Tuning the Metal–Support Interactions in Transition Metal-Anchored Heteroatom-Doped Graphene Single-Atom Catalysts

Abstract

Transition metal-anchored, heteroatom-doped graphene single-atom catalysts have emerged as a promising class of catalysts that combine the strengths of traditional homogeneous and heterogeneous catalysis. Strong metal–support interactions are critical for ensuring long-term catalyst stability and durability. This review assesses strategies for tuning the metal–support interactions in graphene-based single-atom catalysts, with the focus on insights from quantum chemical calculations. By systematically comparing computational studies, we address how variations in key structural and electronic features influence the metal–support bond strength. We evaluate the influence of graphene defect topology by comparing single and double vacancy sites, examine the role of heteroatom dopants (e.g., B, N, or O) in the first coordination sphere, and assess periodic trends by comparing catalytically active transition metals from periods 3, 4, and 5. Overall, this review identifies key structural–electronic features governing metal–support interactions and outlines tuning handles for optimizing metal–support bond strengths.