Highly n-Type Titanium Oxide as an Electronically Active Support for Platinum in the Catalytic Oxidation of Carbon Monoxide

Baker, L. Robert; Hervier, Antoine; Seo, Hyungtak; Kennedy, Griffin; Komvopoulos, K.; Somorjai, Gábor A.

doi:10.1021/jp203151y

Cited by 42 publications

(50 citation statements)

References 35 publications

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“…98,100 Many observations since that time continue to support this picture. 24,94 It is the opinion of the present authors that the unique ability of supported metal clusters to electronically activate O is an area deserving further attention because of its utility for selective partial oxidation catalysis 25,88,158,159 and for energy conversion chemistry 160,161 where O activation appears to be a kinetic bottleneck.…”

Section: Active Sites At the Metal−support Interfacementioning

confidence: 97%

“…This is consistent with early studies on metal− support interactions by Schwab 98,100 and more recent studies using F-doped TiO 2 as an electronically active catalyst support for oxidation reactions. 24,25 The correlation of all these studies suggests that the interface potential plays a key role in the electronic activation of surface O.…”

Section: Solid-state Device For Electronic Control Of Surface Chemistrymentioning

confidence: 99%

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Role of Hot Electrons and Metal–Oxide Interfaces in Surface Chemistry and Catalytic Reactions

2015

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Section: Active Sites At the Metal−support Interfacementioning

confidence: 97%

Section: Solid-state Device For Electronic Control Of Surface Chemistrymentioning

confidence: 99%

Role of Hot Electrons and Metal–Oxide Interfaces in Surface Chemistry and Catalytic Reactions

2015

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“…Enhancement of a metal catalysts reactivity and selectivity by a seemingly inert metal oxide support has been documented in the literature for numerous gas-phase reactions, such as methanol oxidation, [1] CO oxidation, [2] partial hydrogenation of organic molecules, [3][4][5][6] CO and CO 2 hydrogenation, [7] and hydroformylation, [8] on a variety of metals and supporting oxide systems. In some cases, by combining a metal with a metal oxide support the activity of the resulting system can far surpass what would be expected from a simple combination of the two materials.…”

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confidence: 99%

Selective Amplification of CO Bond Hydrogenation on Pt/TiO₂: Catalytic Reaction and Sum‐Frequency Generation Vibrational Spectroscopy Studies of Crotonaldehyde Hydrogenation

2014

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The hydrogenation of crotonaldehyde in the presence of supported platinum nanoparticles was used to determine how the interaction between the metal particles and their support can control catalytic performance. Using gas-phase catalytic reaction studies and in situ sum-frequency generation vibrational spectroscopy (SFG) to study Pt/TiO2 and Pt/SiO2 catalysts, a unique reaction pathway was identified for Pt/TiO2, which selectively produces alcohol products. The catalytic and spectroscopic data obtained for the Pt/SiO2 catalyst shows that SiO2 has no active role in this reaction. SFG spectra obtained for the Pt/TiO2 catalyst indicate the presence of a crotyl-oxy surface intermediate. By adsorption through the aldehyde oxygen atom to an O-vacancy site on the TiO2 surface, the C=O bond of crotonaldehyde is activated, by charge transfer, for hydrogenation. This intermediate reacts with spillover H provided by the Pt to produce crotyl alcohol.

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“…Firstly, using n-type doping with fluorine in TiO 2 to result in conduction band electrons that can migrate into the Pt with enough energy to influence the reaction (it is postulated this occurs by increasing the electron density on chemisorbed oxygen atoms). [91] Reaction rates for CO oxidation have also been controlled simply by biasing the nanodiode or using illumination to change the electronic state of the diode and push electrons into the conduction band. [92] Very recently Pt-CdSe-Pt dumbbell nanostructures have also been used to allow light absorption to promote electrons within the CdSe semiconductor, which migrate to the Pt and enhance the rate of CO oxidation.…”

Section: The Oxide Metal Interfacementioning

confidence: 99%

Conquering Catalyst Complexity: Nanoparticle Synthesis and Instrument Development for Molecular and Atomistic Characterisation Under In Situ Conditions

Somorjai

Beaumont

2015

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. (2015) 'Conquering catalyst complexity : nanoparticle synthesis and instrument development for molecular and atomistic characterisation under in situ conditions.', Topics in catalysis., 58 (10). pp. 560-572. Further information on publisher's website:http://dx.doi.org/10.1007/s11244-015- Publisher's copyright statement:The nal publication is available at Springer via http://dx.doi.org/10.1007/s11244-015-0398-5Additional information: Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. resolution in situ techniques with atomically and molecularly well-defined nanoparticle catalysts to achieve this goal. In particular we focus on mono-dispersed metal nanoparticles in the 0.8 -10 nm range with precise size distribution provided by modern colloidal synthetic techniques. These have been used in conjunction with a range of in situ techniques for understanding the complexity of a number of catalytic phenomena. Drawing on the nanoparticle size discrimination afforded by this approach, most metal nanoparticle catalysed covalent bond making/breaking reactions are identified as being structure sensitive, even when that was previously not thought to be the case. Small nanoparticles, below 2 nm, have been found to have changes of electronic structure that give rise to high oxidation state clusters under reaction conditions. These have been utilized to heterogenize typically homogeneous catalytic reactions using metal nanoclusters in the range of 40 atoms or less to carry out reactions on their heterogenized surfaces that would typically be expected only to occur at the higher oxidation state metal centre of a homogeneous organometallic catalyst. The combination of in-situ techniques and highly controlled metal nanoparticle structure also allows valuable insights to be achieved in understanding the mechanisms of multicomponent catalysts, catalysis occurring in different fluid phases and phenomena occurring at the metal-oxide interface.

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Highly n-Type Titanium Oxide as an Electronically Active Support for Platinum in the Catalytic Oxidation of Carbon Monoxide

Cited by 42 publications

References 35 publications

Role of Hot Electrons and Metal–Oxide Interfaces in Surface Chemistry and Catalytic Reactions

Role of Hot Electrons and Metal–Oxide Interfaces in Surface Chemistry and Catalytic Reactions

Selective Amplification of CO Bond Hydrogenation on Pt/TiO₂: Catalytic Reaction and Sum‐Frequency Generation Vibrational Spectroscopy Studies of Crotonaldehyde Hydrogenation

Conquering Catalyst Complexity: Nanoparticle Synthesis and Instrument Development for Molecular and Atomistic Characterisation Under In Situ Conditions

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Highly n-Type Titanium Oxide as an Electronically Active Support for Platinum in the Catalytic Oxidation of Carbon Monoxide

Cited by 42 publications

References 35 publications

Role of Hot Electrons and Metal–Oxide Interfaces in Surface Chemistry and Catalytic Reactions

Role of Hot Electrons and Metal–Oxide Interfaces in Surface Chemistry and Catalytic Reactions

Selective Amplification of CO Bond Hydrogenation on Pt/TiO2: Catalytic Reaction and Sum‐Frequency Generation Vibrational Spectroscopy Studies of Crotonaldehyde Hydrogenation

Conquering Catalyst Complexity: Nanoparticle Synthesis and Instrument Development for Molecular and Atomistic Characterisation Under In Situ Conditions

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Selective Amplification of CO Bond Hydrogenation on Pt/TiO₂: Catalytic Reaction and Sum‐Frequency Generation Vibrational Spectroscopy Studies of Crotonaldehyde Hydrogenation