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Nanostructures of some metals can sustain localized surface plasmon resonances, collective oscillations of free electrons excited by incident light. This effect results in wavelength-dependent absorption and scattering, enhancement of the incident electric field at the metal surface, and generation of hot carriers as a decay product. The enhanced electric field can be utilized to amplify the spectroscopic signal in surface-enhanced Raman scattering (SERS), while hot carriers can be exploited for catalytic applications. In recent years, cheaper and more earth abundant alternatives to traditional plasmonic Au and Ag have gained growing attention. Here, we demonstrate the ability of plasmonic Mg nanoparticles to enhance Raman scattering and drive chemical transformations upon laser irradiation. The plasmonic properties of Mg nanoparticles are characterized at the bulk and single particle level by optical spectroscopy and scanning transmission electron microscopy coupled with electron energy-loss spectroscopy and supported by numerical simulations. SERS enhancement factors of â¼102 at 532 and 633 nm are obtained using 4-mercaptobenzoic acid and 4-nitrobenzenethiol. Furthermore, the reductive coupling of 4-nitrobenzenethiol to 4,4'-dimercaptoazobenzene is observed on the surface of Mg nanoparticles under 532 nm excitation in the absence of reducing agents, indicating a plasmon-driven catalytic process. Once decorated with Pd, Mg nanostructures display an enhancement factor of 103 along with an increase in the rate of catalytic coupling. The results of this study demonstrate the successful application of plasmonic Mg nanoparticles in sensing and plasmon-enhanced catalysis.
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Magnesium is a recent addition to the plasmonic toolbox: nanomaterials that efficiently utilize photons' energy due to their ability to sustain localized surface plasmon resonances. Magnesium nanoparticles protected by a native oxide shell can efficiently absorb light across the solar spectrum, making them a promising photocatalytic material. However, their inherent reactivity toward oxidation may limit the number of reactions in which Mg-MgO can be used. Here, we investigate the stability of plasmonic Mg-MgO core-shell nanoplates under oxidative conditions. We demonstrate that the MgO shell stabilizes the metallic Mg core against oxidation in air at up to 400 °C. Furthermore, we show that the reactivity of Mg-MgO nanoplates with water vapor (3.5 vol % in N2) decreases with temperature, with no oxidation of the Mg core detected from 200 to 400 °C. This work unravels the potential of Mg-MgO nanoparticles for a broad range of catalytic transformations occurring in oxidative environments.
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A bottom-up approach, the Langmuir-Blodgett technique, is used for the preparation of composite thin films of gold nanoparticles and polymers: poly(styrene-b-2-vinylpyridine), poly-2-vinylpyridine, and polystyrene. The self-assembly of poly(styrene-b-2-vinylpyridine) at the air-water interface leads to the formation of surface micelles, which serve as a template for the organization of gold nanoparticles into ring assemblies. By using poly-2-vinylpyridine in conjunction with low surface pressure, the distance between nanostructures can be increased, allowing for optical characterization of single nanostructures. Once deposited on a solid substrate, the preorganized gold nanoparticles are subjected to further growth by the reduction of additional gold, leading to a variety of nanostructures which can be divided into two categories: nanocrescents and circular arrays of nanoparticles. The optical properties of individual structures are investigated by optical dark-field spectroscopy and numerical calculations. The plasmonic behavior of the nanostructures is elucidated through the correlation of optical properties with structural features and the identification of dominant plasmon modes. Being based on a self-assembly approach, the reported method allows for the formation of interesting plasmonic materials under ambient conditions, at a relatively large scale, and at low cost. These attributes, in addition to the resonances located in the near-infrared region of the spectrum, make nanocrescents candidates for biological and chemical sensing.
