Search Results (324)

This study evaluates and compares the sorption performance of natural zeolite (NZ) and Fe(III)-modified zeolite (FeZ) in removing Cu(II) ions from aqueous solutions, with the goal of assessing their potential for environmental remediation. NZ was modified with Fe(NO₃)₃, NaOH and NaNO₃ solutions to improve its sorption properties. The modification led to a slight decrease in crystallinity (XRD), increase in pore volume (BET), functional groups (FTIR) and negative surface charge (zeta potential), thereby improving the affinity of FeZ towards Cu(II). Batch sorption experiments were conducted to optimize key parameters including pH, solid/liquid ratio (S/L), contact time, and initial Cu(II) concentration. The pH_o and S/L ratio were identified as key factors significantly influencing Cu(II) sorption on both zeolites, with a particularly pronounced effect observed for FeZ. The optimal conditions determined were pH_o = 3–5 for NZ, pH_o = 3 for FeZ, S/L = 10 g/L and a contact time of 600 min. Experimental results confirmed that FeZ has almost twice the sorption capacity for Cu(II) compared to NZ (0.271 mmol/g vs. 0.156 mmol/g), as further supported by elemental analysis, SEM-EDS and mapping analysis of saturated samples. The sorption of Cu(II) followed a mechanism of physical nature driven by ion exchange, dominated by intraparticle diffusion as the rate-controlling step. Leaching of copper-saturated zeolites according to the standard leaching method, DIN 38414 S4, demonstrated the ability of both zeolites to fully retain Cu(II) within their structure over a wide pH range, 4.01 ≤ pH_o ≤ 10.06. These findings highlight the superior performance of FeZ and its potential as an effective material for the remediation of copper-contaminated environments. Full article

Because the interfacial Cu⁰/Cu⁺ in Cu-based electrocatalyst promotes CO₂ electroreduction activity, it would be highly desirable to physically separate Cu-based nanoparticles through coating shells and load them onto porous carriers. Herein, multilayered graphene-coated Cu (Cu@G) nanoparticles with tailorable core diameters (28.2–24.2 nm) and shell thicknesses (7.8–3.0 layers) were fabricated via lased ablation in liquid. A thin Cu₂O layer was confirmed between the interface of the Cu core and the graphene shell, providing an interfacial Cu⁰/Cu⁺. Cu@G cross-linked biochars (Cu@G/Bs) with developed porosity (31.8–155.9 m²/g) were synthesized. Morphology, crystalline structure, porosity, and elemental chemical states of Cu@G and Cu@G/Bs were characterized. Cu@G/Bs captured CO₂ with a maximum sorption capacity of 107.03 mg/g at 0 °C. Furthermore, 95.3–97.1% capture capacity remained after 10 cycles. Cu@G/Bs exhibited the most superior performance with 40.7% of FE_C2H4 and 21.7 mA/cm² of current density at −1.08 V vs. RHE, which was 1.7 and 2.7 times higher than Cu@G. Synergistic integration of developed porosity for efficient CO₂ capture and the fast charge transfer rate of interfacial Cu₂O/Cu enabled this improvement. Favorable long-term stability of the phase/structure and CO₂ electroreduction activity were present. This work provides new insight for integrating Cu@G and a biochar platform to efficiently capture and electro-reduce CO₂. Full article

Hydrofluorocarbons (HFC) are today widely used as refrigerants, solvents, or aerosols for fire protection. Due to their non-negligible environmental impact, there exists an increasing interest towards their effective separation and recovery, which still remains a major challenge. This work presents a comprehensive thermodynamic and transport modeling approach able to describe HFC sorption and transport in different amorphous polymers, including glassy, rubbery, and copolymers, as well as in supported Ionic Liquid membranes (SILMs). In particular, the literature solubility data for refrigerants such as R-32, R-125, R-134a, and R-152a is analyzed by means of the Sanchez–Lacombe Equation of State (SL-EoS), and its non-equilibrium extension (NELF), to predict gas uptake in complex polymeric materials. The Standard Transport Model (STM) is then employed to describe permeability behaviors, incorporating concentration-dependent diffusion using a mobility coefficient and thermodynamic factor. Results demonstrate that fluorinated gases exhibit strong affinity to fluorinated and high free-volume polymers, and that solubility is primarily governed by gas condensability, molecular size, and polymer structure. The combined EoS–STM approach accurately predicts both solubility and permeability across different pressures in all polymers, including SILM. The thorough study of HFC transport in polymer membranes provided both systematic insights and predictive capabilities to guide the design of next-generation materials for refrigerant recovery and low-GWP separation processes. Full article

