Hot-Electron-Induced Dissociation of H<sub>2</sub>on Gold Nanoparticles Supported on SiO<sub>2</sub>

Mukherjee, Shaunak; Zhou, Linan; Goodman, Amanda M.; Large, Nicolas; Ayala-Orozco, Ciceron; Yu, Zhang; Nordlander, Peter; Halas, Naomi J.

doi:10.1021/ja411017b

Cited by 481 publications

(517 citation statements)

References 31 publications

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“…S7 and Table S2) because of the very exothermic and barrier-free dissociative adsorption of H 2 on Pd(111), consistent with recent literature (32,33). Thus, we believe that the more consequential process for Pd-in contrast to earlier reports of plasmon-induced dissociation of H 2 on Au (7,8) and Al (15)-is the interaction of the generated hot carriers with adsorbed H and D atoms on Pd, inducing desorption of HD. The plasmon-induced dissociation, recombination, and desorption processes are all charge-neutral.…”

Section: Resultssupporting

confidence: 88%

Heterometallic antenna−reactor complexes for photocatalysis

Swearer

Zhao

Zhou

et al. 2016

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

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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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Section: Resultssupporting

confidence: 88%

Heterometallic antenna−reactor complexes for photocatalysis

Swearer

Zhao

Zhou

et al. 2016

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

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418

548

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“…3 While the design of heterogeneous photocatalysts has focused largely on semiconducting light absorbers, 4,5 it has recently been demonstrated that metallic nanostructures offer unique characteristics for facilitating photocatalytic reactions. [6][7][8][9] Strong light absorption through the excitation of localized surface plasmons on plasmonic metal nanostructures 10 comprised of Au, [11][12][13] Ag, [14][15][16] Cu, 17 or Al, 18 has been shown to drive photocatalytic processes through the excitation and transient transfer of energetic, or hot, carriers to adsorbates. [19][20][21][22][23][24] However, there is limited evidence that the energies of hot carriers in plasmonic nanostructures can be selectively tailored to target specific catalytic reaction pathways, 25,26 and plasmonic nanostructures are optimal catalysts for only a very few 4 relevant industrial chemical processes.…”

Section: Main Textmentioning

confidence: 99%

Balancing Near-Field Enhancement, Absorption, and Scattering for Effective Antenna–Reactor Plasmonic Photocatalysis

Li¹,

Hogan²,

et al. 2017

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Efficient photocatalysis requires multifunctional materials that absorb photons and generate energetic charge carriers at catalytic active sites to facilitate a desired chemical reaction.Antenna-reactor complexes are an emerging multifunctional photocatalytic structure where the strong, localized near field of the plasmonic metal nanoparticle (e.g. Ag) is coupled to the catalytic properties of the non-plasmonic metal nanoparticle (e.g. Pt) to enable chemical transformations. With an eye towards sustainable solar driven photocatalysis we investigate how the structure of antenna-reactor complexes governs their photocatalytic activity in the light- 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 where the plasmonic nanoparticle is the antenna and the catalytic particle, which can be interchanged based on desired reactivity, is the reactor. In an antenna-reactor complex, the local field induced by the photoexcited antenna particle drives a "forced" plasmon in the nonplasmonic, catalytic nanoparticle: this forced plasmon can serve as a direct source of hot carriers in the catalytic particle to drive chemical processes without the need for charge transfer between the antenna and the reactor components of the nanocomplex. In the initial demonstrations of antenna-reactor coupling, however, the optimal geometric configuration of the constituent materials to maximize photocatalytic performance was not addressed. Furthermore, while it is relatively straightforward to conclude that localizing a plasmonic particle near a non-plasmonic catalytic particle will enhance light absorption in the non-plasmonic particle, it is not clear how this translates to enhanced photocatalysis in the light-limited regime, where all photons must be utilized in a 3-D packed bed of catalytic particles. Optimizing photocatalytic complexes for highest efficiency photon management in the light-limited regime is of critical importance for further development of this approach.In the work reported here, a series of antenna-reactor complexes consisting of core@shell/satellite (Ag@SiO 2 /Pt) heterostructures with varying Ag core diameter (12,25,50 and 100 nm) were synthesized and their photocatalytic properties for the kinetically well-defined CO oxidation reaction were quantitatively compared. Rigorous quantum yield measurements in the light-limited regime demonstrate that for heterostructures with Ag nanoparticles (Ag NPs) in an intermediate size range of 25 and 50 nm diameter, plasmon-enhanced photocatalytic performance was observed at rates more than four times larger than for either smaller (12 nm diameter) or larger (100 nm diameter) Ag particles. Using optical and Monte Carlo simulations, it was shown that if the Ag NPs were too large, the heterostructures scattered light out of the catalyst bed, reducing photocatalytic reactivity. If the Ag NPs were too small, l...

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“…Chen et al showed that Au NPs are active for HCHO oxidation to CO 2 under 600-700 nm red light irradiation [13,33,127,128]. Hot electrons can drive also H 2 dissociation on plasmonic Au NPs at room temperature and laser intensity of~2 W cm −2 [129,130]. Plasmonic nanostructures have also been reported to drive the selective oxidation of secphenethyl alcohol to acetophenone under LSPR excitation of aqueous colloidal Au NPs with visible light [131].…”

Section: Direct Plasmonic Photocatalysismentioning

confidence: 99%

Solar-Powered Plasmon-Enhanced Heterogeneous Catalysis

et al. 2016

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Photocatalysis uses semiconductors to convert sunlight into chemical energy. Recent reports have shown that plasmonic nanostructures can be used to extend semiconductor light absorption or to drive direct photocatalysis with visible light at their surface. In this review, we discuss the fundamental decay pathway of localized surface plasmons in the context of driving solar-powered chemical reactions. We also review different nanophotonic approaches demonstrated for increasing solar-tohydrogen conversion in photoelectrochemical water splitting, including experimental observations of enhanced reaction selectivity for reactions occurring at the metalsemiconductor interface. The enhanced reaction selectivity is highly dependent on the morphology, electronic properties, and spatial arrangement of composite nanostructures and their elements. In addition, we report on the particular features of photocatalytic reactions evolving at plasmonic metal surfaces and discuss the possibility of manipulating the reaction selectivity through the activation of targeted molecular bonds. Finally, using solar-tohydrogen conversion techniques as an example, we quantify the efficacy metrics achievable in plasmon-driven photoelectrochemical systems and highlight some of the new directions that could lead to the practical implementation of solar-powered plasmon-based catalytic devices.

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Hot-Electron-Induced Dissociation of H₂on Gold Nanoparticles Supported on SiO₂

Cited by 481 publications

References 31 publications

Heterometallic antenna−reactor complexes for photocatalysis

Heterometallic antenna−reactor complexes for photocatalysis

Balancing Near-Field Enhancement, Absorption, and Scattering for Effective Antenna–Reactor Plasmonic Photocatalysis

Solar-Powered Plasmon-Enhanced Heterogeneous Catalysis

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Hot-Electron-Induced Dissociation of H2on Gold Nanoparticles Supported on SiO2

Cited by 481 publications

References 31 publications

Heterometallic antenna−reactor complexes for photocatalysis

Heterometallic antenna−reactor complexes for photocatalysis

Balancing Near-Field Enhancement, Absorption, and Scattering for Effective Antenna–Reactor Plasmonic Photocatalysis

Solar-Powered Plasmon-Enhanced Heterogeneous Catalysis

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Product

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Hot-Electron-Induced Dissociation of H₂on Gold Nanoparticles Supported on SiO₂