Sabatier phenomenon in chemoselective gas-sensing reactions induced by Ag cluster coordination

Abstract

The Sabatier principle in heterogeneous catalysis provides guidance for designing optimal catalysts with the highest activity. We report a new Sabatier phenomenon induced by nanoclusters on different atomic scales in gas-sensitive reactions. We prepared a series of Ag nanocluster catalysts with coordination structures ranging from Ag0 to Ag13 through a surface coordination strategy. When used as catalysts for gas-sensitive reactions, a volcano-type relationship between the coordination number of Ag nanoclusters and gas-sensitive activity emerges, with a summit at a moderate coordination of Ag5. Mechanistic studies show that the efficient adsorption of activated *C2H6O on electron-rich Ag5 clusters is a key factor for the Sabatier phenomenon (adsorption energy from −0.322 eV to −0.663 eV), which leads to highly selective sensing. We found that the catalyst electron-rich surface layer induced by Ag5 clusters serves as a descriptor to explain the structure–activity relationship. Furthermore, due to the well-defined geometric and electronic structures in the Ag5 clusters, the optimized catalyst achieves both maximum activity and selectivity in chemoselective sensing reactions. This study reveals the Sabatier principle and provides insightful guidance for the rational design of more efficient and practical nanocluster catalysts for heterogeneous catalysis.