Single‐Source‐Precursor‐Derived Binary FeNi Phosphide Nanoparticles Encapsulated in N, P Co‐Doped Carbon as Electrocatalyst for Hydrogen Evolution Reaction and Oxygen Evolution Reaction.

Water‐splitting processes require advanced catalysts for the electrocatalytic hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). A facile and cost‐effective approach using single‐source precursors (SSPs) to prepare active and durable bifunctional electrocatalysts consisting of core–shell structured transition metal phosphide (TMPs) nanoparticles dispersed and immobilized in a highly defective N‐, P‐codoped carbon matrix. The bimetallic FeNi phosphide supported on N‐, P‐codoped carbon is synthesized through pyrolysis at 900 °C under an argon atmosphere (FeNiP@NPC‐900), displaying promising electrocatalytic performance for both HER and OER, with low overpotentials of 191 and 278 mV, respectively. Furthermore, FeNiP@NPC‐900 exhibits remarkable durability in both acidic and alkaline electrolytes. The excellent catalytic and long‐term performance is attributed to several factors, including the novel SSP approach, which prevents the agglomeration of active TMPs particles, the in situ formation of exposed nanopores during the carbonization of the precursor without using surfactants, and the heterostructure between highly defective carbon and TMPs, which positively influences the electronic structure at the interface and facilitates charge transfer. The unique core–shell nanostructure protects the catalytically active phase from corrosion and synergistically promotes the activity performance. Therefore, a new strategy for designing active and stable heterostructured TMPs@carbon‐based electrocatalysts is provided. [ABSTRACT FROM AUTHOR]