Tuning Synergistic Effect of Au–Pd Bimetallic Nanocatalyst for Aerobic Oxidative Carbonylation of Amines

The activation and utilization of carbon monoxide is of crucial importance to C1 chemistry. Various catalytic transformation processes have been developed and studied in the last century, and oxidative carbonylation of amines is one of them. Catalysts that have been identified to date for the oxidative carbonylation of amines generally show relatively low activity and/or selectivity. Herein, a metal–organic framework (MOF), i.e., MOF-253 prepared from AlCl3·6H2O and 2,2′-bipyridine-5,5′-dicarboxylic acid, was employed as a support of gold–palladium bimetallic nanoparticles (Au–Pd/MOF) for the oxidative carbonylation of amines under mild conditions. Compared to palladium or gold monometallic catalysts, higher catalytic activity (turnover frequency up to 2573 h–1) and selectivity in the carbonylation of amines were achieved by Au–Pd/MOF bimetallic catalysts through adjusting the molar ratio of gold and palladium within the framework. A breathing effect of Au–Pd/MOF in the catalytic process was further observed from kinetic profiles and powder X-ray diffraction for the first time.