<em>In-situ/operando</em> study of Cu-based nanocatalysts for CO₂ electroreduction using electrochemical liquid cell TEM

The structure of a nanocatalyst during electrocatalytic reactions often deviates from its pristine structure due to intrinsic properties, or physical and chemical adsorption at the catalytic surfaces. Taking Cu-based catalysts for CO₂ electroreduction reactions (CO₂RR) as an example, they often experience segregation, leaching, and alloying during reactions. With the recent breakthrough development of high-resolution polymer electrochemical liquid cells, in-situ electrochemical liquid cell transmission electron microscopy (EC-TEM) alongside other advanced microscopy techniques, has become a powerful platform for revealing electrocatalysts restructuring at the atomic level. Considering the complex reactions involving electrified solid-liquid interfaces and catalyst structural evolution with intermediates, systematic studies with multimodal approaches are crucial. In this article, we demonstrate a research protocol for the study of electrocatalysts structural evolution during reactions using the in-situ EC-TEM platform. Using Cu and CuAg nanowire catalysts for CO₂RR as model systems, we describe the experimental procedures and findings. We highlight the platform’s crucial role in elucidating atomic-scale pathways of nanocatalyst restructuring and identifying catalytic active sites, as well as avoiding potential artifacts to ensure unbiased conclusions. Using the multimodal characterization toolbox, we provide the opportunity to correlate the structure of a working catalyst with its performance. Finally, we discuss advancements as well as the remaining gap in elucidating the structural-performance relationship of working catalysts. We expect this article will assist in establishing guidelines for future investigations of complex electrochemical reactions, such as CO₂RR and other catalytic processes, using the in-situ EC-TEM platform.. Authors: Wan, Jiawei [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); University of California, Berkeley, CA (United States)]; Zhang, Qiubo [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)]; Liu, Ershuai [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)]; Chen, Yi [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); University of California, Berkeley, CA (United States)]; Zheng, Jiana [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); University of California, Berkeley, CA (United States)]. DOE Contract: AC02-05CH11231; SC0021266. Subjects: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; CO2 electroreduction; Cu-based catalysts; electrochemical liquid cell TEM; in-situ; nanocatalyst restructuring; nanocatalysts; operando