This study aimed to develop experimental filler-reinforced resin composites for vat-photopolymerization 3D printing and to evaluate the effects of filler addition on their mechanical, physicochemical, and bonding properties for dental restorative applications. Silanized nano- and/or micro-fillers were incorporated into acrylic resin monomers to formulate photocurable resins suitable for vat-photopolymerization. The rheological behavior of these liquid-state resins was assessed through viscosity measurements. Printed resin composites were fabricated and characterized for mechanical properties—including flexural strength, flexural modulus, and Vickers hardness—both before and after 8 weeks of water immersion. Physicochemical properties, such as water sorption, water solubility, and degree of conversion, were also evaluated. Additionally, shear bond strength to a resin-based luting agent was measured before and after artificial aging via thermocycling. A commercial dental CAD-CAM resin composite served as a reference material. Filler incorporation significantly improved the mechanical properties of the printed composites. The highest performance was observed in the composite containing 60 wt% micro-fillers, with a flexural strength of 168 ± 10 MPa, flexural modulus of 6.3 ± 0.4 GPa, and Vickers hardness of 63 ± 1 VHN, while the commercial CAD-CAM composite showed values of 152 ± 8 MPa, 7.9 ± 0.3 GPa, and 66 ± 2 VHN, respectively. Filler addition did not adversely affect the degree of conversion, although the relatively low conversion led to the elution of unpolymerized monomers and increased water solubility. The shear bond strength of the optimal printed composite remained stable after aging without silanization, demonstrating superior bonding performance compared with the CAD-CAM composite. These findings suggest that the developed 3D-printed resin composite is a promising candidate for dental restorative materials. Full article

A facile method was adopted to fabricate β-C₃N₄, and it was then doped with manganese and tellurium to obtain novel 10%MnTeO₃@β-C₃N₄ (10%MnTe@β) and 20%MnTeO₃@β-C₃N₄ (20%MnTe@β) nanohybrids. The β-C₃N₄, 10%MnTe@β, and 20%MnTe@β showed surface areas of 85.86, 97.40, and 109.54 m² g⁻¹, respectively. Using ciprofloxacin (CIP) as a pollutant example, 10%MnTe@β and 20%MnTe@β attained equilibrium at 60 and 45 min with q_t values of 48.88 and 77.41 mg g⁻¹, respectively, and both performed better at pH = 6.0. The kinetic studies revealed a better agreement with the pseudo-second-order model for CIP sorption on 10%MnTe@β and 20%MnTe@β, indicating that the sorption was controlled by a liquid film mechanism, which suggests a high affinity of CIP toward 10%MnTe@β and 20%MnTe@β. The sorption equilibria outputs indicated better alignment with the Freundlich and Langmuir models for CIP removal by 10%MnTe@β and 20%MnTe@β, respectively. The thermodynamic analysis revealed that CIP removal by 10%MnTe@β and 20%MnTe@β was exothermic, which turned more spontaneous as the temperature decreased. Applying 20%MnTe@β as the best sorbent to groundwater and seawater spiked with CIP resulted in average efficiencies of 94.8% and 91.08%, respectively. The 20%MnTe@β regeneration–reusability average efficiency was 95.14% within four cycles, which might nominate 20%MnTe@β as an efficient and economically viable sorbent for remediating CIP-contaminated water. Full article

This study aims to evaluate the potential of Lemna minor (common duckweed) for the removal of galaxolide (HHCB) from polluted water, a compound commonly used in consumer products such as perfumes and detergents. The focus was to identify the optimal conditions for removal, determine the removal efficiency, and elucidate the mechanisms involved. The experiment was conducted by cultivating Lemna minor using as a cultivation medium synthetic sewage and laboratory solutions (MilliQ water) containing galaxolide at two levels of concentration (1034 µg·L⁻¹ and 2326 µg·L⁻¹). The plants were exposed to light for 16 h a day and grown at pH 5. Removal efficiency was assessed through liquid chromatography (HPLC) with fluorescence detection (FLD). Kinetics of observed process was modelled using a pseudo-first-order equation. The study of the HHCB decay mechanism included determining the contributions to the final effect of the following processes occurring simultaneously: sorption on the plant surface, photodegradation, and uptake by Lemna. The removal efficiency (RE%) of galaxolide by Lemna minor was 99.7% when aqueous standard solution was used as the cultivation medium after 14 days, and between 97.8% and 98.6% in the case of wastewater samples. Sorption onto plants surface, photodegradation, and uptake by the plants were identified as the primary mechanisms for HHCB removal. Toxicity studies revealed that galaxolide exposure adversely affected Lemna minor growth, altering photosynthetic pigments (chlorophyll and carotenoid) levels. Full article

