Sabatier Phenomenon in Hydrogenation Reactions Induced by Single-Atom Density

The Sabatier principle is a fundamental concept in heterogeneous catalysis that provides guidance for designing optimal catalysts with the highest activities. For the first time, we here report a new Sabatier phenomenon in hydrogenation reactions induced by single-atom density at the atomic scale. We produce a series of Ir single-atom catalysts (SACs) with a predominantly Ir₁-P₄ coordination structure with densities ranging from 0.1 to 1.7 atoms/nm² through a P-coordination strategy. When used as the catalysts for hydrogenation, a volcano-type relationship between Ir single-atom density and hydrogenation activity emerges, with a summit at a moderate density of 0.7 atoms/nm². Mechanistic studies show that the balance between adsorption and desorption strength of the activated H* on Ir single atoms is found to be a key factor for the Sabatier phenomenon. The transferred Bader charge on these Ir SACs is proposed as a descriptor to interpret the structure–activity relationship. In addition, the maximum activity and selectivity can be simultaneously achieved in chemoselective hydrogenation reactions with the optimized catalyst due to the uniform geometric and electronic structures of single sites in SACs. The present study reveals the Sabatier principle as an insightful guidance for the rational design of more efficient and practicable SACs for hydrogenation reactions.