Liu Xing, Liu Xiaorui, Wang Xuefeng
College of Chemistry and Chemical Engineering , Southwest University , Chongqing 400715 , China.
Shanghai Key Lab of Chemical Assessment and Sustainability, School of Chemical Science and Engineering , Tongji University , Shanghai , 200092 , China.
J Phys Chem A. 2018 Sep 6;122(35):7023-7032. doi: 10.1021/acs.jpca.8b04428. Epub 2018 Aug 22.
The water gas reaction C + HO → CO + H has been employed for centuries; however little is known for analogous reaction M + HS → MS + H (M = Si, Ge, Sn, Pb). In addition, this latter reaction is intriguing in its function of converting pollutant HS to clean energy source H. We report herein the reactions of laser-ablated Group 14 atom M (M = Si, Ge, Sn, Pb) with HS using matrix isolation infrared spectroscopy as well as the state-of-the-art quantum chemical calculations. Important reactive intermediates HMSH with high active H (protonic H and hydridic H) are identified. In addition, the reaction mechanisms are established for insertion reaction M + HS → HMSH, and photoinduced H elimination reactions of HMSH → MS+ H and HSiS → SiS+ H in low-temperature matrices.
水煤气反应C + H₂O → CO + H₂已经被使用了几个世纪；然而，对于类似的反应M + H₂S → MS + H₂（M = Si、Ge、Sn、Pb）却知之甚少。此外，后一种反应在将污染物H₂S转化为清洁能源H₂的功能方面很有趣。我们在此报告使用基质隔离红外光谱以及最先进的量子化学计算对激光烧蚀的第14族原子M（M = Si、Ge、Sn、Pb）与H₂S的反应。确定了具有高活性H（质子H和氢化物H）的重要反应中间体HMSH。此外，还建立了低温基质中插入反应M + H₂S → HMSH以及HMSH → MS + H₂和HSiS → SiS + H₂的光致H消除反应的反应机理。
