Oxygen-Sulfur Exchange and the Gas-Phase Reactivity of Cobalt Sulfide Cluster Anions with Molecular Oxygen

doi:10.1021/jp500837g

CORC > 化学研究所 > 中国科学院化学研究所

	Oxygen-Sulfur Exchange and the Gas-Phase Reactivity of Cobalt Sulfide Cluster Anions with Molecular Oxygen
	Jia, Mei-Ye 1,2; Luo, Zhixun 1; He, Sheng-Gui 1; Ge, Mao-Fa 1
刊名	JOURNAL OF PHYSICAL CHEMISTRY A
	2014-09-18
卷号	118 期号:37 页码:8163-8169
ISSN号	1089-5639
DOI	10.1021/jp500837g
英文摘要	We present here a study of gas-phase reactivity of cobalt sulfide cluster anions ComSn- with molecular oxygen. Nascent ComSn- clusters were prepared via a laser ablation source and reacted with oxygen in a fast flow reactor under thermal collision conditions. We chose O-18(2) in place of O-16(2) to avoid mass degeneration with sulfur, and a time-of-flight (TOF) mass spectrometer was used to detect the cluster distributions in the absence and presence of the reactant. It was found that oxygen-sulfur exchange occurs in the reactions for those with specific compositions (CoS)(n)(-) and (CoS)(n)S- (n = 2-5) according to a consistent pathway, "ComSn- + O-18(2) -> (ComSn-1O-)-O-18 + (SO)-O-18". Typically, for Co2S2- + O-18(2)" we have calculated the reaction coordinates by employing the density functional theory (DFT), where both the oxygen-sulfur exchange and SO molecule release are thermodynamically and kinetically favorable. It is noteworthy that the reaction with molecular oxygen (triplet ground state) needs to overcome a spin excitation as well as a large O-O activation energy. This study sheds light on the activation of molecular oxygen by cobalt sulfides on one hand and also provides insight into the regeneration mechanism of cobalt oxides from the counterpart sulfides in the presence of oxygen gas on the other hand.
语种	英语
出版者	AMER CHEMICAL SOC
WOS记录号	WOS:000342119000016
内容类型	期刊论文
源URL	[http://ir.iccas.ac.cn/handle/121111/50835]
专题	中国科学院化学研究所
通讯作者	Luo, Zhixun
作者单位	1.Chinese Acad Sci, Inst Chem, State Key Lab Struct Chem Unstable & Stable Speci, Beijing Natl Lab Mol Sci, Beijing 100190, Peoples R China 2.Univ Chinese Acad Sci, Beijing 100049, Peoples R China
推荐引用方式 GB/T 7714	Jia, Mei-Ye,Luo, Zhixun,He, Sheng-Gui,et al. Oxygen-Sulfur Exchange and the Gas-Phase Reactivity of Cobalt Sulfide Cluster Anions with Molecular Oxygen[J]. JOURNAL OF PHYSICAL CHEMISTRY A,2014,118(37):8163-8169.
APA	Jia, Mei-Ye,Luo, Zhixun,He, Sheng-Gui,&Ge, Mao-Fa.(2014).Oxygen-Sulfur Exchange and the Gas-Phase Reactivity of Cobalt Sulfide Cluster Anions with Molecular Oxygen.JOURNAL OF PHYSICAL CHEMISTRY A,118(37),8163-8169.
MLA	Jia, Mei-Ye,et al."Oxygen-Sulfur Exchange and the Gas-Phase Reactivity of Cobalt Sulfide Cluster Anions with Molecular Oxygen".JOURNAL OF PHYSICAL CHEMISTRY A 118.37(2014):8163-8169.