Shapes, Plasmonic Properties, and Reactivity of Magnesium Nanoparticles

Localized surface plasmon resonances have attracted much attention due to their ability to enhance light–matter interactions and manipulate light at the subwavelength level. Recently, alternatives to the rare and expensive noble metals Ag and Au have been sought for more sustainable and large-scale plasmonic utilization. Mg supports plasmon resonances, is one of the most abundant elements in earth’s crust, and is fully biocompatible, making it an attractive framework for plasmonics. This feature article first reports the hexagonal, folded, and kite-like shapes expected theoretically from a modified Wulff construction for single crystal and twinned Mg structures and describes their excellent match with experimental results. Then, the optical response of Mg nanoparticles is overviewed, highlighting Mg’s ability to sustain localized surface plasmon resonances across the ultraviolet, visible, and near-infrared electromagnetic ranges. The various resonant modes of hexagons, leading to the highly localized electric field characteristic of plasmonic behavior, are presented numerically and experimentally. The evolution of these modes and the associated field from hexagons to the lower symmetry folded structures is then probed, again by matching simulations, optical, and electron spectroscopy data. Lastly, results demonstrating the opportunities and challenges related to the high chemical reactivity of Mg are discussed, including surface oxide formation and galvanic replacement as a synthetic tool for bimetallics. This Feature Article concludes with a summary of the next steps, open questions, and future directions in the field of Mg nanoplasmonics

Approaches to modelling the shape of nanocrystals.

Unlike in the bulk, at the nanoscale shape dictates properties. The imperative to understand and predict nanocrystal shape led to the development, over several decades, of a large number of mathematical models and, later, their software implementations. In this review, the various mathematical approaches used to model crystal shapes are first overviewed, from the century-old Wulff construction to the year-old (2020) approach to describe supported twinned nanocrystals, together with a discussion and disambiguation of the terminology. Then, the multitude of published software implementations of these Wulff-based shape models are described in detail, describing their technical aspects, advantages and limitations. Finally, a discussion of the scientific applications of shape models to either predict shape or use shape to deduce thermodynamic and/or kinetic parameters is offered, followed by a conclusion. This review provides a guide for scientists looking to model crystal shape in a field where ever-increasingly complex crystal shapes and compositions are required to fulfil the exciting promises of nanotechnology

Nanostars Shine in Light-Driven Water Reduction

The “alchemy of water,” i.e., turning water into fuel (such as hydrogen) with sunlight, is an exciting prospect for sustainable energy. In a recent Chem issue, Atta et al. (2018) developed plasmonic-TiO2 nanostructures that bring photocatalytic water splitting one step closer to reality

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.Engineering and Physical Sciences Research Council (NanoDTC Cambridge (EP/L015978/1

Wulff-Based Approach to Modeling the Plasmonic Response of Single Crystal, Twinned, and Core-Shell Nanoparticles.

The growing interest in plasmonic nanoparticles and their increasingly diverse applications is fuelled by the ability to tune properties via shape control, promoting intense experimental and theoretical research. Such shapes are dominated by geometries that can be described by the kinetic Wulff construction such as octahedra, thin triangular platelets, bipyramids, and decahedra, to name a few. Shape is critical in dictating the optical properties of these nanoparticles, in particular their localized surface plasmon resonance behavior, which can be modeled numerically. One challenge of the various available computational techniques is the representation of the nanoparticle shape. Specifically, in the discrete dipole approximation, a particle is represented by discretizing space via an array of uniformly distributed points-dipoles; this can be difficult to construct for complex shapes including those with multiple crystallographic facets, twins, and core-shell particles. Here, we describe a standalone user-friendly graphical user interface (GUI) that uses both kinetic and thermodynamic Wulff constructions to generate a dipole array for complex shapes, as well as the necessary input files for DDSCAT-based numerical approaches. Examples of the use of this GUI are described through three case studies spanning different shapes, compositions, and shell thicknesses. Key advances offered by this approach, in addition to simplicity, are the ability to create crystallographically correct structures and the addition of a conformal shell on complex shapes

Micro-Extinction Spectroscopy (MExS): a versatile optical characterization technique

Micro-Extinction Spectroscopy (MExS), a flexible, optical, and spatial-scanning hyperspectral technique, has been developed and is described with examples. Software and hardware capabilities are described in detail, including transmission, reflectance, and scattering measurements. Each capability is demonstrated through a case study of nanomaterial characterization, i.e., transmission of transition metal dichalcogenides revealing transition energy and efficiency, reflectance of transition metal dichalcogenides grown on nontransparent substrates identifying the presence of monolayer following electrochemical ablation, and scattering to study single plasmonic nanoparticles and obtain values for the refractive index sensitivity and sensing figure of merit of over a hundred single particles with various shapes and sizes. With the growing integration of nanotechnology in many areas, MExS can be a powerful tool to both characterize and test nanomaterials

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

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.Support for this project was provided by the EU Framework Programme for Research and Innovation Horizon 2020 (Starting Grant SPECs 804523). J.A. wishes to acknowledge financial support from Natural Sciences and Engineering Research Council of Canada and “Fonds de Recherche Québec – Nature et Technologies” postdoctoral fellowships (BP and B3X programs). C.B. is thankful for funding from the Engineering and Physical Sciences Research Council (Standard Research Studentship (DTP) EP/R513180/1), and E.R.H. for support from the EPSRC NanoDTC Cambridge (EP/L015978/1). S.M.C. acknowledges support from the Henslow Research Fellowship at Girton College, Cambridge. We acknowledge access and support in the use of the electron Physical Sciences Imaging Centre (MG21980) at the Diamond Light Source, U.K

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.Support for this project was provided by the EU Framework Programme for Research and Innovation Horizon 2020 (ERC Starting Grant SPECs 804523). E.R.H. is thankful for funding from the EPSRC NanoDTC Cambridge (EP/L015978/1). J.A. acknowledges financial support from Natural Sciences and Engineering Research Council of Canada and Fonds de Recherche du Québec–Nature et Technologies postdoctoral fellowships (BP and B3X programs). C.B. is thankful for funding from the Engineering and Physical Sciences Research Council (Standard Research Studentship (DTP) EP/R513180/1). B.P. and L.T.M. acknowledge support from UK Engineering and Physical Science and Research Council (grant number EP/L020443/2). Thanks to Giulio I. Lampronti for helpful discussions and support