Atomistic Site Control of Pd in Crystalline MnO2 Nanofiber for Enhanced Electrocatalysis

다국어 초록 (Multilingual Abstract)

Oxides supported precious metals have wide applications in (electro‐)catalysis. Although single atom dispersion is known as the most efficient metal utilization strategy, the dependence of the catalytic activity on different sites consisted of various anchoring sites for single atoms is largely unknown. Here, the electrocatalytic activities of crystalline α‐MnO2 with atomistic Pd locating at different sites including substitutional, tunnel, and surface‐bound sites are first predicted, and then experimentally validated by applying different synthetic methods including hydrothermal reaction and impregnation‐calcination. The quantum chemistry calculations together with experimental characterization suggest that substitutional Pd/MnO2 possesses higher activity than the other samples due to the favorable geometric and electronic structures. Substitutional Pd can work synergistically with vicinal Mn sites toward cleavage of OO bonds. This work provides a comprehensive understanding on the impact of atomistic anchoring site and advances the reliable control over the electrocatalytic performance of oxide‐supported single atoms.
This paper demonstrates the first systematic study on the impacts of atomistic doping sites of Pd in MnO2 for oxygen reduction reaction. The theoretical analysis together with experimental characterization suggests that substitutional Pd/MnO2 possesses higher activity than other samples due to favorable geometric and electronic structures. Substitutional Pd can work synergistically with vicinal Mn sites toward cleavage of OO bonds.