Toward the Customized Performance on a Supported Au₄Ru₂ Cluster Catalyst

Abstract Precisely constructing the catalyst structure and composition at the atomic level is highly desirable for unexpected properties, but is extremely challenging. The success in atomically precise nanochemistry provides an opportunity for the active site‐tailoring of the catalysts toward unique catalysis. Here, atomically monodisperse Au₄Ru₂(PPh₃)₂(SC₂H₄Ph)₈ clusters are reported that anchored into the aerogel as heterogeneous catalysts for the carbonylation process of CO₂ hydrogenation coupled with dimethylamine. The aerogel indeed provides a performance stage for the cluster, on which the Au sites in the cluster act as the active centers to participate in the synergistic activation and reaction of H₂ and CO₂, thereby promoting the formylation process toward N,N‐dimethylformamide (DMF), while the Ru sites play a decisive role in the sequent hydrogenation of the DMF to trimethylamine. Notably, the cluster catalyst can not only exhibit a high turnover number for the carbonylation reaction performed in the batch reactor, but also show a long‐term utilization in the flowing fixed‐bed system, which have not been documented in previous catalysts.