Spontaneous Dihydrogen Activation by Neutral TaO<sub>4</sub> Complex at Cryogenic Temperatures

Zhou, Mingfei; Wang, Caixia; Li, Zhen hua; Zhuang, Jia; Zhao, Yanying; Zheng, Xuming; Fan, Kangnian

doi:10.1002/ange.201003001

Cited by 4 publications

(5 citation statements)

References 58 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The investigation of the reaction of matrix‐isolated transition metal clusters is essentially restricted to the metal oxides, MO, and metal dioxides, MO 2 . Reactions with small inorganic molecules like H 2 O, N 2 , CO, CO 2 , and H 2 as well as organic molecules like CH 4 , CH 3 Cl, CH 3 OH, C 2 H 2 , and C 2 H 4 have been investigated. Reactions of monoxides MO with CH 4 have been reviewed by Wang and Zhou…”

Section: Metal Oxide Clustersmentioning

confidence: 99%

“…In contrast, vanadium monoxide does not react with H 2 , and NbO 2 and TaO 2 react with H 2 , as in the case of D 2 and VO 2 : The hydride is formed only by irradiation . However, TaO 2 (O 2 ) reacts spontaneously with H 2 to form the hydride HTaO(OH)(O 2 ); see Scheme …”

Section: Metal Oxide Clustersmentioning

confidence: 99%

“…Reactions of metal clusters have been studied with O 2 , N 2 , CO, N 2 O and H 2 O . There are only a few examples for reactions of clusters with organic molecules …”

Section: Metal Atom Clustersmentioning

confidence: 99%

See 2 more Smart Citations

Metal Cluster Models for Heterogeneous Catalysis: A Matrix‐Isolation Perspective

Hübner

Himmel

2018

Chemistry A European J

View full text Add to dashboard Cite

Metal cluster models are of high relevance for establishing new mechanistic concepts for heterogeneous catalysis. The high reactivity and particular selectivity of metal clusters is caused by the wealth of low-lying electronically excited states that are often thermally populated. Thereby the metal clusters are flexible with regard to their electronic structure and can adjust their states to be appropriate for the reaction with a particular substrate. The matrix isolation technique is ideally suited for studying excited state reactivity. The low matrix temperatures (generally 4-40 K) of the noble gas matrix host guarantee that all clusters are in their electronic ground-state (with only a very few exceptions). Electronically excited states can then be selectively populated and their reactivity probed. Unfortunately, a systematic research in this direction has not been made up to date. The purpose of this review is to provide the grounds for a directed approach to understand cluster reactivity through matrix-isolation studies combined with quantum chemical calculations.

show abstract

Section: Metal Oxide Clustersmentioning

confidence: 99%

Section: Metal Oxide Clustersmentioning

confidence: 99%

See 1 more Smart Citation

Metal Cluster Models for Heterogeneous Catalysis: A Matrix‐Isolation Perspective

Hübner

Himmel

2018

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…Previous gas‐phase studies have shown that O .− was the active species to dissociate H 2 in the reactions of OsO 4 +[15] and V 4 O 10 +[17] with H 2 . For the reaction of TaO 4 with H 2 , the M−O unit was proposed as the active site to induce H 2 dissociation. A recent study on the reaction of gold–cerium heteronuclear oxide cluster AuCeO 2 + with H 2 identified that the separated ion pair, Au + and O 2− , could promote the dissociation of H 2 , and this mechanism paralleled the behavior of H 2 dissociation by supported gold catalysts in the condensed phase ,,.…”

Section: Discussionmentioning

confidence: 99%

Generation of Hydroxyl Radicals in the Reaction of Dihydrogen with AuNbO₄⁺ Cluster Cations

