Decoration of plasmonic Mg nanoparticles by partial galvanic replacement.

Plasmonic structures have attracted much interest in science and engineering disciplines, exploring a myriad of potential applications owing to their strong light-matter interactions. Recently, the plasmonic concentration of energy in subwavelength volumes has been used to initiate chemical reactions, for instance by combining plasmonic materials with catalytic metals. In this work, we demonstrate that plasmonic nanoparticles of earth-abundant Mg can undergo galvanic replacement in a nonaqueous solvent to produce decorated structures. This method yields bimetallic architectures where partially oxidized 200-300 nm Mg nanoplates and nanorods support many smaller Au, Ag, Pd, or Fe nanoparticles, with potential for a stepwise process introducing multiple decoration compositions on a single Mg particle. We investigated this mechanism by electron-beam imaging and local composition mapping with energy-dispersive X-ray spectroscopy as well as, at the ensemble level, by inductively coupled plasma mass spectrometry. High-resolution scanning transmission electron microscopy further supported the bimetallic nature of the particles and provided details of the interface geometry, which includes a Mg oxide separation layer between Mg and the other metal. Depending on the composition of the metallic decorations, strong plasmonic optical signals characteristic of plasmon resonances were observed in the bulk with ultraviolet-visible spectrometry and at the single particle level with darkfield scattering. These novel bimetallic and multimetallic designs open up an exciting array of applications where one or multiple plasmonic structures could interact in the near-field of earth-abundant Mg and couple with catalytic nanoparticles for applications in sensing and plasmon-assisted catalysis.

Seed-mediated synthesis of monodisperse plasmonic magnesium nanoparticles.

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.

Synthesis of Controllable Cu Shells on Au Nanoparticles with Electrodeposition: A Systematic in Situ Single Particle Study.

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.

Plasmonic magnesium nanoparticles decorated with palladium catalyze thermal and light-driven hydrogenation of acetylene.

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.

Bimetallic copper palladium nanorods: plasmonic properties and palladium content effects.

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.

Opportunities and Challenges for Alternative Nanoplasmonic Metals: Magnesium and Beyond.

Materials that sustain localized surface plasmon resonances have a broad technology potential as attractive platforms for surface-enhanced spectroscopies, chemical and biological sensing, light-driven catalysis, hyperthermal cancer therapy, waveguides, and so on. Most plasmonic nanoparticles studied to date are composed of either Ag or Au, for which a vast array of synthetic approaches are available, leading to controllable size and shape. However, recently, alternative materials capable of generating plasmonically enhanced light-matter interactions have gained prominence, notably Cu, Al, In, and Mg. In this Perspective, we give an overview of the attributes of plasmonic nanostructures that lead to their potential use and how their performance is dictated by the choice of plasmonic material, emphasizing the similarities and differences between traditional and emerging plasmonic compositions. First, we discuss the materials limitation encapsulated by the dielectric function. Then, we evaluate how size and shape maneuver localized surface plasmon resonance (LSPR) energy and field distribution and address how this impacts applications. Next, biocompatibility, reactivity, and cost, all key differences underlying the potential of non-noble metals, are highlighted. We find that metals beyond Ag and Au are of competitive plasmonic quality. We argue that by thinking outside of the box, i.e., by looking at nonconventional materials such as Mg, one can broaden the frequency range and, more importantly, combine the plasmonic response with other properties essential for the implementation of plasmonic technologies.

Size Control in the Colloidal Synthesis of Plasmonic Magnesium Nanoparticles.

