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

Area of Science:

• Plasmonics
• Nanotechnology
• Catalysis

Background:

• Plasmonic nanostructures are crucial for light-driven catalysis, enabling sensitive detection via confined optical fields.
• Controlling reaction kinetics in nanostructure-based chemical reactors remains a significant challenge.

Purpose of the Study:

• To develop a highly efficient nanoreactor construct for plasmonic catalysis.
• To investigate the role of palladium (Pd) monolayer placement on catalytic efficiency and reaction kinetics within nanoparticle-on-mirror (NPoM) platforms.

Main Methods:

• Fabrication of nanoparticle-on-mirror (NPoM) platforms with varying chemical surfaces in nanogaps.
• Observation and tracking of palladium-catalyzed C-C coupling reactions.
• Systematic analysis of atomic monolayer coatings of Pd on different gold (Au) facets.

Main Results:

• NPoM nanoreactors exhibit significantly improved catalytic efficiency compared to aggregated nanoparticle platforms.
• The placement of Pd monolayers (on nanoparticle vs. mirror) critically influences surface reaction kinetics.
• Demonstrated tunable reaction kinetics through atomic monolayer coatings on different Au facets.

Conclusions:

• NPoM nanoreactors offer superior catalytic and optical efficiencies for plasmonic catalysis.
• Molecular configuration and Pd monolayer location are key determinants of catalytic performance.
• The findings provide essential design rules for developing advanced plasmonic catalytic systems.