Tungsten-Doped ZnO as an Electron Transport Layer for Perovskite Solar Cells: Enhancing Efficiency and Stability.

This study delves into enhancing the efficiency and stability of perovskite solar cells (PSCs) by optimizing the surface morphologies and optoelectronic properties of the electron transport layer (ETL) using tungsten (W) doping in zinc oxide (ZnO). Through a unique green synthesis process and spin-coating technique, W-doped ZnO films were prepared, exhibiting improved electrical conductivity and reduced interface defects between the ETL and perovskite layers, thus facilitating efficient electron transfer at the interface. High-quality PSCs with superior ETL demonstrated a substantial 30% increase in power conversion efficiency (PCE) compared to those employing pristine ZnO ETL. These solar cells retained over 70% of their initial PCE after 4000 h of moisture exposure, surpassing reference PSCs by 50% PCE over this period. Advanced numerical multiphysics solvers, employing finite-difference time-domain (FDTD) and finite element method (FEM) techniques, were utilized to elucidate the underlying optoelectrical characteristics of the PSCs, with simulated results corroborating experimental findings. The study concludes with a thorough discussion on charge transport and recombination mechanisms, providing insights into the enhanced performance and stability achieved through W-doped ZnO ETL optimization.

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.

Photoswitchable nonlinear optical properties of azobenzene-based supramolecular complexes: insights from density functional theory.

Density functional theory (DFT) calculations were performed for a series of supramolecular assemblies containing azobenzene (Azo-X where X = I, Br and H) and alkoxystilbazole subunits to evaluate their electronic, linear and nonlinear optical properties. These assemblies are derivatives of azobenzene, obtained by the substitution of electron-withdrawing and electron-donating groups onto the molecular skeleton. The interaction energies (Eint) of all the designed supramolecular complexes (IA-IF, IIA-IIF and IIIA-IIIF) range from -1.0 kcal mol-1 to -7.7 kcal mol-1. The electronic properties of these hydrogen/halogen bond driven supramolecular assemblies such as vertical ionization energies (VIE), HOMO-LUMO energy gap (GH-L), excitation energies, density of states (DOS) and natural population (NPA) analyses were also computed. The non-covalent interaction index (NCI) and quantum theory of atoms in molecules (QTAIM) analyses were also performed to validate the nature of inter- and intra-molecular interactions in these complexes. A substantial enhancement in the first hyperpolarizability (ß0) values of the designed supramolecular complexes was observed, which is driven by the charge transfer from the pyridyl moiety of alkoxystilbazole to Azo-X. The highest ß0 value of 1.3 × 104 au was observed for the supramolecular complex of p-nitro substituted azobenzene with alkoxystilbazole (ID complex). Moreover, the results show that the substitution of electron-withdrawing groups on Azo-X can also bring larger ß0 values for such complexes. It was confirmed on a purely theoretical basis that both the types of noncovalent interactions present and the substituent group incorporated influence the nonlinear optical (NLO) response of the systems. Furthermore, the ß0 values of the E (trans) and Z (cis) forms were compared to demonstrate the two-way photoinduced switching mechanism.

An integrated approach for the extraction of lipids from marine macroalgae consortium using RSM optimization and thermo-kinetic analysis.

This work presents an integrated approach for the extraction of lipids from marine macroalgae using RSM optimization and thermo-kinetic analysis. The lipids were extracted from marine macroalgal biomass using a Soxhlet extractor. The Soxhlet extraction parameters, including temperature (60-80 °C), solvent-to-algae ratio (3:1-7:1), algal particle size (0.05-0.25 mm), and extraction time (60-180 min), were optimized using RSM to achieve the maximum possible lipid extraction yield from marine macroalgae. The highest lipid extraction yield of 12.76% was obtained using the optimized conditions, which included an extraction temperature of 72 °C, a solvent-to-algae ratio of 5:1, an algal particle size of 0.16 mm, and an extraction time of 134 min. The kinetic analysis revealed an activation energy of 52.79 kJ mol-1 for the Soxhlet extraction process. The thermodynamic analysis of the Soxhlet extraction process demonstrated the following results: ΔH = 49.98 kJ mol-1, ΔS = -128.24 J K-1 mol-1, and ΔG = 93.98 kJ mol-1. The GC-MS analysis confirmed that the extracted algal lipids exhibited a composition of 14.20% palmitic acid, 4.89% stearic acid, and 76.97% oleic acid. The physiochemical analysis ensured that the extracted algal lipids possess excellent qualities, making them desirable for sustainable biofuel production.

