Noncovalent Bonding Controls Selectivity in Heterogeneous Catalysis: Coupling Reactions on Gold

Stavros Karakalos, Yunfei Xu, Fairoja Cheenicode Kabeer, Wei Chen, Juan Carlos F. Rodríguez-Reyes, Alexandre Tkatchenko, Efthimios Kaxiras, Robert J. Madix, Cynthia M. Friend

Producción científica: Contribución a una revistaArtículorevisión exhaustiva

40 Citas (Scopus)


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.

Idioma originalInglés
Páginas (desde-hasta)15243-15250
Número de páginas8
PublicaciónJournal of the American Chemical Society
EstadoPublicada - 23 nov. 2016


Profundice en los temas de investigación de 'Noncovalent Bonding Controls Selectivity in Heterogeneous Catalysis: Coupling Reactions on Gold'. En conjunto forman una huella única.

Citar esto