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Mg nanoparticles are an emerging plasmonic material due to Mg's abundance and ability to sustain size- and shape-dependent localized surface plasmon resonances across a broad range of wavelengths from the ultraviolet to the near infrared. However, Mg nanoparticles are colloidally unstable due to their tendency to aggregate and sediment. Nanoparticle aggregation can be inhibited by the addition of capping agents that impart surface charges or steric repulsion. Here, we report that the common capping agents poly(vinyl) pyrrolidone (PVP), polyethylene glycol (PEG), cetyltrimethylammonium bromide (CTAB), and sodium dodecyl sulfate (SDS) interact differently and have varied effects on the aggregation and colloidal stability of Mg nanoparticles. Nanoparticles synthesized in the presence of PVP showed improvements in colloidal stability and reduced aggregation, as observed by electron microscopy and optical spectroscopy. The binding of PVP was confirmed through infrared and X-ray photoelectron spectroscopy. The influence of PVP on the reduction of di-n-butyl magnesium was evaluated through analysis of particle size distribution and Mg yield as a function of reaction time, reducing agent, and temperature. Furthermore, the presence of PVP drastically changes the growth pattern of metallic Mg structures obtained from the reduction of the Grignard reagents butylmagnesium chloride and phenylmagnesium chloride by lithium naphthalenide: large polycrystalline aggregates and well-separated faceted nanoparticles grow without and with PVP, respectively. This study provides new synthetic routes that generate colloidally stable and well-dispersed Mg nanoparticles for plasmonic and other applications.
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Magnesium nanoparticles offer an alternative plasmonic platform capable of resonances across the ultraviolet, visible and near-infrared. Crystalline magnesium nanoparticles display twinning on the (101Ì1), (101Ì2), (101Ì3), and (112Ì1) planes leading to concave folded shapes named tents, chairs, tacos, and kites, respectively. We use the Wulff-based Crystal Creator tool to expand the range of Mg crystal shapes with twinning over the known Mg twin planes, i.e., (101Ìx), x = 1, 2, 3 and (112Ìy), y = 1, 2, 3, 4, and study the effects of relative facet expression on the resulting shapes. These shapes include both concave and convex structures, some of which have been experimentally observed. The resonant modes, far-field, and near-field optical responses of these unusual plasmonic shapes as well as their photothermal behaviour are reported, revealing the effects of folding angle and in-filling of the concave region. Significant differences exist between shapes, in particular regarding the maximum and average electric field enhancement. A maximum field enhancement (|E|/|E0|) of 184, comparable to that calculated for Au and Ag nanoparticles, was found at the tips of the (112Ì4) kite. The presence of a 5 nm MgO shell is found to decrease the near-field enhancement by 67% to 90% depending on the shape, while it can increase the plasmon-induced temperature rise by up to 42%. Tip rounding on the otherwise sharp nanoparticle corners also significantly affects the maximum field enhancement. These results provide guidance for the design of enhancing and photothermal substrates for a variety of plasmonic applications across a wide spectral range.
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Chiral plasmonic nanoparticles have attracted much attention because of their strong chiroptical responses and broad scientific applications. However, the types of chiral plasmonic nanoparticles have remained limited. Herein we report on a new type of chiral nanoparticle, chiral Au nanorod (NR) with five-fold rotational symmetry, which is synthesized using chiral molecules. Three different types of Au seeds (Au elongated nanodecahedrons, nanodecahedrons, and nanobipyramids) are used to study the growth behaviors. Different synthesis parameters, including the chiral molecules, surfactant, reductant, seeds, and Au precursor, are systematically varied to optimize the chiroptical responses of the chiral Au NRs. The chiral scattering measurements on the individual chiral Au NRs and their dimers are performed. Intriguingly, the chiroptical signals of the individual chiral Au NRs and their end-to-end dimers are similar, while those of the side-by-side dimers are largely reduced. Theoretical calculations and numerical simulations reveal that the different chiroptical responses of the chiral NR dimers are originated from the coupling effect between the plasmon resonance modes. Our study enriches chiral plasmonic nanoparticles and provides valuable insight for the design of plasmonic nanostructures with desired chiroptical properties.
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Understanding and guiding light at the nanoscale can significantly impact society, for instance, by facilitating the development of efficient, sustainable, and/or cost-effective technologies. One emergent branch of nanotechnology exploits the conversion of light into heat, where heat is subsequently harnessed for various applications including therapeutics, heat-driven chemistries, and solar heating. Gold nanoparticles are overwhelmingly the most common material for plasmon-assisted photothermal applications; yet magnesium nanoparticles present a compelling alternative due to their low cost and superior biocompatibility. Herein, we measured the heat generated and quantified the photothermal efficiency of the gold and magnesium nanoparticle suspensions. Photothermal transduction experiments and optical and thermal simulations of different sizes and shapes of gold and magnesium nanoparticles showed that magnesium is more efficient at converting light into heat compared to gold at near-infrared wavelengths, thus demonstrating that magnesium nanoparticles are a promising new class of inexpensive, biodegradable photothermal platforms.
