Gold-catalyzed oxidative coupling reactions investigated on single-crystal surfaces and nanoporous metallic gold catalysts establish several key principles of reaction and also illustrate the predictive value of fundamental studies.   Selective oxidation of dissimilar alcohols to produce esters is used to illustrate the importance of van der Waal's interactions in determining reaction selectivity.   Atomic oxygen adsorbed on Au creates active sites for creation of key reaction intermediates, whereas Au itself is unreactive.  On the working nanoporous Au catalyst, a small fraction of Ag in the Au facilitates O<sub>2</sub> dissocation to create adsorbed O.  Competition for the active sites in complex reaction mixtures determines the surface concentration of key, alkoxide intermediates on the surface.  The competition for sites is determined by a combination of primary bonding to the surface and weak, van der Waal's interactions.  The same selectivity patterns as a function of reactant concentration are observed for single crystals under ultrahigh vacuum and on the working Au catalyst, demonstrating the role of the van der Waal's interactions.  A combination of atomic scale imaging (STM and TEM), X-ray photoelectron spectroscopy, density functional theory calculations and reactivity measurements were used in this work to establish these principles.

Design principles for sustainable catalysis from fundamental surface chemistry

251st National Meeting (2016)

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