Single-atom catalysis driven by intrinsic high-energy metastable structures

In heterogeneous catalysis, high-energy metastable structures (HEMSs), although present at vanishingly low concentrations under equilibrium conditions, can dominate reaction pathways and are reshaping our understanding of catalytic active sites. This work provides a general account of the formation mechanisms and catalytic properties of HEMSs in single-atom catalysis, emphasizing the pivotal role of theoretical computational approaches in elucidating their fundamental functions. It is demonstrated that HEMSs can be activated under thermal excitation or external potential modulation, and their distinct coordination environments and electronic structures confer exceptional activity and selectivity in both thermal and electrochemical reactions. These insights highlight the decisive role of HEMS as minority, offering both new understanding and a promising avenue for the rational design of high-performance catalysts.