ClAg14(C≡CtBu)12 Nanoclusters as Efficient and Selective Electrocatalysts Toward Industrially Relevant CO2 Conversion

Atomically precise metal nanoclusters (NCs) have emerged as a promising frontier in the field of electrochemical CO2 reduction reactions (CO2RR) because of their distinctive catalytic properties. Although numerous metal NCs are developed for CO2RR, their use in practical applications has suffered from their low‐yield synthesis and insufficient catalytic activity. In this study, the large‐scale synthesis and electrocatalytic performance of ClAg14(C≡CtBu)12+ NCs, which exhibit remarkable efficiency in catalyzing CO2‐to‐CO electroreduction with a CO selectivity of over 99% are reported. The underlying mechanisms behind this extraordinary CO2RR activity of ClAg14(C≡CtBu)12+ NCs are investigated by a combination of electrokinetic and theoretical studies. These analyses reveal that different active sites, generated through electrochemical activation, have unique adsorption properties for the reaction intermediates, leading to enhanced CO2RR and suppressed hydrogen production. Furthermore, industrially relevant CO2‐to‐CO electroreduction using ClAg14(C≡CtBu)12+ NCs in a zero‐gap CO2 electrolyzer, achieving high energy efficiency of 51% and catalyst activity of over 1400 A g−1 at a current density of 400 mA cm−2 is demonstrated. The large‐scale synthesis of atomically precise ClAg14(C≡CtBu)12 nanoclusters is demonstrated, achieving a high yield of 90% on a scale of over 10 g. These nanoclusters exhibit extraordinary electrocatalytic activity for CO2 electroreduction to CO with a CO selectivity exceeding 99% and an energy efficiency of 51% at 400 mA cm−2, demonstrating a remarkable catalyst activity of over 1400 A g−1.