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.

Boosting oxygen evolution by nickel nitrate hydroxide with abundant grain boundaries via segregated high-valence molybdenum.

High-valence metal doping and abundant grain boundaries (GBs) have been proved to be effective strategies to promote the oxygen evolution reaction (OER). However, the reasonable design of the two to facilitate OER collaboratively is challenging. Herein, a convenient and novel one-step molten salt decomposition strategy is proposed to fabricate segregated-Mo doped nickle nitrate hydroxide with substantial GBs on MoNi foam (Mo-NNOH@MNF). When processed in molten salt, the Mo species on the conductive substrate migrates unevenly to the surface of Mo-NNOH@MNF, which not only induces the formation of abundant GBs to modulate electronic structure, but also improves the intrinsic activity as high-valence dopants, synergistically elevating OER activity. As verification, the optimized Mo-NNOH@MNF-10h exhibits low overpotential of 150 mV at 10 mA cm-2, which can be attributed to the reduced valence charge transition energy of Ni by high-valence Mo dopant, coupled with the fine-tuning of d-band center bond and corresponding local electron density by induced GBs and Mo doping, as DFT calculations revealed. Moreover, the intrinsic robustness and strong adhesion ensure the long-term stability of 6 h at 500 mA cm-2. This work provides a promising molten salt decomposition approach to synthesize advanced materials with unique structures.