While traditional noble metal (Ag, Au, and Cu) nanoparticles are well known for their plasmonic properties, they typically only absorb in the ultraviolet and visible regions. The study of metal hexaborides, lanthanum hexaboride (LaB₆) in particular, expands the available absorbance range of these metals well into the near-infrared. As a result, LaB₆ has become a material of interest for its energy and heat absorption properties, most notably to those trying to absorb solar heat. Given the growing popularity of LaB₆, this review focuses on the advances made in the past decade with respect to controlling the plasmonic properties of LaB₆ nanoparticles. This review discusses the fundamental structure of LaB₆ and explains how decreasing the nanoparticle size changes the atomic vibrations on the surface and thus the plasmonic absorbance band. We explain how doping LaB₆ nanoparticles with lanthanide metals (Y, Sm, and Eu) red-shifts the absorbance band and describe research focusing on the correlation between size dependent and morphological effects on the surface plasmon resonance. This work also describes successes that have been made in dispersing LaB₆ nanoparticles for various optical applications, highlighting the most difficult challenges encountered in this field of study.

Lanthanum hexaboride (LaB₆) is notable for its thermionic emission and mechanical strength and is being explored for its potential applications in IR-absorbing photovoltaic cells and thermally insulating window coatings. Previous studies have not investigated how the properties of LaB₆ change on the nanoscale. Despite interest in the tunable plasmonic properties of nanocrystalline LaB₆, studies have been limited due to challenges in the synthesis of phase-pure, size-controlled, high-purity nanocrystals without high temperatures or pressures. Here, we report, for the first time, the ability to control particle size and boron content through reaction temperature and heating ramp rate, which allows the effects of size and defects on the vibrational modes of the nanocrystals to be studied independently. Understanding these effects is important to develop methods to fully control the properties of nanocrystalline LaB₆, such as IR absorbance. In contrast to previous studies on stoichiometric LaB₆ nanocrystals, we report here that boron content and lanthanum vacancies have a greater influence on their vibrational properties than their particle size.

LaB6 has been a material of interest for decades due to its thermionic emission, plasmonic properties, and low work function, and researchers continue to discover new properties even now. In order to meet growing interest in customizing these properties, it is important to gain better control over the system and a better understanding of the fundamental mechanism of LaB6 crystal growth and formation. Traditional synthetic methods require very high temperatures, at which point crystallization happens too quickly to be readily studied. Our discovery that LaB6 may be made using lower temperatures has made it possible to slow down crystal formation enough for lattice growth to be observed. We report here an in situ diffraction study of the reaction between LaCl3 and NaBH4. In observing the evolution of the (1 1 1), (1 1 0), and (2 0 0) lattice planes of LaB6, we have discovered that the Cl of LaCl3 has a strong influence on crystal formation, and that excess Cl, temperature and heating rate may all be used as tools to control the LaB6 final product.

Lanthanum hexaboride (LaB₆) has become a material of intense interest in recent years due to its low work function, thermal stability and intriguing optical properties. LaB₆ is also a semiconductor plasmonic material with the ability to support strong plasmon modes. Some of these modes uniquely stretch into the infrared, allowing the material to absorb around 1000 nm, which is of great interest to the window industry. It is well known that the plasmon of LaB₆ can be tuned by controlling particle size and shape. In this work, we explore the options available to further tune the optical properties by describing how metal vacancies and Eu doping concentrations are additional knobs for tuning the absorbance from the near-IR to far-IR in La_1-xEu_xB₆ (x = 0, 0.2, 0.5, 0.8, and 1.0). We also report that there is a direct correlation between Eu concentration and metal vacancies within the Eu_1-xLa_xB₆.

Multicomponent oxides and their heterostructures are rapidly emerging as promising light absorbers to drive oxidative chemistry. To fully exploit their functionality, precise tuning of their composition and structure is crucial. Here, we report a novel solution-based route to nanostructured bismuth vanadate (BiVO4) that facilitates the assembly of BiVO4/metal oxide (TiO2, WO3, and Al2O3) nanocomposites in which the morphology of the metal oxide building blocks is finely tailored. The combination of transient absorption spectroscopy-spanning from picoseconds to second time scales-and photoelectrochemical measurements reveals that the achieved structural tunability is key to understanding and directing charge separation, transport, and efficiency in these complex oxide heterostructured films.

