Nanostructured NaFeS2 as a cost-effective and robust electrocatalyst for hydrogen and oxygen evolution with reduced overpotentials

•Nanostructured NaFeS2 Electrocatalyst was prepared in this study.•Hydrogen and oxygen evolution reactions were evaluated.•The material showed unprecedented reduced overpotentials.•The microstructure of the electrocatalyst was linked to its reactivity.•DFT calculations estimated the active sites exhibiting preferential adsorption energy. One of the biggest challenges currently in the field of energy generation and conservation is to develop a stable, scalable and cost-effective electrocatalyst with reduced overpotentials for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). This unprecedented effort presents a robust, non-costly ternary alkali metal-based chalcogenide (NaFeS2) as an effective and highly active electrocatalyst prepared by the hydrothermal method. The monocrystalline nature of the NaFeS2 nanostructures was shown using SAED patterns. The differences in the atomic radii of Na and Fe favors the formation of Fe-S bonds largely contributing to the enhanced electrocatalytic activity of NaFeS2. Further, a decrease in the kinetic energy of the catalytic reaction increases the electrocatalytic property of NaFeS2. We also highlighted the contribution of the high surface area, the Fermi level and the d-orbitals of Fe in enhancing the OER. NaFeS2/NF shows a current density of 200 mA cm−2 with a small potential of 1.60 V and an overpotential of 370 mV indicating that the material possesses a remarkable electrocatalytic activity outperforming other electrocatalysts in the category. Further, by displaying a potential of −220 mV, NaFeS2/NF attained a current density of −100 mA cm−2, demonstrating a significantly improved HER performance of the electrocatalyst. Also, at a potential of −220 mV, the material exhibited a high stability at a continuous electrolysis of about 30 h. The density functional theory (DFT) calculations indicated that out of the possible adsorption sites on the NaFeS2 surface, only (010) and (100) exhibit catalytically preferential adsorption energy (EH) values, which are eventually responsible for the superior electrocatalytic activity. Finally, both the experimental studies and the DFT calculations complement each other and present NaFeS2 as a potentially promising bifunctional electrocatalyst for water splitting applications, which can be scaled-up and deployed for large-scale hydrogen productions.