Rare earth metals (REMs) are vital for high-tech industries, but their extraction from secondary sources is challenging due to environmental and technical constraints. This study investigates the ion-exchange extraction of light REMs (neodymium, praseodymium, and samarium) from sulfuric and phosphoric acid solutions, modeling industrial leachates from apatite concentrates and phosphogypsum. The study considers the use of anion- and cation-exchange resins with different functional groups for efficient and environmentally safe REM separation. Experimental sorption isotherms were obtained under static conditions at 298 K and analyzed using a thermodynamic model based on the linearization of the mass action equation. Equilibrium constants and Gibbs energy were calculated, which reveals the spontaneity of the processes. Cation-exchange resins demonstrated high selectivity towards individual REMs, while anion-exchange resins were suitable for group extraction. Infrared spectral analysis confirmed the presence of sulfate and phosphate complexes in the resin matrix, clarifying the ion-exchange mechanisms. Thermal effect measurements indicated exothermic sorption on anion-exchange resins with negative entropy and endothermic sorption on cation-exchange resins with positive entropy. The findings highlight the potential of ion-exchange resins for selective and sustainable REM recovery, offering a safer alternative to liquid extraction and enabling the valorization of industrial wastes like phosphogypsum for resource recovery. Full article

This study evaluated the effect of post-printing polymerization time on residual monomer elution and water sorption in a 3D-printed resin composite. Eighty samples were fabricated and assigned to four groups based on post-curing duration: 0, 20, 40, and 60 min. Each group was subdivided according to two storage conditions (distilled water and 75% ethanol–water solution), and evaluated at 1 and 7 days. High-performance liquid chromatography (HPLC) quantified eluted monomers. Additionally, 40 specimens underwent a 4-month sorption/desorption cycle for water sorption and solubility assessment. Data were statistically analyzed using kernel regression (monomer data) and Welch ANOVA (water sorption and solubility) at a significance level of p < 0.05. BisEMA was the only monomer detected, with significantly higher elution recorded in ethanol-based storage. Increasing post-curing time notably reduced both monomer release and water sorption/solubility (p < 0.001); however, the optimal results were observed at 40 min post-curing. These findings suggest that extending post-curing beyond an optimal threshold does not further improve composite properties, underscoring the importance of identifying precise curing parameters in order to enhance durability and material performance. Full article

The demand for polymer composite materials in the dental market is increasing every year. This rise is due to their excellent properties and ongoing technological advancements. The goal of this study was to develop new photoinitiators included in the liquid organic matrix, which is one of the main components of dental composites. Therefore, a series of compounds based on the indenoquinoxaline skeleton was synthesized, differing in the substituent. The spectroscopic properties of these compounds allowed their use as visible-light photoinitiators of radical polymerization in combination with (phenylthio)acetic acid. In addition to the polymerization kinetics, the lifetime and quantum yield of the triplet-state formation and the rate constants of its quenching by (phenylthio)acetic acid were determined. The durability of the designed composites was also assessed. Ageing tests included hydrothermal ageing, allowing for the determination of sorption, solubility, and mass change. Solutions imitating the oral cavity environment—distilled water, artificial saliva, n-heptane, and 3% acetic acid—as well as solutions containing pigments were used for these studies. Determination of the mass change and colour stability allowed for the assessment of how these materials react to long-term exposure in the oral environment. It was found that the solution simulating the natural oral environment has a significant impact on the hydrolytic stability and colour stability of the materials. Full article