Assessment of thermokinetic behaviour of tannery sludge in slow pyrolysis process through artificial neural network.

In the leather industry, tannery sludge is produced in large volume. This study investigated the thermal degradation behavior of tannery sludge using thermogravimetric analysis (TGA). The experiments were carried out in an inert atmosphere using nitrogen gas at varied heating rates of 5, 10, 20, and 40 °C/min in the temperature range of 30-900 °C. For the kinetic parameters calculation, three different models, Friedman, Kissinger-Akahira-Sunose (KAS) and the Ozawa-Flynn-Wall (OFW), were employed. The average activation energy (Ea) obtained from Friedman, KAS, and the OFW methods were 130.9 kJ mol-1, 143.14 kJ mol-1, and 147.19 kJ mol-1 respectively. Along with that, experiment of pyrolysis was accomplished in fixed bed reactor (FBR) at temperature of 400 °C. Biochar produced from FBR had a yield of about 71%. The analysis of gas chromatography-mass spectroscopy shows the different chemical compounds present in the bio-oil containing hydrocarbons (alkanes and alkenes), oxygen containing compounds (alcohols, aldehyde, ketones, esters carboxylic acids and the esters) and the nitrogen containing compounds. The kinetic assessment was complemented by distributed activation energy model (DAEM). In the pyrolysis of tannery sludge six pseudo-components were found to be involved. Furthermore, artificial neural network (ANN) was used to predict the activation energy from conversion, temperature, and the heating rate data. MLP-3-11-1 (Multilayer Perceptrons) described well the conversion behavior of tannery sludge pyrolysis.

Phytochemical-assisted green synthesis of CuFeOx nano-rose electrocatalysts for oxygen evolution reaction in alkaline media.

This study represents a green synthesis method for fabricating an oxygen evolution reaction (OER) electrode by depositing two-dimensional CuFeOx on nickel foam (NF). Two-dimensional CuFeOx was deposited on NF using in situ hydrothermal synthesis in the presence of Aloe vera extract. This phytochemical-assisted synthesis of CuFeOx resulted in a unique nano-rose-like morphology (petal diameter 30-70 nm), which significantly improved the electrochemical surface area of the electrode. The synthesized electrode was analyzed for its OER electrocatalytic activity and it was observed that using 75% Aloe vera extract in the phytochemical-assisted synthesis of CuFeOx resulted in improved OER electrocatalytic performance by attaining an overpotential of 310 mV for 50 mA cm-2 and 410 mV for 100 mA cm-2. The electrode also sustained robust stability throughout the 50 h of chronopotentiometry studies under alkaline electrolyte conditions, demonstrating its potential as an efficient OER electrode material. This study highlights the promising use of Aloe vera extract as a green and cost-effective way to synthesize efficient OER electrode materials.

Synthesis and performance evaluation of slow-release fertilizers produced from inverse vulcanized copolymers obtained from industrial waste.

