Assembly and photocarrier dynamics of heterostructured nanocomposite photoanodes from multicomponent colloidal nanocrystals

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

Bandgap Tunability in Sb-Alloyed BiVO4 Quaternary Oxides as Visible Light Absorbers for Solar Fuel Applications

One approach to reducing the bandgap is the utilization of ternary and quaternary oxides, which have been receiving increased attention as light absorbers that, critically, also supply the potential needed to drive multi-electron oxidn. reactions. In this work, we report the discovery of antimony-alloyed bismuth vanadate (Sb-BiVO4). Through a combination of theor. predication and exptl. validation, we show that this novel photoanode material possesses a bandgap that linearly decreases below 2.4 eV with increasing Sb content. This work is enabled by the development of a novel two-step synthesis process that will broadly aid new materials discovery by providing synthetic access to a wide range of compositionally complex oxides

Tuning the Surface Plasmon Resonance of Lanthanum Hexaboride to Absorb Solar Heat: A Review

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

Moving the Plasmon of LaB₆ from IR to Near-IR via Eu-Doping.

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 La1-xEuxB₆ (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 Eu1-xLaxB₆

Moving the Plasmon of LaB6 from IR to Near-IR via Eu-Doping

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 La1−xEuxB6 (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 Eu1−xLaxB6