Search Results (104)

This article presents an innovative method for phosphate(V) removal from industrial wastewater using cerium(III) chloride as a coagulant, integrated with reagent recovery. The process combines coagulation, acid extraction, and multistage recovery of cerium and phosphorus, enabling partial reagent loop closure. Based on our previously published studies, at an optimised dose (81.9 mg Ce³⁺/L), phosphate(V) removal reached 99.86% and total phosphorus (sum of all phosphorus forms as elemental P), 99.56%, and 99.94% of the added cerium was retained in sludge. Reductions were also observed for TSS (96.67%), turbidity (98.18%), and COD (81.86%). The sludge (101.5 g Ce/kg, 22.2 g P/kg) was extracted with HCl, transferring 99.6% of cerium and 97.5% of phosphorus to the solution. Cerium was recovered as cerium(III) oxalate and thermally decomposed to cerium(IV) oxide. Redissolution in HCl and H₂O₂ yielded cerium(III) chloride (97.0% recovery and 98.6% purity). The HCl used for extraction can be regenerated on-site from chlorine and hydrogen obtained from gas streams, improving material efficiency. Life cycle assessment (LCA) showed environmental benefits related to eutrophication reduction but burdens from reagent use (notably HCl and oxalic acid). Although costlier than conventional precipitation, this method may suit large-scale applications requiring high phosphorus removal, low sludge, and alignment with circular economy goals. Full article

The transition towards renewable energy necessitates large-scale, cost-effective energy storage solutions. Carnot Batteries (CBs), which store electricity as thermal energy, offer potential advantages for medium-to-long-duration storage, including geographical flexibility and lower energy capacity costs compared to electrochemical batteries. This article examines the evolution and current state-of-the-art of CB technologies, including Pumped Thermal Energy Storage (PTES) and Liquid Air Energy Storage (LAES), discussing their performance metrics, techno-economics, and development challenges. Concurrently, the increasing generation of biomass ash (BA) from bioenergy production presents a waste valorization challenge. This article critically evaluates the potential of using BA, particularly from woody biomass, as an ultra-low-cost thermal energy storage (TES) medium within CBs systems. We analyze BA’s typical composition (SiO₂, CaO, K₂O, etc.) and relevant thermal properties, highlighting significant variability. Key challenges identified include BA’s likely low thermal conductivity, which impedes heat transfer, and poor thermal stability (low ash fusion temperatures, sintering, corrosion) due to alkali and chlorine content, especially problematic for high-temperature CBs. While the low cost is attractive, these technical hurdles suggest direct use of raw BA is challenging. Potential niches in lower-temperature systems or as part of composite materials warrant further investigation, requiring detailed experimental characterization of specific ash types. Full article

A 12-membered pyridinophane scaffold containing two pyridine and two tertiary amine residues is examined as a prototype ligand (^tBuN4) for supporting nitrene transfer to olefins. The known [(^tBuN4)M^II(MeCN)₂]²⁺ (M = Mn, Fe, Co, and Ni) and [(^tBuN4)Cu^I(MeCN)]⁺ cations are synthesized with the hexafluorophosphate counteranion. The aziridination of para-substituted styrenes with PhI=NTs (Ts = tosyl) in various solvents proved to be high yielding for the Cu(I) and Cu(II) reagents, in contrast to the modest efficacy of all other metals. For α-substituted styrenes, aziridination is accompanied by products of aziridine ring opening, especially in chlorinated solvents. Bulkier β-substituted styrenes reduce product yields, largely for the Cu(II) reagent. Aromatic olefins are more reactive than aliphatic congeners by a significant margin. Mechanistic studies (Hammett plots, KIE, and stereochemical scrambling) suggest that both copper reagents operate via sequential formation of two N–C bonds during the aziridination of styrene, but with differential mechanistic parameters, pointing towards two distinct catalytic manifolds. Computational studies indicate that the putative copper nitrenes derived from Cu(I) and Cu(II) are each associated with closely spaced dual spin states, featuring high spin densities on the nitrene N atom. The computed electrophilicity of the Cu(I)-derived nitrene reflects the faster operation of the Cu(I) manifold. Full article

