Methane Activation by Yttrium‐Doped Vanadium Oxide Cluster Cations: Local Charge Effects

Li, Ziyu; Zhao, Yan‐Xia; Wu, Xiao‐Nan; Ding, Xun‐Lei; He, Sheng‐Gui

doi:10.1002/chem.201102055

Cited by 68 publications

(79 citation statements)

References 75 publications

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“…38,46,47 The reactivity of the clusters toward CH 4 can be significantly influenced with the variations of the local charges around the O ·− centers. 62 This study has identified that the gasphase L−FeC 6 − anion, capable of activating CH 4 through oxidative addition, possesses a high dipole moment. The high dipole moment can lead to a strong local electric field along the geometrically most favorable direction (see I1 in Figure 3b) and can facilitate the charge transfer, 63,64 resulting in a polarization of CH 4 and then facile cleavage of C−H bond.…”

Section: Methane Activation By Fecmentioning

confidence: 97%

Methane Activation by Iron-Carbide Cluster Anions FeC₆^–

Liu

et al. 2015

J. Phys. Chem. Lett.

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Laser-ablation-generated and mass-selected iron-carbide cluster anions FeC6(-) were reacted with CH4 in a linear ion trap reactor under thermal collision conditions. The reactions were characterized by mass spectrometry and density functional theory calculations. Adsorption product of FeC6CH4(-) was observed in the experiments. The identified large kinetic isotope effect suggests that CH4 can be activated by FeC6(-) anions with a dissociative adsorption manner, which is further supported by the reaction mechanism calculations. The large dipole moment of FeC6(-) (19.21 D) can induce a polarization of CH4 and can facilitate the cleavage of C-H bond. This study reports the CH4 activation by transition-metal carbide anions, which provides insights into mechanistic understanding of iron-carbon centers that are important for condensed-phase catalysis.

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Section: Methane Activation By Fecmentioning

confidence: 97%

Methane Activation by Iron-Carbide Cluster Anions FeC₆^–

Liu

et al. 2015

J. Phys. Chem. Lett.

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“…30,37 Two related properties are listed in Table II: the energy of the lowest unoccupied molecular orbital (E LUMO ) and the vertical electron affinity of a cation (VEA + ). Note that VEA + is defined as the energy difference (without ZPE) between the cationic and neutral clusters with the same geometry of the optimized cationic cluster, which is different from the vertical ionization potential for which the optimized geometry of the neutral cluster is used.…”

Section: B Interpretation Of the Reactivitymentioning

confidence: 99%

High reactivity of nanosized niobium oxide cluster cations in methane activation: A comparison with vanadium oxides

Ding

Wang

et al. 2015

The Journal of Chemical Physics

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The reactions between methane and niobium oxide cluster cations were studied and compared to those employing vanadium oxides. Hydrogen atom abstraction (HAA) reactions were identified over stoichiometric (Nb2O5)N(+) clusters for N as large as 14 with a time-of-flight mass spectrometer. The reactivity of (Nb2O5)N(+) clusters decreases as the N increases, and it is higher than that of (V 2O5)N(+) for N ≥ 4. Theoretical studies were conducted on (Nb2O5)N(+) (N = 2-6) by density functional calculations. HAA reactions on these clusters are all favorable thermodynamically and kinetically. The difference of the reactivity with respect to the cluster size and metal type (Nb vs V) was attributed to thermodynamics, kinetics, the electron capture ability, and the distribution of the unpaired spin density. Nanosized Nb oxide clusters show higher HAA reactivity than V oxides, indicating that niobia may serve as promising catalysts for practical methane conversion.

