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Activation of Methane Promoted by Adsorption of CO on Mo 2 C 2 − Cluster Anions
Author(s) -
Liu QingYu,
Ma JiaBi,
Li ZiYu,
Zhao Chongyang,
Ning ChuanGang,
Chen Hui,
He ShengGui
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201600618
Subject(s) - chemistry , reactivity (psychology) , molybdenum , dehydrogenation , adsorption , cluster (spacecraft) , methane , inorganic chemistry , alkane , x ray photoelectron spectroscopy , photochemistry , catalysis , organic chemistry , computer science , programming language , medicine , physics , alternative medicine , pathology , nuclear magnetic resonance
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 Mo 2 C 2 − is inert with CH 4 while the CO addition product Mo 2 C 3 O − brings about dehydrogenation of CH 4 under thermal collision conditions. The cluster structures and reactions are characterized by mass spectrometry, photoelectron spectroscopy, and quantum chemistry calculations, which demonstrate that the Mo 2 C 3 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.