Heterogeneous Single-Cluster Catalysts for Selective Semihydrogenation of Acetylene with Graphdiyne-Supported Triatomic Clusters

Graphdiyne (GDY) is a newly discovered, novel carbon material, highly promising for chemical, physical, material, and industrial applications. The unique yet natural pores of GDY provide a novel prospect to design stable metal-cluster catalysts strongly bonded to its carbon framework. We report here a theoretical study using density functional theory on a heterogeneous-surface single-cluster catalyst (SCC) supported by GDY. This SCC features a triatomic metal cluster strongly anchored on the 18-member ring hexagon of the GDY support, MIVI'(3-x)/GDY (M, M' = Ru, Os), and can hydrogenate acetylene to ethylene with significant selectivity. This feature is attributed to a synergistic effect among the metal atoms in the cluster and the role of GDY as a charge buffer. State-of-the-art chemical bonding and microkinetic analyses are performed to understand the mechanism and catalytic performance. Our work highlights the importance of stably anchored surface-isolated metal clusters in heterogeneous catalysis and the synergy among metal atoms in a cluster and the peripheral metal support interfacial atoms.