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“…Employing neutral oxide nanoclusters for the study of catalytic processes is advantageous, as it minimizes the effect of cluster charge, which has been considered to be significant with regard to cluster reactivity. 50,117,118 On the other hand, NONCs often have high vertical ionization energies (>8 eV) and multiphoton ionization with a 10 ns Nd +3 /YAG laser pulse can cause significant cluster fragmentation so as to confuse the mass spectra for reactant and product identification. 115,119 Recently, our group has developed a novel 118 nm, single-photon ionization (SPI) technique, which has proved to be reliable for detecting the distribution and reactivity of NONCs without dissociation.…”

Section: Introductionmentioning

confidence: 99%

“…These cluster systems can serve as a more detailed molecular approach for the understanding of the active sites in catalytic supports and modified catalytic systems. 46,48,49,65,117,[120][121][122][123][124][125][126] The first example of generating, as well as studying, the reactivity of BONCs is reported by He and co-workers: they proposed that the novel AlVO 4 + cluster can activate CH 4 oxidation at room temperature. 49 Additionally, Schwarz and co-workers and He and co-workers report that CH 4 is activated by V 3 PO 10 + .…”

Section: Introductionmentioning

confidence: 99%

Generation and reactivity of putative support systems, Ce-Al neutral binary oxide nanoclusters: CO oxidation and C–H bond activation

Wang

Yin

Bernstein

2013

The Journal of Chemical Physics

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Both ceria (CeO2) and alumina (Al2O3) are very important catalyst support materials. Neutral binary oxide nanoclusters (NBONCs), CexAlyOz, are generated and detected in the gas phase and their reactivity with carbon monoxide (CO) and butane (C4H10) is studied. The very active species CeAlO4 (●) can react with CO and butane via O atom transfer (OAT) and H atom transfer (HAT), respectively. Other CexAlyOz NBONCs do not show reactivities toward CO and C4H10. The structures, as well as the reactivities, of CexAlyOz NBONCs are studied theoretically employing density functional theory (DFT) calculations. The ground state CeAlO4 (●) NBONC possesses a kite-shaped structure with an OtCeObObAlOt configuration (Ot, terminal oxygen; Ob, bridging oxygen). An unpaired electron is localized on the Ot atom of the AlOt moiety rather than the CeOt moiety: this Ot centered radical moiety plays a very important role for the reactivity of the CeAlO4 (●) NBONC. The reactivities of Ce2O4, CeAlO4 (●), and Al2O4 toward CO are compared, emphasizing the importance of a spin-localized terminal oxygen for these reactions. Intramolecular charge distributions do not appear to play a role in the reactivities of these neutral clusters, but could be important for charged isoelectronic BONCs. DFT studies show that the reaction of CeAlO4 (●) with C4H10 to form the CeAlO4H●C4H9 (●) encounter complex is barrierless. While HAT processes have been previously characterized for cationic and anionic oxide clusters, the reported study is the first observation of a HAT process supported by a ground state neutral oxide cluster. Mechanisms for catalytic oxidation of CO over surfaces of AlxOy∕MmOn or MmOn∕AlxOy materials are proposed consistent with the presented experimental and theoretical results.

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Methane Activation by Yttrium‐Doped Vanadium Oxide Cluster Cations: Local Charge Effects

Cited by 68 publications

References 75 publications

Methane Activation by Iron-Carbide Cluster Anions FeC₆^–

Methane Activation by Iron-Carbide Cluster Anions FeC₆^–

High reactivity of nanosized niobium oxide cluster cations in methane activation: A comparison with vanadium oxides

Generation and reactivity of putative support systems, Ce-Al neutral binary oxide nanoclusters: CO oxidation and C–H bond activation

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Methane Activation by Yttrium‐Doped Vanadium Oxide Cluster Cations: Local Charge Effects

Cited by 68 publications

References 75 publications

Methane Activation by Iron-Carbide Cluster Anions FeC6–

Methane Activation by Iron-Carbide Cluster Anions FeC6–

High reactivity of nanosized niobium oxide cluster cations in methane activation: A comparison with vanadium oxides

Generation and reactivity of putative support systems, Ce-Al neutral binary oxide nanoclusters: CO oxidation and C–H bond activation

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Methane Activation by Iron-Carbide Cluster Anions FeC₆^–

Methane Activation by Iron-Carbide Cluster Anions FeC₆^–