Tang Yulong, Li Jiejie, Lin Yichao, Cheng Moxing, Wang Shuibo, Tian Ziqi, Zhou Junjie, Zhang Haolei, Wang Yunan, Chen Liang
Zhejiang Key Laboratory of Advanced Fuel Cells and Electrolyzers Technology, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo, Zhejiang, PR China.
University of Chinese Academy of Sciences, Beijing, PR China.
Nat Commun. 2025 Mar 6;16(1):2236. doi: 10.1038/s41467-025-57462-w.
The electrochemical reduction of acetonitrile (AN) to ethylamine (EA) is an attractive yet challenging process, primarily due to the competing hydrogen evolution reaction (HER). This study demonstrates the ability to halt the HER at Volmer step, where protons migrate to the unsaturated bond of AN on a self-supported CuO@Cu heterostructure. The CuO@Cu catalyst exhibits nearly 100% Faradaic efficiency (FE) over the entire range of potentials tested from -0.1 to -0.4 V vs. RHE, demonstrating remarkable stability over 1000 h at a constant current density of 0.2 A cm. CuO is identified as the active component driving the reaction, while the metallic Cu facilitates efficient electron transfer. Theoretical simulations and experimental evidences indicate that a synergistic hydrogenation process contributes to the AN reduction reaction (ARR), which involves both surface hydrogen migration and proton addition from solution. This study provides an insight into understanding of ARR process, and suggests an efficient strategy to enhance the electrochemical hydrogenation of organic molecules by regulating the Volmer step.
乙腈（AN）电化学还原为乙胺（EA）是一个具有吸引力但具有挑战性的过程，主要是由于存在竞争性析氢反应（HER）。本研究展示了在Volmer步骤中阻止HER的能力，在此步骤中质子迁移到自支撑的CuO@Cu异质结构上AN的不饱和键处。在相对于可逆氢电极（RHE）从-0.1到-0.4 V测试的整个电位范围内，CuO@Cu催化剂表现出近100%的法拉第效率（FE），在0.2 A cm的恒定电流密度下1000 h内显示出卓越的稳定性。CuO被确定为驱动该反应的活性成分，而金属Cu促进了有效的电子转移。理论模拟和实验证据表明，协同氢化过程有助于乙腈还原反应（ARR），该过程涉及表面氢迁移和来自溶液的质子加成。本研究为理解ARR过程提供了见解，并提出了一种通过调节Volmer步骤来增强有机分子电化学氢化的有效策略。
