For catalysts with multiple potential surface features that can contribute to activity, it is often difficult to quantify the proportion of activity that results from each facet. This challenge becomes more pronounced when proximate features in low abundance cooperate to influence reaction rates. Two common examples are metals on active supports, where promoter effects due to hydrogen spillover are often challenging to decouple from unique sites that lie at the metal-support interface. Similarly, in the microporous confines of zeolites, low abundant extra-lattice species may cooperatively stabilize certain transition states. Here we describe how systematic catalyst modifications allow us to study the kinetic relevance of these features for important reactions of interest (C-O1-4 and C-C5-8 activation) in contrast to traditional promoter or bifunctional catalytic effects. We then show how we can use these approaches to quantify rates of surface reconstruction under reaction conditions.
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