TAP reactor investigation of methane coupling over samarium oxide catalysts

The adsorption and reaction characteristics of a Ba/Sr/Sm2O3 catalyst for methane coupling has been investigated using the TAP (Temporal Analysis of Products) reactor system. Pulsed adsorption experiments using methane, oxygen and krypton at temperatures ranging from 17°C to 800°C show that the transient response of methane is similar to that of Kr and is either not adsorbed, or weakly adsorbed on the catalyst. By contrast, oxygen is strongly adsorbed at temperatures above 500°C which suggests incorporation into the lattice with possible formation of surface anions. Pump-probe experiments in which methane and oxygen are introduced over the catalyst were also performed to investigate the effect of lifetimes of suspected surface intermediates on the relative yields of ethane and ethene. It is shown that the relative yields of both species increase with increasing values of the pulse valve time delay between introduction of the oxygen and methane. An explanation of these results using current knowledge and reasonable speculation of the mechanism is provided

Multi-zone TAP-reactors theory and application - IV. Ideal and non-ideal boundary conditions

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Forty years of temporal analysis of products

SSCI-VIDE+ING+YSCInternational audienceA detailed understanding of reaction mechanisms and kinetics is required in order to develop and optimize catalysts and catalytic processes. While steady-state investigations are known to give a global view of the catalytic system, transient studies are invaluable since they can provide more comprehensive insight into elementary steps. For almost forty years temporal analysis of products (TAP) has been successfully utilized for transient studies of gas phase heterogeneous reactions, and there have been a number of advances in instrumentation and numerical modeling methods in that time. Since TAP is a complex methodology it is often viewed as a niche specialty. With the purpose to make TAP more relevant and approachable to a wider segment of the catalytic research community, part of the intention of this work is to highlight the significant contributions TAP has made to elucidating mechanistic and kinetic aspects of complex, multistep heterogeneous reactions. With this in mind, an outlook is also disclosed for the technique in terms of what is needed to revitalize the field and make it more applicable to the recent advances in catalyst characterization (e.g. operando modes)