Microelement deficiencies, often termed “hidden hunger”, represent a significant global health challenge. Optimal human health relies on adequate dietary intake of essential microelements, including selenium (Se), zinc (Zn), copper (Cu), boron (B), manganese (Mn), molybdenum (Mo), iron (Fe), nickel (Ni), and chlorine (Cl). In recent years, there has been a growing focus on vitality and longevity, which are closely associated with the sufficient intake of essential microelements. This review focuses on these nine elements, whose bioavailability in the food chain is critically determined by their geochemical behavior in soils. There is a necessity for an understanding of the sources, soil–plant transfer, and plant uptake mechanisms of these microelements, with particular emphasis on the influence of key soil properties, including pH, redox potential, organic matter content, and mineral composition. There is a dual challenge of microelement deficiencies in agricultural soils, leading to inadequate crop accumulation, and the potential for localized toxicities arising from anthropogenic inputs or geogenic enrichment. A promising solution to microelement deficiencies in crops is biofortification, which enhances nutrient content in food by improving soil and plant uptake. This strategy includes agronomic methods (e.g., fertilization, soil amendments) and genetic approaches (e.g., marker-assisted selection, genetic engineering) to boost microelement density in edible tissues. Moreover, emphasizing the need for advanced predictive modeling techniques, such as ensemble learning-based digital soil mapping, enhances regional soil microelement management. Integrating machine learning with digital covariates improves spatial prediction accuracy, optimizes soil fertility management, and supports sustainable agriculture. Given the rising global population and the consequent pressures on agricultural production, a comprehensive understanding of microelement dynamics in the soil–plant system is essential for developing sustainable strategies to mitigate deficiencies and ensure food and nutritional security. This review specifically focuses on the bioavailability of these nine essential microelements (Se, Zn, Cu, B, Mn, Mo, Fe, Ni, and Cl), examining the soil–plant transfer mechanisms and their ultimate implications for human health within the soil–plant–human system. The selection of these nine microelements for this review is based on their recognized dual importance: they are not only essential for various plant metabolic functions, but also play a critical role in human nutrition, with widespread deficiencies reported globally in diverse populations and agricultural systems. While other elements, such as cobalt (Co) and iodine (I), are vital for health, Co is primarily required by nitrogen-fixing microorganisms rather than directly by all plants, and the main pathway for iodine intake is often marine-based rather than soil-to-crop. Full article

Utilizing renewable energy for green hydrogen production via electrolyzed seawater is a promising technology for the future. However, undesired chlorine evolution and the corrosive nature of seawater are crucial challenges for direct seawater splitting technology. In this work, heterojunctions of CoS₂/FeS₂ encapsulated in N-doped carbon nanocubes (denoted as CoS₂/FeS₂@NC) were designed by proposing the synchronous pyrolysis and vulcanization of polydopamine-coated coordination polymers. Such a synthetic strategy was demonstrated to be effective in increasing the favorable exposure of active sites, moderately regulating electronic structure, and remarkably facilitating charge transfer due to the controllable generation of unique core–shell structures with suitable carbon shells, leading to the excellent bifunctional electrocatalytic performance and enhanced stability of electrocatalysts. As a result, CoS₂/FeS₂@NC can be revealed as a superior water splitting catalyst, possessing a small voltage of 1.75 V and requiring 100.0 mA cm⁻² in 1 M KOH alkaline solution and 1.80 V for alkaline seawater media, with satisfactory long-term stability. This work presents fresh strategies for designing core–shell heterostructures and developing green technology for hydrogen production. Full article

In chlorination disinfection treatment, residual iodinated X-ray contrast media (ICMs) are the precursors to iodinated disinfection by-products (I-DBPs). This study employed CoFe₂O₄ nanoparticle catalytic peracetic acid oxidation (CoFe₂O₄/PAA) to remove iopamidol (IPM) and control I-DBP formation. The experimental results demonstrated that over 90% of the IPM degradation was achieved in 40 min. The metastable intermediate (≡Co(II)-OO(O)CCH₃), rather than the alkoxyl radicals, was identified as the dominant oxidation species (ROS). The electron transfer pathways between the metastable intermediate and IPM were oxygen-atom transfer and single-electron transfer. The monoiodoacetic acid formation potential (MIAAFP) was investigated. In ultraviolet-activated ClO⁻ (UV/chlorine), a portion of I⁻ generated through IPM dehalogenation underwent conversion to reactive iodine species (RIS), consequently elevating the MIAAFP. In CoFe₂O₄/PAA, the MIAAFP was less than 43% of that in UV/chlorine, which can be attributed to the complete conversion of I⁻ into iodate IO₃⁻ without generating RIS. CoFe₂O₄/PAA is thus a promising treatment for removing ICMs and controlling I-DBP formation due to the efficient degradation of ICMs while avoiding the generation of RIS. Full article

