considered as active sites to trigger the oxidation process of small molecules. Isolated atom site catalysts (IASCs) have been developed as an ideal system to precisely regulate the oxidation state and coordination environment of single‐metal centers, and thus optimize their catalytic property. The isolated metal sites in IASCs inherently possess a positive oxidation state, and can be more readily produce homogeneous high‐valence active sites under oxidative potentials than their nanoparticle counterparts. Meanwhile, IASCs merely possess the isolated metal centers but lack ensemble metal sites, which can alter the adsorption configurations of small molecules as compared with nanoparticle counterparts, and thus induce various reaction pathways and mechanisms to change product selectivity. More importantly, the construction of isolated metal centers is discovered to limit metal d‐electron back donation to CO 2p ^* orbital and reduce the overly strong adsorption of CO on ensemble metal sites, which resolve the CO poisoning problems in most small molecules electro‐oxidation reactions and thus improve catalytic stability. Based on these advantages of IASCs in the fields of electrochemical oxidation of small molecules, this review summarizes recent developments and advancements in IASCs in small molecules electro‐oxidation reactions, focusing on anodic HOR in fuel cells and OER in electrolytic cells as well as their alternative reactions, such as formic acid/methanol/ethanol/glycerol/urea/5‐hydroxymethylfurfural (HMF) oxidation reactions as key reactions. The catalytic merits of different oxidation reactions and the decoding of structure–activity relationships are specifically discussed to guide the precise design and structural regulation of IASCs from the perspective of a comprehensive reaction mechanism. Finally, future prospects and challenges are put forward, aiming to motivate more application possibilities for diverse functional IASCs.