Highly Selective Electrochemical Semi-Hydrogenation Via a Palladium Membrane Reactor

作者：Minghao Sun, Jiewen Xiao, Yu Yang, Wei Zhang, Jialei Huang, Yawen Hao, Jinqi Xiong, Yaohui Shi, Yifan Zeng, Adnan Ozden, Tongliang Liu, Aoni Xu, Fengwang Li · 发表于：Nano Letters · 年份：2025 · DOI：10.1021/acs.nanolett.5c03140 · 被引用次数：5 · 研究领域：Electrocatalysts for Energy Conversion、CO2 Reduction Techniques and Catalysts、Ammonia Synthesis and Nitrogen Reduction

The selective semihydrogenation of alkynes is a critical industrial process, yet conventional palladium-based methods often suffer from overhydrogenation, leading to poor alkene selectivity. To address this, we report an electrochemical palladium membrane reactor that employs cysteamine, a simple aliphatic amino thiol, as a surface modifier. This system achieves >99% selectivity for the semihydrogenation of phenylacetylene to styrene at high current densities up to 300 mA/cm 2, under ambient conditions and continuous electrolysis. Spectroscopic analysis and density functional theory calculations indicate that cysteamine forms a surface S 2– adlayer, resulting in a competitive adsorption mechanism where the S 2– species prevents styrene readsorption without impeding the initial hydrogenation of phenylacetylene. This work demonstrates a distinct and operationally simple strategy, using a specific sulfur modifier under continuous hydrogen flux, to achieve ultrahigh selectivity in a targeted alkyne semihydrogenation.