The field of plasmonics has grown to impact a diverse set of scientific disciplines ranging from quantum optics and photovoltaics to metamaterials and medicine. Plasmonics research has traditionally focused on noble metals; however, any material with a sufficiently high carrier density can support surface plasmon modes. Recently, researchers have made great gains in the synthetic (both intrinsic and extrinsic) control over the morphology and doping of nanoscale oxides, pnictides, sulfides, and selenides. These synthetic advances have, collectively, blossomed into a new, emerging class of plasmonic metal chalcogenides that complement traditional metallic materials. Chalcogenide and oxide nanostructures expand plasmonic properties into new spectral domains and also provide a rich suite of chemical controls available to manipulate plasmons, such as particle doping, shape, and composition. New opportunities in plasmonic chalcogenide nanomaterials are highlighted in this article, showing how they may be used to fundamentally tune the interaction and localization of electromagnetic fields on semiconductor surfaces in a way that enables new horizons in basic research and energy-relevant applications.

Laboratory chemical synthesis research typically lacks the preplanned hazard responses found in production-scale industrial laboratories. Chemical safety management is a known challenge in education-based facilities, which is concerning for academic and national laboratory environments working with inexperienced student researchers. At the Molecular Foundry, a U.S. Department of Energy (DOE) user facility, a chemical safety management form has been developed that follows DOE’s Integrated Safety Management (ISM) process, which evaluates the risks and hazards associated with all forms of work. An ISM form for chemical synthesis is described here in detail. It is regularly used to guide chemical safety discussions between researchers and supervisors, to plan accident responses, and to establish triggers, at which point a reevaluation of the work is needed. The form makes it straightforward to know what limits researchers may work within and makes it clear which procedure changes will require a new safety assessment and discussion before work continues. The ISM form for synthesis is being successfully used in three fields of chemistry: Inorganic, Organic, and Biological. The form has also been adapted for liquid sample preparation in electron microscopy. Upper management, supervisors, students, and general users are engaged in this process. It is hoped that sharing this knowledge will enable educational institutions and other laboratories to develop similar methods to help researchers and supervisors understand the hazards as well as the working limits of any protocol, helping researchers to work more independently and safely within the laboratory.

Design of interfaces with thermodynamic and kinetic specificity is of great importance for hydrogen storage from both an applied and fundamental perspective. Here, in order to destabilize the metal hydride and protect the dehydrogenated products from oxidizing, a unique core-shell structure of porous Mg(BH₄ )₂ -based framework with a thin layer (no more than 5 nm) of MgCl₂ additives on the surface, has been proposed and synthesized via a wet-chemical method. The local structure and electronic state of the present complex system are systematically investigated to understand the correlation between the distribution of additives and dehydrogenation property of Mg(BH₄ )₂ . A significant improvement is achieved for hydrogen desorption with chlorides: initial hydrogen release from MgCl₂ decorated γ-phase Mg(BH₄ )₂ particles commences at 100 °C and reaches a maximum of 9.4 wt% at 385 °C. Besides the decreased decomposition temperature, an activation barrier of about 76.4 kJ mol^-1 lower than that of Mg(BH₄ )₂ without MgCl₂ is obtained. Moreover, MgCl₂ decoration can also prevent the whole decomposed system (both Mg- and B- elements) from oxidizing, which is a necessary condition to reversibility.

Sodium borohydride (NaBH4) has been a material of interest for many years in developing metal boride complexes and shows a great deal of potential as a hydrogen storage material. Though many have used various additives as catalysts to weaken the bonds within NaBH4 to create a more energetically favorable material, very little is understood about how the borohydride interacts with and changes the additives being incorporated. This work uses ball milling to incorporate calcium chloride (CaCl2) into NaBH4. Using several x-ray techniques, thermogravimetric analysis, and Raman spectroscopy, this study shows not only that the salt diffuses into NaBH4 but describes how the borohydride changes the additive itself. In gaining a stronger understanding of what happens to the additives needed to weaken the borohydride bonds, future researchers may have an easier time selecting the appropriate additive to create a borohydride complex that will meet their needs.