钪氧团簇负离子与硫化氢的气相反应
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- 英文论文题名：Gas-phase Reactions of Scandium Oxide Cluster Anions with H_2S
- 论文作者：贾美叶 ; 骆智训 ; 何圣贵 ; 葛茂发
- 英文论文作者：Mei-Ye Jia ; Zhi-Xun Luo ; Sheng-Gui He ; Mao-Fa Ge ; State Key Laboratory for Structural Chemistry of Unstable and Stable Species ; Institute of Chemistry ; Chinese Academy of Sciences
- 年：2016
- 作者机构：中国科学院化学研究所分子动态与稳态结构国家重点实验室;
- 论文关键词：钪氧团簇 ; 飞行时间质谱 ; 密度泛函理论计算 ; 硫化氢
- 会议召开时间：2016-07-01
- 会议录名称：中国化学会第30届学术年会摘要集-第四十四分会：化学动力学
- 语种：中文
- 分类号：O643.1
- 学会代码：ZGHY
- 会议名称：中国化学会第30届学术年会-第四十四分会 ; 化学动力学
- 会议地点：中国辽宁大连
- 主办单位：中国化学会
- 学会名称：中国化学会
- 页数：1
- 文件大小：262k
- 原文格式：D
- 会议级别：全国
摘要
采用飞行时间质谱实验(TOF-MS)结合密度泛函理论计算(DFT)研究了钪氧团簇负离子Sc_mO_nˉ与硫化氢的气相反应。激光溅射法产生的Sc_m~(18)Onˉ团簇离子与H_2S在快速流动反应管中发生热碰撞反应,由飞行时间质谱仪检测团簇反应前后的质量分布。实验表明,绝大多数团簇离子与硫化氢发生反应,比如通过氧-硫交换产生水分子:Sc_mO_nˉ+H2S→Sc_mO_n-1ˉ+H_2O;一些团簇还可以依次脱去硫化氢分子的氢原子甚至产生氢气,如Sc_3O_3ˉ。针对一些代表性团簇离子的DFT计算表明,钪氧团簇负离子与H_2S的氧-硫交换反应以及脱氢反应多为常温条件下热力学和动力学允许的过程。本研究不仅提供钪氧化物团簇物种的稳定性及其反应活性的实验数据,也为认识硫化氢催化氧化去除及其微观机理提供理论基础。~([1-2])
The gas-phase reactivity of Sc_m~(18)O_nˉ with H2 S has been investigated by TOF mass spectrometry and DFT calculations. The experiments suggest that dehydration by O/S exchange reaction was evidenced in the reactor for most of the anions Sc_m~(18)O_nˉ, in addition, desulfurization by consecutive H-atom abstraction was also apparently observed for selected clusters. Dehydrogenation through S-atom abstraction was unambiguously ascertained for Sc_3~(18)O_3ˉ through a joint experimental and theoretical examination. Insights into the gas-phase reactivity of scandium oxide cluster anions with H_2S provide fundamentals to scandium oxide clusters enabling to further the mechanisms of H_2S removal.
The gas-phase reactivity of Sc_m~(18)O_nˉ with H2 S has been investigated by TOF mass spectrometry and DFT calculations. The experiments suggest that dehydration by O/S exchange reaction was evidenced in the reactor for most of the anions Sc_m~(18)O_nˉ, in addition, desulfurization by consecutive H-atom abstraction was also apparently observed for selected clusters. Dehydrogenation through S-atom abstraction was unambiguously ascertained for Sc_3~(18)O_3ˉ through a joint experimental and theoretical examination. Insights into the gas-phase reactivity of scandium oxide cluster anions with H_2S provide fundamentals to scandium oxide clusters enabling to further the mechanisms of H_2S removal.
引文
[1]Jia,M.-Y.;Ding,X.-L.;He,S.-G.;Ge,M.-F.J.Phys.Chem.A 2013,117:8377.
[2]Shin,M.Y.;Park,D.W.;Chung,J.S.Appl.Catal.B 2001,30:409.
[2]Shin,M.Y.;Park,D.W.;Chung,J.S.Appl.Catal.B 2001,30:409.