Design-controlled synthesis of IrO2 sub-monolayers on Au nanoflowers: marrying plasmonic and electrocatalytic properties.

We develop herein plasmonic-catalytic Au-IrO2 nanostructures with a morphology optimized for efficient light harvesting and catalytic surface area; the nanoparticles have a nanoflower morphology, with closely spaced Au branches all partially covered by an ultrathin (1 nm) IrO2 shell. This nanoparticle architecture optimizes optical features due to the interactions of closely spaced plasmonic branches forming electromagnetic hot spots, and the ultra-thin IrO2 layer maximizes efficient use of this expensive catalyst. This concept was evaluated towards the enhancement of the electrocatalytic performances towards the oxygen evolution reaction (OER) as a model transformation. The OER can play a central role in meeting future energy demands but the performance of conventional electrocatalysts in this reaction is limited by the sluggish OER kinetics. We demonstrate an improvement of the OER performance for one of the most active OER catalysts, IrO2, by harvesting plasmonic effects from visible light illumination in multimetallic nanoparticles. We find that the OER activity for the Au-IrO2 nanoflowers can be improved under LSPR excitation, matching best properties reported in the literature. Our simulations and electrocatalytic data demonstrate that the enhancement in OER activities can be attributed to an electronic interaction between Au and IrO2 and to the activation of Ir-O bonds by LSPR excited hot holes, leading to a change in the reaction mechanism (rate-determinant step) under visible light illumination.

Controlling Reaction Selectivity over Hybrid Plasmonic Nanocatalysts.

The localized surface plasmon resonance (LSPR) excitation in plasmonic nanoparticles has been used to accelerate several catalytic transformations under visible-light irradiation. In order to fully harness the potential of plasmonic catalysis, multimetallic nanoparticles containing a plasmonic and a catalytic component, where LSPR-excited energetic charge carriers and the intrinsic catalytic active sites work synergistically, have raised increased attention. Despite several exciting studies observing rate enhancements, controlling reaction selectivity remains very challenging. Here, by employing multimetallic nanoparticles combining Au, Ag, and Pt in an Au@Ag@Pt core-shell and an Au@AgPt nanorattle architectures, we demonstrate that reaction selectivity of a sequential reaction can be controlled under visible light illumination. The control of the reaction selectivity in plasmonic catalysis was demonstrated for the hydrogenation of phenylacetylene as a model transformation. We have found that the localized interaction between the triple bond in phenylacetylene and the Pt nanoparticle surface enables selective hydrogenation of the triple bond (relative to the double bond in styrene) under visible light illumination. Atomistic calculations show that the enhanced selectivity toward the partial hydrogenation product is driven by distinct adsorption configurations and charge delocalization of the reactant and the reaction intermediate at the catalyst surface. We believe these results will contribute to the use of plasmonic catalysis to drive and control a wealth of selective molecular transformations under ecofriendly conditions and visible light illumination.

Galvanic replacement reaction: recent developments for engineering metal nanostructures towards catalytic applications.

Metallic nanoparticles have been extensively studied towards applications in catalysis. Among the several methods for their controlled synthesis, galvanic replacement is particularly attractive as it enables the production of bimetallic and hollow nanomaterials displaying ultrathin walls in a single reaction step. This procedure is versatile, but final morphologies are often limited to shapes that represent the hollow analogues of the starting template nanocrystals. For catalytic applications, it is highly desirable to broaden the scope of physicochemical control that can be achieved by this method. This feature article discusses recent strategies developed in our group for the synthesis of hollow bimetallic nanomaterials by galvanic replacement that enable a further level of control over surface morphologies and composition. We begin by briefly explaining the fundamentals of the conventional galvanic replacement reaction between Ag and AuCl4-. This is one of the most characteristic galvanic replacement reactions, and it can be tuned to create a huge variety of nanoparticle morphologies. We will discuss how advanced electron microscopy characterization enables us to uncover surface-segregation behavior as a function of compositions, and relate this to the detected catalytic performance. We will also discuss how galvanic replacement can be extended to trimetallic compositions, leading to improvements in catalytic activities compared to mono or bimetallic counterparts. Furthermore, we will show how surface morphology, size, and anisotropic growth can be controlled by tuning the temperature during the synthesis and by combining galvanic replacement reaction with co-reduction. Finally, we will demonstrate how these approaches are promising for large-scale synthesis of controlled hollow nanostructures and their incorporation into supports to produce catalysts at the gram-scale. We believe the developments described herein shed important insights and may inspire the development of sophisticated and controlled nanomaterials at relatively larger scales for catalytic applications.

Controlling Size, Morphology, and Surface Composition of AgAu Nanodendrites in 15 s for Improved Environmental Catalysis under Low Metal Loadings.

In this work, a simple but powerful method for controlling the size and surface morphology of AgAu nanodendrites is presented. Control of the number of Ag nanoparticle seeds is found to provide a fast and effective route by which to manipulate the size and morphology of nanoparticles produced via a combined galvanic replacement and reduction reaction. A lower number of Ag nanoparticle seeds leads to larger nanodendrites with the particles' outer diameter being tunable in the range of 45-148 nm. The size and surface morphology of the nanodendrites was found to directly affect their catalytic activity. Specifically, we report on the activity of these AgAu nanodendrites in catalyzing the gas-phase oxidation of benzene, toluene and o-xylene, which is an important reaction for the removal of these toxic compounds from fuels and for environmental remediation. All produced nanodendrite particles were found to be catalytically active, even at low temperatures and low metal loadings. Surprisingly, the largest nanodendrites provided the greatest percent conversion efficiencies.