C1-Based Route for Vinyl Chloride Synthesis with Environmental and Economic Benefits.

作者：Yue Wang, Shihui Zou, Abhinandan Nabera, Xutao Chen, Yang Pan, Kunkun Wei, Yunxin Bao, Jingbo Hu, Yilin Zhao, Chengyuan Liu, Juanjuan Liu, Yong Wang, Yutao Ren, G. Guillén-Gosálbez, J. Pérez‐Ramírez, Jie Fan · 发表于：Journal of the American Chemical Society · 年份：2025 · DOI：10.1021/jacs.4c17531 · 被引用次数：8 · 研究领域：Medicine

Selective coupling of C1 platform molecules to C2 olefins is a cornerstone for establishing a sustainable chemical industry based on nonpetroleum sources. Vinyl chloride (C2H3Cl), one of the top commodity petrochemicals, is commercially produced from coal- or oil-derived C2 hydrocarbon (acetylene and ethylene) feedstocks with a high carbon footprint. Here, we report a C1-based route for vinyl chloride synthesis via the selective oxidative coupling of methyl chloride. This is enabled by a solid catalyst, featuring tungstate nanoclusters embedded in a zirconia matrix, which effectively captures ·CH2Cl radicals homogeneously generated in CH3Cl oxy-pyrolysis and selectively couples them into C2H3Cl. In situ synchrotron-based vacuum ultraviolet photoionization mass spectrometry provides direct experimental evidence of the homogeneous-heterogeneous reaction mechanism. The process achieves methyl chloride conversion of 10-65% with a high vinyl chloride selectivity (60-75%) at a reaction temperature of 650-750 °C, which is much lower than the traditional pyrolysis (>850 °C). The catalyst delivers stable performance (at a vinyl chloride yield of ca. 30%) with no deactivation observed during a 50 h test. Furthermore, combining with reaction of methanol and HCl to produce methyl chloride, we establish a methanol-to-vinyl chloride (MTV) route with the potential for significant reductions in climate change impact (24%) and cost (38%) compared to the state-of-the-art ethylene-based balance...