Molecular and Heterojunction Device Engineering of Solution-Processed Conjugated Reticular Oligomers: Enhanced Photoelectrochemical Hydrogen Evolution through High-Effective Exciton Separation.

Covalent organic frameworks (COFs) face limited processability challenges as photoelectrodes in photoelectrochemical water reduction. Herein, sub-10 nm benzothiazole-based colloidal conjugated reticular oligomers (CROs) are synthesized using an aqueous nanoreactor approach, and the end-capping molecular strategy to engineer electron-deficient units onto the periphery of a CRO nanocrystalline lattices (named CROs-Cg). This results in stable and processable "electronic inks" for flexible photoelectrodes. CRO-BtzTp-Cg and CRO-TtzTp-Cg expand the absorption spectrum into the infrared region and improve fluorescence lifetimes. Heterojunction device engineering is used to develop interlayer heterojunction and bulk heterojunction (BHJ) photoelectrodes with a hole transport layer, electron transport layer, and the main active layers, using a CROs/CROs-Cg or one-dimensional (1D) electron-donating polymer HP18 mixed solution via spinning coating. The ITO/CuI/CRO-TtzTp-Cg-HP18/SnO2/Pt photoelectrode shows a photocurrent of 94.9 µA cm‒2 at 0.4 V versus reversible hydrogen electrode (RHE), which is 47.5 times higher than that of ITO/Bulk-TtzTp. Density functional theory calculations show reduced energy barriers for generating adsorbed H* intermediates and increased electron affinity in CROs-Cg. Mott-Schottky and charge density difference analyses indicate enhanced charge carrier densities and accelerated charge transfer kinetics in BHJ devices. This study lays the groundwork for large-scale production of COF nanomembranes and heterojunction structures, offering the potential for cost-effective, printable energy systems.

Nonsacrificial Nitrile Additive for Armoring High-Voltage LiNi0.83 Co0.07 Mn0.1 O2 Cathode with Reliable Electrode-Electrolyte Interface toward Durable Battery.

High-capacity Ni-rich layered oxides are considered as promising cathodes for lithium-ion batteries. However, the practical applications of LiNi0.83 Co0.07 Mn0.1 O2  (NCM83) cathode are challenged by continuous transition metal (TM) dissolution, microcracks and mixed arrangement of nickel and lithium sites, which are usually induced by deleterious cathode-electrolyte reactions. Herein, it is reported that those side reactions are limited by a reliable cathode electrolyte interface (CEI) layer formed by implanting a nonsacrificial nitrile additive. In this modified electrolyte, 1,3,6-Hexanetricarbonitrile (HTCN) plays a nonsacrificial role in modifying the composition, thickness, and formation mechanism of the CEI layers toward improved cycling stability. It is revealed that HTCN and 1,2-Bis(2-cyanoethoxy)ethane (DENE) are inclined to coordinate with the TM. HTCN can stably anchor on the NCM83 surface as a reliable CEI framework, in contrast, the prior decomposition of DENE additives will damage the CEI layer. As a result, the NCM83/graphite full cells with the LiPF6-EC/DEC-HTCN (BE-HTCN) electrolyte deliver a high capacity retention of 81.42% at 1 C after 300 cycles at a cutoff voltage of 4.5 V, whereas BE and BE-DENE electrolytes only deliver 64.01% and 60.05%. This nonsacrificial nitrile additive manipulation provides valuable guidance for developing aggressive high-capacity Ni-rich cathodes.

Modulating the Band Structure of Metal Coordinated Salen COFs and an In Situ Constructed Charge Transfer Heterostructure for Electrocatalysis Hydrogen Evolution.

A series of crystalline, stable Metal (Metal = Zn, Cu, Ni, Co, Fe, and Mn)-Salen covalent organic framework (COF)EDA complex are prepared to continuously tune the band structure of Metal-Salen COFEDA , with the purpose of optimizing the free energy intermediate species during the hydrogen evolution reaction (HER) process. The conductive macromolecular poly(3,4-ethylenedioxythiophene) (PEDOT) is subsequently integrated into the one-dimensional (1D) channel arrays of Metal-Salen COFEDA to form heterostructure PEDOT@Metal-Salen COFEDA via the in situ solid-state polymerization method. Among the Metal-Salen COFEDA and PEDOT@Metal-Salen COFEDA complexes, the optimized PEDOT@Mn-Salen COFEDA displays prominent electrochemical activity with an overpotential of 150 mV and a Tafel slope of 43 mV dec-1 . The experimental results and density of states data show that the continuous energy band structure modulation in Metal-Salen COFEDA has the ability to make the metal d-orbital interact better with the s-orbital of H, which is conducive to electron transport in the HER process. Moreover, the calculated charge density difference indicates that the heterostructures composed of PEDOT and Metal-Salen COFEDA induce an intramolecular charge transfer and construct highly active interfacial sites.

