Design rules for catalysis in single-particle plasmonic nanogap reactors with precisely aligned molecular monolayers

Plasmonic nanostructures can both drive and interrogate light-driven catalytic reactions. Sensitive detection of reaction pathways is achieved by confining optical fields near the active surface. However, effective control of the reaction kinetics remains a challenge to utilize nanostructure constructs as efficient chemical reactors. Here we present a nanoreactor construct exhibiting high catalytic and optical efficiencies, based on a nanoparticle-on-mirror (NPOM) platform. We observe and track pathways of the Pd-catalysed C-C coupling reaction of molecules within a set of nanogaps presenting different chemical surfaces. Atomic monolayer coatings of Pd on the different Au facets enable tuning of the reaction kinetics of surface-bound molecules. Systematic analysis shows the catalytic efficiency of NPOM-based nanoreactors greatly improves on platforms based on aggregated nanoparticles. More importantly, we show Pd monolayers on the nanoparticle or on the mirror play significantly different roles in the surface reaction kinetics. Our data provides clear evidence for catalytic dependencies on molecular configuration in well-defined nanostructures. Such nanoreactor constructs therefore yield clearer design rules for plasmonic catalysis.