Direct observation of chemical reactions on single gold nanocrystals using surface plasmon spectroscopy.
TL;DR: Using surface plasmon spectroscopy, this work directly observed the kinetics of atomic deposition onto a single gold nanocrystal and also monitored electron injection and extraction during a redox reaction involving the oxidation of ascorbic acid on a gold Nanocrystal surface, creating the first direct measurement of the rates of redox catalysis on single nanocrystals.
Abstract: Heterogeneous catalysts have been pivotal to the development of the modern chemical industry and are essential for catalysing many industrial reactions. However, reaction rates are different for every individual catalyst particle and depend upon each particle's morphology and size, crystal structure and composition. Measuring the rates of reaction on single nanocrystals will enable the role of catalyst structure to be quantified. Here, using surface plasmon spectroscopy, we have directly observed the kinetics of atomic deposition onto a single gold nanocrystal and also monitored electron injection and extraction during a redox reaction involving the oxidation of ascorbic acid on a gold nanocrystal surface. These results constitute the first direct measurement of the rates of redox catalysis on single nanocrystals.
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TL;DR: The basic concepts behind plasmonics-enabled light concentration and manipulation are discussed, an attempt to capture the wide range of activities and excitement in this area is made, and possible future directions are speculated on.
Abstract: The unprecedented ability of nanometallic (that is, plasmonic) structures to concentrate light into deep-subwavelength volumes has propelled their use in a vast array of nanophotonics technologies and research endeavours. Plasmonic light concentrators can elegantly interface diffraction-limited dielectric optical components with nanophotonic structures. Passive and active plasmonic devices provide new pathways to generate, guide, modulate and detect light with structures that are similar in size to state-of-the-art electronic devices. With the ability to produce highly confined optical fields, the conventional rules for light-matter interactions need to be re-examined, and researchers are venturing into new regimes of optical physics. In this review we will discuss the basic concepts behind plasmonics-enabled light concentration and manipulation, make an attempt to capture the wide range of activities and excitement in this area, and speculate on possible future directions.
3,953 citations
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...Recent progress in this area has even enabled quantification of reaction rates and atomic deposition processes down to the level of individual metal nanoparticle...
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TL;DR: This work investigates the plasmon resonances of individual ligand-free silver nanoparticles using aberration-corrected transmission electron microscope imaging and monochromated scanning TEM electron energy-loss spectroscopy, and presents an analytical quantum mechanical model that describes this shift due to a change in particle permittivity.
Abstract: The plasmon resonances of metallic nanoparticles have received considerable attention for their applications in nanophotonics, biology, sensing, spectroscopy and solar energy harvesting. Although thoroughly characterized for spheres larger than ten nanometres in diameter, the plasmonic properties of particles in the quantum size regime have been historically difficult to describe owing to weak optical scattering, metal-ligand interactions, and inhomogeneity in ensemble measurements. Such difficulties have precluded probing and controlling the plasmonic properties of quantum-sized particles in many natural and engineered processes, notably catalysis. Here we investigate the plasmon resonances of individual ligand-free silver nanoparticles using aberration-corrected transmission electron microscope (TEM) imaging and monochromated scanning TEM electron energy-loss spectroscopy (EELS). This technique allows direct correlation between a particle's geometry and its plasmon resonance. As the nanoparticle diameter decreases from 20 nanometres to less than two nanometres, the plasmon resonance shifts to higher energy by 0.5 electronvolts, a substantial deviation from classical predictions. We present an analytical quantum mechanical model that describes this shift due to a change in particle permittivity. Our results highlight the quantum plasmonic properties of small metallic nanospheres, with direct application to understanding and exploiting catalytically active and biologically relevant nanoparticles.
1,075 citations
TL;DR: This perspective reviews recent developments in the synthesis, electrochemistry, and optical properties of gold nanoparticles, with emphasis on papers initiating the developments and with an eye to their consequences.
Abstract: This perspective reviews recent developments in the synthesis, electrochemistry, and optical properties of gold nanoparticles, with emphasis on papers initiating the developments and with an eye to their consequences. Key aspects of Au nanoparticle synthesis have included the two-phase synthesis of thiolated nanoparticles, the sequestration and reduction of Au salts within dendrimers, the controlled growth of larger particles of well-defined shapes via the seeded approach, and the assembling of a variety of nanoparticle networks and nanostructures. The electrochemistry of thiolated Au nanoparticles is systemized as regions of bulk-continuum voltammetry, voltammetry reflective of quantized double-layer charging, and molecule-like voltammetry reflective of molecular energy gaps. These features are principally determined by the nanoparticle core. Interesting multielectron Au nanoparticle voltammetry is observed when the thiolate ligand shell has been decorated with redox groupings. Another development is that Au nanoparticles were discovered to exhibit unanticipated properties as heterogeneous catalysts, starting with the low-temperature oxidation of CO. Substantial progress has also been made in understanding the surface plasmon spectroscopy of Au nanoparticles and nanorods. The need to investigate the optical properties of metal particles of a single, well-defined shape and size has motivated the development of a number of new techniques, leading to the study of electron transfer and redox catalysis on single nanoparticles.
940 citations
TL;DR: This Review highlights morphology-dependent properties of nonspherical noble metal nanoparticles with a focus on localized surface plasmon resonance and local field enhancement, as well as their applications in various fields including Raman spectroscopy, fluorescence enhancement, analytics and sensing, photothermal therapy, (bio-)diagnostics, and imaging.
