F-regulated NiP-F3 nanosheets as efficient electrocatalysts for full-water-splitting and urea oxidation

Heteroatomic anion doping represents a powerful approach for manipulating the electronic configuration of the active metal locus in electrocatalysts, resulting in enhanced multifunctional electrocatalytic properties in hydrogen/oxygen evolution reactions (HER/OER). Here, fluorine-tailored Ni 2 P-F3 nanosheets were synthesized and evaluated as a robust multifunctional electrocatalyst for HER, OER, and UOR. Our comprehensive experimental and theoretical investigations reveal that the anionic F effectively tailored the electronic states of the Ni 2 P-F3 nanosheets, resulting in an elevated d-band center and optimizing the sorption capacity of intermediates. In addition to thermodynamically and kinetically favoured redox reactions, F doping facilitates the reconstruction and generation of active γ-NiOOH. Resulting from the optimized electronic configuration and nanosheet architecture, outstanding catalytic activities are demonstrated by Ni 2 P-F3 with low overpotentials to reach 100 mA cm −2 for HER (177 mV) and OER (293 mV), surpassing Ni 2 P by 234 and 205 mV, respectively. Notably, 1.618 V is required for full-water-diversion to reach 10 mA cm −2 , while 1.414 V is required with urea oxidation for 100 mA cm −2 . Ni 2 P-F3 nanosheets were synthesized via vapor phosphorylation and melt fluorination. Fluorine doping was employed to adjust the electronic structure and d-band center, thereby optimizing the adsorption energies of intermediates.