Methane Activation Mediated by a Series of Cerium-Vanadium Bimetallic Oxide Cluster Cations: Tuning Reactivity by Doping

Jia Bi Ma; Jing Heng Meng; Sheng Gui He

doi:10.1002/cphc.201501126

Methane Activation Mediated by a Series of Cerium-Vanadium Bimetallic Oxide Cluster Cations: Tuning Reactivity by Doping

Jia Bi Ma^*, Jing Heng Meng, Sheng Gui He

^*Corresponding author for this work

School of Chemistry and Chemical Engineering

CAS - Institute of Chemistry

Research output: Contribution to journal › Article › peer-review

6 Citations (Scopus)

Abstract

The reactions of cerium-vanadium cluster cations Ce_xV_yO_z⁺ with CH₄ are investigated by time-of-flight mass spectrometry and density functional theory calculations. (CeO₂)_m(V₂O₅)_n⁺ clusters (m=1,2, n=1-5; m=3, n=1-4) with dimensions up to nanosize can abstract one hydrogen atom from CH₄. The theoretical study indicates that there are two types of active species in (CeO₂)_m(V₂O₅)_n⁺, V[(O_t)₂]^. and [(O_b)₂CeO_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 (CeO₂)_m(V₂O₅)_n⁺ clusters falls between those of (CeO₂)_2-4⁺ and (V₂O₅)_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.

Original language	English
Pages (from-to)	1112-1118
Number of pages	7
Journal	ChemPhysChem
Volume	17
Issue number	8
DOIs	https://doi.org/10.1002/cphc.201501126
Publication status	Published - 18 Apr 2016

Keywords

cluster compounds
density functional calculations
mass spectrometry
methane
radical ions

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10.1002/cphc.201501126

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@article{aed250d7fe4b49a7800a78c74ae709b1,

title = "Methane Activation Mediated by a Series of Cerium-Vanadium Bimetallic Oxide Cluster Cations: Tuning Reactivity by Doping",

abstract = "The reactions of cerium-vanadium cluster cations CexVyOz+ with CH4 are investigated by time-of-flight mass spectrometry and density functional theory calculations. (CeO2)m(V2O5)n+ clusters (m=1,2, n=1-5; m=3, n=1-4) with dimensions up to nanosize can abstract one hydrogen atom from CH4. The theoretical study indicates that there are two types of active species in (CeO2)m(V2O5)n+, V[(Ot)2]. and [(Ob)2CeOt]. (Ot and Ob 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 (CeO2)m(V2O5)n+ clusters falls between those of (CeO2)2-4+ and (V2O5)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.",

keywords = "cluster compounds, density functional calculations, mass spectrometry, methane, radical ions",

author = "Ma, {Jia Bi} and Meng, {Jing Heng} and He, {Sheng Gui}",

note = "Publisher Copyright: {\textcopyright} 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.",

year = "2016",

month = apr,

day = "18",

doi = "10.1002/cphc.201501126",

language = "English",

volume = "17",

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journal = "ChemPhysChem",

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T1 - Methane Activation Mediated by a Series of Cerium-Vanadium Bimetallic Oxide Cluster Cations

T2 - Tuning Reactivity by Doping

AU - Ma, Jia Bi

AU - Meng, Jing Heng

AU - He, Sheng Gui

PY - 2016/4/18

Y1 - 2016/4/18

N2 - The reactions of cerium-vanadium cluster cations CexVyOz+ with CH4 are investigated by time-of-flight mass spectrometry and density functional theory calculations. (CeO2)m(V2O5)n+ clusters (m=1,2, n=1-5; m=3, n=1-4) with dimensions up to nanosize can abstract one hydrogen atom from CH4. The theoretical study indicates that there are two types of active species in (CeO2)m(V2O5)n+, V[(Ot)2]. and [(Ob)2CeOt]. (Ot and Ob 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 (CeO2)m(V2O5)n+ clusters falls between those of (CeO2)2-4+ and (V2O5)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.

AB - The reactions of cerium-vanadium cluster cations CexVyOz+ with CH4 are investigated by time-of-flight mass spectrometry and density functional theory calculations. (CeO2)m(V2O5)n+ clusters (m=1,2, n=1-5; m=3, n=1-4) with dimensions up to nanosize can abstract one hydrogen atom from CH4. The theoretical study indicates that there are two types of active species in (CeO2)m(V2O5)n+, V[(Ot)2]. and [(Ob)2CeOt]. (Ot and Ob 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 (CeO2)m(V2O5)n+ clusters falls between those of (CeO2)2-4+ and (V2O5)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.

KW - cluster compounds

KW - density functional calculations

KW - mass spectrometry

KW - methane

KW - radical ions

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DO - 10.1002/cphc.201501126

M3 - Article

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VL - 17

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EP - 1118

JO - ChemPhysChem

JF - ChemPhysChem

IS - 8

ER -

Methane Activation Mediated by a Series of Cerium-Vanadium Bimetallic Oxide Cluster Cations: Tuning Reactivity by Doping

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