Plasmonic Cavity-Catalysis by Standing Hot Carrier Waves

Manipulating active sites of catalysts is crucial butchallengingin catalysis science and engineering. Beyond the design of the compositionand structure of catalysts, the confined electromagnetic field inoptical cavities has recently become a promising method for catalyzingchemical reactions via strong light-matter interactions. Anotherform of confined electromagnetic field, the charge density wave inplasmonic cavities, however, still needs to be explored for catalysis.Here, we present an unprecedented catalytic mode based on plasmoniccavities, called plasmonic cavity-catalysis. We achieve direct controlof catalytic sites in plasmonic cavities through standing hot carrierwaves. Periodic catalytic hotspots are formed because of localizedenergy and carrier distribution and can be well tuned by cavity geometry,charge density, and excitation angle. We also found that the catalyticactivity of the cavity mode increases several orders of magnitudecompared with conventional plasmonic catalysis. We ultimately demonstratethat the locally concentrated long-lived hot carriers in the standingwave mode underlie the formation of the catalytic hotspots. Plasmoniccavity-catalysis provides a new approach to manipulate the catalyticsites and rates and may expand the frontier of heterogeneous catalysis.

Automated summary

The confined electromagnetic field in optical cavities, known as plasmonic cavity-catalysis, provides a promising method for manipulating catalytic sites and rates. Through controlling the standing hot carrier waves in plasmonic cavities, periodic catalytic hotspots can be formed and well tuned by cavity geometry, charge density, and excitation angle. Plasmonic cavity-catalysis exhibits significantly higher catalytic activity compared to conventional plasmonic catalysis. It is demonstrated that the locally concentrated, long-lived hot carriers in the standing wave mode underlie the formation of the catalytic hotspots. This new approach may expand the frontier of heterogeneous catalysis.