Metallofullerenes as Robust Single-Atom Catalysts for Adsorption and Dissociation of Hydrogen Molecules: A Density Functional Study

[Image: see text] Hydrogen is currently considered as the best alternative for traditional fuels due to its sustainable and ecofriendly nature. Additionally, hydrogen dissociation is a critical step in almost all hydrogenation reactions, which is crucial in industrial chemical production. A cost-effective and efficient catalyst with favorable activity for this step is highly desirable. Herein, transition-metal-doped fullerene (TM@C(60)) complexes are designed and investigated as single-atom catalysts for the hydrogen splitting process. Interaction energy analysis (E(int)) is also carried out to demonstrate the stability of designed TM@C(60) metallofullerenes, which reveals that all the designed complexes have higher thermodynamic stability. Furthermore, among all the studied metallofullerenes, the best catalytic efficiency for hydrogen dissociation is seen for the Sc@C(60) catalyst E(a) = 0.13 eV followed by the V@C(60) catalyst E(a) = 0.19 eV. The hydrogen activation and dissociation processes over TM@C(60) metallofullerenes is further elaborated by analyzing charge transfer via the natural bond orbital and electron density difference analyses. Additionally, quantum theory of atoms in molecule analysis is carried out to investigate the nature of interatomic interactions between hydrogen molecules and TMs@C(60) metallofullerenes. Overall, results of the current study declare that the Sc@C(60) catalyst can act as a low cost, highly efficient, and noble metal-free single-atom catalyst to efficiently catalyze hydrogen dissociation reaction.