Selective electrosynthesis of 1,3-butadiene by tailoring the coverage of acetylene and water

1,3-Butadiene (C ₄ H ₆ ), the main raw material for producing important chemicals (nylon, synthetic resin, rubber), relies on petroleum cracking with intensive carbon emissions. The electrocatalytic dimeric hydrogenation of natural gas/coal-derived C ₂ H ₂ to C ₄ H ₆ provides a nonpetroleum pathway. However, C ₄ H ₆ , as a byproduct of C ₂ H ₂ hydrogenation, is usually neglected because of its very low Faradaic efficiency. Here, we theoretically and experimentally report a mechanism comprising acetylene dimerization and subsequent hydrogenation. The first dimerization process can be accelerated under appropriate coverage of acetylene and water. A ligand-modifying strategy is subsequently proposed to regulate the wettability of Cu nanoarrays to enable suitable coverages. The optimized 1-dodecanethiol-modified Cu nanoarrays deliver a 65.3% C ₄ H ₆ Faradaic efficiency at 100 mA cm ⁻² . The C ₄ H ₆ formation kinetics become sluggish at the two ends of the surface C ₂ H ₂ /H ₂ O ratios, and moderate C ₂ H ₂ /H ₂ O coverage accelerates the C‒C coupling process to promote C ₄ H ₆ production. Moreover, life cycle assessment demonstrates its sustainability.