Kyle J. Berean

Wafer-scale two-dimensional semiconductors from printed oxide skin of liquid metals

A variety of deposition methods for two-dimensional crystals have been demonstrated; however, their wafer-scale deposition remains a challenge. Here we introduce a technique for depositing and patterning of wafer-scale two-dimensional metal chalcogenide compounds by transforming the native interfacial metal oxide layer of low melting point metal precursors (group III and IV) in liquid form. In an oxygen-containing atmosphere, these metals establish an atomically thin oxide layer in a self-limiting reaction. The layer increases the wettability of the liquid metal placed on oxygen-terminated substrates, leaving the thin oxide layer behind. In the case of liquid gallium, the oxide skin attaches exclusively to a substrate and is then sulfurized via a relatively low temperature process. By controlling the surface chemistry of the substrate, we produce large area two-dimensional semiconducting GaS of unit cell thickness (∼1.5 nm). The presented deposition and patterning method offers great commercial potential for wafer-scale processes.

2D WS2/carbon dot hybrids with enhanced photocatalytic activity

Two-dimensional (2D) tungsten disulfide (WS2) nanoflakes were synthesised and hybridised with carbon dots (CDs) using a facile two-step method of exfoliation of bulk tungsten disulphide followed by microwave irradiation of nanoflakes in a solution of citric acid. Physicochemical characterisation indicated that the hybrid consists of graphitic carbon dots with diameters of approximately 2–5 nm, attached to monolayer tungsten disulphide via electrostatic attraction forces. This synthesised hybrid material was investigated for photocatalytic applications. We found that within one hour approximately 30% more of the model organic dye was photodegraded by the hybrid material compared with the pristine 2D WS2. This enhancement was associated to the affinity of the CDs to the organic dye rather than heterojunctioning. Comparisons of the photocatalytic efficacy of this hybrid material with those of recently reported 2D transition metal dichalcogenides and their hybrids showed a significantly higher turnover frequency. Additionally, the presented microwave based synthesis method for developing hybrids of 2D WS2 and CDs, without making significant changes to the base 2D crystal structure and its surface chemistry, has not been demonstrated before. Altogether, the hybrid 2D material provides great potential for photocatalysis applications.

Exfoliation Solvent Dependent Plasmon Resonances in Two-Dimensional Sub-Stoichiometric Molybdenum Oxide Nanoflakes.

Few-layer two-dimensional (2D) molybdenum oxide nanoflakes are exfoliated using a grinding assisted liquid phase sonication exfoliation method. The sonication process is carried out in five different mixtures of water with both aprotic and protic solvents. We found that surface energy and solubility of mixtures play important roles in changing the thickness, lateral dimension, and synthetic yield of the nanoflakes. We demonstrate an increase in proton intercalation in 2D nanoflakes upon simulated solar light exposure. This results in substoichiometric flakes and a subsequent enhancement in free electron concentrations, producing plasmon resonances. Two plasmon resonance peaks associated with the thickness and the lateral dimension axes are observable in the samples, in which the plasmonic peak positions could be tuned by the choice of the solvent in exfoliating 2D molybdenum oxide. The extinction coefficients of the plasmonic absorption bands of 2D molybdenum oxide nanoflakes in all samples are found to be high (ε > 10(9) L mol(-1) cm(-1)). It is expected that the tunable plasmon resonances of 2D molybdenum oxide nanoflakes presented in this work can be used in future electronic, optical, and sensing devices.

Intestinal Gas Capsules: A Proof-of-Concept Demonstration

School of Electrical and Computer Engineering, RMIT University, Department of Gastroenterology, The Alfred Hospital, Monash University, Monash Ageing Research Centre, Monash University, Melbourne, School of Applied Sciences, RMIT University, Bundoora, Department of Agriculture and Food Systems, The University of Melbourne, Parkville, and Commonwealth Scientific and Industrial Research Organisation (CSIRO), Australia

2D MoS2 PDMS Nanocomposites for NO2 Separation

At a relatively low loading concentration (≈0.02 wt%) of 2D MoS 2 flakes in PDMS, the composite membrane is able to almost completely block the permeation of NO2 gas molecules at ppm levels. This major reduction is ascribed to the strong physisorption of NO2 gas molecules onto the 2D MoS2 flake basal planes.

Excitation dependent bidirectional electron transfer in phthalocyanine-functionalised MoS2 nanosheets

Two-dimensional (2D) transition metal chalcogenides such as 2D MoS2 are considered prime candidate materials for the design of next generation optoelectronics. Functionalisation of these materials is considered to be a key step in tailoring their properties towards specific applications and unlocking their full potential. Here we present a van der Waals functionalisation strategy for creating MoS2 nanosheets decorated with free base phthalocyanine chromophores. The semiconducting sheets are found to intimately interact with these optoelectronically active chromophores, resulting in an electronic heterostructure that exhibits enhanced optoelectronic properties and exploitable charge transfer. We show that by utilising laterally confined MoS2 nanosheets, the conduction band of the semiconductor could be positioned between the chromophores S1 and S2 states. Consequently, bidirectional photoinduced electron transfer processes are observed, with excitation of the functionalised nanosheets semiconductor transition resulting in electron transfer to the phthalocyanines LUMO, and excitation of the chromophores S2 state leading to electron injection into the MoS2 conduction band. However, charge transfer from the dyes S1 transition to the MoS2 nanosheet is found to be thermodynamically unfavourable, resulting in intense radiative recombination. These findings may enable controlling and tuning the charge carrier density of semiconducting nanosheets via optical means through the exploitation of photoinduced electron transfer. Furthermore this work provides access to 2D semiconductor-hybrids with tailored absorption profiles and photoluminescence.

