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 Ag nanoclusters: Pd Ag (PPh ) (SPh(CF ) ) and Pd Ag (P(Ph- -OMe) ) (SPh) , each with well-defined structures. Notably, in Pd Ag (P(Ph- -OMe) ) (SPh) , 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 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 Ag (PPh ) (SPh(CF ) ) . This work underscores the impact of atomic-level structural manipulation on enhancing nanocatalyst performance.