Recent developments, advances and strategies in heterogeneous photocatalysts for water splitting.

Photocatalytic water splitting (PWS) is an up-and-coming technology for generating sustainable fuel using light energy. Significant progress has been made in the developing of PWS innovations over recent years. In addition to various water-splitting (WS) systems, the focus has primarily been on one- and two-steps-excitation WS systems. These systems utilize singular or composite photocatalysts for WS, which is a simple, feasible, and cost-effective method for efficiently converting prevalent green energy into sustainable H2 energy on a large commercial scale. The proposed principle of charge confinement and transformation should be implemented dynamically by conjugating and stimulating the photocatalytic process while ensuring no unintentional connection at the interface. This study focuses on overall water splitting (OWS) using one/two-steps excitation and various techniques. It also discusses the current advancements in the development of new light-absorbing materials and provides perspectives and approaches for isolating photoinduced charges. This article explores multiple aspects of advancement, encompassing both chemical and physical changes, environmental factors, different photocatalyst types, and distinct parameters affecting PWS. Significant factors for achieving an efficient photocatalytic process under detrimental conditions, (e.g., strong light absorption, and synthesis of structures with a nanometer scale. Future research will focus on developing novel materials, investigating potential synthesis techniques, and improving existing high-energy raw materials. The endeavors aim is to enhance the efficiency of energy conversion, the absorption of radiation, and the coherence of physiochemical processes.

Comprehensive Investigation of Cu2+ Adsorption from Wastewater Using Olive-Waste-Derived Adsorbents: Experimental and Molecular Insights.

This study investigates the efficacy of adsorbents from locally sourced olive waste-encompassing olive skins, leaves, and pits, recovered from the initial centrifugation of olives (OWP)-and a composite with sodium alginate (OWPSA) for the removal of Cu2+ ions from synthetic wastewater. Experimental analyses conducted at room temperature, with an initial Cu2+ concentration of 50 mg/L and a solid/liquid ratio of 1 g/L, showed that the removal efficiencies were approximately 79.54% and 94.54% for OWP and OWPSA, respectively, highlighting the positive impact of alginate on adsorption capacity. Utilizing statistical physics isotherm models, particularly the single-layer model coupled to real gas (SLMRG), allowed us to robustly fit the experimental data, providing insights into the adsorption mechanisms. Thermodynamic parameters affirmed the spontaneity and endothermic nature of the processes. Adsorption kinetics were interpreted effectively using the pseudo-second-order (PSO) model. Molecular modeling investigations, including the conductor-like screening model for real solvents (COSMO-RS), density functional theory (DFT), and atom-in-molecule (AIM) analysis, unveiled intricate molecular interactions among the adsorbent components-cellulose, hemicellulose, lignin, and alginate-and the pollutant Cu2+, confirming their physically interactive nature. These findings emphasize the synergistic application of experimental and theoretical approaches, providing a comprehensive understanding of copper adsorption dynamics at the molecular level. This methodology holds promise for unraveling intricate processes across various adsorbent materials in wastewater treatment applications.

Prolonging the Durability of Maritime Constructions through a Sustainable and Salt-Resistant Cement Composite.

This research investigates the long-term resilience of an environmentally friendly cement blend comprising Egyptian Ordinary Portland Cement OPC and Ground-Granulated Blast Furnace Slag GGBFS when exposed to a corrosive seawater environment. This scientific investigation explores the effects of exposure to seawater on various properties of cement pastes, encompassing parameters such as free lime content (FLC), chemically combined water content (CWC), bulk density (BD), total porosity (ϕ), total sulfate content, total chloride content, and compressive strength (CS). By contrast, Differential Thermal Analysis (DTA), FT-IR spectroscopy, and X-ray diffraction (XRD) analysis can be utilized to investigate the influence of exposure to seawater on the hydration products of GGBFS cement pastes over a period of up to one year. This analytical approach offers valuable insights into the alterations that occur in hydration products and their resilience when subjected to seawater conditions. The results obtained from this investigation reveal that all cement pastes incorporating GGBFS exhibit heightened resistance to deterioration in seawater, with slag cement containing 60 wt. % GGBFS and achieving a notable compressive strength of 85.7 Mpa after one year of immersion in seawater. These findings underscore the capacity of these cement blends to effectively withstand challenges in durability in marine environments.

Modeling and Optimizing the Crystal Violet Dye Adsorption on Kaolinite Mixed with Cellulose Waste Red Bean Peels: Insights into the Kinetic, Isothermal, Thermodynamic, and Mechanistic Study.

