Building Single‐Atom and Single‐Cluster Metal Catalysts Supported on Graphdiyne and Boron‐Graphdiyne

Transition metal (TM) atoms and clusters supported on layered materials can be used to build single‐atom (SAC), and single‐cluster catalysts (SCC), respectively. To gain insight and to contribute to the rational design of SACs and SCCs, we investigate the structure and stability of SACs and SCCs of V, Co, and Pd, built on two supports, graphdiyne (GDY) and boron‐graphdiyne (BGDY), using the density functional formalism. GDY and BGDY are carbon‐based layered materials exhibiting a structure of uniformly distributed nanopores. The triangular pores of GDY and the hexagonal pores of BGDY host TM atoms and clusters attached with high adsorption energies, favoring the stability of these systems. Diffusion of metal atoms on GDY and BGDY is hindered by large activation barriers preventing the aggregation of atoms. Adsorption of metal atoms (one, two or three atoms per cell) or clusters (one TM 6 per cell) induce global distortions in the hexagonal lattice of BGDY. However, the GDY lattice is more robust and its global structure is quite insensitive to metal doping. Local distortions of the carbon chains are observed in both layers in the proximity of the adsorbed atoms and clusters. This work gives support to the development of highly stable SACs and SCCs that can be built through deposition of TM atoms and clusters on GDY and BGDY.