Abstract
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.
Highlights
Plasmonic nanoparticles have emerged as attractive systems to efficiently harvest solar energy in order to drive and control chemical transformations.[1−4] In plasmonic nanoparticles, incident photons resonantly interact with the collective motion of electrons, a phenomenon known as localized surface plasmon resonance (LSPR).[5,6]
Our results demonstrated that the preferential bond interaction between the C−C triple bond and Pt at the surface of our catalysts enabled control of reaction selectivity, in which an increase toward the formation of styrene, the semihydrogenation product, was observed under visible light
This was observed as a result of plasmon hybridization that leads to higher E-field enhancements relative to individual nanostructures as a result of LSPR excitation,[48] indicating that the nanorattle morphology may be promising in terms of activity enhancements and possibly selectivity assessment in plasmonic nanocatalysis.[49−52] here we focus on multimetallic nanorattles as a target architecture
Summary
Letter reaction rates.[7,8,33,34] In addition, this opens the possibility for controlling the reaction selectivity as the injection of these hot carriers to specific molecular orbitals of adsorbates or metal− adsorbate complex can be maneuvered.[17,35−40] despite several studies of rate enhancements and mechanisms,[8,14,22,41,42] achieving control over reaction selectivity in plasmonic nanocatalysis remains challenging. This was demonstrated by the increased selectivity of the catalytic semihydrogenation reaction of the carbon−carbon triple bond under visible light illumination Both nanoparticle architectures were comprised of ultrathin Pt-based catalytic shells and allowed the effective combination of plasmonic and catalytic properties, that is, the harvesting of Au or Au@Ag plasmonic properties to enhance catalytic transformation at the surface of the catalytic active but nonplasmonic metal (Pt). These results indicate that the plasmonic−catalytic nanorattle architecture represents a unique system that combines plasmonic−catalytic properties, provides high active surface area due to the ultrathin catalytic-based shells, and can concentrate high electric field intensities at the surface They enable efficient energy transfer to the nonplasmonic metal (Pt), where the LSPR-excited hot carriers lead to the enhancement of activity and selectivity in liquid phase transformations under visible light.
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