title: Activation of Methane Promoted by Adsorption of CO on Mo2 C2 (-) Cluster Anions.
abstract: Atomic clusters are being actively studied for activation of methane, the most stable alkane molecule. While many cluster cations are very reactive with methane, the cluster anions are usually not very reactive, particularly for noble metal free anions. This study reports that the reactivity of molybdenum carbide cluster anions with methane can be much enhanced by adsorption of CO. The Mo2 C2 (-) is inert with CH4 while the CO addition product Mo2 C3 O(-) brings about dehydrogenation of CH4 under thermal collision conditions. The cluster structures and reactions are characterized by mass spectrometry, photoelectron spectroscopy, and quantum chemistry calculations, which demonstrate that the Mo2 C3 O(-) isomer with dissociated CO is reactive but the one with non-dissociated CO is unreactive. The enhancement of cluster reactivity promoted by CO adsorption in this study is compared with those of reported systems of a few carbonyl complexes.
authors.affiliation: Beijing National Laboratory for Molecular Science, State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China.|University of Chinese Academy of Sciences, Beijing, 100049, China.
authors.forename: Qing-Yu
authors.initials: QY
authors.lastname: Liu
authors.affiliation: Key Laboratory of Cluster Science, Institute for Chemical Physics School of Chemistry, Beijing Institute of Technology, Beijing, 100081, China. majiabi@bit.edu.cn.
authors.forename: Jia-Bi
authors.initials: JB
authors.lastname: Ma
authors.affiliation: Beijing National Laboratory for Molecular Science, State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China.
authors.forename: Zi-Yu
authors.initials: ZY
authors.lastname: Li
authors.affiliation: Beijing National Laboratory for Molecular Science, Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China.|University of Chinese Academy of Sciences, Beijing, 100049, China.
authors.forename: Chongyang
authors.initials: C
authors.lastname: Zhao
authors.affiliation: Department of Physics, State Key Laboratory of Low-Dimensional Quantum Physics, Tsinghua University, Beijing, 100084, China.
authors.forename: Chuan-Gang
authors.initials: CG
authors.lastname: Ning
authors.affiliation: Beijing National Laboratory for Molecular Science, Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China. chenh@iccas.ac.cn.
authors.forename: Hui
authors.initials: H
authors.lastname: Chen
authors.affiliation: Beijing National Laboratory for Molecular Science, State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China. shengguihe@iccas.ac.cn.
authors.forename: Sheng-Gui
authors.initials: SG
authors.lastname: He
keywords: density functional computations; mass spectrometry; methane activation; molybdenum carbides; photoelectron spectroscopy