Sub-nanometer surface chemistry and orbital hybridization in lanthanum-doped ceria nano-catalysts revealed by 3D electron microscopy

Abstract Surface chemical composition, electronic structure, and bonding characteristics determine catalytic activity but are not resolved for individual catalyst particles by conventional spectroscopy. In particular, the nano-scale three-dimensional distribution of aliovalent lanthanide dopants in...

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Main Authors:	Sean M. Collins, Susana Fernandez-Garcia, José J. Calvino, Paul A. Midgley
Format:	Article
Language:	English
Published:	Nature Publishing Group 2017-07-01
Series:	Scientific Reports
Online Access:	https://doi.org/10.1038/s41598-017-05671-9

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spelling	doaj-32fb9a2e6937421198f202f96570e9782020-12-08T00:54:01ZengNature Publishing GroupScientific Reports2045-23222017-07-01711910.1038/s41598-017-05671-9Sub-nanometer surface chemistry and orbital hybridization in lanthanum-doped ceria nano-catalysts revealed by 3D electron microscopySean M. Collins0Susana Fernandez-Garcia1José J. Calvino2Paul A. Midgley3Department of Materials Science and Metallurgy, University of CambridgeDepartamento de Ciencia de los Materiales, Ingeniería Metalúrgica y Química Inorgánica, Facultad de Ciencias, Universidad de CadizDepartamento de Ciencia de los Materiales, Ingeniería Metalúrgica y Química Inorgánica, Facultad de Ciencias, Universidad de CadizDepartment of Materials Science and Metallurgy, University of CambridgeAbstract Surface chemical composition, electronic structure, and bonding characteristics determine catalytic activity but are not resolved for individual catalyst particles by conventional spectroscopy. In particular, the nano-scale three-dimensional distribution of aliovalent lanthanide dopants in ceria catalysts and their effect on the surface electronic structure remains unclear. Here, we reveal the surface segregation of dopant cations and oxygen vacancies and observe bonding changes in lanthanum-doped ceria catalyst particle aggregates with sub-nanometer precision using a new model-based spectroscopic tomography approach. These findings refine our understanding of the spatially varying electronic structure and bonding in ceria-based nanoparticle aggregates with aliovalent cation concentrations and identify new strategies for advancing high efficiency doped ceria nano-catalysts.https://doi.org/10.1038/s41598-017-05671-9
collection	DOAJ
language	English
format	Article
sources	DOAJ
author	Sean M. Collins Susana Fernandez-Garcia José J. Calvino Paul A. Midgley
spellingShingle	Sean M. Collins Susana Fernandez-Garcia José J. Calvino Paul A. Midgley Sub-nanometer surface chemistry and orbital hybridization in lanthanum-doped ceria nano-catalysts revealed by 3D electron microscopy Scientific Reports
author_facet	Sean M. Collins Susana Fernandez-Garcia José J. Calvino Paul A. Midgley
author_sort	Sean M. Collins
title	Sub-nanometer surface chemistry and orbital hybridization in lanthanum-doped ceria nano-catalysts revealed by 3D electron microscopy
title_short	Sub-nanometer surface chemistry and orbital hybridization in lanthanum-doped ceria nano-catalysts revealed by 3D electron microscopy
title_full	Sub-nanometer surface chemistry and orbital hybridization in lanthanum-doped ceria nano-catalysts revealed by 3D electron microscopy
title_fullStr	Sub-nanometer surface chemistry and orbital hybridization in lanthanum-doped ceria nano-catalysts revealed by 3D electron microscopy
title_full_unstemmed	Sub-nanometer surface chemistry and orbital hybridization in lanthanum-doped ceria nano-catalysts revealed by 3D electron microscopy
title_sort	sub-nanometer surface chemistry and orbital hybridization in lanthanum-doped ceria nano-catalysts revealed by 3d electron microscopy
publisher	Nature Publishing Group
series	Scientific Reports
issn	2045-2322
publishDate	2017-07-01
description	Abstract Surface chemical composition, electronic structure, and bonding characteristics determine catalytic activity but are not resolved for individual catalyst particles by conventional spectroscopy. In particular, the nano-scale three-dimensional distribution of aliovalent lanthanide dopants in ceria catalysts and their effect on the surface electronic structure remains unclear. Here, we reveal the surface segregation of dopant cations and oxygen vacancies and observe bonding changes in lanthanum-doped ceria catalyst particle aggregates with sub-nanometer precision using a new model-based spectroscopic tomography approach. These findings refine our understanding of the spatially varying electronic structure and bonding in ceria-based nanoparticle aggregates with aliovalent cation concentrations and identify new strategies for advancing high efficiency doped ceria nano-catalysts.
url	https://doi.org/10.1038/s41598-017-05671-9
work_keys_str_mv	AT seanmcollins subnanometersurfacechemistryandorbitalhybridizationinlanthanumdopedceriananocatalystsrevealedby3delectronmicroscopy AT susanafernandezgarcia subnanometersurfacechemistryandorbitalhybridizationinlanthanumdopedceriananocatalystsrevealedby3delectronmicroscopy AT josejcalvino subnanometersurfacechemistryandorbitalhybridizationinlanthanumdopedceriananocatalystsrevealedby3delectronmicroscopy AT paulamidgley subnanometersurfacechemistryandorbitalhybridizationinlanthanumdopedceriananocatalystsrevealedby3delectronmicroscopy
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Sub-nanometer surface chemistry and orbital hybridization in lanthanum-doped ceria nano-catalysts revealed by 3D electron microscopy

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