Rational design of electrocatalytic materials with low cost and high efficiency for both electrochemical water splitting and nitrogen reduction reaction (NRR) at moderate conditions is vital to meet the growing demand for sustainable energy production. In this study, we used density functional theory (DFT) calculations to systematically study hydrogen evolution reaction (HER), oxygen evolution reaction (OER) and NRR activities on various nano-materials including endohedral fullerenes, double transition metal MXenes, and Gr/MoS2 heterostructures. Our results show that among the various endohedral fullerenes studied, both Sc3N@D3hC78 and Sc3N@D5hC80 with the combination of higher NRR selectivity and activity, shows better electrocatalytic activity for NRR compared to other endohedral catalysts. Apart from the consideration of high NRR performance, we observed that U@C76 with the lowest Gibbs energy change values exhibits excellent performance for HER. Furthermore, the construction of Gr/MoS2 heterostructure is expected to improve the OER activity owing to the increased charge transfer and modification of the electronic structure of MoS2. For MXenes, we observed enhanced adsorption energies for NRR reaction intermediates because of strong chemical interactions and are believed to promote the reaction pathways with the lowest limiting potentials. We elucidate Bader charge analysis, charge density difference analysis, and projected density of states (PDOS) to understand the underlying adsorption and catalytic behaviour of the materials considered. Overall our theoretical results provide a practical route for the rational design of the electrocatalytically active materials incorporating various 2D materials for both electrochemical water splitting and nitrogen reduction reactions which is a significant step forward towards designing the novel catalytic materials.

First-principles investigation of noble metal free electrocatalysts for efficient water splitting and nitrogen reduction reactions

ACS Spring Meeting 2021

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