To improve crop nutrient uptake efficacy (NUE) and better manage fertilization, slow-release fertilizers (SRFs) are developed by either coating the urea granules or making a composite. Several materials have already been developed, nevertheless, scalability of those materials is still a challenge due to their inherit drawbacks (such as hydrophilicity, crystallinity, non-biodegradability, etc.). Herein, we utilized a biodegradable, green and sustainable copolymer produced from industrial waste (sulfur-petroleum industry waste and myrcene-citrus industry waste) to coat the urea using a facile coating method to develop novel SRFs and achieve better agronomic and environmental advantages. The copolymer was first synthesized using a facile, solvent-free one-pot method called inverse vulcanization followed by Fourier transform infrared spectroscopy (FTIR) analysis to confirm the successful reaction between myrcene and sulfur subsequently coating the copolymer on urea granule. The morphology and coating thickness of coated fertilizers were analysed using scanning electron microscopy (SEM), followed by a nitrogen release test in distilled water and a soil burial test to confirm the biodegradability. The nitrogen release test revealed that the SRF with the maximum coating thickness of 1733 µm releases only 16% of its total nitrogen after 4 days of incubation compared to the pristine urea which releases all its nutrient within 1 day. The soil burial test confirms the biodegradability of the copolymer, as after 50 days of incubation in soil the copolymer loses almost 18.25% of its total weight indicating that the copolymer is degrading.

Algal-derived biochar as an efficient adsorbent for removal of Cr (VI) in textile industry wastewater: Non-linear isotherm, kinetics and ANN studies.

Textile industries release effluent that contains the vast majority of heavy metals in which Cr (VI) is a toxic carcinogenic element that causes an environmental problem. The aim of the work is to synthesize algae-derived biochar derived from algae using slow pyrolysis at an operating temperature of 500 °C, a heating rate of 10 °C/min and a residence time of 60 min and to use it as an adsorbent to remove Cr (VI). The batch experiment was carried out using different concentrations of Cr (VI) (1, 10, 25, 50, 100, 125, 150 and 200 ppm) at different intervals of time (2.5, 5, 10, 15, 30, 60, 120 and 240 min). The maximum removal percentage of Cr (VI) is 97.88% for the metal concentration of 1 ppm exhibiting non-linear adsorption isotherm (Langmuir, Freundlich, Dubinin-Radushkevich, and Temkin models) and kinetic models (pseudo-first order, pseudo-second order, nth order, and intra-particle diffusion) were analyzed using a solver add-in of Microsoft Excel. According to the results, the Langmuir isotherm model (R2 = 0.999) and pseudo-nth order models are suitable to describe monolayer adsorption and the process kinetics, respectively. The maximum adsorption capacity of algal biochar to adsorb is 186.94 mg/g. For the prediction of the optimal removal efficacy, an artificial neural network of the MLP-2-7-1 model was used. The results obtained are useful for future work using algal biochar as an adsorbent of Cr (VI) from textile wastewater to achieve sustainable development goals.

Re-Entrant Honeycomb Auxetic Structure with Enhanced Directional Properties.

This paper presents a modified re-entrant honeycomb auxetic structure. The structure is constructed by adding an additional horizontal member between the vertical and re-entrant member of the semi-re-entrant honeycomb model to increase the overall compliance of the structure in order to obtain higher values of negative Poisson's ratio (NPR). An analytical model of the structure is presented, taking into account the bending, shear, and axial deformations. The model is verified using finite element analysis (FEA) and tensile testing. The results of FEA and tensile testing corroborate the results of the presented mathematical model. The structure is also compared to the existing re-entrant honeycomb structure. The newly added strut has shown a direct effect on the directional properties of the overall structure. With an increase in the newly added strut to re-entrant lengths, NPR was significantly enhanced in the x-direction and reduced in the y-direction loadings. The structure shows an improved Young's modulus compared to solid material in both loading directions, especially for the low values of the new strut and re-entrant lengths ratio. The structure also shows that high NPR can be achieved for low relative density compared to semi re-entrant honeycomb structure.

Nanomaterials for biogas augmentation towards renewable and sustainable energy production: A critical review.

