Ligand-controlled exposure of active sites on the Pd 1 Ag 14 nanocluster surface to boost electrocatalytic CO 2 reduction.

Advancing catalyst design requires meticulous control of nanocatalyst selectivity at the atomic level. Here, we synthesized two Pd 1 Ag 14 nanoclusters: Pd 1 Ag 14 (PPh 3 ) 8 (SPh(CF 3 ) 2 ) 6 and Pd 1 Ag 14 (P(Ph- p -OMe) 3 ) 7 (SPh) 6 , each with well-defined structures. Notably, in Pd 1 Ag 14 (P(Ph- p -OMe) 3 ) 7 (SPh) 6 , the detachment of a phosphine ligand from the top silver atom facilitates the exposure of singular active sites. This exposure significantly enhances its selectivity for the electrocatalytic reduction of CO 2 to CO, achieving a Faraday efficiency of 83.3% at -1.3 V, markedly surpassing the 28.1% performance at -1.2 V of Pd 1 Ag 14 (PPh 3 ) 8 (SPh(CF 3 ) 2 ) 6 . This work underscores the impact of atomic-level structural manipulation on enhancing nanocatalyst performance.