Nanoparticles of plasmonic materials can sustain oscillations of their free electron density, called localized surface plasmon resonances (LSPRs), giving them a broad range of potential applications. Mg is an earth-abundant plasmonic material attracting growing attention owing to its ability to sustain LSPRs across the ultraviolet, visible, and near-infrared wavelength range. Tuning the LSPR frequency of plasmonic nanoparticles requires precise control over their size and shape; for Mg, this control has previously been achieved using top-down fabrication or gas-phase methods, but these are slow and expensive. Here, we systematically probe the effects of reaction parameters on the nucleation and growth of Mg nanoparticles using a facile and inexpensive colloidal synthesis. Small NPs of 80 nm were synthesized using a low reaction time of 1 min and ∼100 nm NPs were synthesized by decreasing the overall reaction concentration, replacing the naphthalene electron carrier with biphenyl or using metal salt additives of FeCl3 or NiCl2 at longer reaction times of 17 h. Intermediate sizes up to 400 nm were further selected via the overall reaction concentration or using other metal salt additives with different reduction potentials. Significantly larger particles of over a micrometer were produced by reducing the reaction temperature and, thus, the nucleation rate. We showed that increasing the solvent coordination reduced Mg NP sizes, while scaling up the reaction reduced the mixing efficiency and produced larger NPs. Surprisingly, varying the relative amounts of Mg precursor and electron carrier had little impact on the final NP sizes. These results pave the way for the large-scale use of Mg as a low-cost and sustainable plasmonic material.

Improving the stability of plasmonic magnesium nanoparticles in aqueous media.

This work describes two different core-shell architectures based on Mg nanoparticles (NPs) synthesised in order to improve Mg's stability in aqueous solutions. The shell thickness in Mg-polydopamine NPs can be modulated from 5 to >50 nm by ending the polymerization at different times; the resulting structures stabilize the metallic, plasmonic core in water for well over an hour. Mg-silica NPs with shells ranging from 5 to 30 nm can also be prepared via a modified Stöber procedure and they retain optical properties in 5% water-in-isopropanol solutions. These new architectures allow Mg nanoplasmonics to be investigated as an alternative to Ag and Au in a broader range of experimental conditions for a rich variety of applications.

On the identification of twinning in body-centred cubic nanoparticles.

Many metals and alloys, including Fe and W, adopt body-centred cubic (BCC) crystal structures and nanoparticles of these metals are gaining significant scientific and industrial relevance. Twinning has a marked effect on catalytic activity, yet there is little evidence for or against the presence of twinning in BCC nanoparticles. Here, we explore the potential shapes of twinned BCC nanoparticles, and predict their electron microscopy and diffraction signatures. BCC single crystal and twinned shapes often appear similar and diffraction patterns along common, low-index zone axes are often indistinguishable, casting doubt on many claims of single crystallinity. We conclude by outlining how nanoparticles can be characterized to conclusively prove the presence or absence of twinning.

Tents, Chairs, Tacos, Kites, and Rods: Shapes and Plasmonic Properties of Singly Twinned Magnesium Nanoparticles.

Nanostructures of some metals can sustain light-driven electron oscillations called localized surface plasmon resonances, or LSPRs, that give rise to absorption, scattering, and local electric field enhancement. Their resonant frequency is dictated by the nanoparticle (NP) shape and size, fueling much research geared toward discovery and control of new structures. LSPR properties also depend on composition; traditional, rare, and expensive noble metals (Ag, Au) are increasingly eclipsed by earth-abundant alternatives, with Mg being an exciting candidate capable of sustaining resonances across the ultraviolet, visible, and near-infrared spectral ranges. Here, we report numerical predictions and experimental verifications of a set of shapes based on Mg NPs displaying various twinning patterns including (101̅1), (101̅2), (101̅3), and (112̅1), that create tent-, chair-, taco-, and kite-shaped NPs, respectively. These are strikingly different from what is obtained for typical plasmonic metals because Mg crystallizes in a hexagonal close packed structure, as opposed to the cubic Al, Cu, Ag, and Au. A numerical survey of the optical response of the various structures, as well as the effect of size and aspect ratio, reveals their rich array of resonances, which are supported by single-particle optical scattering experiments. Further, corresponding numerical and experimental studies of the near-field plasmon distribution via scanning transmission electron microscopy electron-energy loss spectroscopy unravels a mode nature and distribution that are unlike those of either hexagonal plates or cylindrical rods. These NPs, made from earth-abundant Mg, provide interesting ways to control light at the nanoscale across the ultraviolet, visible, and near-infrared spectral ranges.