Controlled Electrochemical Deformation of Liquid-Phase Gallium

Pure gallium is a soft metal with a low temperature melting point of 29.8 °C. This low melting temperature can potentially be employed for creating optical components with changeable configurations on demand by manipulating gallium in its liquid state. Gallium is a smooth and highly reflective metal that can be readily maneuvered using electric fields. These features allow gallium to be used as a reconfigurable optical reflector. This work demonstrates the use of gallium for creating reconfigurable optical reflectors manipulated through the use of electric fields when gallium is in a liquid state. The use of gallium allows the formed structures to be frozen and preserved as long as the temperature of the metal remains below its melting temperature. The lens can be readily reshaped by raising the temperature above the melting point and reapplying an electric field to produce a different curvature of the gallium reflector.

Surface Water Dependent Properties of Sulfur-Rich Molybdenum Sulfides: Electrolyteless Gas Phase Water Splitting

Sulfur-rich molybdenum sulfides are an emerging class of inorganic coordination polymers that are predominantly utilized for their superior catalytic properties. Here we investigate surface water dependent properties of sulfur-rich MoSx (x = 32/3) and its interaction with water vapor. We report that MoSx is a highly hygroscopic semiconductor, which can reversibly bind up to 0.9 H2O molecule per Mo. The presence of surface water is found to have a profound influence on the semiconductors properties, modulating the materials photoluminescence by over 1 order of magnitude, in transition from dry to moist ambient. Furthermore, the conductivity of a MoSx-based moisture sensor is modulated in excess of 2 orders of magnitude for 30% increase in humidity. As the core application, we utilize the discovered properties of MoSx to develop an electrolyteless water splitting photocatalyst that relies entirely on the hygroscopic nature of MoSx as the water source. The catalyst is formulated as an ink that can be coated onto insulating substrates, such as glass, leading to efficient hydrogen and oxygen evolution from water vapor. The concept has the potential to be widely adopted for future solar fuel production.

Highly active two dimensional α-MoO3−x for the electrocatalytic hydrogen evolution reaction

The development of earth-abundant electrocatalysts for hydrogen evolution, with high activity and stability, is of great interest in the field of clean energy. The highly tunable chemical and physical properties of earth-abundant molybdenum oxides make them versatile for their incorporation into electrochemical and catalytic systems. Due to the layered crystal arrangement of orthorhombic α-MoO3, this material can be exfoliated into two dimensional (2D) nanosheets, featuring a large surface area. Variations in the oxidation states of molybdenum facilitate the crystal structure, morphology and oxygen vacancy tuning, making these oxide compounds suitable for electrochemical activities. Here, oxygen deficient 2D α-MoO3−x nanosheets (x = 0.045) are successfully synthesised, using a liquid phase exfoliation method, which display superior activity for the electrocatalytic hydrogen evolution reaction (HER) with a low overpotential and fast electron transfer. In alkaline media, the 2D compound exhibits an overpotential value of 142 mV at the standard current density of 10 mA cm−2 with excellent stability. Here, the 2D morphology, structural defects and oxygen vacancies in the planar construction of molybdenum oxide nanosheets significantly increase the active sites of the catalyst, which act as key factors to promote the HER performance. This work presents 2D α-MoO3−x nanosheets as strong candidates for the HER.

A Gallium-Based Magnetocaloric Liquid Metal Ferrofluid

We demonstrate a magnetocaloric ferrofluid based on a gadolinium saturated liquid metal matrix, using a gallium-based liquid metal alloy as the solvent and suspension medium. The material is liquid at room temperature, while exhibiting spontaneous magnetization and a large magnetocaloric effect. The magnetic properties were attributed to the formation of gadolinium nanoparticles suspended within the liquid gallium alloy, which acts as a reaction solvent during the nanoparticle synthesis. High nanoparticle weight fractions exceeding 2% could be suspended within the liquid metal matrix. The liquid metal ferrofluid shows promise for magnetocaloric cooling due to its high thermal conductivity and its liquid nature. Magnetic and thermoanalytic characterizations reveal that the developed material remains liquid within the temperature window required for domestic refrigeration purposes, which enables future fluidic magnetocaloric devices. Additionally, the observed formation of nanometer-sized metallic particles within the supersaturated liquid metal solution has general implications for chemical synthesis and provides a new synthetic pathway toward metallic nanoparticles based on highly reactive rare earth metals.