Operando formation of highly efficient electrocatalysts induced by heteroatom leaching

Heterogeneous nano-electrocatalysts doped with nonmetal atoms have been studied extensively based on the so-called dopant-based active sites, while little attention has been paid to the stability of these dopants under working conditions. In this work, we reveal significantly, when the redox working potential is too low negatively or too high positively, the active sites based on these dopants actually tend to collapse. It means that some previously observed “remarkable catalytic performance” actually originated from some unknown active sites formed in situ. Take the Bi-F for the CO 2 RR as an example, results show that the observed remarkable activity and stability were not directly from F-based active sites, but the defective Bi sites formed in situ after the dopant leaching. Such a fact is unveiled from several heteroatom-doped nanocatalysts for four typical reactions (CO 2 RR, HER, ORR, and OER). This work provides insight into the role of dopants in electrocatalysis. Stability of catalyst dopant species under working conditions is often unexplored. Here, the authors reveal that the dopant sites tend to collapse when the applied potential is too negative or too positive and describe a protocol for the in-situ formation of highly efficient active sites via the leaching of dopants.