Zhao Jie, Wang Xuefeng
School of Chemistry and Chemical Engineering, Guizhou University, Guiyang 550025, Guizhou, China.
School of Chemical Science and Engineering, Tongji University, Shanghai 200092, China.
ACS Omega. 2022 Aug 10;7(33):29337-29343. doi: 10.1021/acsomega.2c03594. eCollection 2022 Aug 23.
Hydrogen sulfide is toxic and corrosive gas abundantly available in nature. The activation of hydrogen sulfide to produce hydrogen and elemental sulfur is of great significance for possible applications in toxic pollutant control and hydrogen energy regeneration. The activation of HS by transition metal atoms (M = Cr, Mn, and Fe) has been studied by low-temperature matrix isolation infrared spectroscopy and quantum chemical calculations. Experimental and theoretical results indicate that the reaction between ground-state M atoms and HS is inhibited by the repulsive interactions between the reactants. After being excited upon photolysis, the corresponding excited-state M atoms react with HS molecules spontaneously. The produced insertion product HMSH further decomposed to metal sulfides upon full-arc mercury lamp irradiation by the splitting of hydrogen.
硫化氢是自然界中大量存在的有毒且具腐蚀性的气体。硫化氢的活化以产生氢气和元素硫，对于在有毒污染物控制和氢能再生中的可能应用具有重要意义。过渡金属原子（M = Cr、Mn和Fe）对HS的活化已通过低温基质隔离红外光谱和量子化学计算进行了研究。实验和理论结果表明，基态M原子与HS之间的反应受到反应物间排斥相互作用的抑制。光解激发后，相应的激发态M原子会自发地与HS分子反应。生成的插入产物HMSH在全弧汞灯照射下通过氢的分裂进一步分解为金属硫化物。
