Controllable Conversion of CO2on Non‐Metallic Gold Clusters

Abstract Gold nanoparticles in metallic or plasmonic state have been widely used to catalyze homogeneous and heterogeneous reactions. However, the catalytic behavior of gold catalysts in non‐metallic or excitonic state remain elusive. Atomically precise Au n clusters ( n =number of gold atoms) bridge the gap between non‐metallic and metallic catalysts and offer new opportunities for unveiling the hidden properties of gold catalysts in the metallic, transition regime, and non‐metallic states. Here, we report the controllable conversion of CO 2 over three non‐metallic Au n clusters, including Au 9 , Au 11 , and Au 36 , towards different target products: methane produced on Au 9 , ethanol on Au 11 , and formic acid on Au 36 . Structural information encoded in the non‐metallic clusters permits a precise correlation of atomic structure with catalytic properties and hence, provides molecular‐level insight into distinct reaction channels of CO 2 hydrogenation over the three non‐metallic Au catalysts.