Electronic structure and catalytic activity of TM@Mg12O12 nanocages for ambient ammonia synthesis

Bano, Rehana and Viskolcz, Béla and Fiser, Béla (2026) Electronic structure and catalytic activity of TM@Mg12O12 nanocages for ambient ammonia synthesis. MATERIALS & DESIGN, 261. No. 115370. ISSN 0264-1275 (print); 1873-4197 (online)

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Abstract

The development of low-cost and efficient electrocatalysts for the ambient nitrogen reduction reaction (NRR) is essential for the synthesis of NH3 and offers a substitute for the conventional Haber-Bosch process. In the present work, density functional theory (DFT) is employed to investigate the electrochemical nitrogen reduction reaction (NRR) catalysed by TM@Mg12O12 (TM=Sc ~ Zn) nanocages. All complexes exhibit chemisorption interactions with interaction energies ranging from − 2.49 eV to − 1.11 eV, except Zn@ Mg12O12 (− 0.48 eV) which shows physisorption. The energy gaps (Eg) of TM@Mg12O12 are significantly reduced compared with pristine Mg12O12 indicating enhanced conductivity. Electronic properties and interaction types were analyzed using density of states, natural bond orbital, interaction region indicator, and quantum theory of atoms in molecules analyses. The results reveal that TM doping notably enhances N2 activation relative to pure Mg12O12. Among all candidates, Mn@Mg12O12 exhibits the highest NRR activity, with a limiting potential of − 0.84 V along the alternating pathway. The stability and energetics of intermediates were further assessed to determine the optimal reaction mechanism for NH3 synthesis. This study provides fundamental insights into the rational design of single-atom catalysts supported on three-dimensional nanocages, contributing to the development of efficient electrocatalysts for ambient ammonia synthesis.

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