Adsorption and dissociation of H2 molecule over first-row transition metal doped C24 nanocage as remarkable SACs: A comparative study.

Transition metal doped carbon materials such as carbon nanotubes and fullerenes have been extensively investigated for hydrogen adsorption and storage applications. However, the strength of these hydrogen storage material is mainly dependent on the metal-support and hydrogen-metal interaction energies. In this work, we have designed, and explored transition metal doped C24 (TM@C24) complexes as single atom catalysts for hydrogen dissociation. Adsorption energy results for all studied TM@C24 complexes reveal the high thermodynamic stability of designed TM@C24 catalysts. Among all considered TMs@C24 catalysts, the highest adsorption energy (−6.22 eV) is calculated for Mn@C24 catalyst. Moreover, H 2 dissociation mechanism is evaluated for both gas phase and in aqueous media to get insight into the solvent effect. In both gas phase and in aqueous media, the best catalytic activity for hydrogen dissociation is computed for Mn@C24 catalyst with the lowest energy barrier of 0.04 eV and 0.30 eV, respectively. NCI analysis is carried out to confirm the shared shell interactions (covalent interactions) between adsorbed hydrogen and TM@C24 complexes. Furthermore, natural bond orbital and electron density differences analysis are also performed to explore the activation and dissociation of H 2 molecule. Overall results reveal that Mn@C24 complex can at as a promising low cost, highly abundant and noble metal free single atom catalyst to effectively catalyze hydrogen dissociation reaction. • First row transition metal doped C24 complexes are theoretically investigated for hydrogen dissociation reaction. • The transition metal act as an active center for the dissociation of hydrogen molecule. • Hydrogen dissociation is proceeded through homolytic cleavage or oxidative addition of H 2 molecule. • Mn@C24 catalyst has the best catalytic activity with the lowest energy barrier of 0.04 eV. • NBO and EDD analysis show the transfer of charge participated in dissociation process. [ABSTRACT FROM AUTHOR]