The recent developments of nanostructured WO3 thin films synthesized through the electrochemical route of electrochemical anodization and cathodic electrodeposition for the application in photoelectrochemical (PEC) water splitting are reviewed. The key fundamental reaction mechanisms of electrochemical anodization and cathodic electrodeposition methods for synthesizing nanostructured WO3 thin films are explained. In addition, the effects of metal oxide precursors, electrode substrates, applied potentials and current densities, and annealing temperatures on size, composition, and thickness of the electrochemically synthesized nanostructured WO3 thin films are elucidated in detail. Finally, a summary is given for the general evaluation practices used to calculate the energy conversion efficiency of nanostructured WO3 thin films and a recommendation is provided to standardize the presentation of research results in the field to allow for easy comparison of reported PEC efficiencies in the near future.
Impetus to minimise the energy and carbon footprints of evolving wastewater resource recovery facilities has promoted the development of microbial electrochemical systems (MES) as an emerging energy-neutral and sustainable platform technology. Using separators in dual-chamber MES to isolate anodic and cathodic environments creates endless opportunities for its myriad applications. Nevertheless, the high internal resistance and the complex interdependencies among various system factors have challenged its scale-up. This critical review employed a systems approach to examine the complex interdependencies and practical issues surrounding the implementation and scalability of dual-chamber MES, where the anodic and cathodic reactions are mutually appraised to improve the overall system efficiency. The robustness and stability of anodic biofilms in large-volume MES is dependent on its inoculum source, antecedent history and enrichment strategies. The composition and anode-respiring activity of these biofilms are modulated by the anolyte composition, while their performance demands a delicate balance between the electrode size, macrostructure and the availability of substrates, buffers and nutrients when using real wastewater as anolyte. Additionally, the catholyte governed the reduction environment and associated energy consumption of MES with scalable electrocatalysts needed to enhance the sluggish reaction kinetics for energy-efficient resource recovery. A comprehensive assessment of the dual-chamber reactor configuration revealed that the tubular, spiral-wound, or plug-in modular MES configurations are suitable for pilot-scale, where it could be designed more effectively using efficient electrode macrostructure, suitable membranes and bespoke strategies for continuous operation to maximise their performance. It is anticipated that the critical and analytical understanding gained through this review will support the continuous development and scaling-up of dual-chamber MES for prospective energy-neutral treatment of wastewater and simultaneous circular management of highly relevant environmental resources.
Microbial fuel cells (MFC) are emerging energy-efficient systems for copper (Cu) electrowinning from waste streams by coupling it with anodic oxidation of organics in wastewater. However, there is a lack of research examining scalable electrocatalysts for Cu electrowinning at low cathodic overpotentials in highly saline catholytes often found in e-waste leachates. The challenge of developing resilient anodic biofilms that withstand the antagonistic effects of ions migrating from catholytes in saline MFC also needs to be addressed. In this study, polypyrrole (PPy) cathodic electrocatalysts were developed and coupled with a robust halophilic anodic biofilm in MFC to improve the kinetics of Cu electrowinning from acidic chloride-based catholytes. Electrochemical characterisation of these cathodes revealed shuttling of electrons by redox-active PPy via the formation of intermediate Cu+-complexes as an energy-efficient pathway for producing metallic Cu. High power densities ranging from 0.63 ± 0.17 to 0.73 ± 0.05 W m-2 were achieved with undoped-PPy and phytic acid doped-PPy cathodes with simultaneous recovery of ∼97% Cu. These electrocatalysts also exhibited low charge transfer resistance (3-8 mΩ m2) that met the requisites for scalable cathodes in MFC. However, a decrease in the efficiency of PPy cathodes was observed over 5 d due to competing reactions at their interfaces, including re-oxidation of deposited Cu and cathodic corrosion, with further studies suggested to enhance their corrosion resistance. Nonetheless, integrating PPy electrocatalysts for Cu electrowinning in saline MFC has advanced its outlooks as an energy-efficient downstream process for urban mining of Cu from e-waste.
