Transition Metals-Based Water Splitting Electrocatalysts on Copper-Based Substrates: The Integral Role of Morphological Properties.

Electrocatalytic water splitting is a promising alternative to produce high purity hydrogen gas as the green substitute for renewable energy. Thus, development of electrocatalysts for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) are vital to improve the efficiency of the water splitting process particularly based on transition metals which has been explored extensively to replace the highly active electrocatalytic activity of the iridium and ruthenium metals-based electrocatalysts. In situ growth of the material on a conductive substrate has also been proven to have the capability to lower down the overpotential value significantly. On top of that, the presence of substrate has given a massive impact on the morphology of the electrocatalyst. Among the conductive substrates that have been widely explored in the field of electrochemistry are the copper based substrates mainly copper foam, copper foil and copper mesh. Copper-based substrates possess unique properties such as low in cost, high tensile strength, excellent conductor of heat and electricity, ultraporous with well-integrated hierarchical structure and non-corrosive in nature. In this review, the recent advancements of HER and OER electrocatalysts grown on copper-based substrates has been critically discussed, focusing on their morphology, design, and preparation methods of the nanoarrays.

Synergistic Effect of Allium-like Ni9 S8 & Cu7 S4 Electrodeposited on Nickel Foam for Enhanced Water Splitting Activity.

This study explores a water-splitting activity using a biphasic electrodeposited electrode on nickel foam (NF). The *Ni9 S8 /Cu7 S4 /NF electrode with citric acid reduction exhibits superior OER (oxygen evolution reaction) and HER (hydrogen evolution reaction) performance with reduced overpotential and a steeper Tafel slope. The *Ni9 S8 /Cu7 S4 /NF electrode displays the ultra-low overpotential value of 212 mV for OER and 109 mV for HER at the current density of 10 mA cm-2 . The Tafel slope of 25.4 mV dec-1 for OER and 108 mV dec-1 for HER was found from that electrode. The maximum electrochemical surface area (ECSA), lowest series resistance and lowest charge transfer resistance are found in citric acid reduced electrode, showing increased electrical conductivity and quick charge transfer kinetics. Remarkably, the *Ni9 S8 /Cu7 S4 /NF electrode demonstrated excellent stability for 80 hours in pure water splitting and 20 hours in seawater splitting. The synergistic effect of using bimetallic (Cu&Ni) sulfide and enhanced electrical conductivity of the electrode are caused by reduction of metal sulfide into metallic species resulting in improved water splitting performance.

Metal organic framework derived NiO x nanoparticles for application as a hole transport layer in perovskite solar cells.

NiO x as a hole transport layer (HTL) has gained a lot of research interest in perovskite solar cells (PSCs), owing to its high optical transmittance, high power conversion efficiency, wide band-gap and ease of fabrication. In this work, four different nickel based-metal organic frameworks (MOFs) using 1,3,5-benzenetricarboxylic acid (BTC), terephthalic acid (TPA), 2-aminoterephthalic acid (ATPA), and 2,5-dihydroxyterephthalic acid (DHTPA) ligands respectively, have been employed as precursors to synthesize NiO x NPs. The employment of different ligands was found to result in NiO x NPs with different structural, optical and morphological properties. The impact of calcination temperatures of the MOFs was also studied and according to field emission scanning electron microscopy (FESEM), all MOF-derived NiO x NPs exhibited lower particle size at lower calcination temperature. Upon optimization, Ni-TPA MOF derived NiO x NPs calcined at 600 °C were identified to be the best for hole transport layer application. To explore the photovoltaic performance, these NiO x NPs have been fabricated as a thin film and its structural, optical and electrical characteristics were analyzed. According to the findings, the band energy gap (E g) of the fabricated thin film has been found to be 3.25 eV and the carrier concentration, hole mobility and resistivity were also measured to be 6.8 × 1014 cm-3; 4.7 × 1014 Ω cm and 2.0 cm2 V-1 s-1, respectively. Finally, a numerical simulation was conducted using SCAPS-1D incorporating the optical and electrical parameters from the thin film analysis. FTO/TiO2/CsPbBr3/NiO x /C has been utilized as the device configuration which recorded an efficiency of 13.9% with V oc of 1.89 V, J sc of 11.07 mA cm-2, and FF of 66.6%.

Metal-Organic Framework-Based Composites for the Detection and Monitoring of Pharmaceutical Compounds in Biological and Environmental Matrices.

