Surface Lattice Oxygen Confined Hydrogen Transfer for Electrochemical Acetonitrile Hydrogenation

作者：Hao Zhang, Linghao Yu, Yancai Yao, Biao Zhou, Jundi Cheng, Xupeng Liu, Ziyue Chen, Hao Zhang, Long Zhao, Lizhi Zhang · 发表于：ACS Catalysis · 年份：2025 · DOI：10.1021/acscatal.4c07928 · 被引用次数：27 · 研究领域：Electrocatalysts for Energy Conversion、Advanced Photocatalysis Techniques、Nanomaterials for catalytic reactions

Electrochemical synthesis of ethylamine from acetonitrile with H 2 O is a promising alternative to the traditional H 2 -based process but is challenged by the sluggish hydrogenation process with the inefficient supply of active hydrogen species (H*). Herein, we report an accelerated hydrogen transfer strategy to facilitate on-site electrochemical hydrogenation of acetonitrile for ethylamine synthesis. This strategy was realized by a monolithic electrode composed of oxygen vacancies (OVs)-rich titanium dioxide nanoarrays grown on Ti foam in combination with Ni single atoms (Ni 1 /OVs-TiO 2 NA), which enabled the efficient electrochemical water dissociation into H* along with the optimized electronic structure of surface lattice oxygens by leveraging adjacent OVs, effectively weakening the binding strength of O–H bonds for the subsequent fast transfer of confined H* mediated by surface lattice oxygens. With further incorporation of Ni single atoms as H* trapping centers for the hydrogenation step, the as-prepared Ni 1 /OVs-TiO 2 NA delivered an impressive electrocatalytic performance of acetonitrile hydrogenation with an ethylamine yield rate of 6.93 mmol h –1 mg Ni –1 and a Faraday efficiency of 94%, 8.8-fold higher than that of OVs-free counterpart (0.78 mmol h –1 mg Ni –1, 39%). This work clarifies the promotion effect of surface lattice oxygen on hydrogen-transfer-related electrochemical hydrogenation reactions and offers a water-based ethylamine synthesis strategy.