Jiang

et al. 2016

Chemistry An Asian Journal

View full text Add to dashboard Cite

A molecular-level insight into the nature of reactive oxygen species involved in dihydrogen (H ) dissociation is of great importance to understand gold catalysis. In this study, laser ablation generated and mass-selected AuNbO oxide cluster cations could dissociate H in an ion-trap reactor. The reaction has been characterized by time-of-flight mass spectrometric experiments and density functional calculations. The lowest energy isomer of AuNbO contains two lattice oxygen (O ) and one superoxide (O ) species. The gold atom anchors the H molecule in the first step and then delivers one hydrogen atom to the O ion in H dissociation. At the same time, O is reduced into a peroxide unit that can accept the second hydrogen atom of H with the generation of a hydroxyl radical as the main product. In this study, the important roles of the O unit in the dissociation of H have been identified.

show abstract

“…35,36 Moreover, in the TaO 4 + H 2 reaction systems, the M−O unit was also viewed as the active site to induce heterolytic cleavage of the H−H bond. 37 Recently, the lattice oxygen ions (O 2− ) in the gold-containing oxide clusters have also been demonstrated to be reactive for H 2 oxidation in collaboration with the separate gold species, in which the H−H bond cleavage follows a heterolytic cleavage manner. 38 It is noteworthy that the oxygen species in the above-mentioned reactive clusters are O ).…”

Section: Introductionmentioning

confidence: 99%

Consecutive H₂ Oxidation Mediated by Au₂VO₄⁺ Clusters

Zhou

et al. 2016

J. Phys. Chem. C

View full text Add to dashboard Cite

Laser-ablation generated gold–vanadium oxide cluster cations Au2VO x + (x = 3, 4) were mass-selected by a quadrupole mass filter and interacted with H2 in an ion trap reactor. The reactions were characterized by mass spectrometry and density functional theory calculations. The Au2VO4 + cluster can oxidize two H2 molecules consecutively to produce Au2VO3 + and then Au2VO2 +, the latter of which can react with one O2 molecule to regenerate Au2VO4 +. Therefore, a catalytic cycle for H2 oxidation by O2 mediated with the Au2VO2 + clusters can be proposed. The theoretical studies predict that the gold atoms in both Au2VO4 + and Au2VO3 + are the active adsorption sites and facilitate the heterolytic cleavage of H2 in collaboration with the separate O2– ions of the vanadium oxide support. The consecutively oxidative reactivity of Au2VO4 + is attributed to the activation and dissociation of the superoxide or peroxide species (O2 •– or O2 2–) into two reactive atomic oxygen species (O2–) with the promotional effect of gold atoms acting as electron donors. This study provides molecular-level insights into the elementary mechanisms of the H2 catalytic oxidation on the surface.

show abstract

Spontaneous Dihydrogen Activation by Neutral TaO₄ Complex at Cryogenic Temperatures

Cited by 4 publications

References 58 publications

Metal Cluster Models for Heterogeneous Catalysis: A Matrix‐Isolation Perspective

Metal Cluster Models for Heterogeneous Catalysis: A Matrix‐Isolation Perspective

Generation of Hydroxyl Radicals in the Reaction of Dihydrogen with AuNbO₄⁺ Cluster Cations

Consecutive H₂ Oxidation Mediated by Au₂VO₄⁺ Clusters

Contact Info

Product

Resources

About

Spontaneous Dihydrogen Activation by Neutral TaO4 Complex at Cryogenic Temperatures

Cited by 4 publications

References 58 publications

Metal Cluster Models for Heterogeneous Catalysis: A Matrix‐Isolation Perspective

Metal Cluster Models for Heterogeneous Catalysis: A Matrix‐Isolation Perspective

Generation of Hydroxyl Radicals in the Reaction of Dihydrogen with AuNbO4+ Cluster Cations

Consecutive H2 Oxidation Mediated by Au2VO4+ Clusters

Contact Info

Product

Resources

About

Spontaneous Dihydrogen Activation by Neutral TaO₄ Complex at Cryogenic Temperatures

Generation of Hydroxyl Radicals in the Reaction of Dihydrogen with AuNbO₄⁺ Cluster Cations

Consecutive H₂ Oxidation Mediated by Au₂VO₄⁺ Clusters