title: Noncovalent Bonding Controls Selectivity in Heterogeneous Catalysis: Coupling Reactions on Gold.
abstract: Enhancing the selectivity of catalytic processes has potential for substantially increasing the sustainability of chemical production. Herein, we establish relationships between reaction selectivity and molecular structure for a homologous series of key intermediates for oxidative coupling of alcohols on gold using a combination of experiment and theory. We establish a scale of binding for molecules with different alkyl structures and chain lengths and thereby demonstrate the critical nature of noncovalent van der Waals interactions in determining the selectivity by modulating the stability of key reaction intermediates bound to the surface. The binding hierarchy is the same for Au(111) and Au(110), which demonstrates a relative lack of sensitivity to the surface structure. The hierarchy of binding established in this work provides guiding principles for predicting how molecular structure affects the competition for binding sites more broadly. Besides the nature of the primary surface-molecule bonding, three additional factors that affect the stabilities of the reactive intermediates are clearly established: (1) the number of C atoms in the alkyl chain, (2) the presence of C-C bond unsaturation, and (3) the degree of branching of the alkyl group of the adsorbed molecules. We suggest that this is a fundamental principle that is generally applicable to a broad range of reactions on metal catalysts.
authors: Stavros
authors: S
authors: Karakalos
authors: Yunfei
authors: Y
authors: Xu
authors: Fritz-Haber-Institut der Max-Planck-Gesellschaft , Faradayweg 4-6, Berlin D-14195, Germany.
authors: Fairoja
authors: F
authors: Cheenicode Kabeer
authors: ICQD, Hefei National Laboratory for Physical Sciences at Microscale, and Synergetic Innovation Center of Quantum Information and Quantum Physics, University of Science and Technology of China , Hefei, Anhui 230026, China.
authors: Wei
authors: W
authors: Chen
authors: Department of Industrial Chemical Engineering, Universidad de Ingeniería y Tecnología , Avenida Cascanueces 2221, Lima 43 15063, Peru.
authors: Juan Carlos F
authors: JC
authors: Rodríguez-Reyes
authors: Fritz-Haber-Institut der Max-Planck-Gesellschaft , Faradayweg 4-6, Berlin D-14195, Germany.|Physics and Materials Science Research Unit, University of Luxembourg , Luxembourg City L-1511 Luxembourg.
authors: Alexandre
authors: A
authors: Tkatchenko
authors: Efthimios
authors: E
authors: Kaxiras
authors: Robert J
authors: RJ
authors: Madix
authors: Cynthia M
authors: CM
authors: Friend