In this study, a new eco-friendly kaolinite-cellulose (Kaol/Cel) composite was prepared from waste red bean peels (Phaseolus vulgaris) as a source of cellulose to serve as a promising and effective adsorbent for the removal of crystal violet (CV) dye from aqueous solutions. Its characteristics were investigated through the use of X-ray diffraction, Fourier-transform infrared spectroscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and zero-point of charge (pHpzc). The Box-Behnken design was used to improve CV adsorption on the composite by testing its primary affecting factors: loading Cel into the composite matrix of Kaol (A: 0-50%), adsorbent dosage (B: 0.02-0.05 g), pH (C: 4-10), temperature (D: 30-60 °C), and duration (E: 5-60 min). The significant interactions with the greatest CV elimination efficiency (99.86%) are as follows: BC (adsorbent dose vs. pH) and BD (adsorbent dose vs. temperature) at optimum parameters (A: 25%, B: 0.05 g, C: 10, D: 45 °C, and E: 17.5 min) for which the CV's best adsorption capacity (294.12 mg/g) was recorded. The Freundlich and pseudo-second-order kinetic models were the best isotherm and kinetic models fitting our results. Furthermore, the study investigated the mechanisms responsible for eliminating CV by utilizing Kaol/Cel-25. It detected multiple types of associations, including electrostatic, n-π, dipole-dipole, hydrogen bonding interactions, and Yoshida hydrogen bonding. These findings suggest that Kaol/Cel could be a promising starting material for developing a highly efficient adsorbent that can remove cationic dyes from aqueous environments.

Corrosion Inhibition of Azo Compounds Derived from Schiff Bases on Mild Steel (XC70) in (HCl, 1 M DMSO) Medium: An Experimental and Theoretical Study.

The inhibitory activity of three prepared azo compounds derived from Schiff bases, namely, bis[5-(phenylazo)-2-hydroxybenzaldehyde]-4,4'-diaminophenylmethane (C1), bis[5-(4-methylphenylazo)-2-hydroxybenzaldehyde]-4,4'-diaminophenylmethane (C2), and bis[5-(4-bromophenylazo)-2-hydroxybenzaldehyde]-4,4'-diaminophenylmethane (C3), against corrosion of steel type XC70 in (HCl, 1 M DMSO) medium was investigated experimentally by electrochemical measurements and theoretically using density functional theory (DFT). The correlation between corrosion inhibition and concentration is direct. The maximum inhibition efficiency at 6 × 10-5 M for the three azo compounds derived from Schiff bases was 64.37, 87.27, and 55.47% for C1, C2, and C3, respectively. The Tafel curves indicate that the inhibitors follow a mixed but predominantly anodic inhibitor system and have a Langmuir isothermal adsorption process. The observed inhibitory behavior of compounds was supported by DFT calculation. It was also found that there was a strong correspondence between the theoretical and experimental results.

Applying Chitin Enhanced Diafiltration Process (CEFP) in Removing Cobalt from Synthetic Wastewater.

This research aims to study the removal of Cobalt (Co) using chitin. The optimum conditions for removing Co were ascertained through batch experiments. This study involves the determination of chitin metal-binding efficiency by using a polymer enhanced diafiltration setup that utilizes a membrane process (ultrafiltration) to keep the Chitin. The effects of several parameters on sorption like pH, the concentrations of chitin, and Co were examined. The best efficiency was reached if the setup was run at pH < 6.3 (i.e., chitin pKa). At acidic conditions and by employing 6 g/L of chitin, Co level (20 mg/L) was decreased at 95%. To further investigate the kinetics of sorption for each gram of chitin, equilibrium experiments were carried out. For 1−100 mM Co, the performed rheological measurements show that chitin was observed to be moderately shear thickening at relatively lower levels (4 and 6 g/L); further, it was moderately shear thinning at slightly more important levels (12 and 20 g/L). Some improvement of the raw polymer will be necessary to enhance sorption to a sustainable limit and make this scheme an economically viable process.

Comparative Study of Chemical Coagulation and Electrocoagulation for the Treatment of Real Textile Wastewater: Optimization and Operating Cost Estimation.