Nanotechnology is considered one of the most significant advancements in science and technology over the last few decades. However, the contemporary use of nanomaterials in bioenergy production is very deficient. This study evaluates the application of nanomaterials for biogas production from different kinds of waste. A state-of-the-art comprehensive review is carried out to elaborate on the deployment of different categories of nano-additives (metal oxides, zero-valent metals, various compounds, carbon-based nanomaterials, nano-composites, and nano-ash) in several kinds of biodegradable waste, including cattle manure, wastewater sludge, municipal solid waste, lake sediments, and sanitary landfills. This study discusses the pros and cons of nano-additives on biogas production from the anaerobic digestion process. Several all-inclusive tables are presented to appraise the literature on different nanomaterials used for biogas production from biomass. Future perspectives to increase biogas production via nano-additives are presented, and the conclusion is drawn on the productivity of biogas based on various nanomaterials. A qualitative review of relevant literature published in the last 50 years is conducted using the bibliometric technique for the first time in literature. About 14,000 research articles are included in this analysis, indexed on the Web of Science. The analysis revealed that the last decade (2010-20) was the golden era for biogas literature, as 84.4% of total publications were published in this timeline. Moreover, it was observed that nanomaterials had revolutionized the field of anaerobic digestion, methane production, and waste activated sludge; and are currently the central pivot of the research community. The toxicity of nanomaterials adversely affects anaerobic bacteria; therefore, using bioactive nanomaterials is emerging as the best alternative. Conducting optimization studies by varying substrate and nanomaterials' size, concentration and shape is still a field. Furthermore, collecting and disposing nanomaterials at the end of the anaerobic process is a critical environmental challenge to technology implementation that needs to be addressed before the nanomaterials assisted anaerobic process could pave its path to the large-scale industrial sector.

Recent progress in microalgae-derived biochar for the treatment of textile industry wastewater.

Textile industry utilize a massive amount of dyes for coloring. The dye-containing effluent is released into wastewater along with heavy metals that are part of dye structure. The treatment of textile industry wastewater using conventional techniques (coagulation, membrane technique, electrolysis ion exchange, etc.) is uneconomical and less efficient (for a low concentration of pollutants). Moreover, most of these techniques produce toxic sludge, making them less environmentally friendly. Algae base industry is growing for food, cosmetics and energy needs. Algae biomass in unique compared to lignocellulosic biomass due to presence of various functional group on its surface and presence of various cations. These two characteristics are unique for biochar as a tool for environmental decontamination. Algae biomass contain functional groups and cations that can be effective for removal of organic contaminants (dyes) and heavy metals. Algae can be micro and macro and both have entirely different biomass composition which will lead to a synthesis of different biochar even under same synthesis process. This study reviews the recent progress in the development of an economically viable and eco-friendly approach for textile industry wastewater using algae biomass-derived absorbents. The strategy employed microalgal biochar to remove organic pollutants (dyes) and heavy metals from textile effluents by biosorption. This article discusses different methods for preparing algal biochar (pyrolysis, hydrothermal carbonization and torrefaction), and the adsorption capacity of biochar for dyes and heavy metals. Work on hydrothermal carbonization and torrefaction of microalgal biomass for biochar is limited. Variation in structural and functional groups changes on biochar compared to original microalgal biomass are profound in contract with lignocellulosic biomass. Existing Challenges, future goals, and the development of these technologies at the pilot level are also discussed.

Sulfur enriched slow-release coated urea produced from inverse vulcanized copolymer.

