Optical enhancement of plasmonic activity of catalytic metal nanoparticles

Antosiewicz, Tomasz J.; Apell, S. Peter

doi:10.1039/c4ra13399d

Cited by 12 publications

(12 citation statements)

References 41 publications

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“…However, their optical spectra explain the reason for this behavior. 23 The observed enhancement order is the same as that of the plasma frequencies as observed qualitatively based on absorption efficiencies. Ru has the largest plasma frequency and correspondingly has large absorption enhancement.…”

Section: Coupled Nanostructures With Large Catalytic Metal Elementssupporting

confidence: 65%

“…Thus, shifting their plasmonic activity into the visible spectrum is important from an applications point of view. 22,23 Here, we show how to do just this using hybridized hetero-metallic nanostructures 24 which utilize a low-loss nanoantenna to collect incident light and direct it into LSPRs on the catalytic metal nanoparticles.…”

Section: Increasing Light and Plasmon Absorption In Catalytic Metalsmentioning

confidence: 99%

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Optical activity of catalytic elements of hetero-metallic nanostructures

et al. 2015

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Interaction of light with metals in the form of surface plasmons is used in a wide range of applications in which the scattering decay channel is important. The absorption channel is usually thought of as unwanted and detrimental to the efficiency of the device. This is true in many applications, however, recent studies have shown that maximization of the decay channel of surface plasmons has potentially significant uses. One of these is the creation of electron-hole pairs or hot electrons which can be used for e.g. catalysis. Here, we study the optical properties of hetero-metallic nanostructures that enhance light interaction with the catalytic elements of the nanostructures. A hybridized LSPR that matches the spectral characteristic of the light source is excited. This LSPR through coupling between the plasmonic elements maximizes light absorption in the catalytic part of the nanostructure. Numerically calculated visible light absorption in the catalytic nanoparticles is enhanced 12-fold for large catalytic disks and by more 30 for small nanoparticles on the order of 5 nm. In experiments we measure a sizable increase in the absorption cross section when small palladium nanoparticles are coupled to a large silver resonator. These observations suggest that heterometallic nanostructures can enhance catalytic reaction rates.

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Section: Coupled Nanostructures With Large Catalytic Metal Elementssupporting

confidence: 65%

Section: Increasing Light and Plasmon Absorption In Catalytic Metalsmentioning

confidence: 99%

Optical activity of catalytic elements of hetero-metallic nanostructures

et al. 2015

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“…Increasing transition metal nanoparticle size redshifts optical absorption, but it increases cost and reduces surface area, and therefore catalytic activity. Recently, it has been shown that plasmonic nanoparticles can be used to increase optical absorption in adjacent nanoparticles (19)(20)(21)(22), for instance, enabling hydrogen detection (23,24).Previous reports of photocatalytic transformation in plasmonic metal nanoparticle systems rely on the metal to double as both the Significance Plasmon-enhanced photocatalysis holds significant promise for controlling chemical reaction rates and outcomes. Unfortunately, traditional plasmonic metals have limited surface chemistry, while conventional catalysts are poor optical absorbers.…”

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confidence: 99%

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confidence: 99%

Heterometallic antenna−reactor complexes for photocatalysis

Swearer

Zhao

Zhou

et al. 2016

Proc. Natl. Acad. Sci. U.S.A.

