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The Impact of Optically Rectified Fields on Plasmonic Electrocatalysis

Abstract

Studies have shown the excitation of plasmon resonances on nanostructured materials can drive catalytic processes. Plasmon resonances can be tuned across the solar spectrum, offering intriguing application possibilities for plasmonic catalysis. Previous work in our group indicates that nanostructures with tight junctions can create direct current (DC) electric fields. These fields arise from an optical rectification of the plasmon resonance on the plasmonic surface, and our group has shown these fields modulate photocatalytic activity. This work looks to shed further light on the impact optically rectified fields can have on catalytic reactions. Cyclic voltammetry shows that the electrochemical reduction and oxidation potentials of a 2 mM CuSO4 solution occur at ~100 mV lower overpotential on an optically excited Ag nanodendrite electrode. Stark spectroscopy of nitriles absorbed to these surfaces indicate photo-associated changes in surface potential across the Ag nanodendrites. Localized areas evince photo-induced changes in surface potential upwards of 300 mV. These results provide evidence of optically rectified fields altering electrochemical reactivity on plasmonic surfaces and suggest optimizing this nonlinear phenomenon may improve plasmonic photocatalysts.

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Publication details

The article was received on 18 Sep 2018, accepted on 15 Nov 2018 and first published on 15 Nov 2018


Article type: Paper
DOI: 10.1039/C8FD00135A
Citation: Faraday Discuss., 2018, Accepted Manuscript
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    The Impact of Optically Rectified Fields on Plasmonic Electrocatalysis

    D. A. Nelson and Z. D. Schultz, Faraday Discuss., 2018, Accepted Manuscript , DOI: 10.1039/C8FD00135A

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