Slow-release fertilizers are developed to enhance the nutrient use efficiency (NUE), by coating urea with less water soluble or hydrophobic material. Diverse range of materials have been utilized to coat urea, however, their inherit non-biodegradability, hydrophilicity, crystallinity, and high synthesis cost limits their scalability. Herein, we reported the preparation of a novel slow-release sulfur enriched urea fertilizers using sustainable hydrophobic, biodegradable, crosslinked copolymer made from sulfur and rubber seed oil (Poly(S-RSO)) through the use of dip coating method. Scanning electron microscopy (SEM) was employed to study the fertilizers morphology and estimate the coating film thickness. A nitrogen release test was carried out in distilled water, which revealed that the coated fertilizers with a coating thickness of 165 µm, 254 µm and 264 µm released only 65 % of its total nutrient content after 2, 19 and 43 days of incubation, respectively: hence, showing an excellent slow-release property. In soil, fertilizer with 264 µm coating thickness released only 17 % nitrogen after 20 days of incubation, in line with the European standard (EN 13266, 2001). The release kinetic data best fits the Ritger-Peppas model with a R2 value of 0.99 and the n value of 0.65 indicated the release was mainly due to diffusion. Submerged cultivation (SmC) demonstrated the potential of poly(S-RSO) to enhance sulfur oxidation; it was observed that the copolymer oxidation was 50 % greater than that of elemental sulfur. A comparison between the newly developed fertilizers and existing coated fertilizers was also presented. On the whole, the results demonstrated outstanding slow-release characteristics and improved sulfur oxidation.

Novel Wastewater Treatment by Using Newly Prepared Green Seaweed-Zeolite Nanocomposite.

A dependent step-by-step study that included experimental and field study was applied to explore the simplest and most effective system that could be applied for adsorption of Congo Red (CR) dye from the effluent of wastewater that comes out from different industries. Zeolite (Z) surface and pores were subjected to a modification process using green seaweed (GS) algae. Thereafter, each Z, GS, and composite from both were evaluated based on the adsorption efficacy to clean up CR dyes from aqueous solutions. A wet impregnation method was followed to fabricate the zeolite/algae (ZGS) nanocomposite which was characterized using the most appropriate characterization techniques. Batch experiments were selected to be the method of choice in order to follow up the performance of the adsorption process versus different practical variables. Moreover, dye adsorption kinetics and isotherms were investigated as well. At lowered concentrations of CR, the novel nanocomposite ZGS revealed more efficacy than its counterparts, Z and GS, in terms of the adsorption capacity. The maximum adsorption capacities were found to be 8.10, 10.30, and 19.70 mg/g for Z, GS, and ZGS, respectively. Laboratory tests confirmed that the novel nanocomposite ZGS could be introduced as a new and economical nanoadsorbent to capture and remove negatively charged dyes from wastewater effluents that come out from industries at lower concentrations of CR dye and analogous compounds. The dye adsorption on GS, Z, and ZGS coincide with the pseudo-first, Langmuir isotherm, and second-order models. Evaluation for the sorption mechanism was conducted using a diffusion model known as Weber's intraparticle. Depending on the last findings, field experiments on removing dyes from industrial wastewater revealed optimistic findings as the efficiency of our modern and eco-friendly nanoadsorbent reached 91.11%, which helps in the reuse of industrial wastewater.

Fabrication and Characterization of Steel-Base Metal Matrix Composites Reinforced by Yttria Nanoparticles through Friction Stir Processing.

Friction Stir Processing (FSP) was used to fabricate metal matrix composite, based on steel and reinforced with nano-sized yttrium oxide powder. The powder was packed in a narrow longitudinal groove of 2 mm depth and 1 mm width cut in the steel plate's rear surface. Different rotation speeds of 500-1500 rpm were used, at a fixed traveling speed of 50 mm·min-1. Single-pass and two passes, with the same conditions, were applied. The direction of the second pass was opposite to that of the first pass. After the first pass, complete nugget zones were obtained when the rotation speeds were more than 700 rpm with some particles agglomeration. The added particles showed as narrow elliptical bands, with a band pitch equal to the rotation speed over traveling speed. Performing the second FSP pass in the opposite direction resulted in better particles distributions. Almost defect-free composite materials, with homogenously distributed yttria nano-sized particles, were obtained after two passes when rotation speeds more than 700 rpm were used. The resulting steel matrix grains were refined from ~60 µm of the base metal to less than 3 µm of the processed nugget zone matrix. The hardness and the tensile strength of the fabricated materials improved almost two-fold over the base metal. Uniform microhardness values within the nugget areas were observed at higher rotational speeds. The ductility and toughness of the fabricated composites were reduced compared to the base metal.