Polyelectrolyte-complex bilayer membrane (PCBM) was fabricated using biodegradable chitosan and alginate polymers for subsequent application in the treatment of bathroom greywater. In this study, the properties of PCBMs were studied and it was found that the formation of polyelectrolyte network reduced the molecular weight cut-off (MWCO) from 242kDa in chitosan membrane to 2.71kDa in PCBM. The decrease in MWCO of PCBM results in better greywater treatment efficiency, subsequently demonstrated in a greywater filtration study where treated greywater effluent met the household reclaimed water standard of <2 NTU turbidity and <30ppm total suspended solids (TSS). In addition, a further 20% improvement in chemical oxygen demand (COD) removal was achieved as compared to a single layer chitosan membrane. Results from this study show that the biodegradable PCBM is a potential membrane material in producing clean treated greywater for non-potable applications.
While bulk zinc oxide (ZnO) is of non-toxic in nature, ZnO nanoarchitectures could potentially induce the macroscopic characteristics of oxidative, lethality and toxicity in the water environment. Here we report a systematic study through state-of-the-art controllable synthesis of multi-dimensional ZnO nanoarchitectures (i.e. 0D-nanoparticle, 1D-nanorod, 2D-nanosheet, and 3D-nanoflowers), and subsequent in-depth understanding on the fundamental factor that determines their photoactivities. The photoactivities of resultant ZnO nanoarchitectures were interpreted in terms of the photodegradation of salicylic acid as well as inactivation of Bacillus subtilis and Escherichia coli under UV-A irradiation. Photodegradation results showed that 1D-ZnO nanorods demonstrated the highest salicylic acid photodegradation efficiency (99.4%) with a rate constant of 0.0364 min-1. 1D-ZnO nanorods also exhibited the highest log reductions of B. subtilis and E. coli of 3.5 and 4.2, respectively. Through physicochemical properties standardisation, an intermittent higher k value for pore diameter (0.00097 min-1 per mm), the highest k values for crystallite size (0.00171 min-1 per nm) and specific surface area (0.00339 min-1 per m2/g) contributed to the exceptional photodegradation performance of nanorods. Whereas, the average normalised log reduction against the physicochemical properties of nanorods (i.e. low crystallite size, high specific surface area and pore diameter) caused the strongest bactericidal effect.
E-waste, or waste generated from electrical and electronic equipment, is considered as one of the fastest-growing waste categories, growing at a rate of 3-5% per year in the world. In 2016, 44.7 million tonnes of e-waste were generated in the world, which is equivalent to 6.1 kg for each person. E-waste is classified as a hazardous waste, but unlike other categories, e-waste also has significant potential for value recovery. As a result it is traded significantly between the developed and developing world, both as waste for disposal and as a resource for metal recovery. Only 20% of global e-waste in 2016 was properly recycled or disposed of, with the fate of the remaining 80% undocumented - likely to be dumped, traded or recycled under inferior conditions. This review paper provides an overview of the global e-waste resource and identifies the major challenges in the sector in terms of generation, global trade and waste management strategies. It lists the specific hazards associated with this type of waste that need to be taken into account in its management and includes a detailed overview of technologies employed or proposed for the recovery of value from e-waste. On the basis of this overview the paper identifies future directions for effective e-waste processing towards sustainable waste/resource management. It becomes clear that there is a strong divide between developed and developing countries with regard to this sector. While value recovery is practiced in centralised facilities employing advanced technologies in a highly regulated industrial environment in the developed world, in the developing world such recovery is practiced in a largely unregulated artisanal industry employing simplistic, labour intensive and environmentally hazardous approaches. Thus value is generated safely in the hi-tech environment of the developed world, whereas environmental burdens associated with exported waste and residual waste from simplistic processing remain largely in developing countries. It is argued that given the breadth of available technologies, a more systematic evaluation of the entire e-waste value chain needs to be conducted with a view to establishing integrated management of this resource (in terms of well-regulated value recovery and final residue disposal) at the appropriately local rather than global scale.