436

548

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Metallic nanoparticles with strong optically resonant properties behave as nanoscale optical antennas, and have recently shown extraordinary promise as light-driven catalysts. Traditionally, however, heterogeneous catalysis has relied upon weakly light-absorbing metals such as Pd, Pt, Ru, or Rh to lower the activation energy for chemical reactions. Here we show that coupling a plasmonic nanoantenna directly to catalytic nanoparticles enables the light-induced generation of hot carriers within the catalyst nanoparticles, transforming the entire complex into an efficient light-controlled reactive catalyst. In Pd-decorated Al nanocrystals, photocatalytic hydrogen desorption closely follows the antenna-induced local absorption cross-section of the Pd islands, and a supralinear power dependence strongly suggests that hot-carrier-induced desorption occurs at the Pd island surface. When acetylene is present along with hydrogen, the selectivity for photocatalytic ethylene production relative to ethane is strongly enhanced, approaching 40:1. These observations indicate that antenna−reactor complexes may greatly expand possibilities for developing designer photocatalytic substrates.plasmon | photocatalysis | nanoparticle | catalysis | aluminum I ndustrial processes depend extensively on heterogeneous catalysts for chemical production and mitigation of environmental pollutants. These processes often rely on metal nanoparticles dispersed into high surface area support materials to both maximize catalytically active surface area and for the most cost-effective use of expensive catalysts such as Pd, Pt, Ru, or Rh (1, 2). However, catalytic processes utilizing transition metal nanoparticles are often energyintensive, relying on high temperatures and pressures to maximize catalytic activity. A transition from extreme, high-temperature conditions to low-temperature activation of catalytically active transition metal nanoparticles could have widespread impact, substantially reducing the current energy demands of heterogeneous catalysis.Light-driven chemical transformations offer an attractive and ultimately sustainable alternative to traditional high-temperature catalytic reactions. Metallic plasmonic nanostructures are a new paradigm in photoactive heterogeneous catalysts (3-6). Plasmonic nanoparticles uniquely couple electron density with electromagnetic radiation, leading to a collective oscillation of the conduction electrons in resonance with the frequency of incident light, known as a localized surface plasmon resonance (LSPR). These resonances lead to enhanced light absorption in an area much larger than the physical cross-section of the nanoparticle, and such optical antenna effects result in strongly enhanced electromagnetic fields near the nanoparticle surface. An LSPR can be damped through radiative reemission of a photon, or nonradiative Landau damping with the creation of energetic "hot" carriers: electrons above the Fermi energy of the metal and/or holes below the Fermi energy. In this context, "hot" refers to carri...

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“…Most of the previous investigations were limited to dimers with ordinary shapes or materials with similar compositions. [13][14][15][16][17][18] In this report, we extend our study to the NM structure with different metal compositions and sizes. This method allows us investigating the plasmon resonance behavior in symmetry-lacking structures.…”

Section: Introductionmentioning

confidence: 95%

Resonance coupling in plasmonic nanomatryoshka homo- and heterodimers

2016

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Here, we examine the electromagnetic (EM) energy coupling and hybridization of plasmon resonances between closely spaced concentric nanoshells known as “nanomatryoshka” (NM) units in symmetric and antisymmetric compositions using the Finite Difference Time Domain (FDTD) analysis. Utilizing plasmon hybridization model, we calculated the energy level diagrams and verified that, in the symmetric dimer (in-phase mode in a homodimer), plasmonic bonding modes are dominant and tunable within the considered bandwidth. In contrast, in the antisymmetric dimer (out-of-phase mode in a heterodimer), due to the lack of the geometrical symmetry, new antibonding modes appear in the extinction profile, and this condition gives rise to repeal of dipolar field coupling. We also studied the extinction spectra and positions of the antibonding and bonding modes excited due to the energy coupling between silver and gold NM units in a heterodimer structure. Our analysis suggest abnormal shifts in the higher energy modes. We propose a method to analyze the behavior of multilayer concentric nanoshell particles in an antisymmetric orientation employing full dielectric function calculations and the Drude model based on interband transitions in metallic components. This study provides a method to predict the behavior of the higher energy plasmon resonant modes in entirely antisymmetric structures such as compositional heterodimers.

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Optical enhancement of plasmonic activity of catalytic metal nanoparticles

Abstract: Plasmon-assisted direct photocatalysis through enhanced light absorption in catalytic metal nanoparticles. Enhancement is achieved by coupling the plasmon resonance of a silver nanoantenna to that of a catalytic metal nanoparticle.

Cited by 12 publications

References 41 publications

Optical activity of catalytic elements of hetero-metallic nanostructures

Optical activity of catalytic elements of hetero-metallic nanostructures

Heterometallic antenna−reactor complexes for photocatalysis

Resonance coupling in plasmonic nanomatryoshka homo- and heterodimers

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