Design, characterization, and adsorption properties of Padina gymnospora/zeolite nanocomposite for Congo red dye removal from wastewater.

A comprehensive study combined experimental, computational and field experiments was conducted to find out the most appropriate adsorbent system for industrial elimination of congo red (CR) dye from simulated industrial wastewater. Modification of the zeolite (Z) by the Padina gymnospora algae (PG) (Egyptian marine algae) was evaluated in terms of the adsorption capability of the zeolite (Z) to remove CR dye from aqueous solutions. The zeolite/algae composite (ZPG) was fabricated using the wet impregnation technique. Various techniques were used to characterize the PG, Z, and the produced ZPG nanocomposite. Batch experiments were performed to study the influence of various practical variables on adsorption processes. The isotherms and kinetics of dye adsorption were also studied. The newly synthesized ZPG nanocomposite exhibits much higher adsorption capacity, especially at low CR concentrations than that of Z. The computational calculations have shown that owing to the presence of intermolecular interactions, the adsorption of the CR molecule on zeolite surfaces is exothermic, energetically favorable, and spontaneous. For all configurations, increasing the zeolite size does not have a noticeable impact on the adsorption energies. The experimental results revealed that the ZPG nanocomposite can be applied as an economical nanoadsorbent to eliminate anionic dyes from simulated industrial wastewater at low CR dye concentrations. The adsorption isotherm of dye onto Z, PG, and ZPG almost agreed with Langmuir isotherm and pseudo-second-order kinetics. The sorption mechanism was also evaluated using Weber's intra-particle diffusion module. Finally, the field experiments revealed optimistic results for the newly synthesized adsorbent in removing dyes from industrial wastewater with 82.1% efficiency, which in turn confirmed the foundation of new eco-friendly materials that aid in the reuse of industrial wastewater.

Fabrication and Application of Zeolite/Acanthophora Spicifera Nanoporous Composite for Adsorption of Congo Red Dye from Wastewater.

Systematic investigations involving laboratory, analytical, and field trials were carried out to obtain the most efficient adsorbent for the removal of congo red (CR) dye from industrial effluent. Modification of the zeolite (Z) by the Acanthophora Spicifera algae (AS; marine algae) was evaluated in terms of adsorption capability of the zeolite to remove CR dye from aqueous solution. The zeolite/algae composite (ZAS) was fabricated using the wet impregnation technique. The AS, Z, and the synthesized ZAS composite were analyzed utilizing various characterization techniques. The newly synthesized ZAS composite has an adsorption capacity that is significantly higher than that of Z and AS, particularly at low CR concentrations. Batch experiments were carried out to explore the effects of different experimental factors, as well as the dye adsorption isotherms and kinetics. Owing to the presence of intermolecular interactions, the computational analysis showed that the adsorption of the CR molecule on zeolite surfaces is exothermic, energetically favorable, and spontaneous. Furthermore, growing the zeolite surface area has no discernible effect on the adsorption energies in all configurations. The ZAS composite may be used as a low-cost substitute adsorbent for the removal of anionic dyes from industrial wastewater at lower dye concentrations, according to the experimental results. Adsorption of CR dye onto Z, AS, and ZAS adsorbents was adequately explained by pseudo-second-order kinetics and the Langmuir isotherm. The sorption mechanism was also evaluated using Weber's intra-particle diffusion module. Finally, field testing revealed that the newly synthesized adsorbent was 98.0% efficient at extracting dyes from industrial wastewater, proving the foundation of modern eco-friendly materials that aid in the reuse of industrial wastewater.