Manuel E. G. Winkler, Rafael G. Yoshimura, Pâmella S. Rodrigues, Matheus P. Sales, Kauan L. Gomes, Itamar T. Neckel, Santiago J. A. Figueroa, J. V. A. e Souza, Edson A. Ticianelli, Nirala Singh, Fabio H. B. Lima, Serhiy Cherevko, Raphael Nagao
High Resolution Image Download MS PowerPoint Slide Cobalt- and copper-based oxides have emerged as cost-effective electrocatalysts for the electrochemical nitrate reduction reaction (NO 3 RR) to ammonia. However, the cathodic potentials required for NO 3 RR induce irreversible structural transformations that often compromise catalyst stability and selectivity, depending on the applied electrochemical protocol. To understand the resulting dynamic structure–performance relationships and improve nitrate-to-ammonia conversion, a tandem Co 3 O 4 /Cu x O electrocatalyst was prepared by electrodeposition followed by thermal treatment, and two surface activation strategies were employed: by cycles of cyclic voltammetry (CV) or by holding at a constant potential by chronoamperometry (CA). The CA-reconstructed Co/Cu mixed oxide-derived electrocatalyst exhibited a higher faradaic efficiency (FE) toward ammonia across the entire potential window studied (0.00 to −0.40 V RHE ). The reconstruction effects induced by both electrochemical protocols were systematically investigated, revealing morphological, structural, and compositional changes that underpin the improved nitrate-to-ammonia conversion. Furthermore, in situ and online electrochemical techniques were employed to identify intermediates and active sites, providing new mechanistic insights into the electrochemical nitrate-to-ammonia conversion pathway. These findings contribute to understanding dynamic reconstruction phenomena and offer design guidelines for more stable and selective mixed oxide electrocatalysts for sustainable ammonia production.