Relationship between Structure and Performance of Atomic‐Scale Electrocatalysts for Water Splitting

Abstract Atomic‐scale electrocatalysts greatly improve the performance and efficiency of water splitting but require special adjustments of the supporting structures for anchoring and dispersing metal single atoms. Here, the structural evolution of atomic‐scale electrocatalysts for water splitting is reviewed based on different synthetic methods and structural properties that create different environments for electrocatalytic activity. The rate‐determining step or intermediate state for hydrogen or oxygen evolution reactions is energetically stabilized by the coordination environment to the single‐atom active site from the supporting material. In large‐scale practical use, maximizing the loading amount of metal single atoms increases the efficiency of the electrocatalyst and reduces the economic cost. Dual‐atom electrocatalysts with two different single‐atom active sites react with an increased number of water molecules and reduce the adsorption energy of water derived from the difference in electronegativity between the two metal atoms. In particular, single‐atom dimers induce asymmetric active sites that promote the degradation of H 2 O to H 2 or O 2 evolution. Consequently, the structural properties of atomic‐scale electrocatalysts clarify the atomic interrelation between the catalytic active sites and the supporting material to achieve maximum efficiency.