Light Capture and Energy Conversion in Plasmonic-Polymeric Hybrid Nanoelectrodes

Abstract

Plasmonic nanomaterials have absorption cross-sections exceeding other classes of materials but dephase quickly into their dielectric environment. In this work, plasmonic-polymeric nanoantenna-reactor systems are hybridized to increase the electron-hole pair lifetime through interfacial redistribution. The electron-hole pair can then be extracted to drive catalysis as the selected polymeric acceptor, a metallophthalocyanine, has been shown to catalysis O2 and CO2 reduction efficiently. Single particle spectroelectrochemistry was used to characterize the energy transfer efficiencies of the hybrid structures by recording the surface plasmon resonance energy linewidth change during in situ polymerization. The electrochemical polymerization is selective and photoenhanced on the surface of the gold nanorods. We complement resonance energy transfer efficiencies calculated from single particle changes in linewidth with calculations from excitation polarization-dependent photoluminescence measurements. Non-radiative energy transfer efficiencies up to 50% are achieved for plasmonic-polymeric nano-antenna reactors. The understanding of interfacial transfer pathways between plasmonic-polymeric materials will lead to control and tunability of scalable hybrid nanoelectrodes.