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Cu is an inexpensive alternative plasmonic metal with optical behaviour comparable to Au but with much poorer environmental stability. Alloying with a more stable metal can improve stability and add functionality, with potential effects on the plasmonic properties. Here we investigate the plasmonic behaviour of Cu nanorods and Cu-CuPd nanorods containing up to 46 mass percent Pd. Monochromated scanning transmission electron microscopy electron energy-loss spectroscopy first reveals the strong length dependence of multiple plasmonic modes in Cu nanorods, where the plasmon peaks redshift and narrow with increasing length. Next, we observe an increased damping (and increased linewidth) with increasing Pd content, accompanied by minimal frequency shift. These results are corroborated by and expanded upon with numerical simulations using the electron-driven discrete dipole approximation. This study indicates that adding Pd to nanostructures of Cu is a promising method to expand the scope of their plasmonic applications.
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Surface curvature can be used to focus light and alter optical processes. Here, we show that curved surfaces (spheres, cylinders, and cones) with a radius of around 5 µm lead to maximal optoplasmonic properties including surface-enhanced Raman scattering (SERS), photocatalysis, and photothermal processes. Glass microspheres, microfibers, pulled fibers, and control flat substrates were functionalized with well-dispersed and dense arrays of 45 nm Au NP using polystyrene-block-poly-4-vinylpyridine (PS-b-P4VP) and chemically modified with 4-mercaptobenzoic acid (4-MBA, SERS reporter), 4-nitrobenzenethiol (4-NBT, reactive to plasmonic catalysis), or 4-fluorophenyl isocyanide (FPIC, photothermal reporter). The various curved substrates enhanced the plasmonic properties by focusing the light in a photonic nanojet and providing a directional antenna to increase the collection efficacy of SERS photons. The optoplasmonic effects led to an increase of up to 1 order of magnitude of the SERS response, up to 5 times the photocatalytic conversion of 4-NBT to 4,4'-dimercaptoazobenzene when the diameter of the curved surfaces was about 5 µm and a small increase in photothermal effects. Taken together, the results provide evidence that curvature enhances plasmonic properties and that its effect is maximal for spherical objects around a few micrometers in diameter, in agreement with a theoretical framework based on geometrical optics. These enhanced plasmonic effects and the stationary-phase-like plasmonic substrates pave the way to the next generation of sensors, plasmonic photocatalysts, and photothermal devices.
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Magnetic vector electron tomography (VET) is a promising technique that enables better understanding of micro- and nano-magnetic phenomena through the reconstruction of 3D magnetic fields at high spatial resolution. Here we introduce WRAP (Wavelet Regularised A Program), a reconstruction algorithm for magnetic VET that directly reconstructs the magnetic vector potential A using a compressed sensing framework which regularises for sparsity in the wavelet domain. We demonstrate that using WRAP leads to a significant increase in the fidelity of the 3D reconstruction and is especially robust when dealing with very limited data; using datasets simulated with realistic noise, we compare WRAP to a conventional reconstruction algorithm and find an improvement of ca. 60% when averaged over several performance metrics. Moreover, we further validate WRAP's performance on experimental electron holography data, revealing the detailed magnetism of vortex states in a CuCo nanowire. We believe WRAP represents a major step forward in the development of magnetic VET as a tool for probing magnetism at the nanoscale.
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Magnesium nanoparticles (MgNPs) exhibit localized surface plasmon resonances across the ultraviolet, visible, and near-infrared parts of electromagnetic spectrum and are attracting increasing interest due to their sustainability and biocompatibility. In this study, we used tip-enhanced Raman spectroscopy (TERS) to examine the photocatalytic properties of MgNP protected by a thin native oxide layer and their Au-modified bimetallic analogs produced by partial galvanic replacement, Au-MgNPs. We found no reduction of 4-nitrobenzenethiol (4-NBT) to p,p'-dimercaptoazobisbenzene (DMAB) when a Au-coated tip was placed in contact with a self-assembled monolayer of 4-NBT molecules adsorbed on MgNPs alone. However, decorating Mg with Au made these bimetallic structures catalytically active. The DMAB signal signature of photocatalytic activity was more delocalized around AuNPs attached to Mg than around AuNPs on a Si substrate, indicating coupling between the Mg core and Au decorations. This report on photocatalytic activity of a bimetallic structure including plasmonic Mg paves the way for further catalyst architectures benefiting from Mg's versatility and abundance.
