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<p>Electrosynthesis of 1,3-butadiene from acetylene offers a promising alternative to energy-intensive industrial processes. Nonetheless, achieving selective hydrodimerization of acetylene remains challenging due to competing side reactions, particularly for dilute coal-derived acetylene. Herein, we synthesize a series of dicopper paddlewheel Cu<sub>2</sub>(LCOO)<sub>4</sub> (L = tert-butyl, isopropyl, ethyl, and methyl), featuring bidentate bridging carboxylate ligands with specific Cu···Cu distances for electrocatalytic hydrodimerization of acetylene to 1,3-butadiene. Through catalyst benchmarking, in situ spectroscopy and computational analysis, we reveal that sequential modulation of carboxylate ligands (methyl → ethyl → isopropyl → tert-butyl) progressively enriches electron density at dicopper sites while strengthening structural robustness across the Cu<sub>2</sub>(LCOO)<sub>4</sub> series. The optimized Cu<sub>2</sub>(tert-butylCOO)<sub>4</sub> exhibits favorable reaction energetics for acetylene dimerization and subsequent hydrogenation, achieving 91% Faradaic efficiency with a 1,3-butadiene formation rate of 0.93 mmol h<sup>−1</sup> cm<sup>−2</sup> in a flow cell. For simulated production of 1,3-butadiene from coal-derived acetylene (15%) in a membrane electrode assembly system, this catalyst demonstrates 83% Faradaic efficiency at −300 mA. This work highlights an effective coordination modulation strategy for producing 1,3-butadiene via dicopper molecular catalysts.</p>

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Electrosynthesis of 1,3-butadiene from dilute acetylene over coordination-modulated dicopper molecular catalysts

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2026年5月7日

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  • Wenzhe Xu,
  • Pengfei Gao,
  • Jianfeng Wu,
  • Ran Du,
  • Mengtao Li,
  • Lingfeng Tang,
  • Mingrui Li,
  • Na Feng,
  • Baoliang Zhang,
  • Zongjing Lu,
  • Lei Zhang

摘要

Electrosynthesis of 1,3-butadiene from acetylene offers a promising alternative to energy-intensive industrial processes. Nonetheless, achieving selective hydrodimerization of acetylene remains challenging due to competing side reactions, particularly for dilute coal-derived acetylene. Herein, we synthesize a series of dicopper paddlewheel Cu2(LCOO)4 (L = tert-butyl, isopropyl, ethyl, and methyl), featuring bidentate bridging carboxylate ligands with specific Cu···Cu distances for electrocatalytic hydrodimerization of acetylene to 1,3-butadiene. Through catalyst benchmarking, in situ spectroscopy and computational analysis, we reveal that sequential modulation of carboxylate ligands (methyl → ethyl → isopropyl → tert-butyl) progressively enriches electron density at dicopper sites while strengthening structural robustness across the Cu2(LCOO)4 series. The optimized Cu2(tert-butylCOO)4 exhibits favorable reaction energetics for acetylene dimerization and subsequent hydrogenation, achieving 91% Faradaic efficiency with a 1,3-butadiene formation rate of 0.93 mmol h−1 cm−2 in a flow cell. For simulated production of 1,3-butadiene from coal-derived acetylene (15%) in a membrane electrode assembly system, this catalyst demonstrates 83% Faradaic efficiency at −300 mA. This work highlights an effective coordination modulation strategy for producing 1,3-butadiene via dicopper molecular catalysts.