Investigating Reactive Superoxide Units Bound to Zirconium Oxide Cations

Tyo, Eric C.; Nößler, Melanie; Harmon, Christopher L.; Mitrić, Roland; Bonačić‐Koutecký, Vlasta; Castleman, A. W.

doi:10.1021/jp204453a

Cited by 5 publications

(5 citation statements)

References 37 publications

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“…Recent experimental and theoretical studies on gas-phase metal-oxide clusters and their reactivity − identified different oxygen sites such as terminal MO, bridging M–O–M, oxygen radical M–O*, superoxide, and peroxide on the clusters. It will be interesting to see if the ACN descriptor can be applied to describe the reactivity of those oxygen sites as well.…”

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confidence: 99%

General Structure–Reactivity Relationship for Oxygen on Transition-Metal Oxides

Fung

Tao

Jiang

2017

J. Phys. Chem. Lett.

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Despite many recent developments in designing and screening catalysts for improved performance, transition-metal oxides continue to prove to be challenging due to the myriad inherent complexities of the systems and the possible morphologies that they can exhibit. Herein we propose a structural descriptor, the adjusted coordination number (ACN), which can generalize the reactivity of the oxygen sites over the many possible surface facets and defects of a transition-metal oxide. We demonstrate the strong correlation of this geometric descriptor with the electronic and energetic properties of the active sites on five facets of four transition-metal oxides. We then use the structural descriptor to predict C-H activation energies to show the great potential of using ACN for the prediction of catalytic performance. This study presents a first look into quantifying the relation between active site structure and reactivity of transition-metal-oxide catalysts.

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confidence: 99%

General Structure–Reactivity Relationship for Oxygen on Transition-Metal Oxides

Fung

Tao

Jiang

2017

J. Phys. Chem. Lett.

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“…+ (Δ = 3) clusters possess superoxide moieties and are oxidative toward alkenes and C 2 H 2 , which were investigated through guidedion-beam mass spectrometry and density functional theory (DFT) calculations 30. It is noteworthy that O −• and O 2 −• bonded TMO clusters are typical open-shell species.…”

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Gas-phase reaction of CeVO₅⁺cluster ions with C₂H₄: the reactivity of cluster bonded peroxides

Meng

2015

Dalton Trans.

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Cerium-vanadium oxide cluster cations CeVO5(+) were generated by laser ablation, mass-selected using a quadrupole mass filter, thermalized through collisions with helium atoms, and then reacted with ethene molecules in a linear ion trap reactor. The cluster reactions have been characterized by time-of-flight mass spectrometry and density functional theory calculations. The CeVO5(+) cluster has a closed-shell electronic structure and contains a peroxide (O2(2-)) unit. The cluster bonded O2(2-) species is reactive enough to oxidize a C2H4 molecule to generate C2H4O2 that can be an acetic acid molecule. Atomic oxygen radicals (O(-)˙), superoxide radicals (O2(-)˙), and peroxides are the three common reactive oxygen species. The reactivity of cluster bonded O(-)˙ and O2(-)˙ radicals has been widely studied while the O2(2-) species were generally thought to be much less reactive or inert toward small molecules under thermal collision conditions. This work is among the first to report the reactivity of the peroxide unit on transition metal oxide clusters with hydrocarbon molecules, to the best of our knowledge.

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“…Surface chemistry methods have proven to be valuable in characterizing the surface structure of the catalyst materials as well as for identification of intermediates. − However, the identification of structure–reactivity relationships is difficult due to the presence of different active sites as well as other surface inhomogeneities. In order to design more efficient catalysts, determination of the structure–reactivity relationship is mandatory and can be achieved by cluster studies. − Moreover, cluster-like surface chemical bonds involving surface metal and next nearest neighbors were identified to enable catalytic reactions…”

Section: Introductionmentioning

confidence: 99%

“…Thus, a considerable theoretical and experimental effort by us ,,− and others − ,− has been undertaken in recent years with the aim to gain molecular level understanding of important catalytic reactions. The resulting findings allowed us to reveal mechanisms of oxidation reactions of CO and small organic molecules catalyzed by transition-metal oxide clusters containing oxygen radical centers depending on the size, composition, and charge state.…”

Section: Introductionmentioning

confidence: 99%

“…The resulting findings allowed us to reveal mechanisms of oxidation reactions of CO and small organic molecules catalyzed by transition-metal oxide clusters containing oxygen radical centers depending on the size, composition, and charge state. In particular, our common studies with the experimental group of A. W. Castleman Jr. led to identification of radical centers for the cationic zirconium and titanium oxide clusters of stoichiometric composition (ZrO 2 ) n + and (TiO 2 ) n + that are responsible for the oxidation reactions with CO, ethylene and acetylene. , …”

Section: Introductionmentioning

confidence: 99%

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Binary Neutral Metal Oxide Clusters with Oxygen Radical Centers for Catalytic Oxidation Reactions: From Cluster Models Toward Surfaces

2012

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We present theoretical results based on DFT calculations of the reactivity of binary neutral stoichiometric Zr n-1 ScO 2n clusters with oxygen radical centers toward CO and acetylene with the aim to build a bridge between clusters and surface models. Following the concept of the same total valence electron count, the studied series of binary clusters mimics cationic stoichiometric (ZrO 2 ) n + species characterized also by the presence of an oxygen radical center. In the case of Zr 11 ScO 24 , representing a section of the (ZrO 2 ) n bulk, in addition to the oxygen radical center, the presence of neighboring Zr atoms effectively promotes oxidation reactions toward CO and acetylene, showing the importance of the surrounding of active centers.

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Investigating Reactive Superoxide Units Bound to Zirconium Oxide Cations

Cited by 5 publications

References 37 publications

General Structure–Reactivity Relationship for Oxygen on Transition-Metal Oxides

General Structure–Reactivity Relationship for Oxygen on Transition-Metal Oxides

Gas-phase reaction of CeVO₅⁺cluster ions with C₂H₄: the reactivity of cluster bonded peroxides

Binary Neutral Metal Oxide Clusters with Oxygen Radical Centers for Catalytic Oxidation Reactions: From Cluster Models Toward Surfaces

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Investigating Reactive Superoxide Units Bound to Zirconium Oxide Cations

Cited by 5 publications

References 37 publications

General Structure–Reactivity Relationship for Oxygen on Transition-Metal Oxides

General Structure–Reactivity Relationship for Oxygen on Transition-Metal Oxides

Gas-phase reaction of CeVO5+cluster ions with C2H4: the reactivity of cluster bonded peroxides

Binary Neutral Metal Oxide Clusters with Oxygen Radical Centers for Catalytic Oxidation Reactions: From Cluster Models Toward Surfaces

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Gas-phase reaction of CeVO₅⁺cluster ions with C₂H₄: the reactivity of cluster bonded peroxides