ABSTRACT
We have synthesized the first reported example of quantum confined high-entropy (HE) nanoparticles, using the lanthanide oxysulfide, Ln2SO2, system as the host phase for an equimolar mixture of Pr, Nd, Gd, Dy, and Er. A uniform HE phase was achieved via the simultaneous thermolysis of a mixture of lanthanide dithiocarbamate precursors in solution. This was confirmed by powder X-ray diffraction and high-resolution scanning transmission electron microscopy, with energy dispersive X-ray spectroscopic mapping confirming the uniform distribution of the lanthanides throughout the particles. The nanoparticle dispersion displayed a significant blue shift in the absorption and photoluminescence spectra relative to our previously reported bulk sample with the same composition, with an absorption edge at 330 nm and a λmax at 410 nm compared to the absorption edge at 500 nm and a λmax at 450 nm in the bulk, which is indicative of quantum confinement. We support this postulate with experimental and theoretical analysis of the bandgap energy as a function of strain and surface effects (ligand binding) as well as calculation of the exciton Bohr radiii of the end member compounds.
ABSTRACT
Metal oxides, sulphides, selenides and tellurides have routinely been investigated and utilised for a wide range of applications, in particular in the areas of energy (photovoltaic, thermoelectric) and catalysis (thermocatalysis, electrocatalysis and photoelectrocatalysis). A recent development in this chemical space is high entropy and entropy-stabilised inorganic materials, which took inspiration from preceding work on high entropy metal alloys (multicomponent alloys). High entropy inorganic materials typically have many (often ≥6) different cations or anions to yield a high configurational entropy, which can give unexpected structures and properties that are conducive to a broad range of applications in energy and catalysis. More recently still, high entropy metal chalcogenides have been developed and have been investigated for thermoelectric energy generation, batteries for energy storage and electrocatalysis. This review sets out to define entropic stabilisation in high entropy materials, along with a discussion of synthetic techniques to produce these compounds, focusing on high entropy metal chalcogenides including extant routes to high entropy sulfides, selenides and tellurides. The resulting advantageous properties of these materials due to their multi-element nature and the currently proposed and investigated applications of these materials are reviewed. We end the perspective with an opinion on future directions.
ABSTRACT
High entropy (HE) materials have received significant attention in recent years, due to their intrinsically high levels of configurational entropy. While there has been significant work exploring HE alloys and oxides, new families of HE materials are still being revealed. In this work we present the synthesis of a novel family of HE materials based on lanthanide oxysulfides. Here, we implement lanthanide dithiocarbamates as versatile precursors that can be mixed at the molecular scale prior to thermolysis in order to produce the high entropy oxysulfide. The target of our synthesis is the HE Ln2SO2 phase, where Ln = Pr, Nd, Gd, Dy, Er and where Ln = Pr, Nd, Gd, Dy for 5 and 4 lanthanide samples, respectively. We confirmed the structure of samples produced by powder X-ray diffraction, electron microscopy, and high-resolution energy dispersive X-ray spectroscopy. Optical spectroscopy shows a broad emission feature centered around 450 nm as well as a peak in absorption at around 280 nm. From this data we calculate the band gap and Urbach energies of the materials produced.