Abstract: Nanoparticles of noble metals belong to the most extensively studied colloidal systems in the field of nanoscience and nanotechnology. Due to continuing progress in the synthesis of nanoparticles with controlled morphologies, the exploration of unique morphology-dependent properties has gained momentum. Anisotropic features in nonspherical nanoparticles make them ideal candidates for enhanced chemical, catalytic, and local field related applications. Nonspherical plasmon resonant nanoparticles offer favorable properties for their use as analytical tools, or as diagnostic and therapeutic agents. This Review highlights morphology-dependent properties of nonspherical noble metal nanoparticles with a focus on localized surface plasmon resonance and local field enhancement, as well as their applications in various fields including Raman spectroscopy, fluorescence enhancement, analytics and sensing, photothermal therapy, (bio-)diagnostics, and imaging.
922 citations
TL;DR: This work places a single palladium nanoparticle near the tip region of a gold nanoantenna and detects the changing optical properties of the system upon hydrogen exposure, demonstrating antenna-enhanced hydrogen sensing at the single-particle level.
Abstract: Plasmonic resonances are widely used for sensing applications. The plasmon resonance of a single nanoantenna structure is now used to detect changes in the dielectric properties of a nearby palladium nanoparticle exposed to hydrogen gas, enabling highly sensitive sensing in ultrasmall volumes. The approach can be easily extended to other sensing and catalysis schemes.
896 citations
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TL;DR: In this article, a method was used for preparing gold NRs with aspect ratios ranging from 1.5 to 4.5 for which the surface plasmon absorption maxima are between 600 and 1300 nm.
Abstract: A method is used for preparing gold NRs with aspect ratios ranging from 1.5 to 10 for which the surface plasmon absorption maxima are between 600 and 1300 nm. This method has been adapted from a previously published seed-mediated growth method (Jana et al. Adv. Mater. 2001, 13, 1389). The disadvantages and limitations of the earlier method (i.e., formation of noncylindrical NRs, φ-shaped particles, and formation of a large fraction of spherical particles) have been overcome by use of a hexadecyltrimethylammonium bromide (CTAB)-capped seed instead of a citrate-capped one. In a single-component surfactant system, the silver content of the growth solution was used to grow NRs to a desired length. This results in reproducible formation of NRs with aspect ratios ranging from 1.5 to 4.5. To grow longer NRs with aspect ratios ranging from 4.6 to 10, a binary surfactant mixture composed of benzyldimethylhexadecylammoniumchloride (BDAC) and CTAB was used. NRs are grown in this mixture either by aging or by additio...
4,645 citations
TL;DR: In this paper, the use of optical measurements to monitor electrochemical changes on the surface of nanosized metal particles is discussed within the Drude model, and the absorption spectrum of a metal sol in water is shown to be strongly affected by cathodic or anodic polarization, chemisorption, metal adatom deposition, and alloying.
Abstract: The use of optical measurements to monitor electrochemical changes on the surface of nanosized metal particles is discussed within the Drude model. The absorption spectrum of a metal sol in water is shown to be strongly affected by cathodic or anodic polarization, chemisorption, metal adatom deposition, and alloying. Anion adsorption leads to strong damping of the free electron absorption. Cathodic polarization leads to anion desorption. Underpotential deposition (upd) of electropositive metal layers results in dramatic blue-shifts of the surface plasmon band of the substrate. The deposition of just 0.1 monolayer can be readily detected by eye. In some cases alloying occurs spontaneously during upd. Alloy formation can be ascertained from the optical absorption spectrum in the case of gold deposition onto silver sols. The underpotential deposition of silver adatoms onto palladium leads to the formation of a homogeneous silver shell, but the mean free path is less than predicted, due to lattice strain in t...
3,454 citations
TL;DR: In this paper, the effects of surface modification on colloidal metal particles in aqueous solution were investigated. And the resulting changes in the chemical, photochemical, and optical properties were discussed.
Abstract: The study of nanometer and subnanometer colloidal metal particles in aqueous solution complements the investigation of small particles in molecular beams, frozen solutions, and inorganic clusters. The electronic properties of the metal particles are changed by surface modification, for example by chemisorption of a nucleophilic molecule or by deposition of a second metal. The resulting changes in the chemical, photochemical, and optical properties are discussed. Methods are described which enable one to store excess electrons or positive holes on the particles in a controlled manner and to investigate the accompanying changes in the optical properties. Metal particles carrying excess electrons initiate electrochemical reactions such as the reduction of water or the deposition of metals
1,633 citations
TL;DR: The optical properties of noble metal nanoparticles, specifically gold, silver, and their combinations, prepared in solution through colloid chemical methods are shown to be mainly influenced by the surface plasmon resonance of conduction electrons.
Abstract: Metal nanoparticles can be used as building blocks for the formation of nanostructured materials. For the design of materials with specific (optical) properties, several approaches can be followed, even when starting from the very same basic units. In this article, a survey is provided of the optical properties of noble metal nanoparticles, specifically gold, silver, and their combinations, prepared in solution through colloid chemical methods. The optical properties are shown to be mainly influenced by the surface plasmon resonance of conduction electrons, the frequency of which is not only determined by the nature of the metal but also by a number of other parameters, such as particle size and shape, the presence of a capping shell on the particle surface, or the dielectric properties of the surrounding medium. Recent results showing how these various parameters affect the optical properties are reviewed. The results highlight the high degree of control that can now be achieved through colloid chemical synthesis.
1,514 citations