Addressing the water-energy nexus: A focus on the barriers and potentials of harnessing wastewater treatment processes for biogas production in Sub Saharan Africa.

Several anthropogenic activities reduce the supply of freshwater to living organisms in all ecological systems, particularly the human population. Organic matter in derived wastewater can be converted into potential energy, such as biogas (methane), through microbial transformation during anaerobic digestion (AD). To address the current lack of data and values for wastewater generation in Sub-Saharan Africa, this review analyzes and estimates (at 50% and 90% conversion rates) the potential amount of wastewater-related sludge that can be generated from domestic freshwater withdrawals using the most recent update in 2017 from the World Bank repository and database on freshwater status in Sub-Saharan Africa. The Democratic Republic of the Congo (DRC) could potentially produce the highest estimate of biogas in Sub-Saharan Africa from domestic wastewater sludge of approximately 90 billion m3, which could be converted to 178 million MWh of electricity annually, based on this extrapolation at 50% conversion rates. Using same conversion rates estimates, at least nine other countries, including Guinea, Liberia, Nigeria, Sierra Leone, Angola, Cameroon, Central African Republic, Gabon, and Congo Republic, could potentially produce biogas in the range of 1-20 billion m3. These estimates show how much energy could be extracted from wastewater treatment plants in Sub-Saharan Africa. AD process to produce biogas and energy harvesting are essential supplementary operations for Sub-Saharan African wastewater treatment plants. This approach could potentially solve the problem of data scarcity because these values for Freshwater withdrawals are readily available in the database could be used for estimation and projections towards infrastructure development and energy production planning. The review also highlights the possibilities for energy generation from wastewater treatment facilities towards wastewater management, clean energy, water, and sanitation sustainability, demonstrating the interconnections and actualization of the various related UN Sustainable Development Goals.

Adsorption of dibenzothiophene in model diesel fuel by amarula waste biomass as a low-cost adsorbent.

The effectiveness of the adsorption process is determined by the type of adsorbent used, but some adsorbents require a significant amount of processing to achieve the desired quality, and this has become a drawback economically and environmentally. This study focused on mitigating the issue of waste management and land pollution by using amarula waste biomass, which is a low-cost adsorbent that is obtained from the industrial waste by-product. The amarula shell (AmSh) waste was found to have a higher adsorption efficiency of 30 ± 3% compared to the amarula seed (AmSe) waste and the amarula fruit (AmWa) waste, which had 19 ± 5% and 9.5 ± 0.7% efficiency, respectively. It was found that the amarula waste biomass performed better at lower adsorption temperatures. The adsorption capacity was found to decrease with an increase in the quantity of the biomass. Kinetic models were applied to the experimental data. Thermodynamic parameters were also studied to determine the spontaneity of the adsorption process. The characteristics of both the fresh and used amarula waste biomass was analyzed by using Fourier Transform Infrared Spectroscopy (FTIR), Field Emission Scanning Electron Microscopy with Energy Dispersive Spectroscopy (FESEM-EDS), Brunauer-Emmett-Teller (BET) and Thermogravimetric Analysis (TGA). It was then concluded that cellulose and hemicellulose structures in amarula waste biomass played a major role in reducing the content of dibenzothiophene in model diesel fuel.

The simultaneous adsorption, activation and in situ reduction of carbon dioxide over Au-loading BiOCl with rich oxygen vacancies.

The main process of carbon dioxide (CO2) photoreduction is that excited electrons are transported to surface active sites to reduce adsorbed CO2 molecules. Obviously, electron transfer to the active site is one of the key steps in this process. However, current catalysts for CO2 adsorption, activation, and electron reduction occur in different locations, which greatly reduce the efficiency of photocatalysis. Herein, through a spontaneous chemical redox approach, the plasmonic photocatalysts of Au-BiOCl-OV with enhanced interfacial interaction were fabricated for visible light CO2 reduction through the simultaneous adsorption, activation and in situ reduction of CO2 without a sacrificial agent. By loading gold (Au) on the oxygen vacancy (OV), Au and BiOCl-OV formed a direct and tight interface contact, whose fine structure was confirmed by SEM, TEM, EPR and XPS, which not only effectively boosts the light utilization efficiency and the light carrier separation ability, but also can simultaneously adsorb, activate and in situ reduce carbon dioxide for highly efficient visible light photocatalysis. Thanks to the synergistic influence of Au and OV, Au-BiOCl-OV exhibits excellent photocatalytic performance without sacrificial agent and outstanding stability with a high CO and CH4 production yield, reaching 4.85 µmol g-1 h-1, which were 2.8 times higher than C-Au-BiOCl-OV (obtained by traditional NaBH4 reduction). This study proposes a new strategy for the production of high-performance collaborative catalysis in photocatalytic CO2 reduction.

