Hydride formation thermodynamics and hysteresis in individual Pd nanocrystals with different size and shape

Syrenova, Svetlana; Wadell, Carl; Nugroho, Ferry Anggoro Ardy; Gschneidtner, Tina; Fernandez, Yuri Diaz; Nalin, Giammarco; Świtlik, Dominika; Westerlund, Fredrik; Antosiewicz, Tomasz J.; Zhdanov, Vladimir P.; Moth‐Poulsen, Kasper; Langhammer, Christoph

doi:10.1038/nmat4409

Cited by 169 publications

(209 citation statements)

References 48 publications

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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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Heterometallic antenna−reactor complexes for photocatalysis

Swearer

Zhao

Zhou

et al. 2016

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

384

531

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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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confidence: 99%

mentioning

confidence: 99%

Heterometallic antenna−reactor complexes for photocatalysis

Swearer

Zhao

Zhou

et al. 2016

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

384

531

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“…The phase transformation behaviour of PdH x is well known in the bulk, but the changes at the level of individual nanoparticles are only now starting to be addressed, thanks to the development of several single-particle techniques, including in situ transmission electron microscopy (TEM)232728, plasmonic nanospectroscopy2930 and coherent X-ray diffractive imaging21. These studies have demonstrated that single crystalline particles do not exhibit phase coexistence at equilibrium2329, in contrast to multiply twinned particles27.…”

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confidence: 99%

Direct visualization of hydrogen absorption dynamics in individual palladium nanoparticles

et al. 2017

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Many energy storage materials undergo large volume changes during charging and discharging. The resulting stresses often lead to defect formation in the bulk, but less so in nanosized systems. Here, we capture in real time the mechanism of one such transformation—the hydrogenation of single-crystalline palladium nanocubes from 15 to 80 nm—to better understand the reason for this durability. First, using environmental scanning transmission electron microscopy, we monitor the hydrogen absorption process in real time with 3 nm resolution. Then, using dark-field imaging, we structurally examine the reaction intermediates with 1 nm resolution. The reaction proceeds through nucleation and growth of the new phase in corners of the nanocubes. As the hydrogenated phase propagates across the particles, portions of the lattice misorient by 1.5%, diminishing crystal quality. Once transformed, all the particles explored return to a pristine state. The nanoparticles' ability to remove crystallographic imperfections renders them more durable than their bulk counterparts.

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“…We define the standard deviation of the Δλ signal as the spectral noise, σ, and find that σ res ≈ 0.1 nm, in good agreement with similar studies. 26,44 We further define the smallest reliably measurable Δλ signal as Δλ min = σ res = 0.1 nm. With Δλ for 5× TBE equal to 1.5 nm (Figure 4b), we thus derive a detection limit σ N ≈ 0.3× TBE.…”

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confidence: 99%

Single Particle Nanoplasmonic Sensing in Individual Nanofluidic Channels

Fritzsche¹,

Albinsson²,

Fritzsche³

et al. 2016

Nano Lett.

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Nanoplasmonics allows label-free optical sensing and spectroscopy at the single nanoparticle level by exploiting plasmonic excitations in metal nanoparticles. Nanofluidics offers exclusive possibilities for applying and controlling fluid flow and mass transport at the nanoscale and toward nanosized objects. Here, we combine these two concepts in a single device, by integrating single particle nanoplasmonic sensing with nanofluidics using advanced nanofabrication. The developed devices enable on-chip referenced parallel single particle nanoplasmonic sensing inside multiple individual nanofluidic channels with dimensions down to the 100 nm range. Beyond detailed discussion of the nanofabrication, general device characterization, and parallelized single particle plasmonic readout concepts, we demonstrate device function on two examples: (i) in situ measurements of local buffer concentrations inside a nanofluidic channel; (ii) real time binding kinetics of alkanethiol molecules to a single plasmonic nanonatenna sensor in a single nanochannel. Our concept thus provides a powerful solution for controlling mass transport to and from individual (plasmonic) nanoparticles, which in a long-term perspective offers unique opportunities for label-free detection of analyte molecules at low concentrations and for fundamental studies of fluids in extreme confinement.

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Hydride formation thermodynamics and hysteresis in individual Pd nanocrystals with different size and shape

Cited by 169 publications

References 48 publications

Heterometallic antenna−reactor complexes for photocatalysis

Heterometallic antenna−reactor complexes for photocatalysis

Direct visualization of hydrogen absorption dynamics in individual palladium nanoparticles

Single Particle Nanoplasmonic Sensing in Individual Nanofluidic Channels

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