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    Intensified near-field by localizing surface plasmon for enhancing photoelectrochemical responses via periodically patterned Au assemblies

    Year: 2023

    Journal: Chemical Engineering Journal, Volume 461, 2023-04-01, page 142082

    Authors: Choi, Young Moon; Roh, Seung Hun; Kwak, Eujin; Choi, Dae-Geun; Kwon, Seok Joon; Kim, Jung Kyu; Park, Jong Hyeok

    Keywords: Near field effect; Patterned Au assembles; Photoelectrochemical cells; Surface plasmon resonance

    The introduction of plasmon induced energy transfer (PIET) is a promising approach to enhance the photoelectrochemical (PEC) responses on metal-oxide based photoelectrodes. Most approaches of harnessing surface plasmon resonance use metal nanoparticles (NPs) spread over the electrode surface. However, crucial challenges remain for exploiting the strongly amplified near-field by coupling the NPs and underlying photoelectrodes. Herein, we demonstrate effective localization of a plasmon-induced near-field on a photoelectrode via patterned Au NP assemblies (Au-PAT) that improves the PEC responses for efficient oxidation reactions in aqueous electrolytes. The coupling effect between Au-PAT and the hematite (α-Fe2O3) photoanode promoted the photoexcitation of charge carriers around the space charge region. We computationally analyzed the plasmonic effects boosted by Au-PAT and found that Au-PAT with an optimized grating pitch enhanced the light absorption efficiency and increased the interband transition rate via PIET. Consequently, the effective surface near-field induced by the rationally designed Au-PAT suppressed the undesired surface charge recombinations and enhanced the charge transfer, resulting in a 1.9-fold higher photocurrent density at 1.23 V versus reversible hydrogen electrode (RHE). Furthermore, the near-field effect was also effective for the PEC hydrazine oxidation reaction, with 3.2-fold increased photocurrent density at 1.23 V versus RHE. This demonstrates that implementing Au-PAT is a versatile strategy as an application for various PEC reactions.
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