The role of atomic carbon in directing electrochemical CO reduction to multicarbon products

• Published in: Energy & environmental science Vol. 14; no. 1; pp. 473 - 482
• Main Authors: Peng, Hongjie, Tang, Michael T, Liu, Xinyan, Schlexer Lamoureux, Philomena, Bajdich, Michal, Abild-Pedersen, Frank
• Format: Journal Article
• Language: English
• Published: Cambridge Royal Society of Chemistry 01.01.2021; Royal Society of Chemistry (RSC)
• Subjects: Carbon; Carbon monoxide; Catalysis; Catalysts; Chemical reduction; Chemical synthesis; Copper; Density functional theory; Electrochemistry; Materials selection; Selectivity
• ISSN: 1754-5692; 1754-5706
• DOI: 10.1039/d0ee02826f

Electrochemical reduction of carbon-dioxide/carbon-monoxide (CO (2) R) to fuels and chemicals presents an attractive approach for sustainable chemical synthesis, but it also poses a serious challenge in catalysis. Understanding the key aspects that guide CO (2) R towards value-added multicarbon (C 2+ ) products is imperative in designing an efficient catalyst. Herein, we identify the critical steps toward C 2 products on copper through a combination of energetics from density functional theory and micro-kinetic modeling. We elucidate the importance of atomic carbon in directing C 2+ selectivity and how it introduces surface structural sensitivity on copper catalysts. This insight enables us to propose two simple thermodynamic descriptors that effectively identify C 2+ selectivity on metal catalysts beyond copper and hence it defines an intelligible protocol to screen for materials that selectively catalyze CO (2) to C 2+ products. Atomic carbon plays a role in steering selectivity in electrochemical carbon mono-/dioxide reduction. Appropriate binding strengths of CO and C, combined with four-fold sites, constitute fundamental features toward selective multicarbon production.