Abstract
Precise control over the dynamic transformations that electrocatalysts undergo under operating conditions offers a powerful strategy for tailoring catalytic selectivity. Herein, the electrochemical modification of Cu(2-x)S-derived catalysts to generate selective active sites for the electroreduction of CO(2) to formate is investigated. Through a combination of in situ and ex situ characterization techniques, it is demonstrated that electrochemical cycling induces sulfur leaching, resulting in the formation of reduced, amorphous copper structures that exhibit enhanced selectivity toward formate production. Compared to the pristine material, the electrochemically modified catalyst achieves a twofold improvement in Faradaic efficiency, reaching values as high as 75% for CO(2)-to-formate conversion. These findings not only establish a cost-effective and scalable platform for catalyst fabrication and activation, but also open new avenues for advancing sustainable CO(2) conversion technologies toward industrial implementation.