Photocatalytic Degradation of Rhodamine B Dye and Hydrogen Evolution by Hydrothermally Synthesized NaBH4-Spiked ZnS Nanostructures.

Metal sulphides, including zinc sulphide (ZnS), are semiconductor photocatalysts that have been investigated for the photocatalytic degradation of organic pollutants as well as their activity during the hydrogen evolution reaction and water splitting. However, devising ZnS photocatalysts with a high overall quantum efficiency has been a challenge due to the rapid recombination rates of charge carriers. Various strategies, including the control of size and morphology of ZnS nanoparticles, have been proposed to overcome these drawbacks. In this work, ZnS samples with different morphologies were prepared from zinc and sulphur powders via a facile hydrothermal method by varying the amount of sodium borohydride used as a reducing agent. The structural properties of the ZnS nanoparticles were analysed by X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS) techniques. All-electron hybrid density functional theory calculations were employed to elucidate the effect of sulphur and zinc vacancies occurring in the bulk as well as (220) surface on the overall electronic properties and absorption of ZnS. Considerable differences in the defect level positions were observed between the bulk and surface of ZnS while the adsorption of NaBH4 was found to be highly favourable but without any significant effect on the band gap of ZnS. The photocatalytic activity of ZnS was evaluated for the degradation of rhodamine B dye under UV irradiation and hydrogen generation from water. The ZnS nanoparticles photo-catalytically degraded Rhodamine B dye effectively, with the sample containing 0.01 mol NaBH4 being the most efficient. The samples also showed activity for hydrogen evolution, but with less H2 produced compared to when untreated samples of ZnS were used. These findings suggest that ZnS nanoparticles are effective photocatalysts for the degradation of rhodamine B dyes as well as the hydrogen evolution, but rapid recombination of charge carriers remains a factor that needs future optimization.

Facemasks and ferrous metallurgy: improving gasification reactivity of low-volatile coals using waste COVID-19 facemasks for ironmaking application.

The global pandemic response to COVID-19 has led to the generation of huge volumes of unrecyclable plastic waste from single use disposable face coverings. Rotary hearth furnaces can be used to recover Zn and Fe from non-recyclable steelmaking by-product dusts, and waste plastic material such as facemasks could be utilized as a supplementary reductant for the rotary hearth furnace (RHF), but their fibrous form makes milling and processing to appropriate sizing for RHF application extremely challenging. A scalable method of grinding facemasks to powder by melting and mixing with Welsh coal dust reported herein provides a solution to both environmental challenges. The melt-blended PPE/coal dust shows a dramatically improved CO2 gasification reactivity (Ea = 133-159 kJmol-1) when compared to the untreated coal (Ea = 183-246 kJmol-1), because of improved pore development in the coal during the pyrolysis stage of heating and the catalytic activity of the CaO based ash present in the facemask plastic. The results are promising for the application of waste facemasks in recycling steelmaking by-product dusts in rotary hearth furnaces and may also be suitable for direct injection to the blast furnace subject to further study.

Woven Stainless-Steel Mesh as a Gas Separation Membrane for Alkaline Water-Splitting Electrolysis.

A 316-grade woven stainless-steel mesh membrane was investigated as a gas-separation membrane for alkaline water-splitting electrolysis. Its resistance was measured using electrochemical impedance spectroscopy (EIS) and linear sweep voltammetry (LSV), with the conclusion that it presented approximately half the resistance of a comparable commercial alternative (ZirfonTM). Its gas-separation performance was analysed using gas chromatography (GC) at 140 mA cm-2, where it achieved 99.25% purity at the hydrogen outlet of the electrolyser. This fell to 97.5% under pumped circulation, which highlights that it is sensitive to pressure differentials. Nevertheless, this mixture is still more than a factor two inside the upper flammability limit of hydrogen in oxygen. It is hoped that such a low-cost material may bring entry-level electrolysis to many hitherto discounted applications.

Photocapacitive CdS/WOx nanostructures for solar energy storage.

Through a facile solvothermal procedure, a CdS/WOx nanocomposite has been synthesised which exhibits photocapacitive behaviour under white light illumination at a radiant flux density of 99.3 mW cm-2. Photoelectrochemical experiments were undertaken to examine the self-charging properties of the material and to develop an understanding of the underlying electronic band structure responsible for the phenomenon. By employing XPS, UPS and UV-Vis diffuse reflectance spectroscopy for further characterisation, the ability of the composite to generate current following the removal of incident light was related to the trapping of photoexcited electrons by the WOx component. The presence of WOx yielded an order of magnitude increase in the transient photocurrent response relative to CdS alone, an effect attributed to the suppression of electron-hole recombination in CdS due to hole transfer across the CdS/WOx interface. Moreover, current discharge from the material persisted for more than twenty minutes after final illumination, an order of magnitude improvement over many existing binary composites. As a seminal investigation into the photocapacitive characteristics of CdS/WOx composites, the work offers insight into how the constituent materials might be utilised as part of a future self-charging solar device.

Vapor Phase Processing of α-Fe2O3 Photoelectrodes for Water Splitting: An Insight into the Structure/Property Interplay.

Harvesting radiant energy to trigger water photoelectrolysis and produce clean hydrogen is receiving increasing attention in the search of alternative energy resources. In this regard, hematite (α-Fe2O3) nanostructures with controlled nano-organization have been fabricated and investigated for use as anodes in photoelectrochemical (PEC) cells. The target systems have been grown on conductive substrates by plasma enhanced-chemical vapor deposition (PE-CVD) and subjected to eventual ex situ annealing in air to further tailor their structure and properties. A detailed multitechnique approach has enabled to elucidate the interrelations between system characteristics and the generated photocurrent. The present α-Fe2O3 systems are characterized by a high purity and hierarchical morphologies consisting of nanopyramids/organized dendrites, offering a high contact area with the electrolyte. PEC data reveal a dramatic response enhancement upon thermal treatment, related to a more efficient electron transfer. The reasons underlying such a phenomenon are elucidated and discussed by transient absorption spectroscopy (TAS) studies of photogenerated charge carrier kinetics, investigated on different time scales for the first time on PE-CVD Fe2O3 nanostructures.

On the effects of electric fields in aerosol assisted chemical vapour deposition reactions of vanadyl acetylacetonate solutions in ethanol.

Thin films of thermochromic vanadium dioxide have been deposited on glass substrates at 530 degrees C from the aerosol assisted chemical vapour deposition of vanadyl acetylacetonate solutions in ethanol under the influence of electric fields. Electric fields were generated by applying a potential difference between the top plate and the substrate of the reactor. The deposited films were analysed and characterised using scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy and variable temperature UV/Visible spectroscopy. The application of an electric field led to significant changes in the deposited films microstructure and functional properties. It was found that an increase in electric field strength caused a decrease in crystallite size and in an increase in the change in transmission in the near infrared when compared to films grown without the use of an electric field.

Electric fields in the chemical vapour deposition growth of vanadium dioxide thin films.

Thin films of thermochromic vanadium dioxide have been the subject of intensive research in recent years year due to their postulated use as "intelligent" window coatings. The usefulness of such technology depends on a semi-conducting to metal transition with an associated change in infra-red optical properties. This exact nature of this transition depends on a large number of factors such as doping, crystallite size, strain, crystallographic orientation etc. In this paper we discuss the nature of these factors with a particular focus on how the application of electric fields in the deposition affects crystallite size and film strain with reference to recent results.