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Electron tomography (ET) has become an important tool for understanding the 3D nature of nanomaterials, with recent developments enabling not only scalar reconstructions of electron density, but also vector reconstructions of magnetic fields. However, whilst new signals have been incorporated into the ET toolkit, the acquisition schemes have largely kept to conventional single-axis tilt series for scalar ET, and dual-axis schemes for magnetic vector ET. In this work, we explore the potential of using multi-axis tilt schemes including conical and spiral tilt schemes to improve reconstruction fidelity in scalar and magnetic vector ET. Through a combination of systematic simulations and a proof-of-concept experiment, we show that spiral and conical tilt schemes have the potential to produce substantially improved reconstructions, laying the foundations of a new approach to electron tomography acquisition and reconstruction.
Asunto(s)
Tomografía con Microscopio Electrónico , Procesamiento de Imagen Asistido por Computador , Tomografía con Microscopio Electrónico/métodos , Procesamiento de Imagen Asistido por Computador/métodos , Campos MagnéticosRESUMEN
Enriching the library of chiral plasmonic nanoparticles that can be chemically mass-produced will greatly facilitate the applications of chiral plasmonics in areas ranging from constructing optical metamaterials to sensing chiral molecules and activating immune cells. Here we report on a halide-assisted differential growth strategy that can direct the anisotropic growth of chiral Au nanoparticles with tunable sizes and diverse morphologies. Anisotropic Au nanodisks are employed as seeds to yield triskelion-shaped chiral nanoparticles with threefold rotational symmetry and high dissymmetry factors. The averaged scattering g-factors of the L- and D-nanotriskelions are as large as 0.57 and - 0.49 at 650 nm, respectively. The Au nanotriskelions have been applied in chiral optical switching devices and chiral nanoemitters. We also demonstrate that the manipulation of the directional growth rate enables the generation of a variety of chiral morphologies in the presence of homochiral ligands.
Asunto(s)
Nanopartículas del Metal , Nanopartículas del Metal/química , Oro/química , Estereoisomerismo , AnisotropíaRESUMEN
We reduce di-n-butylmagnesium with arene (naphthalene, biphenyl, phenanthrene) radical anions and dianions to obtain metallic, plasmonic Mg nanoparticles. Their size and shape depends on the dianion concentration and reduction potential. Based on these results, we demonstrate a seeded growth Mg nanoparticle synthesis and report homogeneous shapes with controllable monodisperse size distributions.
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Bimetallic Cu on Au nanoparticles with controllable morphology and optical properties were obtained via electrochemical synthesis. In particular, multilobed structures with good homogeneity were achieved through the optimization of experimental parameters such as deposition current, charge transfer, and metal ion concentration. A hyperspectral dark field scattering setup was used to characterize the electrodeposition on a single particle level, with changes in localized surface plasmon resonance frequency correlated with deposition charge transfer and amount of Cu deposited as determined by electron microscopy. This demonstrated the ability to tune morphology and spectra through electrochemical parameters alone. Time-resolved in situ measurements of single particle spectra were obtained, giving an insight into the kinetics of the deposition process. Nucleation of multiple cubes of Cu initially occurs preferentially on the tips of Au nanoparticles, before growing and coalescing to form a multilobed, lumpy shell. Modifying the surface of Au nanoparticles by plasma treatment resulted in thicker and more uniform Cu shells.
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Bimetallic Pd-Mg nanoparticles were synthesized by partial galvanic replacement of plasmonic Mg nanoparticles, and their catalytic and photocatalytic properties in selective hydrogenation of acetylene have been investigated. Electron probe studies confirm that the Mg-Pd structures mainly consist of metallic Mg and sustain several localized plasmon resonances across a broad wavelength range. We demonstrate that, even without light excitation, the Pd-Mg nanostructures exhibit an excellent catalytic activity with selectivity to ethylene of 55% at 100% acetylene conversion achieved at 60 °C. With laser excitation at room temperature over a range of intensities and wavelengths, the initial reaction rate increased up to 40 times with respect to dark conditions and a 2-fold decrease of the apparent activation energy was observed. A significant wavelength-dependent change in hydrogenation kinetics strongly supports a catalytic behavior affected by plasmon excitation. This report of coupling between Mg's plasmonic and Pd's catalytic properties paves the way for sustainable catalytic structures for challenging, industrially relevant selective hydrogenation processes.
