Controlling the surface environment of heterogeneous catalysts using self-assembled monolayers.

Rationally designing and producing suitable catalysts to promote specific reaction pathways remains a major objective in heterogeneous catalysis. One approach involves using traditional catalytic materials modified with self-assembled monolayers (SAMs) to create a more favorable surface environment for specific product formation. A major advantage of SAM-based modifiers is their tendency to form consistent, highly ordered assembly structures on metal surfaces. In addition, both the attachment chemistry and tail structures can easily be tuned to facilitate specific interactions between reactants and the catalyst. In this Account, we summarize our recent modification approaches for tuning monolayer structure to improve catalytic performance for hydrogenation reactions on palladium and platinum catalysts. Each approach serves to direct selectivity by tuning a particular aspect of the system including the availability of specific active sites (active-site selection), intermolecular interactions between the reactants and modifiers (molecular recognition), and general steric or crowding effects. We have demonstrated that the tail moiety can be tuned to control the density of SAM modifiers on the surface. Infrared spectra of adsorbed CO probe molecules reveal that increasing the density of the thiols restricts the availability of contiguous active sites on catalyst terraces while maintaining accessibility to sites located at particle edges and steps. This technique was utilized to direct selectivity for the hydrogenation of furfural. Results obtained from SAM coatings with different surface densities indicated that, for this reaction, formation of the desirable products occurs primarily at particle edges and steps, whereas the undesired pathway occurs on particle terrace sites. As an alternative approach, the tail structure of the SAM precursor can be tuned to promote specific intermolecular interactions between the modifier and reactant in order to position reactant molecules in a desired orientation. This technique was utilized for the hydrogenation of cinnamaldehyde, which contains an aromatic phenyl moiety. By using a phenyl-containing SAM modifier with an appropriate tether length, > 90% selectivity toward reaction of the aldehyde group was achieved. In contrast, employing a modifier where the phenyl moiety was closer to the catalyst surface biased selectivity toward the hydrogenation of the C═C bond due to reorienting the molecule to a more "lying down" conformation. In addition to approaches that target specific interactions between the reactant and modified catalyst, we have demonstrated the use of SAMs to impose a steric or blocking effect, for example, during the hydrogenation of polyunsaturated fatty acids. The SAMs facilitated hydrogenation of polyunsaturated to monounsaturated fatty acids but inhibited further hydrogenation to the completely saturated species due to the sterically hindered, single "kink" shape of the monounsaturated product. The recent contributions discussed in this Account demonstrate the significant potential for this approach to design improved catalysts and to develop a deeper understanding of mechanistic effects due to the near surface environment.