Transition Metal-Doped C(20) Fullerene-Based Single-Atom Catalysts with High Catalytic Activity for Hydrogen Dissociation Reaction

[Image: see text] Hydrogen dissociation is a key step in almost all hydrogenation reactions; therefore, an efficient and cost-effective catalyst with a favorable band structure for this step is highly desirable. In the current work, transition metal-based C(20) (M@C(20)) complexes are designed and evaluated as single-atom catalysts (SACs) for hydrogen dissociation reaction (HDR). Interaction energy (E(int)) analysis reveals that all the M@C(20) complexes are thermodynamically stable, whereas the highest stability is observed for the Ni@C(20) complex (E(int) = −6.14 eV). Moreover, the best catalytic performance for H(2) dissociation reaction is computed for the Zn@C(20) catalyst (E(ads) = 0.53 eV) followed by Ti@C(20) (E(ads) = 0.65 eV) and Sc@C(20) (E(ads) = 0.76 eV) among all considered catalysts. QTAIM analyses reveal covalent or shared shell interactions in H(2)* + M@C(20) systems, which promote the process of H(2) dissociation over M@C(20) complexes. NBO and EDD analyses declare that transfer of charge from the metal atom to the antibonding orbital of H(2) causes dissociation of the H–H bond. Overall outcomes of this study reveal that the Zn@C(20) catalyst can act as a highly efficient, low-cost, abundant, and precious metal-free SAC to effectively catalyze HDR.