Search

A simple model to describe rate changes during the reversible electrochemical promotion of supported metal catalysts has been formulated. Polarisation of the interface between the ion-conducting support and the metal modifies the electron extraction potential of the metal as a result of the spillover of ionic oxygen species. By considering a simple reaction mechanism that involves a charged transition state and accounting for the effect of long-range electrostatic interactions, it is possible to express reaction rates as a function of applied overpotential. It is shown that under certain conditions reaction rates are predicted to increase on application of both negative and positive overpotentials, in agreement with some experimental studies (e.g. Refs. [Catal. Today 11 (1992) 303; J. Catal. 159 (1996) 189]), as a result of electron donation and acceptance from both the metal catalyst and the surface O/O2− redox couple. [Copyright &y& Elsevier]

Strong-metal support interaction between Pd and ceria cubes and rods were investigated. Ceria cubes have the ability to access deep layers of ceria oxygen through the (100) surface indicated by STEM-EELS. Polar (100) surface on ceria cubes showed faster oxygen mobility. These oxygens oxidise adsorbate(s) on Pd due to strong electrostatic repulsion. When ceria is used as a support for many redox catalysis involved in green catalysis, it is well-known that the overlying noble metal can gain access to a significant quantity of oxygen atoms with high mobility and fast reduction and oxidation properties under mild conditions. However, it is as yet unclear what the underlying principle and the nature of the ceria surface involved are. By using two tailored morphologies of ceria nanocrystals, namely cubes and rods, it is demonstrated from Scanning Transmission Electron Microscopy with Electron Energy Loss Spectroscopy (STEM-EELS) mapping and Pulse Isotopic Exchange (PIE) that ceria nanocubes terminated with a polar surface (100) can give access to more than the top most layer of surface oxygen atoms. Also, they give higher oxygen mobility than ceria nanorods with a non-polar facet of (110). A new insight for the possible additional role of polar ceria surface plays in the oxygen mobility is obtained from Density Functional Theory (DFT) calculations which suggest that the (100) surface sites that has more than half-filled O on same plane can drive oxygen atoms to oxidise adsorbate(s) on Pd due to the strong electrostatic repulsion. [ABSTRACT FROM AUTHOR]