Substrate augmented catalytic activity towards NRR: A case study of Li doped Al clusters on defective graphene

Abstract Density Functional Theory (DFT) based methods are applied to examine the potential of lithium doped aluminium clusters consisting of 3–13 atoms for dinitrogen molecule activation in terms of N N bond length, redshift in N N bond stretching frequency, nitrogen interaction energy and frontier molecular orbitals analysis. The present work highlights the role of monovacant C3 defective graphene as a support in fine tuning the catalytic activity of Li doped Al clusters for reduction of N2. Fundamental insights to synergic binding of clusters with defective graphene is brought out and its role in enhancing activation of dinitrogen molecule is explained. Supported Aln-1Li clusters with six or more atoms are noted to be more active towards N2 molecule activation as compared to the clusters without support. Dinitrogen molecule undergoes a maximum bond elongation of 1.56 A corresponding to redshift of 1690 cm−1 on Al7Li@graphene and Al12Li@graphene. This is maximum value reported in context of activation for N2 molecule till date.