Incorporation of solar-thermal energy into a gasification process to co-produce bio-fertilizer and power.

Biomass integrated gasification combined cycle (IGCC) is attracting increased interest because it can achieve high system energy efficiency (>50%), which is predicted to increase with the increase in the solar share in biomass IGCC. This study evaluated the potential of crop residues numerically for the co-production of power and bio-fertilizer using ASPEN Plus® simulation software. The results showed that the gas yield increases with increasing temperature and decreasing pressure while the yield of bio-fertilizer is dependent on the biomass composition. The biomass with a low ash content produces high bio-fertilizer at the designated gasification temperature. The IGCC configuration conserves more energy than a directly-fired biomass power plant. In addition, the solar-assisted IGCC attains a higher net electricity output per unit of crop residue feed and achieves net thermal efficiencies of around 53%. The use of such hybrid systems offer the potential to produce 0.55 MW of electricity per unit of solar-thermal energy at a relatively low cost. The ASPEN Plus model predicted that the solar biomass-based IGCC set up is more efficient in increasing the power generation capacity than any other conversion system. The results showed that a solar to electricity efficiency of approximately 55% is achievable with potential improvements. This work will contribute for the sustainable bioenergy production as the relationship between energy production and biomass supplies very important to ensure the food security and environmental sustainability.

Toward Respiratory Support of Critically Ill COVID-19 Patients Using Repurposed Kidney Hollow Fiber Membrane Dialysers to Oxygenate the Blood.

The COVID-19 pandemic has highlighted resource constraints in respiratory support. The oxygen transfer characteristics of a specific hollow fiber membrane dialyser was investigated with a view to repurposing the device as a low-cost, readily available blood oxygenator. Oxygen transfer in a low-flux hollow fiber dialyser with a polysulfone membrane was studied by passing first water and then blood through the dialyser in countercurrent to high-purity oxygen. Oxygen transfer rates of about 15% of the nominal 250 ml (STP)/min of a typical adult oxygen consumption rate were achieved for blood flow rates of 500 ml/min. Using two such dialysis devices in parallel could provide up to 30% of the nominal oxygen consumption. Specific hollow fiber dialysis devices operating with suitable pumps in a veno-venous access configuration could provide a cost-effective and readily available supplementation of respiratory support in the face of severe resource constraints.

Thermodynamic considerations in renal separation processes.

BACKGROUND: Urine production in the kidney is generally thought to be an energy-intensive process requiring large amounts of metabolic activity to power active transport mechanisms. This study uses a thermodynamic analysis to evaluate the minimum work requirements for urine production in the human kidney and provide a new perspective on the energy costs of urine production. In this study, black-box models are used to compare the Gibbs energy inflow and outflow of the overall kidney and physiologically-based subsections in the kidney, to calculate the work of separation for urine production. RESULTS: The results describe the work done during urine production broadly and for specific scenarios. Firstly, it shows glomerular filtration in both kidneys requires work to be done at a rate of 5 mW under typical conditions in the kidney. Thereafter, less than 54 mW is sufficient to concentrate the filtrate into urine, even in the extreme cases considered. We have also related separation work in the kidney with the excretion rates of individual substances, including sodium, potassium, urea and water. Lastly, the thermodynamic calculations indicate that plasma dilution significantly reduces the energy cost of separating urine from blood. CONCLUSIONS: A comparison of these thermodynamic results with physiological reference points, elucidates how various factors affect the energy cost of the process. Surprisingly little energy is required to produce human urine, seeing that double the amount of work can theoretically be done with all the energy provided through pressure drop of blood flow through the kidneys, while the metabolic energy consumption of the kidneys could possibly drive almost one hundred times more separation work. Nonetheless, the model's outputs, which are summarised graphically, show the separation work's nuances, which can be further analysed in the context of more empirical evidence.

Glomerular protein separation as a mechanism for powering renal concentrating processes.

Various models have been proposed to explain the urine concentrating mechanism in mammals, however uncertainty remains regarding the origin of the energy required for the production of concentrated urine. We propose a novel mechanism for concentrating urine. We postulate that the energy for the concentrating process is derived from the osmotic potentials generated by the separation of afferent blood into protein-rich efferent blood and protein-deplete filtrate. These two streams run in mutual juxtaposition along the length of the nephron and are thus suitably arranged to provide the osmotic potential to concentrate the urine. The proposed model is able to qualitatively explain the production of various urine concentrations under different clinical conditions. An approach to testing the feasibility of the hypothesis is proposed.