The production of synthetic drugs is considered a huge milestone in the healthcare sector, transforming the overall health, aging, and lifestyle of the general population. Due to the surge in production and consumption, pharmaceutical drugs have emerged as potential environmental pollutants that are toxic with low biodegradability. Traditional chromatographic techniques in practice are time-consuming and expensive, despite good precision. Alternatively, electroanalytical techniques are recently identified to be selective, rapid, sensitive, and easier for drug detection. Metal-organic frameworks (MOFs) are known for their intrinsic porous nature, high surface area, and diversity in structural design that provides credible drug-sensing capacities. Long-term reusability and maintaining chemo-structural integrity are major challenges that are countered by ligand-metal combinations, optimization of synthetic conditions, functionalization, and direct MOFs growth over the electrode surface. Moreover, chemical instability and lower conductivities limited the mass commercialization of MOF-based materials in the fields of biosensing, imaging, drug release, therapeutics, and clinical diagnostics. This review is dedicated to analyzing the various combinations of MOFs used for electrochemical detection of pharmaceutical drugs, comprising antibiotics, analgesics, anticancer, antituberculosis, and veterinary drugs. Furthermore, the relationship between the composition, morphology and structural properties of MOFs with their detection capabilities for each drug species is elucidated.

Investigation of Morphological, Optical, and Dielectric Properties of RF Sputtered WOx Thin Films for Optoelectronic Applications.

Tungsten oxide (WOx) thin films were synthesized through the RF magnetron sputtering method by varying the sputtering power from 30 W to 80 W. Different investigations have been conducted to evaluate the variation in different morphological, optical, and dielectric properties with the sputtering power and prove the possibility of using WOx in optoelectronic applications. An Energy Dispersive X-ray (EDX), stylus profilometer, and atomic force microscope (AFM) have been used to investigate the dependency of morphological properties on sputtering power. Transmittance, absorbance, and reflectance of the films, investigated by Ultraviolet-Visible (UV-Vis) spectroscopy, have allowed for further determination of some necessary parameters, such as absorption coefficient, penetration depth, optical band energy gap, refractive index, extinction coefficient, dielectric parameters, a few types of loss parameters, etc. Variations in these parameters with the incident light spectrum have been closely analyzed. Some important parameters such as transmittance (above 80%), optical band energy gap (~3.7 eV), and refractive index (~2) ensure that as-grown WOx films can be used in some optoelectronic applications, mainly in photovoltaic research. Furthermore, strong dependencies of all evaluated parameters on the sputtering power were found, which are to be of great use for developing the films with the required properties.

Effect of Calcination Temperature on Structural, Morphological and Optical Properties of Copper Oxide Nanostructures Derived from Garcinia mangostana L. Leaf Extract.

Synthesis of copper oxide (CuO) nanostructures via biological approach has gained attention to reduce the harmful effects of chemical synthesis. The CuO nanostructures were synthesized through a green approach using the Garcinia mangostana L. leaf extract and copper (II) nitrate trihydrate as a precursor at varying calcination temperatures (200-600 °C). The effect of calcination temperatures on the structural, morphological and optical properties of CuO nanostructures was studied. The red shifting of the green-synthesized CuO nanoparticles' absorption peak was observed in UV-visible spectrum, and the optical energy bandgap was found to decrease from 3.41 eV to 3.19 eV as the calcination temperatures increased. The PL analysis shown that synthesized CuO NPs calcinated at 500 °C has the maximum charge carriers separation. A peak located at 504-536 cm-1 was shown in FTIR spectrum that indicated the presence of a copper-oxygen vibration band and become sharper and more intense when increasing the calcination temperature. The XRD studies revealed that the CuO nanoparticles' crystalline size was found to increase from 12.78 nm to 28.17 nm, and dislocation density decreased from 61.26 × 1014 cm-1 to 12.60 × 1014 cm-1, while micro strain decreased from 3.40 × 10-4 to 1.26 × 10-4. From the XPS measurement, only CuO single phase without impurities was detected for the green-mediated NPs calcinated at 500 °C. The morphologies of CuO nanostructures were examined using FESEM and became more spherical in shape at elevated calcination temperature. More or less spherical nanostructure of green-mediated CuO calcinated at 500 °C were also observed using TEM. The purity of the green-synthesized CuO nanoparticles was evaluated by EDX analysis, and results showed that increasing calcination temperature increases the purity of CuO nanoparticles.

Transformation of Oil Palm Waste-Derived Cellulose into Solid Polymer Electrolytes: Investigating the Crucial Role of Plasticizers.