Pollutants derived from real textile wastewater present a high environmental risk. This work involves the study of the removal of chemical oxygen demand (COD), color, and turbidity from Tunisian real textile wastewater by two different water treatment technologies: chemical coagulation (CC) and electrocoagulation (EC). A comparative study between these two methods was conducted based on the separation performance and operating cost (OC). The effects of different operational parameters including electrolysis time (t), voltage, and pH for EC and the coagulant concentration, initial pH, and time of slow mixing (t sm) for CC were studied using response surface methodology. The developed quadratic models for the responses were in good agreement with the experimental data. The experiments proved the efficiency of both chemical and electrochemical techniques for the treatment of textile effluent. Indeed, by using EC, the reduction efficiencies of COD, color, and turbidity were 63.05, 99.07, and 96.31%, respectively, under optimal conditions (pH 9, t = 36.26 min, and voltage 4 V). For CC treatment, the achieved removal efficiencies of COD, color, and turbidity were 54.02, 96.21, and 93.7%, respectively, at pH 8.57, a coagulant concentration of 204.75 mg/L, and a t sm of 28.41 min as optimal operating conditions. The OC obtained for EC and CC was about 0.47 and 0.2 USD/m3, respectively. Even if the OC of the EC process was higher as compared to the CC process, the treated water obtained by EC meets the Tunisian Standards (NT 106.03 and NT 09-14) for textile wastewater discharge into the environment and demonstrates a high potential for its reuse in various industrial activities. EC technology can be integrated into a wastewater management system that ensures a zero liquid discharge of wastewater into the environment.

Greywater reuse: an assessment of the Jordanian experience in rural communities.

Water conservation is a critical issue, particularly in arid countries and countries that suffer a lack of natural water resources. Jordan is one of the most water-scarce countries in the world; this fact has forced the search for alternative sustainable solutions. With the support of several regional and international organizations, tens of projects were implemented across the country over the past 30 years that aimed to reuse greywater in rural communities. The current review provides a wide overview of Jordan's experience in greywater treatment and its reuse for non-potable purposes in rural areas. To the best knowledge of the authors, the present review is the first to assess the Jordanian experience in this field. Many governmental authorities and non-governmental organizations have been involved in Jordan's experience. The greywater reuse systems were established to achieve advantageous environmental and socio-economic consequences on the rural communities. The strategy of greywater treatment was based on a local on-site greywater treatment system in households or the so-called 'autonomous water management'. The applied greywater treatment technologies in households were found efficient in rendering greywater adequate for agricultural uses. However, further improvements and territorial expansion of the experiment are needed.

Current Application of Chemometrics Analysis in Authentication of Natural Products: A Review.

BACKGROUND: The efficiency of herbal medicinal products depends on the quantity of active ingredients in them, which can vary considerably in different contents. Hence, the quality control of herbal medicines is a critical concern. OBJECTIVE: This paper aims to provide a succinct review of recent chemometrics applications in solving the uncertainty of the authentication of herbal medicines over the last two decades. METHODS: Studies involving chemometrics applications in conjunction with various analytical methods have been categorized according to the type of research used in the quality evaluation of different samples, including chromatographic (HPLC, GC-MS) and spectroscopic analysis (UVVis, FTIR, NMR, and MS). RESULTS: This review consists of over 90 studies illustrating the relevance of chemometrics methods in the discrimination based on the key bioactive components and phytochemical diversity of several herbs from closely related species. In addition to the prediction of the active components, the distinction between varieties and hybrids was accomplished through quantitative analysis techniques. CONCLUSION: Methods of chemometrics have provided an important and potent tool for the quality control and authentication of various herbs.

Determination of Blood Calcium and Lead Concentrations in Osteoporotic and Osteopenic Patients in Pakistan.

Osteoporosis is the leading cause of deformity and bones fracture all over the world and has some relationship with the blood concentrations of calcium and lead. Therefore, in the current study, the blood samples of 58 control and 56 clinically diagnosed osteoporotic and osteopenic patients were taken from different hospitals in Pakistan and analyzed for calcium and lead concentrations using atomic absorption spectrometry. In female control samples, the mean calcium value was found to be 98.53 ± 4.81 µg/mL, and in male control samples, the mean blood calcium level was found to be 121.33 ± 7.27 µg/mL. In female control samples, the mean lead value was found to be 0.133 ± 0.005 µg/mL, and in male control samples, the mean lead level was found to be 0.183 ± 0.008 µg/mL. All the male and female control samples showed a mean value of calcium of 115.63 ± 5.2 µg/mL and a mean value of lead of 0.153 ± 0.007 µg/mL. In osteoporotic female patients, the decline in the mean calcium value was found to be 34.93 ± 1.9 µg/mL, and in male patients, the decrease in the mean calcium level was found to be 47.73 ± 2.5 µg/mL. The increase in the mean value of lead in osteoporotic females was 4.13 ± 0.22 µg/mL, whereas in male patients, the increase in the mean lead value was 0.95 ± 0.07 µg/mL. All the male and female patients showed a decrease in the mean value of calcium of 41.43 ± 2.2 µg/mL and an increase in the mean value of Pb of 3.63 ± 0.16 µg/mL.

