Li Huizhi, Li Qian, Guo Shuoshuo, Gao Ying, Zhang Bin, Liu Cuibo
Department of Chemistry, School of Science, Tianjin University, Tianjin 300072, China.
Institute of Molecular Plus, Tianjin University, Tianjin 300072, China.
J Am Chem Soc. 2025 May 28;147(21):17849-17859. doi: 10.1021/jacs.5c01911. Epub 2025 May 15.
Ineffective control of alkene adsorption on a palladium membrane (PM) and the flux of active hydrogen (H*) diffusing from the aqueous side to the organic side through the PM cause low selectivity and Faradaic efficiency (FE) of alkynes to alkenes in a PM reactor. Here, a PM with a phenylthiolate-modified palladium sulfide thin layer coupled with pulsed electrolysis is reported to enable alkyne-to-alkene electrosynthesis with up to 98% selectivity and 80% FE. Electrochemical in situ Raman spectra reveal weak alkene adsorption and specific σ-alkynyl adsorption rather than flat adsorption of alkynes on the modified PM, accounting for the high alkene selectivity and functional group tolerance. Pulsed electrolysis causes reduced H* generation and restricted H* diffusion to the organic side, which better balances the generation and utilization of H*, suppresses H evolution, and improves the FE. The high alkene selectivity and FE in a wide potential and current range, over 50 examples of (deuterated) alkenes with functional group tolerance and deuterated drug applications (-, -, -, , and ), and scalable electrosynthesis of deuterated styrene for deuterated polystyrene with improved thermal stability demonstrate potential utility.
钯膜（PM）对烯烃吸附的无效控制以及活性氢（H*）通过PM从水相扩散到有机相的通量，导致PM反应器中炔烃对烯烃的选择性和法拉第效率（FE）较低。在此，报道了一种具有苯硫醇盐修饰的硫化钯薄层并结合脉冲电解的PM，能够实现炔烃到烯烃的电合成，选择性高达98%，FE为80%。电化学原位拉曼光谱揭示了烯烃在修饰的PM上的弱吸附以及特定的σ-炔基吸附，而非炔烃的平面吸附，这解释了高烯烃选择性和官能团耐受性。脉冲电解导致H生成减少且向有机相的H扩散受限，从而更好地平衡了H*的生成和利用，抑制了析氢，并提高了FE。在宽电位和电流范围内的高烯烃选择性和FE、超过50个具有官能团耐受性的（氘代）烯烃实例以及氘代药物应用（-、-、-、和），以及用于热稳定性提高的氘代聚苯乙烯的氘代苯乙烯的可扩展电合成，证明了其潜在应用价值。