This study explores the possibility of transforming lignocellulose-rich agricultural waste materials into value-added products. Cellulose was extracted from an empty fruit bunch of oil palm and further modified into carboxymethyl cellulose (CMC), a water-soluble cellulose derivative. The CMC was then employed as the polymeric content in fabrication of solid polymer electrolyte (SPE) films incorporated with lithium iodide. To enhance the ionic conductivity of the solid polymer electrolytes, the compositions were optimized with different amounts of glycerol as a plasticizing agent. The chemical and physical effects of plasticizer content on the film composition were studied by Fourier transform infrared (FTIR) and X-ray diffraction (XRD) analysis. FTIR and XRD analysis confirmed the interaction plasticizer with the polymer matrix and the amorphous nature of fabricated SPEs. The highest ionic conductivity of 6.26 × 10-2 S/cm was obtained with the addition of 25 wt % of glycerol. By fabricating solid polymer electrolytes from oil palm waste-derived cellulose, the sustainability of the materials can be retained while reducing the dependence on fossil fuel-derived materials in electrochemical devices.

Muntingia calabura Leaves Mediated Green Synthesis of CuO Nanorods: Exploiting Phytochemicals for Unique Morphology.

In this study, phytochemical assisted nanoparticle synthesis was performed using Muntingia calabura leaf extracts to produce copper oxide nanoparticles (CuO NPs) with interesting morphology. Scanning electron microscope (SEM) and transmission electron microscope (TEM) analysis of the biosynthesized CuO NPs reveal formation of distinct, homogeneous, and uniform sized CuO nanorods structure with thickness and length of around 23 nm and 79 nm, respectively. Based on Fourier-transform infrared (FTIR) analysis, the unique combinations of secondary metabolites such as flavonoid and polyphenols in the plant extract are deduced to be effective capping agents to produce nanoparticles with unique morphologies similar to conventional chemical synthesis. X-ray diffraction (XRD) analysis verified the monoclinical, crystalline structure of the CuO NPs. The phase purity and chemical identity of the product was consolidated via X-Ray photoelectron spectroscopy (XPS) and Raman spectroscopic data which indicate the formation of a single phase CuO without the presence of other impurities. The direct and indirect optical band gap energies of the CuO nanorods were recorded to be 3.65 eV and 1.42 eV.

Recovery of FTO coated glass substrate via environment-friendly facile recycling perovskite solar cells.

Organic-inorganic perovskite solar cells (PSCs) have recently emerged as a potential candidate for large-scale and low-cost photovoltaic devices. However, the technology is still susceptible to degradation issues and toxicity concerns due to the presence of lead (Pb). Therefore, investigation on ideal methods to deal with PSC wastes once the device attains its end-of-life is crucial and to recycle the components within the cell is the most cost effective and energy effective method by far. This paper reported on a layer-by-layer extraction approach to recycle the fluorine-doped tin oxide (FTO) coated glass substrate which is the most expensive component in the device architecture of mesoporous planar PSC. By adapting the sequential removal of each layer, chemical properties of individual components, including spiro-OMeTAD and gold can be preserved, enabling the material to be easily reused. It also ensured that the toxic Pb component could be isolated without contaminating other materials. The removal of all individual layers allows the retrieval of FTO conductive glass which can be used in various applications that are not only restricted to photovoltaics. Comparison of electrical, morphological and physical properties of recycled FTO glasses to commercial ones revealed minimal variations. This confirmed that the recycling approach was useful in retrieving the substrate without affecting its physicochemical properties.

Current trends and prospects of tidal energy technology.

Generation of energy across the world is today reliant majorly on fossil fuels. The burning of these fuels is growing in line with the increase in the demand for energy globally. Consequently, climate change, air contamination, and energy security issues are rising as well. An efficient alternative to this grave hazard is the speedy substitution of fossil fuel-based carbon energy sources with the shift to clean sources of renewable energy that cause zero emissions. This needs to happen in conjunction with the continuing increase in the overall consumption of energy worldwide. Many resources of renewable energy are available. These include thermal, solar photovoltaic, biomass and wind, tidal energy, hydropower, and geothermal. Notably, tidal energy exhibits great potential with regard to its dependability, superior energy density, certainty, and durability. The energy mined from the tides on the basis of steady and anticipated vertical movements of the water, causing tidal currents, could be converted into kinetic energy to produce electricity. Tidal barrages could channel mechanical energy, while tidewater river turbines can seize the energy from tidal currents. This study discusses the present trends, ecological effects, and the prospects for technology related to tidal energy.

Resorcinol-Formaldehyde (RF) as a Novel Plasticizer for Starch-Based Solid Biopolymer Electrolyte.

