Operando formation of highly efficient electrocatalysts induced by heteroatom leaching

Abstract

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 CO2RR 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 (CO2RR, HER, ORR, and OER). This work provides insight into the role of dopants in electrocatalysis.

Solid Electrolytes for Low-Temperature Carbon Dioxide Valorization: A Review

“…Efforts are critically needed to gain a deeper understanding of the precise reaction mechanisms involved in CO 2 capture and CO 2 RR, by conducting a comprehensive approach including spectrochemical analysis, theoretical calculations, and isotopic labeling. − For example, utilizing multimodal operando techniques in combination with theoretical calculations can provide insights into the dynamic changes in catalyst structure during CO 2 RR . These molecular-scale understandings are essential for customizing the microenvironment of the dynamic solid–liquid interface to favor desired reaction pathways. , …”