Abstract
Integrating renewable electricity and concentrated CO(2) from direct air capture, electrochemical CO(2) reduction reactions (eCO(2)RR) offer a promising pathway for converting CO(2) into fuel chemicals, enabling the closure of the carbon loop in a sustainable manner. The clean H(2) produced via the hydrogen evolution reaction (HER) during water electrolysis can replace traditional fossil fuels without additional CO(2) emissions. Achieving large-scale and high-efficiency eCO(2)RR and HER requires the development of rational electrolyzer designs, which are crucial for industrial implementation. This review examines recent innovations in system designs for eCO(2)RR, HER, and the latest advances in in situ cell designs for operando characterization during electrochemical reactions. It focuses on cell improvements in flow patterns, membrane electrode assemblies, and electrolyte engineering to maximize catalytic activities at the industrial level. Besides, the review discusses optimizing counter-anodic reactions to improve the energy efficiency of eCO(2)RR and water electrolysis, offering insights into the design of catalytic systems with efficient energy utilization. Furthermore, it explores the integration of eCO(2)RR and HER with other electrochemical systems (e.g., fuel cells), highlighting their potential role in the decarbonization of future industrial processes. Finally, the summary, challenge, and outlook on the industrial-scale eCO(2)RR and water electrolysis system designs are concluded.