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A comparative study between a classic and a wireless electrochemical promotion experiment was undertaken as a tool towards the better understanding of both systems. The catalytic modification of a platinum catalyst for ethylene oxidation was studied. The catalyst was supported on yttria-stabilised-zirconia (YSZ), a known pure oxide ion conductor, for the classic experiment and La0.6Sr0.4Co0.2Fe0.8O3–δ—a mixed oxide ion electronic conductor—was used for the wireless experiment. The two systems showed certain similarities in terms of the reaction classification (in both cases electrophobic behaviour was observed) and the promotion mechanism. Significant difference was observed in the time scales and the reversibility of the induced rate modification. [ABSTRACT FROM AUTHOR]

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]

Abstract: The effect of spillover processes on the activity of a catalyst system consisting of a mixed oxygen ion and electronic conducting support La0.6Sr0.4Co0.2Fe0.8O3− δ and a metal catalyst (Pt) were investigated. Two types of model single-pellet catalysts were used employing Pt deposited on both sides of a dense LSCF disc pellet. One of these single pellets employed highly disperse, physically non-continuous Pt, in contrast to studies on electrochemical promotion, while the other used a low dispersion continuous film. Driving forces for promoter migration were controlled through the manipulation of the oxygen chemical potential difference across the membrane. Catalyst rate modification was observed in all cases. However, it was found that there is a complex relationship between the rate modification, the driving forces for spillover and the geometrical arrangement of the catalyst on the support (i.e. catalyst dispersion). [Copyright &y& Elsevier]

Abstract: Spillover processes (i.e. the migration of ionic species from the support to the catalyst and vice versa) are known to play a very important role in catalysis and electrocatalysis. These spillover processes can be influenced by impurities (pre-existing on the catalyst surface) and by the catalyst morphology that may differ as a result of the differences in catalyst manufacturing processes. This work investigates the influence of impurities present in three commercial platinum (Pt) precursors. The resulting platinum films studied here were supported on yttria-stabilised-zirconia (YSZ). It was found that the three different catalyst films contained a range of impurities (determined by ICP-OES) that appear to affect the oxygen charge transfer reaction as studied by cyclic voltammetry (CV). [Copyright &y& Elsevier]

Abstract: High temperature ceramic membranes have interesting possibilities for application in areas of new and developing technologies such as hydrocarbon combustion with carbon dioxide capture and electrochemical promotion of catalysis (EPOC). However, membrane module sealing remains a significant technical challenge. In this work a borosilicate glass sealant (50SiO2·25B2O3·25Na2O, mol%) was developed to fit the requirements of sealing an air separation membrane system at intermediate temperatures (300–600°C). The seal was assessed by testing the leak rates under a range of conditions. The parameters tested included the effect of flowrate on the leak rate, the heating and cooling rates of the reactor and the range of temperatures under which the system could operate. Tests for durability and reliability were also performed. It was found that the most favourable reactor configuration employed a reactor with the ceramic pellet placed underneath the inner chamber alumina tube (inverted configuration), using a quartz wool support to keep the membrane in place prior to sealing. Using this configuration the new glass-based seal was found to be a more suitable sealant than traditional alternatives; it produced lower leak rates at all desirable flowrates, with the potential for rapid heating and cooling and multiple cycling, allowing for prolonged usage. [Copyright &y& Elsevier]