Thermal desorption of oxygen from near-stoichiometric cationic vanadium oxide clusters

Kurokawa, Hodaka; Mafuné, Fumitaka

doi:10.1016/j.cplett.2016.02.072

Cited by 13 publications

(12 citation statements)

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“…The composition found here for vanadium oxide cluster cations was consistent with the abundant species found by Kurokawa and Mafunéfor cluster sizes m = 2−10. 8 Also, in previous photodissociation experiments 4,5,14 and a collision-induced dissociation experiment, 6 the compositions observed in this study were commonly produced as fragments from various parent ions (m < 10 , along with other ions with different number of oxygen atoms. The present results of the most abundantly observed compositions were also consistent with the observations made by Castleman et al The observation was that anions tend to have a one-oxygen richer composition than the cations, 6,9 and in addition, we are able to extend this observation to cluster sizes up to m = 20.…”

Section: Experimental and Computational Methodsmentioning

confidence: 58%

“…Gas-phase vanadium oxide clusters (V m O n ) were studied experimentally and were often complemented by theoretical studies to achieve a better understanding of their reactivity and their roles in catalysis. Experimentally, mass spectrometry was applied to studies not only on cationic − and anionic clusters, but also on neutral − vanadium oxide clusters. The collision-induced dissociation studies by Castleman and co-workers on the small vanadium oxide clusters ions of m = 2–7 indicated that VO 2 , VO 3 , and V 2 O 5 were the main building blocks for both cationic and anionic species.…”

Section: Introductionmentioning

confidence: 99%

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Compositions and Structures of Vanadium Oxide Cluster Ions V_mO_n^± (m = 2–20) Investigated by Ion Mobility Mass Spectrometry

Moriyama

Tahara

et al. 2016

J. Phys. Chem. A

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Stable compositions and geometrical structures of vanadium oxide cluster ions, VmOn(±), were investigated by ion mobility mass spectrometry (IM-MS). The most stable compositions of vanadium oxide cluster cations were (V2O4)(V2O5)(m-2)/2(+) and (VO2)(V2O5)(m-1)/2(+), depending on the clusters with even and odd numbers of vanadium atoms. Compositions one-oxygen richer than the cations, such as (V2O5)m/2(-) and (VO3)(V2O5)(m-1)/2(-), were predominantly observed for cluster anions. Assignments of these stable cluster ion compositions, which were determined as a result of collision-induced dissociations in IM-MS, can partly be explained with consideration of spin density distribution. By comparing the experimental collision cross sections (CCSs) obtained from ion mobility measurement with CCSs of the theoretically calculated structures, we confirmed the patterned growth of geometrical structures partially discussed in previous theoretical and spectroscopic studies. We showed that even sized (V2O5)m/2(±) where m = 6-12 had right polygonal prism structures except for the anionic V12O30(-), and for the clusters of odd numbers of vanadium m, cations and anions can either have bridged or pyramid structures. Both of the odd sized structures proposed were derivatives from the even sized right polygonal prism structures. The exception, V12O30(-), which had a CCS almost equal to that of the neighboring smaller V11O28(-), should have a structure of higher density than the right hexagonal prism, in which it was proposed to be a captured pyramid structure, derived from V11O28(-).

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Section: Experimental and Computational Methodsmentioning

confidence: 58%

Section: Introductionmentioning

confidence: 99%

Compositions and Structures of Vanadium Oxide Cluster Ions V_mO_n^± (m = 2–20) Investigated by Ion Mobility Mass Spectrometry

Moriyama

Tahara

et al. 2016

J. Phys. Chem. A

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“…The thermal dissociation of the niobium–vanadium oxide clusters (Nb n V m O k + ) was studied by mass spectrometry in combination with gas phase thermal desorption spectrometry (Figure S1). − The gas phase Nb n V m O k + clusters ( n + m = 2–8) were synthesized by pulsed laser ablation inside a cluster source. Here, Nb and V metal rods were vaporized by the focused third and second harmonics of separate Nd:YAG pulsed lasers at 355 and 532 nm, respectively.…”

Section: Experimental Sectionmentioning

confidence: 99%

“…11 −10)] were synthesized in the gas phase. 19,20 The thermal desorption of oxygen from the near-stoichiometric (n:k = 2:5) clusters was investigated using mass spectrometry in combination with gas phase thermal desorption spectrometry (TDS). 19−22 For niobium oxide clusters and vanadium oxide clusters with even values of n, M n O (5/2)n+1 + (M = Nb, V; n = 2, 4, 6, ...), an O 2 molecule was released upon heating.…”

