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Methane Activation Mediated by a Series of Cerium–Vanadium Bimetallic Oxide Cluster Cations: Tuning Reactivity by Doping
Author(s) -
Ma JiaBi,
Meng JingHeng,
He ShengGui
Publication year - 2016
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201501126
Subject(s) - bimetallic strip , reactivity (psychology) , chemistry , cluster (spacecraft) , density functional theory , cerium , vanadium , cerium oxide , vanadium oxide , hydrogen , doping , inorganic chemistry , crystallography , oxide , catalysis , computational chemistry , materials science , organic chemistry , medicine , alternative medicine , optoelectronics , pathology , computer science , programming language
The reactions of cerium–vanadium cluster cations Ce x V y O z + with CH 4 are investigated by time‐of‐flight mass spectrometry and density functional theory calculations. (CeO 2 ) m (V 2 O 5 ) n + clusters ( m =1,2, n =1–5; m =3, n =1–4) with dimensions up to nanosize can abstract one hydrogen atom from CH 4 . The theoretical study indicates that there are two types of active species in (CeO 2 ) m (V 2 O 5 ) n + , V[(O t ) 2 ] . and [(O b ) 2 CeO t ] . (O t and O b represent terminal and bridging oxygen atoms, respectively); the former is less reactive than the latter. The experimentally observed size‐dependent reactivities can be rationalized by considering the different active species and mechanisms. Interestingly, the reactivity of the (CeO 2 ) m (V 2 O 5 ) n + clusters falls between those of (CeO 2 ) 2–4 + and (V 2 O 5 ) 1–5 + in terms of C−H bond activation, thus the nature of the active species and the cluster reactivity can be effectively tuned by doping.