Water Adsorption and Dissociation at Metal-Supported Ceria Thin Films: Thickness and Interface-Proximity Effects Studied with DFT+U Calculations
| Autor: | Stefano Fabris, Lucie Szabová, Yoshitaka Tateyama, Vladimír Matolín |
|---|---|
| Rok vydání: | 2015 |
| Předmět: |
Materials science
Dissociation (chemistry) Relative stability Surfaces Coatings and Films Electronic Optical and Magnetic Materials Catalysis Metal General Energy Adsorption Chemical engineering Computational chemistry visual_art visual_art.visual_art_medium Density functional theory Water Adsorption and Dissociation at Metal-Supported Ceria Thin Films: Thickness and Interface-Proximity Effects Studied with DFT plus U Calculations Physical and Theoretical Chemistry Thin film Adsorption energy |
| Zdroj: | Journal of physical chemistry. C 119 (2015): 2537–2544. doi:10.1021/jp5109152 info:cnr-pdr/source/autori:Lucie Szabová+?, Yoshitaka Tateyama+¶, Vladimír Matolín?, and Stefano Fabris*§?/titolo:Water Adsorption and Dissociation at Metal-Supported Ceria Thin Films: Thickness and Interface-Proximity Effects Studied with DFT plus U Calculations/doi:10.1021%2Fjp5109152/rivista:Journal of physical chemistry. C/anno:2015/pagina_da:2537/pagina_a:2544/intervallo_pagine:2537–2544/volume:119 |
| ISSN: | 1932-7455 1932-7447 |
| Popis: | The chemistry of several catalytic processes can be controlled by tuning metaloxide interfaces, as demonstrated by fundamental studies on inverse model catalysts. We investigate the effects of the metaloxide interface on the surface reactivity of ceria (CeO2) thin films supported by a copper metal surface. Our density functional theory (DFT+U) calculations reveal that the interface has impact on the surface water adsorption and dissociation when the thickness of the ceria film is below approximate to 9 angstrom. On thinner films, the energetics of adsorption and dissociation display a significant variation, which arises from a combination of thickness and interface-proximity effects, and which we rationalize in terms of charge-density response at the adsorbate-oxide and oxide-metal interfaces. The adsorption energy is maximized for film thicknesses of 5.5 angstrom (corresponding to two OCeO trilayers), while thinner films affect primarily the relative stability between molecular, semidissociated, and dissociated water adsorption. These results provide useful insights into the effect of low-dimensional ceria species in Cu/CeO2 catalysts. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|