Flavonoid alcohols, particularly quercetin, as emerging antioxidants, demand advanced detection methodologies to comprehensively explore and evaluate their potential environmental and health risks. In this study, nitrogen–chlorine co-doped carbon dots (N, Cl-CDs), featuring an extended wavelength emission at 625 nm, were synthesized via the reaction of 4-chloro-1,2-phenylenediamine with polyethyleneimine. The engineered N, Cl-CDs exhibit superior photostability, exceptional aqueous dispersibility, and anti-interference capability in complex matrices. Leveraging static electron transfer mechanisms, the N, Cl-CDs demonstrate selective fluorescence quenching toward quercetin with an ultralow detection limit of 60.42 nM. Validation through rigorous spiked recovery assays in apple peel and red wine has been proficiently performed with satisfactory accuracy, highlighting the significant prospect of the constructed N, Cl-CDs for quercetin identification in real samples. This study provides valuable insights into the analytical determination of flavonoid compounds in complex environmental matrices, highlighting the potential of N, Cl-CDs for environmental and food safety monitoring. Full article

Organic–inorganic hybrid flexible perovskite solar cells (F-PSCs) have garnered considerable interest owing to their exceptional power conversion efficiency (PCE) and stable operational characteristics. However, F-PSCs continue to exhibit significantly lower PCE than their rigid counterparts. Herein, we employed 3-chloro-4-methoxybenzylamine hydrochloride (CMBACl) treatment to grow in situ two-dimensional (2D) perovskite layers on three-dimensional (3D) perovskite films. Through comprehensive physicochemical characterization, including X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and photoluminescence (PL) mapping, we demonstrated that CMBACl treatment enabled the in situ growth of two-dimensional (2D) perovskite layers on three-dimensional (3D) perovskite films via chemical interactions between CMBA⁺ cations and undercoordinated Pb²⁺ sites. The organic cation (CMBA⁺) bound to uncoordinated Pb²⁺ ions and residual PbI₂, while the chlorine anion (Cl⁻) filled iodine vacancies in the perovskite lattice, thereby forming a high-quality 2D/3D heterojunction structure. The CMBACl treatment effectively passivated surface defects in the perovskite films, prolonged charge carrier lifetimes, and enhanced the operational stability of the photovoltaic devices. Additionally, the hybrid 2D/3D architecture also improved energy band matching, thereby boosting charge transfer performance. The optimized flexible devices demonstrated a PCE of 23.15%, while retaining over 82% of their initial efficiency after enduring 5000 bending cycles under a 5 mm curvature radius (R = 5 mm). The unpackaged devices retained 94% of their initial efficiency after 1000 h under ambient conditions with a relative humidity (RH) of 45 ± 5%. This strategy offers practical guidelines for selecting interface passivation materials to enhance the efficiency and stability of F-PSCs. Full article

In agricultural production, pesticides play an important role in increasing crop yields. However, pesticide residues are caused by improper handling by users during the production process. Chlorine dioxide and ozone, as strong oxidants with similarity in spatial structure, effectively degrade pesticide residues and are widely used in water treatment and the food industry. In order to better understand the mechanism of chlorine dioxide and ozone on pesticides, the properties of chlorine dioxide and ozone are introduced in this review. Herbicides, insecticides, and fungicides were selected for this study, and the influencing factors, kinetics, and degradation pathways of degraded pesticides are presented. The degradation of pesticides by chlorine dioxide follows the second-order kinetic model, reacting with functional groups with high electron density in pesticides by electron transfer. Ozone selectively undergoes electrophilic reactions with pesticides in solution. In addition, when the reaction system is alkaline, ozone accelerates the decomposition to form hydroxyl radicals ($·\mathrm{O}\mathrm{H}$), which react with pesticides. Ozone degradation of pesticides satisfies the pseudo-first-order kinetic model. By comparing the mechanism of pesticide degradation by chlorine dioxide and ozone, this paper provides a theoretical basis for solving the problem of pesticide residues in the food industry and water treatment in the future. Full article

