Vanadium doped FeP nanoflower with optimized electronic structure for efficient hydrogen evolution

Reasonable design of hydrogen evolution reaction (HER) electrocatalyst from the perspective of electronic structure is a vital way to optimize the catalytic activity. Mono-metallic iron-based phosphates have been shown to be active toward HER, but their performance remains unsatisfactory despite their abundant reserves and low preparation cost. Here, guided by the d-band center and band structure theories, V-doped FeP nanoflower grown directly on iron foam are constructed. Combining the density functional theory (DFT) simulations with physical characterizations reveal that the enhanced HER activity is mainly attributed to the lowed d-band central position, increased water dissociation capacity, decreased hydrogen formation energy barrier and reduced charge transfer impedance. As a HER catalyst in 1 M KOH, the obtained V-FeP shows low overpotentials of ∼149, ∼246 and ∼290 mV to deliver the current densities of 100, 500 and 1000 mA cm^-2 with at least 24 h. When coupled with other highly active oxygen evolution reaction (OER) catalyst (NiFe-LDH/IF), the NiFe-LDH/IF⁽⁺⁾ || V-FeP/IF^(-) pair also performs a low cell voltage and over 100-h stability at high current density of 1000 mA cm^-2, which endows it a large potential in the practical electrolytic water industry. Our work may provide a reference for the enhancement of inert and low-cost HER-active iron phosphide.