Catalytic Oxidation of Methanol to Formaldehyde by Mass-Selected Vanadium Oxide Clusters Supported on a TiO<sub>2</sub>(110) Surface

Price, Scott P.; Tong, Xiao; Ridge, Claron J.; Neilson, Hunter L.; Buffon, Joshua Woodbridge; Robins, Jeremy C.; Metiu, Horia; Bowers, Michael T.; Buratto, Steven K.

doi:10.1021/jp5011378

Cited by 20 publications

(16 citation statements)

References 24 publications

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“…The anatase (1 0 1) surface was selected as the anchoring surface as this surface is the most abundant reactive facet in anatase. The oxidized VO x moiety is depicted as containing a terminal vanadyl oxygen (V=O), as previously reported . Three different bond types involving oxygen atoms are defined in our model: terminal V=O, bridging V−O−Ti and bridging V−O−V.…”

Section: Resultsmentioning

confidence: 95%

Supported Vanadium Oxide Clusters in Partial Oxidation Processes: Catalytic Consequences of Size and Electronic Structure

2017

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The catalytic activity for ethanol partial oxidation of vanadium oxide (VOx) anchored on titanium oxide was correlated to their electronic structure. In situ Raman spectroscopy and temperature‐programmed desorption (TPD) experiments indicate that the presence of catalytically active VOx moieties is very sensitive to vanadia loading: highly dispersed VOx predominantly exists at low VOx contents whereas larger vanadia clusters coexist at higher VOx loadings. In situ UV/Vis spectroscopy revealed that a significant fraction of these larger clusters remain reduced during catalysis, and thus do not fully participate in catalytic turnovers. The electronic structures of model VOx nanoclusters of different sizes (monomer, dimer, trimer, and one‐dimensional polymers) were investigated by using periodic density functional theoretical calculations. Results indicate that their electronic structures are significantly affected by their size. Our analysis also revealed that the formation of reduced VOx species (V4+) during catalysis is concomitant to the reduction of adjacent Ti cations (Ti3+). Theoretically calculated optical absorption spectra matched the experimental spectroscopic results obtained under in situ reaction conditions. Furthermore, the determination of defect formation enthalpies reported previously as the main descriptor for catalytic activity of vanadia nanoclusters, predicted that isolated monomeric VOx clusters predominantly take part in catalytic turnovers.

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Section: Resultsmentioning

confidence: 95%

Supported Vanadium Oxide Clusters in Partial Oxidation Processes: Catalytic Consequences of Size and Electronic Structure

2017

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“…We have chosen to study a TiO 2 support because VO x /TiO 2 is an industrially important catalyst, 3 its structure can be imaged by STM, 4−10 and experiments with mass selected clusters have been performed. 9,10 The quality and the quantity of the information we have for this system is better than for any other support.…”

Section: Introductionmentioning

confidence: 95%

Interaction between Monomeric Vanadium Oxide Clusters Supported on Titania and Its Influence on Their Reactivity

Kristoffersen

Metiu

2016

J. Phys. Chem. C

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Density functional theory is used to study monomeric vanadium oxide clusters formed by exposing to oxygen a rutile TiO 2 (110) surface on which vanadium atoms have been preadsorbed. Past calculations examined such systems by using one V atom per supercell. This forces all VO x clusters to be identical and precludes interactions between them. To examine the consequences of this choice, we examine a VO x and a VO y cluster in the same supercell. We find that the most stable configuration is obtained when the supercell contains one VO 2 and one VO 3 cluster. The stabilization occurs because of a Lewis acid−base interaction: VO 2 donates electron charge to VO 3 and this lowers the energy substantially. No such interactions were found when the supercell contained VO x clusters with the same number of oxygen atoms. These finding demonstrate that in some cases it is essential to have two clusters in the supercell and that results obtained with one cluster in the supercell can be misleading. We have also studied the reactivity of the clusters with hydrogen, which is considered a descriptor of the ability of the cluster to catalyze the breaking of a C−H bond in an alkane.

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“…This prediction could be verified since the breakup of the cluster should be observable by STM. [58][59][60] The V2O6 2-clusters whose energy we have examined as possible products are presented in Figure S3 in Supporting Information.…”

Section: V2o5 Breakup When An O Atom Is Present On the V-tio2 Surfacementioning

confidence: 99%

Stability of V₂O₅ Supported on Titania in the Presence of Water, Bulk Oxygen Vacancies, and Adsorbed Oxygen Atoms

et al. 2017

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Catalytic Oxidation of Methanol to Formaldehyde by Mass-Selected Vanadium Oxide Clusters Supported on a TiO₂(110) Surface

Cited by 20 publications

References 24 publications

Supported Vanadium Oxide Clusters in Partial Oxidation Processes: Catalytic Consequences of Size and Electronic Structure

Supported Vanadium Oxide Clusters in Partial Oxidation Processes: Catalytic Consequences of Size and Electronic Structure

Interaction between Monomeric Vanadium Oxide Clusters Supported on Titania and Its Influence on Their Reactivity

Stability of V₂O₅ Supported on Titania in the Presence of Water, Bulk Oxygen Vacancies, and Adsorbed Oxygen Atoms

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Catalytic Oxidation of Methanol to Formaldehyde by Mass-Selected Vanadium Oxide Clusters Supported on a TiO2(110) Surface

Cited by 20 publications

References 24 publications

Supported Vanadium Oxide Clusters in Partial Oxidation Processes: Catalytic Consequences of Size and Electronic Structure

Supported Vanadium Oxide Clusters in Partial Oxidation Processes: Catalytic Consequences of Size and Electronic Structure

Interaction between Monomeric Vanadium Oxide Clusters Supported on Titania and Its Influence on Their Reactivity

Stability of V2O5 Supported on Titania in the Presence of Water, Bulk Oxygen Vacancies, and Adsorbed Oxygen Atoms

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Product

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Catalytic Oxidation of Methanol to Formaldehyde by Mass-Selected Vanadium Oxide Clusters Supported on a TiO₂(110) Surface

Stability of V₂O₅ Supported on Titania in the Presence of Water, Bulk Oxygen Vacancies, and Adsorbed Oxygen Atoms