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

The water gas reaction C + H2O → CO + H2 has been employed for centuries; however little is known for analogous reaction M + H2S → MS + H2 (M = Si, Ge, Sn, Pb). In addition, this latter reaction is intriguing in its function of converting pollutant H2S to clean energy source H2. 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 HMSH with high active H (protonic Hδ+ and hydridic Hδ-) are identified. In addition, the reaction mechanisms are established for insertion reaction M + H2S → HMSH, and photoinduced H2 elimination reactions of HMSH → MS+ H2 and H2SiS → SiS+ H2 in low-temperature matrices.