An Atomic-Scale View of CO and H-2 Oxidation on a Pt/Fe3O4 Model Catalyst

Roland Bliem; Jessi van der Hoeven; Adam Zavodny; Oscar Gamba; Jiri Pavelec; Petra E. de Jongh; Michael Schmid; Ulrike Diebold; Gareth S. Parkinson

doi:10.1002/anie.201507368

An Atomic-Scale View of CO and H-2 Oxidation on a Pt/Fe3O4 Model Catalyst

Roland Bliem
, Jessi van der Hoeven
, Adam Zavodny
, Oscar Gamba
, Jiri Pavelec
, Petra E. de Jongh
, Michael Schmid
, Ulrike Diebold
, Gareth S. Parkinson^*

^*Corresponding author for this work

Sub Soft Condensed Matter

Research output: Contribution to journal › Article › Academic › peer-review

Abstract

Metal-support interactions are frequently invoked to explain the enhanced catalytic activity of metal nanoparticles dispersed over reducible metal oxide supports, yet the atomic-scale mechanisms are rarely known. In this report, scanning tunneling microscopy was used to study a Pt1-6/Fe3O4 model catalyst exposed to CO, H-2, O-2, and mixtures thereof at 550 K. CO extracts lattice oxygen atoms at the cluster perimeter to form CO2, creating large holes in the metal oxide surface. H-2 and O-2 dissociate on the metal clusters and spill over onto the support. The former creates surface hydroxy groups, which react with the support, ultimately leading to the desorption of water, while oxygen atoms react with Fe from the bulk to create new Fe3O4(001) islands. The presence of the Pt is crucial because it catalyzes reactions that already occur on the bare iron oxide surface, but only at higher temperatures.

Original language	English
Pages (from-to)	13999-14002
Number of pages	4
Journal	Angewandte Chemie-International Edition
Volume	54
Issue number	47
DOIs	https://doi.org/10.1002/anie.201507368
Publication status	Published - 16 Nov 2015

Funding

This material is based upon work supported as part of the Centre for Atomic-Level Catalyst Design, an Energy Frontier Research Centre funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences (DE-SC0001058). G.S.P. and O.G. acknowledge support from the Austrian Science Fund (P24925-N20). R.B. acknowledges a stipend from the Vienna University of Technology and the Austrian Science Fund as part of the doctoral college SOLIDS4FUN (W1243). U.D. and J.P. acknowledge support by the European Research Council (Advanced Grant "OxideSurfaces"). A.Z. acknowledges support from the European Regional Development Fund (CEITEC, CZ.1.05/1.1.00/02.0068). We thank Prof. Mao (Tulane University) for providing the synthetic Fe<INF>3</INF>O<INF>4</INF> sample used in the work.

Keywords

Mars-van Krevelen mechanism
metal-support interactions
oxide surfaces
scanning probe microscopy
supported catalysts
SUPPORTED GOLD
OXIDE SUPPORT
REDUCTION
SURFACE
INTERFACE
MAGNETITE
OXYGEN
WATER
SIZE
REDUCIBILITY

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Bliem_et_al-2015-Angewandte_Chemie_International_EditionFinal published version, 2.23 MBLicence: Taverne

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title = "An Atomic-Scale View of CO and H-2 Oxidation on a Pt/Fe3O4 Model Catalyst",

abstract = "Metal-support interactions are frequently invoked to explain the enhanced catalytic activity of metal nanoparticles dispersed over reducible metal oxide supports, yet the atomic-scale mechanisms are rarely known. In this report, scanning tunneling microscopy was used to study a Pt1-6/Fe3O4 model catalyst exposed to CO, H-2, O-2, and mixtures thereof at 550 K. CO extracts lattice oxygen atoms at the cluster perimeter to form CO2, creating large holes in the metal oxide surface. H-2 and O-2 dissociate on the metal clusters and spill over onto the support. The former creates surface hydroxy groups, which react with the support, ultimately leading to the desorption of water, while oxygen atoms react with Fe from the bulk to create new Fe3O4(001) islands. The presence of the Pt is crucial because it catalyzes reactions that already occur on the bare iron oxide surface, but only at higher temperatures.",

keywords = "Mars-van Krevelen mechanism, metal-support interactions, oxide surfaces, scanning probe microscopy, supported catalysts, SUPPORTED GOLD, OXIDE SUPPORT, REDUCTION, SURFACE, INTERFACE, MAGNETITE, OXYGEN, WATER, SIZE, REDUCIBILITY",

author = "Roland Bliem and \{van der Hoeven\}, Jessi and Adam Zavodny and Oscar Gamba and Jiri Pavelec and \{de Jongh\}, \{Petra E.\} and Michael Schmid and Ulrike Diebold and Parkinson, \{Gareth S.\}",

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AU - Bliem, Roland

AU - van der Hoeven, Jessi

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AU - Gamba, Oscar

AU - Pavelec, Jiri

AU - de Jongh, Petra E.

AU - Schmid, Michael

AU - Diebold, Ulrike

AU - Parkinson, Gareth S.

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N2 - Metal-support interactions are frequently invoked to explain the enhanced catalytic activity of metal nanoparticles dispersed over reducible metal oxide supports, yet the atomic-scale mechanisms are rarely known. In this report, scanning tunneling microscopy was used to study a Pt1-6/Fe3O4 model catalyst exposed to CO, H-2, O-2, and mixtures thereof at 550 K. CO extracts lattice oxygen atoms at the cluster perimeter to form CO2, creating large holes in the metal oxide surface. H-2 and O-2 dissociate on the metal clusters and spill over onto the support. The former creates surface hydroxy groups, which react with the support, ultimately leading to the desorption of water, while oxygen atoms react with Fe from the bulk to create new Fe3O4(001) islands. The presence of the Pt is crucial because it catalyzes reactions that already occur on the bare iron oxide surface, but only at higher temperatures.

AB - Metal-support interactions are frequently invoked to explain the enhanced catalytic activity of metal nanoparticles dispersed over reducible metal oxide supports, yet the atomic-scale mechanisms are rarely known. In this report, scanning tunneling microscopy was used to study a Pt1-6/Fe3O4 model catalyst exposed to CO, H-2, O-2, and mixtures thereof at 550 K. CO extracts lattice oxygen atoms at the cluster perimeter to form CO2, creating large holes in the metal oxide surface. H-2 and O-2 dissociate on the metal clusters and spill over onto the support. The former creates surface hydroxy groups, which react with the support, ultimately leading to the desorption of water, while oxygen atoms react with Fe from the bulk to create new Fe3O4(001) islands. The presence of the Pt is crucial because it catalyzes reactions that already occur on the bare iron oxide surface, but only at higher temperatures.

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KW - SURFACE

KW - INTERFACE

KW - MAGNETITE

KW - OXYGEN

KW - WATER

KW - SIZE

KW - REDUCIBILITY

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M3 - Article

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JO - Angewandte Chemie-International Edition

JF - Angewandte Chemie-International Edition

IS - 47

ER -

An Atomic-Scale View of CO and H-2 Oxidation on a Pt/Fe3O4 Model Catalyst

Abstract

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Keywords

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