Untangling the role of single-atom substitution on the improvement of the hydrogen evolution reaction of Y2NS2 MXene in acidic media

Abstract

The production of hydrogen (H₂) fuel through electrocatalysis is emerging as a sustainable alternative to conventional and environmentally harmful energy sources. However, the discovery of cost-effective and efficient materials for this purpose remains a significant challenge. In this study, we explore the potential of the transition-metal-substituted Y₂NS₂ MXene as a promising candidate for hydrogen production through the hydrogen evolution reaction (HER). Using density functional theory (DFT) calculations, we first analyzed the Pourbaix diagram, and dissolution potential which showed the stability and resistance to corrosion of the sulfur termination. Later, we address the kinetic limitations of HER on bare Y₂NS₂ by introducing single-atom substitutions of Y atoms with 3d transition metals. Nine distinct structures were evaluated, revealing that Fe-substituted Y₂NS₂ exhibits the highest HER activity under acidic conditions, as indicated by volcano plot analyses. Further investigation of the bonding characteristics and electronic density of states highlights the crucial role of Fe d-orbitals and the weak interactions at the sulfur-terminated surface in enhancing the HER efficiency. These findings provide insights into the design of advanced, cost-effective materials for HER catalysis, paving the way for their application as efficient electrochemical catalysts across a wide pH range.