Highly permeable, anti-bacterial, gas selective membranes for the measurement of intra-ruminant gas production

In the recent past, researchers have turned to advancements in membrane technology for gas separation to help solve the enormous challenges faced by society in regards to limited resources and environmental sustainability. Compared with conventional gas separation methods, membrane technology is environmentally benign and energy-efficient. Furthermore, membranes require less space and can be operated in a continuous mode at low cost. Ideal membrane attributes include high permeate flux, high gas selectivity and operational longevity. The aim of this PhD project is to synthesise, optimise, characterise and evaluate the gas permeation properties of polymdimethylsiloxane (PDMS) nanocomposites and finally to prolong their lifetime through the addition of antimicrobial properties. The author of this thesis thoroughly reviewed the fundamental properties and synthesis methods for gas permeable nanocomposite membranes. Based on the literature, the author recognised the lack in a standardised synthesis condition for the chosen base polymer PDMS. Additionally the author identified the significant enhancements that two dimensional (2D) nanomaterials had over other standard fillers when engineering the composites properties, due to an increased surface to volume ratio. Finally, in order to prolong the lifetime of membranes operating in aqueous or humid environments, bacterial growth needs to be controlled. The author explores novel experimental techniques to evaluate the antimicrobial effects of the developed material. Overall, the author strongly believes that the objectives achieved in this PhD research work, have contributed significantly to the advancement of gas separating membranes, antimicrobial materials and in vivo experimental techniques regarding the investigation of microbial growth onto materials, thus creating new systems and adding significantly to the knowledge of the field

CNT/PDMS composite membranes for H2 and CH4 gas separation

Polydimethylsiloxane (PDMS) composites with different weight amounts of multi-walled carbon nanotubes (MWCNT) were synthesised as membranes to evaluate their gas separation properties. The selectivity of the membranes was investigated for the separation of H2 from CH4 gas species. Membranes with MWCNT concentrations of 1% increased the selectivity to H2 gas by 94.8%. Furthermore, CH4 permeation was almost totally blocked through membranes with MWCNT concentrations greater than 5%. Vibrational spectroscopy and X-ray photoelectron spectroscopy techniques revealed that upon the incorporation of MWCNT a decrease in the number of available Si–CH3 and Si–O bonds as well as an increase in the formation of Si–C bonds occurred that initiated the reduction in CH4 permeation. As a result, the developed membranes can be an efficient and low cost solution for separating H2 from larger gas molecules such as CH4

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 (Îμ > 109 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

Nanocomposite carbon-PDMS membranes for gas separation

Polydimethylsiloxane (PDMS) composites containing variable weight amounts of carbon black (CB) have been synthesized as membranes to evaluate the effect of CB concentration on gas selectivity and separation. The membranes were used in conjunction with a commercial semiconducting methane (CH4) gas sensor that had a strong cross-talk with hydrogen (H2) gas. The selectivity of the CB-PDMS composite membranes for gas separation was tested using CH4 and H2. It was found that at 6 wt% of CB in PDMS, the permeability of CH4 was significantly and selectively attenuated through the composite membrane. This work demonstrates that CB is an effective additive for tuning H2/CH4 gas selectivity of the composite membranes. The selectivity is attributed to a chemical transition occurring with increasing CB doping, which was observed by vibrational spectroscopy measurements

Exfoliation of quasi-stratified Bi2S3 crystals into micron-scale ultrathin corrugated nanosheets

There is ongoing interest in exploring new two-dimensional materials and exploiting their functionalities. Here, a top-down approach is used for developing a new morphology of ultrathin nanosheets from highly ordered bismuth sulfide crystals. The efficient chemical delamination method exfoliates the bulk powder into a suspension of corrugated ultrathin sheets, despite the fact that the Bi2S3 fundamental layers are made of atomically thin ribbons that are held together by van der Waals forces in two dimensions. Morphological analyses show that the produced corrugated sheets are as thin as 2.5 nm and can be as large as 20 mu m across. Determined atomic ratios indicate that the exfoliation process introduces sulfur vacancies into the sheets, with a resulting stoichiometry of Bi2S2.6. It is hypothesized that the nanoribbons were cross-linked during the reduction process leading to corrugated sheet formation. The material is used for preparing field effect devices and was found to be highly p-doped, which is attributed to the substoichiometry. These devices show a near-linear response to the elevation of temperature. The devices demonstrate selective and relatively fast response to NO2 gas when tested as gas sensors. This is the first report showing the possibility of exfoliating planar morphologies of metal chalcogenide compounds such as orthorhombic Bi2S3, even if their stratified crystal structures constitute van der Waals forces within the fundamental planes

Surface water dependent properties of sulphur-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 semiconductor's properties, modulating the material's 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

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

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

© The Author(s) 2017. 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

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

Nature Communications 8: Article number: 14482; published: 17 February 2017; Updated: 22 March 2017 The original version of this Article contained a typographical error in the spelling of the author Omid Kavehei, which was incorrectly given as Omid Kevehei. This has now been corrected in both the PDF and HTML versions of the Article.</jats:p

In-beam internal conversion electron spectroscopy with the SPICE detector

The SPectrometer for Internal Conversion Electrons (SPICE) has been commissioned for use in conjunction with the TIGRESS $\gamma$-ray spectrometer at TRIUMF's ISAC-II facility. SPICE features a permanent rare-earth magnetic lens to collect and direct internal conversion electrons emitted from nuclear reactions to a thick, highly segmented, lithium-drifted silicon detector. This arrangement, combined with TIGRESS, enables in-beam $\gamma$-ray and internal conversion electron spectroscopy to be performed with stable and radioactive ion beams. Technical aspects of the device, capabilities, and initial performance are presented