Structure‐tailored non‐noble metal‐based ternary chalcogenide nanocrystals for Pt‐like Electrocatalytic Hydrogen Production

Abstract

A facile microwave-assisted strategy was employed to synthesize Ni₃Bi₂S₂ nanocrystals. Variation in the synthesis conditions tuned the composition of monoclinic and orthorhombic phases of Ni₃Bi₂S₂. The electrochemical hydrogen evolution activity of the catalyst with highest percentage of monoclinic phase demonstrated a negligible onset potential of only 24 mV close to that of state-of-the-art Pt/C with an overpotential as low as 88 mV. Density functional theory calculations predicted the monoclinic phase exhibit the lowest adsorption free energy corresponding to hydrogen adsorption (ΔG^H*_ads) and, therefore, the highest hydrogen evolution activity amongst the considered phases. The quasi-2D structure of monoclinic phase facilitated an increased charge-transfer between Ni and Bi, favoring the downward shift of the d-band center to enhance the catalytic activity.