Relating the surface reactivity of model systems identified under ultra-high vacuum to the performance of catalytic materials under ambient flow conditions is a highly debated topic in catalysis. Here we report that, through use of Knudsen flow pulse/ response reactor analysis, trends in selectivity with temperature and reactant pressure can be accurately predicted for a catalytic flow reactor utilizing the kinetics and mechanism obtained from model studies on gold single crystals in ultrahigh vacuum. Specifically, for the oxygen-aassisted self-coupling of methanol microkinetic modelling of the complex sequence of elementary steps governing this reaction shows the dramatic effect of reactant partial pressure on the product distribution and leads to conclusion that the concentration of surface bound methoxy is the primary determinant of methyl formate selectivity. Thorough analysis of the reaction network indicates that the product distribution becomes insensitive to kinetic effects at pressures near 1 bar, leading toward 100% selectivity methyl formate. A rigorous kinetic sensitivity analysis also demonstrates the complex interplay of the kinetics of each elementary step and the overall catalytic behavior.<br/>

Gaining Insights into catalytic performance from fundamental studies in ultrahigh vacuum combined with Knudsen pulse flow reactor analysis

2019 Spring National Meeting

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