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

Phys Chem Chem Phys. 2017 Oct 18;19(40):27191-27203. doi: 10.1039/c7cp04144f.

Authors

Arunabhiram Chutia¹, Emma K Gibson¹, Matthew R Farrow², Peter P Wells³, David O Scanlon⁴, Nikolaos Dimitratos⁵, David J Willock⁵, C Richard A Catlow⁶

Affiliations

¹ UK Catalysis Hub, RCaH, Rutherford Appleton Laboratory, Didcot, OX11 0FA, UK. a.chutia@ucl.ac.uk c.r.a.catlow@ucl.ac.uk and Department of Chemistry, University College London, Gordon Street, London, WC1H 0AJ, UK.
² Department of Chemistry, University College London, Gordon Street, London, WC1H 0AJ, UK.
³ UK Catalysis Hub, RCaH, Rutherford Appleton Laboratory, Didcot, OX11 0FA, UK. a.chutia@ucl.ac.uk c.r.a.catlow@ucl.ac.uk and School of Chemistry, University of Southampton, Southampton, 50718J, UK and Diamond Light Source Ltd., Diamond House, Harwell Science and Innovation Campus, Didcot, Oxfordshire OX11 0DE, UK.
⁴ Department of Chemistry, University College London, Gordon Street, London, WC1H 0AJ, UK and Diamond Light Source Ltd., Diamond House, Harwell Science and Innovation Campus, Didcot, Oxfordshire OX11 0DE, UK.
⁵ Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Cardiff, CF10 3AT, UK.
⁶ UK Catalysis Hub, RCaH, Rutherford Appleton Laboratory, Didcot, OX11 0FA, UK. a.chutia@ucl.ac.uk c.r.a.catlow@ucl.ac.uk and Department of Chemistry, University College London, Gordon Street, London, WC1H 0AJ, UK and Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Cardiff, CF10 3AT, UK.

PMID: 28926035
DOI: 10.1039/c7cp04144f

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.