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Plasmonic nanomaterials have outstanding optoelectronic properties potentially enabling the next generation of catalysts, sensors, lasers and photothermal devices. Owing to optical and electron techniques, modern nanoplasmonics research generates large datasets characterizing features across length scales. Furthermore, optimizing syntheses leading to specific nanostructures requires time-consuming multiparametric approaches. These complex datasets and trial-and-error practices make nanoplasmonics research ripe for the application of machine learning (ML) and advanced data processing methods. ML algorithms capture relationships between synthesis, structure and performance in a way that far exceeds conventional simulation and theory approaches, enabling effective performance optimization. For example, neural networks can tailor the nanostructure morphology to target desired properties, identify synthetic conditions and extract quantitative information from complex data. Here we discuss the nascent field of ML for nanoplasmonics, describe the opportunities and limitations of ML in nanoplasmonic research, and conclude that ML is potentially transformative, especially if the community curates and shares its big data.
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Plasmonic nanoparticles (NPs) have garnered excitement over the past several decades stemming from their unique optoelectronic properties, leading to their use in various sensing applications and theranostics. Symmetry dictates the properties of many nanomaterials, and nanostructures with low, but still defined symmetries, often display markedly different properties compared to their higher symmetry counterparts. While numerous methods are available to manipulate symmetry, surface protecting groups such as polymers are finding use due to their ability to achieve regioselective modification of NP seeds, which can be removed after overgrowth as shown here. Specifically, poly(styrene-b-polyacrylic acid) (PSPAA) is used to asymmetrically passivate cubic Au seeds through competition with hexadecyltrimethylammonium bromide (CTAB) ligands. The asymmetric passivation via collapsed PSPAA causes only select vertices and faces of the Au cubes to be available for deposition of new material (i.e., Au, Au-Ag alloy, and Au-Pd alloy) during seeded overgrowth. At low metal precursor concentrations, deposition follows observations from unpassivated seeds but with new material growing from only the exposed seed portions. At high metal precursor concentrations, nanobowl-like structures form from interaction between the depositing phase and the passivating PSPAA. Through experiment and simulation, the optoelectronic properties of these nanobowls were probed, finding that the interiors and exteriors of the nanobowls can be functionalized selectively as revealed by surface enhanced Raman spectroscopy (SERS).
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Chiral plasmonic nanocrystals with varied symmetries were synthesized by L-glutathione-guided overgrowth from Au tetrahedra, nanoplates, and octahedra, highlighting the importance of chiral molecule adsorption at transient kink sites. Large g-factors are possible and depend on symmetry. Simulations of their chiroptical properties from tomographically obtained nanocrystal models further verify their chirality.
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The reduction of 4-nitrophenol (4-NiP) to 4-aminophenol (4-AP) with an excess of sodium borohydride is commonly used as a model reaction to assess the catalytic activity of metallic nanoparticles. This reaction is considered both a potentially important step in industrial water treatment and an attractive, commercially relevant synthetic pathway. Surprisingly, an important factor, the role of the reaction medium on the reduction performance, has so far been overlooked. Here, we report a pronounced effect of the solvent on the reaction kinetics in the presence of silver and gold nanoparticles. We demonstrate that the addition of methanol, ethanol, or isopropanol to the reaction mixture leads to a dramatic decrease in the reaction rate. For typical concentrations of reactants, the reduction is completely suppressed in the presence of 50 vol% alcohols. 4-NiP reduction rate in aqueous alcohol mixtures can, however, be improved noticeably by increasing the borohydride concentration or the reaction temperature. The analysis of various factors responsible for solvent effects reveals that the decrease in the reduction rate in the presence of alcohols is related, amongst others, to a substantially higher oxygen solubility in alcohols compared to water. The results of this work show that the effects of solvent properties on reaction kinetics must be considered for unambiguous comparison and optimization of the catalytic performance of metallic nanoparticles in the liquid phase 4-NiP reduction.