Section: ■ Introductionmentioning

confidence: 99%

“…In our previous studies, cationic niobium oxide clusters [Nb n O k + ( n = 2–10)] and vanadium oxide clusters [V n O k + ( n = 2–10)] were synthesized in the gas phase. , The thermal desorption of oxygen from the near-stoichiometric ( n : k = 2:5) clusters was investigated using mass spectrometry in combination with gas phase thermal desorption spectrometry (TDS). − For niobium oxide clusters and vanadium oxide clusters with even values of n , M n O (5/2) n +1 + (M = Nb, V; n = 2, 4, 6, ...), an O 2 molecule was released upon heating. The vanadium oxide clusters released O 2 readily at a lower temperature than the niobium oxide clusters, implying lower desorption energies of O 2 from the clusters.…”

Section: Introductionmentioning

confidence: 99%

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Oxygen Release from Cationic Niobium–Vanadium Oxide Clusters, Nb_nV_mO_k⁺, Revealed by Gas Phase Thermal Desorption Spectrometry and Density Functional Theory Calculations

2017

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Thermal dissociation of the cationic niobium-vanadium oxide clusters, NbVO (n + m = 2-8), was investigated by gas phase thermal desorption spectrometry. The oxygen-rich NbVO released O and O for odd and even values of n + m, respectively. Substitution of more than one Nb atom in NbO by V drastically lowered the desorption temperature of O for even values of n + m, whereas the substitution of more than two Nb atoms opened a new desorption path involving the release of O for odd values of n + m. The substitution effects can be explained by the fact that Nb atoms display the +5 state, whereas V atoms can exist in either the +4 or +5 states. The geometrical structures of selected NbVO clusters were optimized and the energetics of the release of O/O from the clusters was discussed on the basis of the results of DFT calculations.

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Formation of Gas‐Phase Formate in Thermal Reactions of Carbon Dioxide with Diatomic Iron Hydride Anions

Jiang

Zhao

et al. 2017

Angewandte Chemie

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The hydrogenation of carbon dioxide involves the activation of the thermodynamically very stable molecule CO2 and formation of a C−H bond. Herein, we report that HCO2− and CO can be formed in the thermal reaction of CO2 with a diatomic metal hydride species, FeH−. The FeH− anions were produced by laser ablation, and the reaction with CO2 was analyzed by mass spectrometry and quantum‐chemical calculations. Gas‐phase HCO2− was observed directly as a product, and its formation was predicted to proceed by facile hydride transfer. The mechanism of CO2 hydrogenation in this gas‐phase study parallels similar behavior of a condensed‐phase iron catalyst.

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Thermal desorption of oxygen from near-stoichiometric cationic vanadium oxide clusters

Cited by 13 publications

References 14 publications

Compositions and Structures of Vanadium Oxide Cluster Ions V_mO_n^± (m = 2–20) Investigated by Ion Mobility Mass Spectrometry

Compositions and Structures of Vanadium Oxide Cluster Ions V_mO_n^± (m = 2–20) Investigated by Ion Mobility Mass Spectrometry

Oxygen Release from Cationic Niobium–Vanadium Oxide Clusters, Nb_nV_mO_k⁺, Revealed by Gas Phase Thermal Desorption Spectrometry and Density Functional Theory Calculations

Formation of Gas‐Phase Formate in Thermal Reactions of Carbon Dioxide with Diatomic Iron Hydride Anions

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Thermal desorption of oxygen from near-stoichiometric cationic vanadium oxide clusters

Cited by 13 publications

References 14 publications

Compositions and Structures of Vanadium Oxide Cluster Ions VmOn± (m = 2–20) Investigated by Ion Mobility Mass Spectrometry

Compositions and Structures of Vanadium Oxide Cluster Ions VmOn± (m = 2–20) Investigated by Ion Mobility Mass Spectrometry

Oxygen Release from Cationic Niobium–Vanadium Oxide Clusters, NbnVmOk+, Revealed by Gas Phase Thermal Desorption Spectrometry and Density Functional Theory Calculations

Formation of Gas‐Phase Formate in Thermal Reactions of Carbon Dioxide with Diatomic Iron Hydride Anions

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Compositions and Structures of Vanadium Oxide Cluster Ions V_mO_n^± (m = 2–20) Investigated by Ion Mobility Mass Spectrometry

Compositions and Structures of Vanadium Oxide Cluster Ions V_mO_n^± (m = 2–20) Investigated by Ion Mobility Mass Spectrometry

Oxygen Release from Cationic Niobium–Vanadium Oxide Clusters, Nb_nV_mO_k⁺, Revealed by Gas Phase Thermal Desorption Spectrometry and Density Functional Theory Calculations