Electrochemical reduction is a promising strategy for the dechlorination of halogenated organic compounds, offering advantages such as enhanced electron transfer efficiency and increased hydrogen atom concentration. It has garnered significant attention for application in mitigating halogenated disinfection by-products (DBPs) in drinking water, owing to its high efficiency and simple operation. In this study, trichloroacetic acid (TCAA), a representative DBP, was selected as the target contaminant. A novel composite cathode comprising a metal–organic framework MIL-53(Fe)@C supported on an Nd magnet (MIL-53(Fe)@C-MAG) and its dechlorination performance for TCAA were systematically investigated. The innovative aspect of this study is the magnetic attachment of the MOF catalyst to the carbonized cathode surface treated through carbonization, which fundamentally differs from conventional solvent-based adhesion methods. Compared to the bare electrode, the MIL-53(Fe)@C-MAG achieved a TCAA removal efficiency exceeding 96.03% within 8 h of contact time. The structural characterization revealed that the α-Fe⁰ crystalline phase serves as the primary active center within the MIL-53(Fe)@C catalyst, facilitating efficient electron transfer and TCAA degradation. The scavenger experiments revealed that TCAA reduction involves a dual pathway: direct electron transfer and atomic hydrogen generation. The modified MIL-53(Fe)@C-MAG electrode exhibited robust electrolytic performance over a broad pH range of 3–7, with TCAA removal efficiency showing a positive correlation with current density within the range of 10–50 mA/cm². Furthermore, the electrode maintained exceptional stability, retaining more than 90% removal efficiency after five consecutive operational cycles. The versatility of the system was further validated by the rapid and efficient dechlorination of various chlorinated DBPs, demonstrating the broad applicability of the electrode. The innovative magnetic composite electrode demonstrates a significant advancement in electrochemical dechlorination technology, offering a reliable and efficient solution for the purification of drinking water contaminated with diverse halogenated DBPs. These results provide valuable insights into the development of electrolysis for dechlorination in water treatment applications. Full article

Protolytic reactions on the surface of a titania photocatalyst (TiO₂ P25 containing chlorine impurities) were studied using potentiometric and calorimetric acid-base titration. The impurity was removed by either washing or heat treatment. The efficiency of purification was tested by chlorine (TOX) analysis and acid-base titration. Common intersection points of −0.023 and −0.021 mmol/g were obtained for the original and 400 °C heat-treated samples, which are in good agreement with the measured TOX value of 28 mmol/kg. The point of zero charge of the purified sample was determined to be 6.50. Titration data were fitted to simulate protolytic reactions during isothermal calorimetric titrations of purified titania. The evolved heat was measured, and data points were corrected with the heat of mixing and neutralization. The quantity of charged surface species formed in each step of titration was calculated using the parameters from the constant capacitance model fit. The partial molar enthalpy values of the exothermic and endothermic processes of surface protonation (ΔH_pr, −17.47 to −16.10 kJ/mol) and deprotonation (ΔH_depr, 32.53 to 27.08 kJ/mol) depend slightly on the ionic strength of suspensions. The average standard enthalpy of one proton transfer reaction is −23.54 ± 1.75 kJ/mol, which is consistent with the literature. Full article

Nitrogen oxides (NOx) and chlorinated volatile organic compounds (CVOCs) are major environmental pollutants, posing severe risks to human health and ecosystems. Traditional single-component catalysts often fail to remove both pollutants efficiently, making synergistic catalytic technologies a critical research focus. In this study, a mesoporous HPW-CS-Ce-Ti oxide catalyst, modified with H₃PW₁₂O₄₀ (HPW) and chitosan (CS), was synthesized via self-assembly. The optimized 10HPW-CS-Ce_0.3-Ti catalyst achieved nearly 100% NO conversion at 167–288 °C and a T₉₀ of 291 °C for CVOC conversion, demonstrating superior dual-pollutant removal. HPW and chitosan facilitated mesoporous structure formation, enhancing mass transfer and active site availability. HPW doping also modulated the Ce⁴⁺/Ce³⁺ ratio, boosting redox capacity and surface-active oxygen species, while increasing acidity to promote NH₃ and CVOC adsorption. This study presents a novel catalyst and synthesis method with significant potential for environmental protection and human health. Full article

