Cheng Chuanqi, Wang Jiajun, Chen Fanpeng, Han Yanran, He Yichen, Zhang Bin, Zhao Bo-Hang
Department of Chemistry, School of Science, Tianjin University, Tianjin, China.
Institute of Molecular Plus, Tianjin University, Tianjin, China.
Nat Commun. 2025 Jul 1;16(1):5685. doi: 10.1038/s41467-025-60881-4.
1,3-Butadiene (CH), 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 CH to CH provides a nonpetroleum pathway. However, CH, as a byproduct of CH 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% CH Faradaic efficiency at 100 mA cm. The CH formation kinetics become sluggish at the two ends of the surface CH/HO ratios, and moderate CH/HO coverage accelerates the C‒C coupling process to promote CH production. Moreover, life cycle assessment demonstrates its sustainability.
1,3-丁二烯（CH）是生产重要化学品（尼龙、合成树脂、橡胶）的主要原料，依赖于碳排放密集的石油裂解。将天然气/煤衍生的CH电催化二聚加氢为CH提供了一条非石油途径。然而，CH作为CH加氢的副产物，由于其法拉第效率极低，通常被忽视。在此，我们通过理论和实验报道了一种包括乙炔二聚和随后加氢的机理。在适当的乙炔和水覆盖下，第一个二聚过程可以加速。随后提出了一种配体修饰策略来调节铜纳米阵列的润湿性，以实现合适的覆盖度。优化后的1-十二烷硫醇修饰的铜纳米阵列在100 mA cm下的CH法拉第效率为65.3%。表面CH/HO比两端的CH生成动力学变得迟缓，适度的CH/HO覆盖加速了C-C偶联过程，促进了CH的生成。此外，生命周期评估证明了其可持续性。