Effect of Different Quaternary Ammonium Groups on the Hydroxide Conductivity and Stability of Anion Exchange Membranes.

Anion exchange membrane fuel cells (AEMFCs) are encouraging electrochemical structures for the competent and complaisant conversion of energy. Herein, the development of brominated poly(2,6-dimethyl phenylene oxide) (BPPO)-based anion exchange membranes (AEMs) with different quaternary ammonium groups for AEMFCs was reported. The successful preparation of AEMs was proved by utilizing proton nuclear magnetic resonance and Fourier transform infrared spectroscopy. They were explored in terms of water uptake (W R), ion exchange capacity (IEC), hydration number (λ), linear swelling ratio (LSR), morphology, tensile strength (TS), and elongation at break (E b). The alkaline stability of the prepared AEMs was assessed and compared with each other. The experimental outcomes demonstrated that the N-methylpyrrolidinium-based membrane (MPyPPO) exhibited higher alkaline stability, whereas the N-methylimidazolium-based membrane (MImPPO) showed the lowest alkaline stability among the prepared AEMs. Similarly, the hydroxide conductivity of the prepared AEMs was measured and compared with each other. The pyrrolidinium-based membrane (MPyPPO) exhibited higher hydroxide conductivity among the prepared AEMs.

ATR-FTIR Spectroscopy, HPLC Chromatography, and Multivariate Analysis for Controlling Bee Pollen Quality in Some Algerian Regions.

Bee pollen collected by honeybees (Apis mellifera) is one of the bee products, and it is as valuable as honey, propolis, royal jelly, or beebread. Its quality varies according to its geographic location or plant sources. This study aimed to apply rapid, simple, and accurate analytical methods such as attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) and high-performance liquid chromatography (HPLC) along with chemometrics analysis to construct a model aimed at discriminating between different pollen samples. In total, 33 samples were collected and analyzed using principal component analysis (PCA), hierarchical clustering analysis (HCA), and partial least squares regression (PLS) to assess the differences and similarities between them. The PCA score plot based on both HPLC and ATR-FTIR revealed the same discriminatory pattern, and the samples were divided into four major classes depending on their total content of polyphenols. The results revealed that spectral data obtained from ATR-FTIR acquired in the region (4000-500 cm-1) were further subjected to a standard normal variable (SNV) method that removes scattering effects from spectra. However, PCA, HCA, and PLS showed that the best PLS model was obtained with a regression coefficient (R 2) of 0.9001, root-mean-square estimation error (RMSEE) of 0.0304, and root-mean-squared error cross-validation (RMSEcv) of 0.036. Discrimination between the three species has also been possible by combining the pre-processed ATR-FTIR spectra with PCA and PLS. Additionally, the HPLC chromatograms after pre-treatment (SNV) were subjected to unsupervised analysis (PCA-HCA) and supervised analysis (PLS). The PLS model confers good results by factors (R 2 = 0.98, RMSEE = 8.22, and RMSEcv = 27.86). Prospects for devising bee pollen quality assessment methods include utilizing ATR-FTIR and HPLC in combination with multivariate methods for rapid authentication of the geographic location or plant sources of bee pollen.

Higher Acid Recovery Efficiency of Novel Functionalized Inorganic/Organic Composite Anion Exchange Membranes from Acidic Wastewater.

In this work, the synthesis of a series of the functionalized inorganic/organic composite anion exchange membranes (AEMs) was carried out by employing the varying amount of inorganic filler consist of N-(trimethoxysilylpropyl)-N,N,N-trimethylammonium chloride (TMSP-TMA+Cl-) into the quaternized poly (2, 6-dimethyl-1, 4-phenylene oxide) (QPPO) matrix for acid recovery via diffusion dialysis (DD) process. Fourier transform infrared (FTIR) spectroscopy clearly demonstrated the fabrication of the functionalized inorganic/organic composite AEMs and the subsequent membrane characteristic measurements such as ion exchange capacity (IEC), linear swelling ratio (LSR), and water uptake (WR) gave us the optimum loading condition of the filler without undesirable filler particle aggregation. These composite AEMs exhibited IEC of 2.18 to 2.29 meq/g, LSR of 13.33 to 18.52%, and WR of 46.11 to 81.66% with sufficient thermal, chemical, and mechanical stability. The diffusion dialysis (DD) test for acid recovery from artificial acid wastewater of HCl/FeCl2 showed high acid DD coefficient (UH+) (0.022 to 0.025 m/h) and high separation factor (S) (139-260) compared with the commercial membrane. Furthermore, the developed AEMs was acceptably stable (weight loss < 20%) in the acid wastewater at 60 °C as an accelerated severe condition for 2 weeks. These results clearly indicated that the developed AEMs have sufficient potential for acid recovery application by DD process.

