Splitting of Hydrogen Sulfide by Group 14 Elements (Si, Ge, Sn, Pb) in Excess Argon at Cryogenic Temperatures

摘要

The water gas reaction C + H2O - CO + H-2 has been employed for centuries; however little is known for analogous reaction M + H2S - MS + H-2 (M = Si, Ge, Sn, Pb). In addition, this latter reaction is intriguing in its function of converting pollutant H2S to clean energy source H-2. We report herein the reactions of laser-ablated Group 14 atom M (M = Si, Ge, Sn, Pb) with H2S using matrix isolation infrared spectroscopy as well as the state-of-the-art quantum chemical calculations. Important reactive intermediates FINISH with high active H (protonic H delta+ and hydridic H delta-) are identified. In addition, the reaction mechanisms are established for insertion reaction M + H2S - HMSH, and photoinduced H-2 elimination reactions of HMSH - MS+ H-2 and H2SiS - SiS+ H-2 in low-temperature matrices.