Pushing the Performance Limit of Cu/CeO₂ Catalyst in CO₂ Electroreduction: A Cluster Model Study for Loading Single Atoms.

Abstract

Pushing the performance limit of catalysts is a major goal of CO₂ electroreduction toward practical application. A single-atom catalyst is recognized as a solution for achieving this goal, which is, however, a double-edged sword considering the limited loading amount and stability of single-atom sites. To overcome the limit, the loading of single atoms on supports should be well addressed, requiring a suitable model system. Herein, we report the model system of an ultrasmall CeO₂ cluster (2.4 nm) with an atomic precise structure and a high surface-to-volume ratio for loading Cu single atoms. The combination of multiple characterizations and theoretical calculations reveals the loading location and limit of Cu single atoms on CeO₂ clusters, determining an optimal configuration for CO₂ electroreduction. The optimal catalyst achieves a maximum Faradaic efficiency (FE) of 67% and a maximum partial current density of -364 mA/cm² for CH₄, and can maintain high CH₄ FE values over 50% in a wide range of applied current densities (-50 ∼ -600 mA/cm²), exceeding those of the reported catalysts.