This study aimed to evaluate the impacts of morphological-controlled ZnO nanoarchitectures on aerobic microbial communities during real wastewater treatment in an aerobic-photocatalytic system. Results showed that the antibacterial properties of ZnO nanoarchitectures were significantly more overwhelming than their photocatalytic properties. The inhibition of microbial activities in activated sludge by ZnO nanoarchitectures entailed an adverse effect on wastewater treatment efficiency. Subsequently, the 16S sequencing analysis were conducted to examine the impacts of ZnO nanoarchitectures on aerobic microbial communities, and found the significantly lower microbial diversity and species richness in activated sludge treated with 1D-ZnO nanorods as compared to other ZnO nanoarchitectures. Additionally, 1D-ZnO nanorods reduced the highest proportion of Proteobacteria phylum in activated sludge due to its higher proportion of active polar surfaces that facilitates Zn2+ ions dissolution. Pearson correlation coefficients showed that the experimental data obtained from COD removal efficiency and bacterial log reduction were statistically significant (p-value
Carbon capture and storage (CCS) via microalgae cultivations is getting renewed interest as climate change mitigation effort, owing to its excellent photosynthetic and CO2 fixation capability. Microalgae growth is monitored based on their biomass, cell concentrations and cell sizes. The key parametric relationships on microalgae growth under CO2 are absent in previous studies and this inadequacy hampers the design and scale-up of microalgae-based CCS. In this study, three representative microalgae species, Chlorella, Nostoc and Chlamydomonas, were investigated for establishing key correlations of cell concentrations and sizes towards their biomass fluctuations under CO2 influences of 0% to 20% volume ratios (v/v). This revealed that Chlorella and Chlamydomonas cell concentrations significantly contributed towards increasing biomass concentration under CO2 elevations. Chlorella and Nostoc cell sizes were enhanced at 20% (v/v). These findings provided new perspectives on growth responses under increasing CO2 treatment, opening new avenues on CCS schemes engineering designs and biochemical production.
Microalgae's exceptional photosynthetic prowess, CO2 adaptation, and high-value bioproduct accumulation make them prime candidates for microorganism-based biorefineries. However, most microalgae research emphasizes downstream processes and applications rather than fundamental biomass and biochemical balances and kinetic under the influence of greenhouse gases such as CO2. Therefore, three distinctly different microalgae species were cultivated under 0% to 20% CO2 treatments to examine their biochemical responses, biomass production and metabolite accumulations. Using a machine learning approach, it was found that Chlorella sorokiniana showed a positive relationship between biomass and chl a, chl b, carotenoids, and carbohydrates under increasing CO2 treatments, while Chlamydomonas angulosa too displayed positive relationships between biomass and all studied biochemical contents, with minimal trade-offs. Meanwhile, Nostoc sp. exhibited a negative correlation between biomass and lipid contents under increasing CO2 treatment. The study showed the potential of Chlorella, Chlamydomonas and Nostoc for commercialization in biorefineries and carbon capture systems where their trade-offs were identified for different CO2 treatments and could be prioritized based on commercial objectives. This study highlighted the importance of understanding trade-offs between biomass production and biochemical yields for informed decision-making in microalgae cultivation, in the direction of mass carbon capture for climate change mitigation.
Density functional theory was used to investigate the effects of doping alkaline earth metal atoms (beryllium, magnesium, calcium and strontium) on graphene. Electron transfer from the dopant atom to the graphene substrate was observed and was further probed by a combined electron localization function/non-covalent interaction (ELF/NCI) approach. This approach demonstrates that predominantly ionic bonding occurs between the alkaline earth dopants and the substrate, with beryllium doping having a variant characteristic as a consequence of electronegativity equalization attributed to its lower atomic number relative to carbon. The ionic bonding induces spin-polarized electronic structures and lower workfunctions for Mg-, Ca-, and Sr-doped graphene systems as compared to the pristine graphene. However, due to its variant bonding characteristic, Be-doped graphene exhibits non-spin-polarized p-type semiconductor behavior, which is consistent with previous works, and an increase in workfunction relative to pristine graphene. Dirac half-metal-like behavior was predicted for magnesium doped graphene while calcium doped and strontium doped graphene were predicted to have bipolar magnetic semiconductor behavior. These changes in the electronic and magnetic properties of alkaline earth doped graphene may be of importance for spintronic and other electronic device applications.