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We develop herein plasmonic-catalytic Au-IrO$_2$ nanostructures with amorphology optimized for efficient light harvesting and catalytic surface area;the nanoparticles have a dendritic morphology, with closely spaced Au branchesall partially covered by an ultrathin (1 nm) IrO$_2$ shell. This nanoparticlearchitecture optimizes optical features due to the interactions of closelyspaced plasmonic branches forming electromagnetic hot spots, and the ultra-thinIrO$_2$ layer maximizes efficient use of this expensive catalyst. This conceptwas evaluated towards the enhancement of the electrocatalytic performancestowards the oxygen evolution reaction (OER) as a model transformation. The OERcan play a central role in meeting future energy demands but the performance ofconventional electrocatalysts in this reaction is limited by the sluggish OERkinetics. We demonstrate an improvement of the OER performance for one of themost active OER catalysts, IrO$_2$, by harvesting plasmonic effects fromvisible light illumination in multimetallic nanoparticles. We find that the OERactivity for the Au-IrO$_2$ nanodendrites can be improved under LSPRexcitation, matching best properties reported in the literature. Oursimulations and electrocatalytic data demonstrate that the enhancement in OERactivities can be attributed to an electronic interaction between Au andIrO$_2$ and to the activation of Ir-O bonds by LSPR excited hot holes, leadingto a change in the reaction mechanism (rate-determinant step) under visiblelight illumination.

Design-controlled Synthesis of IrO$_2$ sub-monolayers on Au Nanodendrites: Marrying Plasmonic and Electrocatalytic Properties