Self‐adaptive copper pairs on <scp>CuO</scp>(111) boosting ammonia catalytic combustion

Abstract Copper oxides exhibit outstanding performance in ammonia catalytic combustion, but a limited understanding of reaction mechanisms and the nature of active sites under operating conditions hinders further catalyst optimization. Utilizing density functional theory‐based microkinetic simulations, we herein establish a comprehensive reaction mechanism on CuO(111), which enables the successful prediction of the experimental light‐off temperature and identifies the self‐adaptive copper pairs as key active sites. The NH 2 coupling over the copper pairs is the critical step for N 2 formation, which, along with H 2 O production, governs the overall reaction rate. Interestingly, the copper atom pairs can adjust their atomic distance ranging from 2.42 to 2.90 Å and their oxidation states between Cu I and Cu II in response to the adsorbed intermediates, thereby facilitating the catalytic cycle and specifically inhibiting NH 2 dehydrogenation. Moreover, reducing copper pair distance through surface compressive strain can further lower the activation energies of rate‐determining steps and enhance the reactivity.