Electro-chlorination (E-Cl) is an emerging and promising electrochemical advanced oxidation technology for wastewater treatment with the advantages of high efficiency, deep mineralization, a green process, and easy operation. It was found that the mechanism of pollutant removal by electro-chlorination mainly involves an indirect oxidation process, in which pollutant removal is mainly driven by the intermediate active species, especially RCS and chlorine radicals, with a strong oxidization ability produced at the anodes. In this work, we summarized the principles and pathways of the removal/degradation of pollutants (organic pollutants and ammonia nitrogen) by E-Cl and the major affecting factors including the applied current density, voltage, electrolyte concentration, initial pH value, etc. In the E-Cl system, the DSA and BDD electrodes were the most widely used electrode materials. The flow-through electrode reactor was considered to be the most promising reactor since it had a high porosity and large pore size, which could effectively improve the mass transfer efficiency and electron transfer efficiency of the reaction. Of the many detection methods for chlorine radicals and RCS, electron paramagnetic resonance (EPR) and spectrophotometry with N, N-diethyl-1,4-phenylenediamine sulfate (DPD) as the chromogenic agent were the two most widely used methods. Overall, the E-Cl process had excellent performance and prospects in treating salt-containing wastewater. Full article

Background/Objectives: Pathogen inactivation and harmful gene destruction from water just before drinking is the last line of defense to protect people from waterborne diseases. However, commonly used disinfection methods, such as chlorination, ultraviolet irradiation, and membrane filtration, experience several challenges such as continuous chemical dosing, the spread of antibiotic resistance genes (ARGs), and intensive energy consumption. Methods: Here, we perform a simultaneous elimination of pathogens and ARGs in drinking water using local electric fields and in-situ generated trace copper ions (LEF-Cu) without external chemical dosing. A 100-μm thin copper wire placed in the center of a household water pipe can generate local electric fields and trace copper ions near its surface after an external low voltage is applied. Results: The local electric field rapidly damages the outer structure of microorganisms through electroporation, and the trace copper ions can effectively permeate the electroporated microorganisms, successfully damaging their nucleic acids. The LEF-Cu disinfection system achieved complete inactivation (>6 log removal) of Escherichia coli O157:H7, Pseudomonas aeruginosa PAO1, and bacteriophage MS2 in drinking water at 2 V for 2 min, with low energy consumption (10⁻² kWh/m³). Meanwhile, the system effectively damages both intracellular (0.54~0.64 log) and extracellular (0.5~1.09 log) ARGs and blocks horizontal gene transfer. Conclusions: LEF-Cu disinfection holds promise for preventing horizontal gene transfer and providing safe drinking water for household applications. Full article

Short-chain chlorinated paraffins (SCCPs) are a persistent organic pollutant, and limited information is available on their bioaccumulation and trophic transfer, which would be affected by carbon chain length, chlorine content, and hydrophobicity. In this study, relevant data on SCCPs in water, sediments, and organisms collected from Laizhou Bay were analyzed to investigate the specific distribution of SCCPs and their bioaccumulation and trophic transfer. In water and sediments, the average SCCP concentrations (ΣSCCPs) were 362.23 ± 81.03 ng/L and 609.68 ± 90.28 ng/g d.w., respectively. In 28 species of organisms, the ΣSCCPs varied from 70.05 to 47,244.13 ng/g l.w. (average = 648 ± 7360) and the predominant homologs were C₁₃ (average = 34.91%) and Cl_5–7 (average = 93.13%), differing from those in water (average = C₁₁ 32.75% and average = Cl_5–7 88%) and sediments (average = C₁₃ 31.60% and average = Cl_6–8 87.16%). The logarithm bioaccumulation factors (BAFs) of ΣSCCPs were 1.18–2.74 and were positively correlated with the log K_ow. A significant negative linear relationship was observed between biota-sediment accumulation factors (BSAFs) and log K_ow. It is suggested that the hydrophobicity may affect the bioaccumulation of SCCPs. SCCPs demonstrated a trophic magnification factor (TMF) ranging from 2.19 to 3.00 (average = 2.51) and exhibited a significant linear correlation with carbon chain length (p < 0.05) and log K_ow values (p < 0.05), suggesting that SCCPs have biomagnification potential in Laizhou Bay that is affected by hydrophobicity and carbon chain length. Full article