The adsorption of Cu on the CeO2(110) surface

Arunabhiram Chutia; Emma K. Gibson; Matthew R. Farrow; Peter P. Wells; David O. Scanlon; Nikolaos Dimitratos; David J. Willock; C. Richard A. Catlow

doi:10.1039/c7cp04144f

The adsorption of Cu on the CeO₂(110) surface

Arunabhiram Chutia^*, Emma K. Gibson, Matthew R. Farrow, Peter P. Wells, David O. Scanlon, Nikolaos Dimitratos, David J. Willock, C. Richard A. Catlow

^*Corresponding author for this work

Chemistry

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

Abstract

We report a detailed density functional theory (DFT) study in conjunction with extended X-ray absorption fine structure (EXAFS) experiments on the geometrical and local electronic properties of Cu adatoms and Cu(ii) ions in presence of water molecules and of CuO nanoclusters on the CeO₂(110) surface. Our study of (CuO)_n(=1,2&4) clusters on CeO₂(110) shows that based on the Cu-O environment, the geometrical properties of these clusters may vary and their presence may lead to relatively high localization of charge on the exposed surfaces. We find that in the presence of an optimum concentration of water molecules, Cu has a square pyramidal geometry, which agrees well with our experimental findings; we also find that Cu(ii) facilitates water adsorption on the CeO₂(110) surface. We further show that a critical concentration of water molecules is required for the hydrolysis of water on Cu(OH)₂/CeO₂(110) and on pristine CeO₂(110) surfaces.

Original language	English
Pages (from-to)	27191-27203
Number of pages	13
Journal	Physical Chemistry Chemical Physics
Volume	19
Issue number	40
DOIs	https://doi.org/10.1039/c7cp04144f
Publication status	Published - 2017

Bibliographical note

Funding Information:
We thank Dr Ricardo Grau-Crespo for his helpful discussions during the initial phase of this work. We thank Prof. Stefania Albonetti and Dr Alice Lolli for the synthesis of materials. We acknowledge Diamond Light Source for beamtime through awards SP10306 and SP15151, and thank the beamline scientists Dr Diego Gianolio and Dr Giannantonio Cibin. The UK Catalysis is thanked for resources and support provided via our membership of the UK Catalysis Hub consortium and funded by EPSRC (grants EP/K014706/1, EP/K014668/1, EP/K014854/1, EP/K014714/1, EP/M013219/1). Via our membership of the UK’s HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202), this work used the ARCHER UK National Supercomputing Service (http://www.archer.ac.uk). We also thank HPCWales for computer time.

Publisher Copyright:
© 2017 the Owner Societies.

ASJC Scopus subject areas

General Physics and Astronomy
Physical and Theoretical Chemistry

Access to Document

10.1039/c7cp04144f

Cite this

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title = "The adsorption of Cu on the CeO2(110) surface",

abstract = "We report a detailed density functional theory (DFT) study in conjunction with extended X-ray absorption fine structure (EXAFS) experiments on the geometrical and local electronic properties of Cu adatoms and Cu(ii) ions in presence of water molecules and of CuO nanoclusters on the CeO2(110) surface. Our study of (CuO)n(=1,2&4) clusters on CeO2(110) shows that based on the Cu-O environment, the geometrical properties of these clusters may vary and their presence may lead to relatively high localization of charge on the exposed surfaces. We find that in the presence of an optimum concentration of water molecules, Cu has a square pyramidal geometry, which agrees well with our experimental findings; we also find that Cu(ii) facilitates water adsorption on the CeO2(110) surface. We further show that a critical concentration of water molecules is required for the hydrolysis of water on Cu(OH)2/CeO2(110) and on pristine CeO2(110) surfaces.",

author = "Arunabhiram Chutia and Gibson, {Emma K.} and Farrow, {Matthew R.} and Wells, {Peter P.} and Scanlon, {David O.} and Nikolaos Dimitratos and Willock, {David J.} and Catlow, {C. Richard A.}",

note = "Funding Information: We thank Dr Ricardo Grau-Crespo for his helpful discussions during the initial phase of this work. We thank Prof. Stefania Albonetti and Dr Alice Lolli for the synthesis of materials. We acknowledge Diamond Light Source for beamtime through awards SP10306 and SP15151, and thank the beamline scientists Dr Diego Gianolio and Dr Giannantonio Cibin. The UK Catalysis is thanked for resources and support provided via our membership of the UK Catalysis Hub consortium and funded by EPSRC (grants EP/K014706/1, EP/K014668/1, EP/K014854/1, EP/K014714/1, EP/M013219/1). Via our membership of the UK{\textquoteright}s HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202), this work used the ARCHER UK National Supercomputing Service (http://www.archer.ac.uk). We also thank HPCWales for computer time. Publisher Copyright: {\textcopyright} 2017 the Owner Societies.",

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AU - Gibson, Emma K.

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AU - Dimitratos, Nikolaos

AU - Willock, David J.

AU - Catlow, C. Richard A.

N1 - Funding Information: We thank Dr Ricardo Grau-Crespo for his helpful discussions during the initial phase of this work. We thank Prof. Stefania Albonetti and Dr Alice Lolli for the synthesis of materials. We acknowledge Diamond Light Source for beamtime through awards SP10306 and SP15151, and thank the beamline scientists Dr Diego Gianolio and Dr Giannantonio Cibin. The UK Catalysis is thanked for resources and support provided via our membership of the UK Catalysis Hub consortium and funded by EPSRC (grants EP/K014706/1, EP/K014668/1, EP/K014854/1, EP/K014714/1, EP/M013219/1). Via our membership of the UK’s HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202), this work used the ARCHER UK National Supercomputing Service (http://www.archer.ac.uk). We also thank HPCWales for computer time. Publisher Copyright: © 2017 the Owner Societies.

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N2 - We report a detailed density functional theory (DFT) study in conjunction with extended X-ray absorption fine structure (EXAFS) experiments on the geometrical and local electronic properties of Cu adatoms and Cu(ii) ions in presence of water molecules and of CuO nanoclusters on the CeO2(110) surface. Our study of (CuO)n(=1,2&4) clusters on CeO2(110) shows that based on the Cu-O environment, the geometrical properties of these clusters may vary and their presence may lead to relatively high localization of charge on the exposed surfaces. We find that in the presence of an optimum concentration of water molecules, Cu has a square pyramidal geometry, which agrees well with our experimental findings; we also find that Cu(ii) facilitates water adsorption on the CeO2(110) surface. We further show that a critical concentration of water molecules is required for the hydrolysis of water on Cu(OH)2/CeO2(110) and on pristine CeO2(110) surfaces.

AB - We report a detailed density functional theory (DFT) study in conjunction with extended X-ray absorption fine structure (EXAFS) experiments on the geometrical and local electronic properties of Cu adatoms and Cu(ii) ions in presence of water molecules and of CuO nanoclusters on the CeO2(110) surface. Our study of (CuO)n(=1,2&4) clusters on CeO2(110) shows that based on the Cu-O environment, the geometrical properties of these clusters may vary and their presence may lead to relatively high localization of charge on the exposed surfaces. We find that in the presence of an optimum concentration of water molecules, Cu has a square pyramidal geometry, which agrees well with our experimental findings; we also find that Cu(ii) facilitates water adsorption on the CeO2(110) surface. We further show that a critical concentration of water molecules is required for the hydrolysis of water on Cu(OH)2/CeO2(110) and on pristine CeO2(110) surfaces.

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