Anchoring of Transition Metals to Graphene Derivatives as an Efficient Approach for Designing Single‐Atom Catalysts

Abstract Graphene derivatives with anchored metal atoms represent a promising class of single‐atom catalysts (SACs). To elucidate factors determining the bond strength between metal atoms and graphene derivatives, a series of late 3d and 4d elements, including the iron triad, light platinum group elements, and coinage metals (Fe, Co, Ni, Ru, Rh, Pd, Cu, Ag, and Au), in different oxidation states (from 0 to +III) bonded to either cyanographene (CG) or graphene acid (GA) is explored. The vast diversity of N···Me and O···Me bond dissociation energies is related to charge transfer between the metal and substrate. The ability of CG and GA to reduce metal cations and oxidize metal atoms is attributed to the π‐conjugated lattice of the graphene derivatives. The binding energies of core electrons of the anchored metals are predicted to enable experimental identification via X‐ray photoelectron spectroscopy. The anchoring of metals is accompanied by either complete or partial spin quenching, leading in most cases to the same oxidation state of the metal regardless of its initial charge. The identified features can be utilized in designing new materials with a high potential in heterogenous SACs as well as electrochemical and spintronic applications.