Microscopic‐Level Insights into P‐O‐Induced Strong Electronic Coupling Over Nickel Phosphide with Efficient Benzyl Alcohol Electrooxidation

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Electrooxidation of biomass into fine chemicals coupled with energy‐saving hydrogen production for a zero‐carbon economy holds great promise. Advanced anode catalysts determine the cell voltage and electrocatalytic efficiency greatly, further the rational design and optimization of their active site coordination remains a challenge. Herein, a phosphorus‐oxygen terminals‐rich species (Ni 2 P‐O‐300) via an anion‐assisted pyrolysis strategy is reported to induce strong electronic coupling and high valence state of active nickel sites over nickel phosphide. This ultimately facilitates the rapid yet in‐situ formation of high‐valence nickel with a high reaction activity under electrochemical conditions, and exhibits a low potential of 1.33 V vs. RHE at 10 mA cm −2 , exceeding most of reported transition metal‐based catalysts. Advanced spectroscopy, theoretical calculations, and experiments reveal that the functional P‐O species can induce the favorable local bonding configurations for electronic coupling, promoting the electron transfer from Ni to P and the adsorption of benzyl alcohol (BA). Finally, the hydrogen production efficiency and kinetic constant of BA electrooxidation by Ni 2 P‐O‐300 are increased by 9‐ and 2.8‐ fold compared with the phosphorus‐oxygen terminals‐deficient catalysts (Ni 2 P‐O‐500). This provides an anion‐assisted pyrolysis strategy to modulate the electronic environment of the Ni site, enabling a guideline for Ni‐based energy/catalysis systems.