Transition metal nanoparticles are uniquely suited for applications in heterogeneous catalysis. Small NPs are typically the most catalytically active, yet are most disposed to aggregation. Thus, a variety of solid support strategies, including the use of simple oxides and (meso)porous materials, have been utilized in practical catalytic systems for the stabilization and recycling/reuse of NPs. These supporting materials have been shown to strongly affect the catalytic properties of NPs, sometimes acting as synergistic co-catalysts. Such supported NP catalysts are extremely useful, yet in many cases the nature of NP-support interaction is poorly understood. Strategies for the rational design of supported NP catalysts and better understanding of the NP-support interaction are highly desirable.<br/>In this presentation, we describe a strategy of supporting small Au NPs on mesoporous SBA-15 modified by mixtures of functional silanes. The use of such mixed surface modifiers allows easy access to a range of surface chemistries and modalities of interaction between NPs and supports. We discovered that a combination of thiol groups and linear semifluorinated chains effectively stabilizes the Au NPs against aggregation. The thiol-fluorous-supported catalyst is active in Ullmann homocoupling of arenes and shows exceptional selectivity in this reaction.

Thiols make for better catalysts: Au nanoparticles supported on modified SBA-15 for catalysis of Ullmann homocouplings

252nd National Meeting (2016)

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