Energizing periodic mesoporous organosilica (PMOS) with bismuth and cerium for photo-degrading methylene blue and methyl orange in water.

This work reported an efficient catalyst to reduce the organic pollutants by using an energetic periodic mesoporous organosilica (PMOS) supported with bismuth (Bi-PMOS) and cerium (Ce-PMOS). PMOS support was designed through co-condensation of sodium silicate and 3-methacryloxypropyltrimethoxysilane on polysorbate templates. The resultant PMOSs were fabricated with bismuth and cerium oxides to formulate Bi-PMOS and Ce-PMOS, respectively. These materials showed photo-degradations of methylene blue (MB, 74.7% and 41.1% with Bi-PMOS and Ce-PMOS, respectively) and methyl orange (MO, 53.2% and 39.4% with Bi-PMOS and Ce-PMOS, respectively). Such efficient photo-degradations were attributed to the precise doping of metallic nodes of Bi2 O3 and CeO2 on the porous structure of PMOS with high surface area. The results also showed that Bi and Ce were more effective in PMOS support for photo-degradation of dyes as the support provides more lifetime to photo-generated electron-hole pairs than other materials. Moreover, active reusability and high degradation efficiencies of Bi-PMOS and Ce-PMOS proved them better analytical tools to reduce organic pollutants under visible lights. PRACTITIONER POINTS: The oxides of bismuth and cerium have impressive photocatalytic characteristics. New material energizing mesoporous organosilica with bismuth and cerium for photo-degradation of methylene blue and methyl orange in water. The use of an efficient catalyst to reduce the organic pollutants by using an energetic periodic mesoporous organosilica (PMOS) supported with bismuth (Bi-PMOS) and cerium (Ce-PMOS).

Enhancing the Extraction of Phenolic Compounds from Juniper Berries Using the Box-Behnken Design.

Juniper berry is an important medicinal plant used in pharmaceutical and petrochemical industries thanks to its strong antioxidant potential, which is attributed to the presence of phenolic compounds. In this study, four different solvents, namely, aqueous acetone, aqueous ethanol, aqueous NaOH, and water, were used in the extraction process with a view to optimize and determine the polyphenolic contents in the juniper berry using ultraviolet (UV) spectrophotometry. Many experiments were performed at different solvent concentrations, time, temperature, and liquid-solid ratio. The models to evaluate the effects and the optimum of these variables on the polyphenols extraction using the response surface methodology (RSM) were developed. The predicted values of the polyphenol content of juniper berry were thus highly correlated with costly measured values (SECV = 0.14 and R 2 = 0.97), and the optimal conditions of extraction were determined for the different solvents. Following the numerical optimization, the maximum predicted polyphenol contents obtained under the optimum extraction conditions are as follows: 17.57% for 58 °C extraction temperature, 78.5 min extraction time, 60% acetone concentration, and 29.8 liquid-solid ratio for the aqueous ethanol extraction; 20.68% for 71.46 °C extraction temperature, 79.2 min extraction time, 21.9% ethanol concentration, and 26.4:1 liquid-solid ratio for the aqueous acetone extraction; 34.51% for 96.4 °C extraction temperature, 37.7 min extraction time, 1.48% NaOH concentration, and 15.2:1 liquid-solid ratio for the aqueous NaOH extraction; and 9.8% was obtained under the optimum extraction conditions of 69 °C extraction temperature, 126 min extraction time, and 23:1 liquid-solid ratio for the water extraction. The GC-MS analysis of the chemical composition of juniper Berry revealed 60 identified components that represent 97.43% of the sample. The predominant fraction was monoterpene representing 80.87% especially for α-pinene (39.12%), ß-pinene (12. 68%), and myrcene (12.92%). In the other fraction of sesquiterpene representing 16.54%, the predominant components were ß-caryophyllene (4.41%) and germacrene D (4.23%).