A starch-resorcinol-formaldehyde (RF)-lithium triflate (LiTf) based biodegradable polymer electrolyte membrane was synthesized via the solution casting technique. The formation of RF crosslinks in the starch matrix was found to repress the starch's crystallinity as indicated by the XRD data. Incorporation of the RF plasticizer improved the conductivity greatly, with the highest room-temperature conductivity recorded being 4.29 × 10-4 S cm-1 achieved by the starch:LiTf:RF (20 wt.%:20 wt.%:60 wt.%) composition. The enhancement in ionic conductivity was an implication of the increase in the polymeric amorphous region concurrent with the suppression of the starch's crystallinity. Chemical complexation between the plasticizer, starch, and lithium salt components in the electrolyte was confirmed by FTIR spectra.

Organosoluble Starch-Cellulose Binary Polymer Blend as a Quasi-Solid Electrolyte in a Dye-Sensitized Solar Cell.

This work is a pioneer attempt to fabricate quasi-solid dye-sensitized solar cell (QSDDSC) based on organosoluble starch derivative. Rheological characterizations of the PhSt-HEC blend based gels exhibited viscoelastic properties favorable for electrolyte fabrication. From amplitude sweep and tack test analyses, it was evident that the inclusion of LiI improved the rigidity and tack property of the gels. On the other hand, the opposite was true for TPAI based gels, which resulted in less rigid and tacky electrolytes. The crystallinity of the gels was found to decline with increasing amount of salt in both systems. The highest photoconversion efficiency of 3.94% was recorded upon addition of 12.5 wt % TPAI and this value is one of the highest DSSC performance recorded for starch based electrolytes. From electrochemical impedance spectroscopy (EIS), it is deduced that the steric hindrance imposed by bulky cations aids in hindering recombination between photoanode and electrolyte.

Ternary natural deep eutectic solvent (NADES) infused phthaloyl starch as cost efficient quasi-solid gel polymer electrolyte.

A first-of-its-kind, eco-friendly quasi-solid bioelectrolyte derived from potato starch was prepared. Starch was chemically modified via phthaloylation to synthesize amorphous, hydrophobic starch derivative and the attachment of the phthaloyl group was confirmed via FTIR which showed phthalate ester peak at 1715cm-1; and 1H NMR peaks between 7.30-7.90ppm attributed to the aromatic protons of the phthaloyl group. The resulting starch derivative was then infused with ternary natural deep eutectic solvent (NADES) made from different molar ratios of choline chloride, urea and glycerol. Electrochemical Impedance Spectroscopy (EIS) revealed that the highest ionic conductivity was obtained by the system consisting of NADES with choline chloride:urea:glycerol in molar ratios of 4:6:2, with a magnitude of 2.86mScm-1, hence validating the prospects of the materials to be further experimented as an alternative electrolyte in various electrochemical devices.

pH Sensitive Hydrogels in Drug Delivery: Brief History, Properties, Swelling, and Release Mechanism, Material Selection and Applications.

Improving the safety efficacy ratio of existing drugs is a current challenge to be addressed rather than the development of novel drugs which involve much expense and time. The efficacy of drugs is affected by a number of factors such as their low aqueous solubility, unequal absorption along the gastrointestinal (GI) tract, risk of degradation in the acidic milieu of the stomach, low permeation of the drugs in the upper GI tract, systematic side effects, etc. This review aims to enlighten readers on the role of pH sensitive hydrogels in drug delivery, their mechanism of action, swelling, and drug release as a function of pH change along the GI tract. The basis for the selection of materials, their structural features, physical and chemical properties, the presence of ionic pendant groups, and the influence of their pKa and pKb values on the ionization, consequent swelling, and targeted drug release are also highlighted.

Erratum: pH Sensitive Hydrogels in Drug Delivery: Brief History, Properties, Swelling, and Release Mechanism, Material Selection and Applications. Polymers 2017, 9, 137.

The authors wish to make a change to their published paper [1]. [...].

Artificial Neural Network and Response Surface Methodology Modeling in Ionic Conductivity Predictions of Phthaloylchitosan-Based Gel Polymer Electrolyte.

A gel polymer electrolyte system based on phthaloylchitosan was prepared. The effects of process variables, such as lithium iodide, caesium iodide, and 1-butyl-3-methylimidazolium iodide were investigated using a distance-based ternary mixture experimental design. A comparative approach was made between response surface methodology (RSM) and artificial neural network (ANN) to predict the ionic conductivity. The predictive capabilities of the two methodologies were compared in terms of coefficient of determination R² based on the validation data set. It was shown that the developed ANN model had better predictive outcome as compared to the RSM model.