Reclaimed seawater discharge - Desalination brine treatment and resource recovery system.

With the proliferation of reverse osmosis technology, seawater reverse osmosis desalination has been heralded as the solution to water scarcity for coastal regions. However, the large volume of desalination brine produced may pose an adverse environmental impact when directly discharged into the sea and result in energy wastage as the seawater pumped out is dumped back into the sea. Recently, zero liquid discharge has been extensively studied as a way to eliminate the aquatic ecotoxicity impact completely, despite being expensive and having a high carbon footprint. In this work, we propose a new strategy towards the treatment of brine to seawater level for disposal, dubbed reclaimed seawater discharge (RSD). This process is coupled with existing resource recovery techniques and waste alkali CO2 capture processes to produce an economically viable waste treatment process with minimal CO2 emissions. In this work, we placed significant focus on the electrolysis of brine, which simultaneously lowers the salinity of the desalination brine (56.0 ± 2.1 g/L) to seawater level (32.0 ± 1.4 g/L), generates alkali brine from seawater (pH 13.6) to remove impurities in brine (Mg2+ and Ca2+ to below ppm level), and recovers magnesium hydroxide, calcium carbonate, chlorine, bromine, and hydrogen gas as valuable resources. The RSD is further chemically dechlorinated and neutralised to pH 7.3 to be safe to discharge into the sea. The excess alkali brine is used to capture additional CO2 in the form of bicarbonates, achieving net abatement in climate change impact (9.90 CO2 e/m3) after product carbon abatements are accounted.

Polyolefin-derived substrate-grown carbon nanotubes as binder-free electrode for hydrogen evolution in alkaline media.

Switching from a linear mode of waste management to a circular loop by transforming plastic waste into carbon nanotubes (CNTs) is a promising approach to current plastic waste treatment. One of the many applications of CNTs is its use for electrocatalytic water splitting for hydrogen evolution. Existing methods of CNTs-based hydrogen evolution reaction (HER) electrode fabrication involve additives like polymeric binders and additional steps to improve CNT dispersion, which are detrimental to the CNT structure and properties. The in-situ fabrication approach can potentially be a one-pot solution to HER electrode synthesis. In this study, polyolefins pyrolysis gas and a Co:Ni:Mg catalyst were used to fabricate binder-free CNTs-based electrodes on different substrates for HER. The study assessed CNT quality on conductive carbon paper, semiconductive silicon, and dielectric glass substrates, evaluating their HER performance in 1 M KOH. A mixture of hollow-core, bamboo-like, and cup-stacked arrangement nanotubes were synthesized on the substrates, with CNTs on glass and carbon paper substrates possessing better graphitization than CNTs grown on silicon. This is in agreement with HER performance, whereby the as-prepared electrodes required overpotentials of 267 mV, 241 mV, and 216 mV for silicon, glass, and carbon paper, respectively, to achieve 10 mA/cm2. Despite being poorly conductive, the glass substrate electrode achieved a lower overpotential than the silicon electrode. Additionally, the as-prepared silicon electrode faced a delamination issue likely attributed to the lower surface energy of the silicon substrate surface, demonstrating the weaker adhesion between the CNTs and silicon surface. The proposed approach thus showed that the in-situ fabricated electrodes performed better than separately synthesized CNTs prepared into electrodes by 27.4% and 14.2% for carbon paper and glass substrates, respectively. The improved performance of the as-prepared, binder-free electrodes can be linked to the lower charge-transfer resistance and reduced contact resistance between the CNTs and substrate.

Transient Laser-Annealing-Induced Mesophase Transitions of Block Copolymer-Resol Thin Films.

Block copolymer self-assembly-derived thin films provide direct access to two- and three-dimensional periodically ordered mesostructures as enablers for many nanotechnology applications. This report describes laser-annealing-induced disorder-order mesophase transitions of polystyrene-block-poly(ethylene oxide)/resol hybrid thin films over a range of laser temperatures (∼45 to 525 °C) and short dwell times (0.25 to 100 ms), revealing the non-equilibrium ordering and disordering kinetics and behaviors. We found that a combination of transient laser temperature of ∼275 °C and annealing dwell time of 100 ms provided the most optimal kinetic and thermodynamic control of the diffusivities of hybrid mesophases and photothermal-induced resol polymerization, yielding long-range ordered films resembling an in-plane body-centered cubic sphere morphology. A clear understanding of hybrid thin film mesophase self-assembly under non-equilibrium laser annealing could open new avenues to introduce novel chemistries and rapidly achieve nanoscale periodic order suitable for the patterning of complex structures, electronics, sensing, and emerging quantum materials.

Computational design of small phenothiazine dyes for dye-sensitized solar cells by functionalizations affecting the thiophene unit.

We present a computational density functional theory study of the potential to improve the solar absorbance of small organic dyes featuring a phenothiazine donor and an acceptor moiety that combines a thiophene unit and a cyanoacrylic group. We consider different conjugation orders and functional groups on and around the thiophene unit, including electron-donating and electron-withdrawing moieties (H, F, CH3, CF3, and CN). We predict that by combining change of conjugation order and functionalization with electron withdrawing CN groups, it must be possible to decrease the excitation energy by up to 60 % vs. the parent dye (which would correspond to a redshift of the absorption peak maximum from 450 nm to 726 nm), effectively enabling red light absorption with small dyes. The contraction of the band gap is mostly due to the stabilization of the LUMO (by up to 1.8 eV), so that-in spite of the kinetic redundancy of the parent dye with respect to the conduction-band minimum of TiO2-care must be taken to ensure efficient injection when using the dyes in dye-sensitized solar cells. By studying 50 dyes, of which 44 are new dyes that are studied for the first time in this work, we identify parameters (such as charges, dihedral angles between donor and acceptor groups, bond length alternation) which can serve as predictors of the band gap. We find that bond length alternation or dihedral angles are not good predictors, while the charge on the thiophene unit is.