van der Waals Interactions Determine Selectivity in Catalysis by Metallic Gold
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Rodriguez-Reyes, Juan Carlos F.[Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, Massachusetts 02138, United States > > > ; School of Engineering and Applied Sciences, Harvard University, 12 Oxford Street, Cambridge, Massachusetts 02138, United States > > > ; Department of Industrial Chemical Engineering, Universidad de Ingeniería y Tecnología, Avenida Cascanueces 2221, Lima 43, Peru]
Siler, Cassandra G. F.[School of Engineering and Applied Sciences, Harvard University, 12 Oxford Street, Cambridge, Massachusetts 02138, United States]
Liu, Wei[Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, D-14195, Berlin, Germany]
Tkatchenko, Alexandre[Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, D-14195, Berlin, Germany]
Friend, Cynthia M.[Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, Massachusetts 02138, United States > > > ; School of Engineering and Applied Sciences, Harvard University, 12 Oxford Street, Cambridge, Massachusetts 02138, United States]
Madix, Robert J.[School of Engineering and Applied Sciences, Harvard University, 12 Oxford Street, Cambridge, Massachusetts 02138, United States]
[en] To achieve high selectivity for catalytic reactions between two or more reactants on a heterogeneous catalyst, the relative concentrations of the reactive intermediates on the surface must be optimized. If species compete for binding sites, their concentrations depend on their relative binding strengths to the surface. In this article we describe a general framework for predicting the relative stability of organic intermediates involved in oxygen-assisted reactions on metallic gold with broad relevance to catalysis by metals. Combining theory and experiment, we establish that van der Waals interactions between the reactive intermediates and the surface, although weak, determine relative stabilities and thereby dictate the conditions for optimum selectivity. The inclusion of these interactions is essential for predicting these trends. The concepts and methods employed here have broad applicability for determining the stability of intermediates on the surfaces of catalytic metals and specifically demonstrate the critical role of weak interactions in determining reaction selectivity among reactions of complex molecules.
[Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, D-14195, Berlin, Germany]
