Moderate Active Hydrogen Generation over a Ni 2 P/CoP Heterostructure for One-Step Electrosynthesizing of Azobenzene with High Selectivity

作者：Yuekun Zhang, Zhongling Lang, Qiu Zhang, Ruiqi Yao, Wensi Tang, Tianyu Qiu, Yingqi Li, Yingqi Li, Huaqiao Tan, Yonghui Wang, Yangguang Li, Yangguang Li · 发表于：Nano Letters · 年份：2025 · DOI：10.1021/acs.nanolett.4c05315 · 被引用次数：5 · 研究领域：Electrocatalysts for Energy Conversion、Advanced Memory and Neural Computing、Advanced Photocatalysis Techniques

Through hydrogenation and N–N coupling, azobenzene can be produced via highly selective electrocatalytic nitrobenzene reduction, offering a mild, cost-effective, and sustainable industrial route. Inspired by the density functional theory calculations, the introduction of H* active Ni 2 P into CoP, which reduces the water dissociation energy barrier, optimizes H* adsorption, and moderates key intermediates’ adsorption, is expected to assist its hydrogenation ability for one-step electrosynthesizing azobenzene. A self-supported NiCo@Ni 2 P/CoP nanorod array electrode was synthesized, featuring NiCo alloy nanoparticles within a Ni 2 P/CoP shell. By virtue of the thermodynamically optimal Ni 2 P/CoP heterostructure, along with overall fast electron transport in a core–shell integrated electrode, NiCo@Ni 2 P/CoP with abundant interfacial structure attains a great nitrobenzene conversion of 94.3%, especially prominent azobenzene selectivity of 97.2%, and Faradaic efficiency of 94.1% at −0.9 V (vs Hg/HgO). High-purity azobenzene crystals can also self-separate under refrigeration postelectrolysis. This work provides an energy-efficient and scalable pathway for the economical preparation of azobenzene in the electrocatalytic nitrobenzene hydrogenation.