烯烃
炔烃
试剂
选择性
法拉第效率
电化学
化学
电解
吸附
吉布斯自由能
硫黄
催化作用
组合化学
无机化学
电解质
有机化学
电极
物理化学
热力学
物理
作者
Ying Gao,Rong Yang,Changhong Wang,Cuibo Liu,Yongmeng Wu,Huizhi Li,Bin Zhang
出处
期刊:Science Advances
[American Association for the Advancement of Science (AAAS)]
日期:2022-02-25
卷期号:8 (8)
被引量:41
标识
DOI:10.1126/sciadv.abm9477
摘要
Efficient electrocatalytic alkyne semihydrogenation with potential/time-independent selectivity and Faradaic efficiency (FE) is vital for industrial alkene productions. Here, sulfur-tuned effects and field-induced reagent concentration are proposed to promote electrocatalytic alkyne semihydrogenation. Density functional theory calculations reveal that bulk sulfur anions intrinsically weaken alkene adsorption, and surface thiolates lower the activation energy of water and the Gibbs free energy for H* formation. The finite element method shows high-curvature structured catalyst concentrates K+ by enhancing electric field at the tips, accelerating more H* formation from water electrolysis via sulfur anion-hydrated cation networks, and promoting alkyne transformations. So, self-supported Pd nanotips with sulfur modifiers are developed for electrochemical alkyne semihydrogenation with up to 97% conversion yield, 96% selectivity, 75% FE, and a reaction rate of 465.6 mmol m-2 hour-1. Wide potential window and time irrelevance for high alkene selectivity, good universality, and easy access to deuterated alkenes highlight the promising potential.
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