To ensure agricultural safety and ecological security, it is crucial to effectively immobilize emerging organic pollutants, such as plasticizers, to prevent their migration in various environmental matrices. However, the ideal immobilization agent with the advantages of being environmentally friendly is very rare. In this study, low-cost and stable near-natural immobilization agents, char-derived artificial humic acids, CHAs, were proposed and prepared via hydrothermal humification (180 °C) and pyrolysis (300, 500, or 700 °C) of agroforestry biowaste. The resulting CHAs exhibit high purity (composed primarily of C (67.28–81.35%), O (6.65–21.64%), H (1.40–5.28%), and N (0.36–0.58%)) with remarkably low ash content (5.43–10.02%). Characterization revealed a compact structure with a limited porosity with small surface area (0.27–0.32 m² g⁻¹) and pore volume (2.99–3.43 × 10⁻⁴ cm³ g⁻¹). Notably, high-temperature pyrolysis induced consumption of oxygen-containing functional groups while promoting aromatic structure formation. The sorption behavior of diethyl phthalate, a representative plasticizer, on CHAs was well described by both Langmuir isotherm and pseudo-second-order kinetic models. The CHAs exhibited remarkable sorption performance for diethyl phthalate, with a maximum sorption capacity reaching 3345 mg kg⁻¹ as determined by the Langmuir model. The sorption of diethyl phthalate onto CHAs is mainly multi-layer sorption dominated by physical processes, mainly including pore filling, partitioning, hydrogen bonding, and π–π stacking. Mean sorption energies ranging from 2.56 to 4.99 × 10⁻³ kJ mol⁻¹ indicate the predominance of physical sorption mechanisms. This study developed a method to convert the liquid by-product produced during hydrothermal humification of biowaste into stable near-natural and carbon-rich char materials, and the proposed materials show great promise in immobilizing pollutants from various environmental matrices. Full article

Liquid fuels obtained from CO₂ and green hydrogen (i.e., e-fuels) are powerful tools for decarbonizing economy. Improvements provided by Process Intensification in the existing conventional reactors aim to decrease energy consumption, increase yield, and ensure more compact and safe processes. This review describes the advances in the production of methanol, dimethyl ether, and hydrocarbons by Fischer–Tropsch using different Process Intensification tools, mainly membrane reactors, sorption-enhanced reactors, and structured reactors. Due to the environmental interest, this review article focused on discussing methanol and dimethyl ether synthesis from CO₂ + H₂, which also represented the most innovative approach. The use of syngas (CO + H₂) is generally preferred for the Fischer–Tropsch process; hence, studies examining this process were included in the present review. Both mathematical models and experimental results are discussed. Achievements in the improvement of catalytic reactor performance are described. Experimental results in membrane reactors show increased performance in e-fuels production compared to the conventional packed bed reactor. The combination of sorption and reaction also increases the single-pass conversion and yield, although this improvement is limited by the saturation capacity of the sorbent in most cases. Full article

A series of ionic liquids consisting of anilinium cations with varying alkyl chains and metallic (Sb and Bi) halides as anions have been synthesized and thoroughly characterized by using multinuclear (¹H and ¹³C) NMR, FT-IR, Raman and XPS techniques. They have been exploited as adsorbents for the dye’s removal, such as malachite green, rhodamine B and Sudan II, from the aqueous solution. Various parameters like the effect of stirring rate, pH, reaction time, adsorbent amount and initial dye concentration have been optimized. Both antimony- and bismuth-based ionic liquids exhibit high adsorption efficiencies and have comparable performance for each dye. Kinetic data have been analyzed by applying kinetic models, and the best-fitted model was found to be pseudo-second order with an R² value greater than 0.98. Adsorption capacity has been determined by analyzing the sorption data using the Langmuir and Freundlich equations, and the Langmuir isotherm model has been found to be the best fitting. The maximum adsorption capacities (q_max) derived from the Langmuir isotherm for malachite green, Sudan II and rhodamine B by M-Sb ILs were 217.36, 162.10 and 62.94 mg·g⁻¹, whereas by M-Bi ILs, the adsorption capacities were slightly higher, at 230.18, 170.00 and 64.21 mg·g⁻¹, respectively. Kinetic studies indicated pseudo-second-order behavior (R² > 0.98), while thermodynamic analysis demonstrated an endothermic adsorption, and a spontaneous reaction was carried out by a physisorption process. These findings accentuate the potential of Sb- and Bi-based ionic liquids as efficient and reusable adsorbents for removing dyes from wastewater. Full article

In this study, polymer films based on the inorganic sorbents Al₂O₃, ZrO₂ and SiO₂-phenyl with repellent N,N-diethyl-3-methylbenzamide were prepared and used as functional textile coatings. The high sorption activity of oxides with respect to N,N-diethyl-3-methylbenzamide (63–239 mg/g) allows for the use of these compounds as repellent carrier materials, and their mixture with polyacrylates allows for the formation of functional coatings–polymer films. Scanning electron microscopy and Fourier transform infrared spectroscopy results revealed that the inorganic sorbents Al₂O₃, ZrO₂ and SiO₂-phenyl were successfully anchored in the polyacrylate structure, and the FTIR spectra confirmed the presence of repellent molecules. The thermal diffusion parameters of N,N-diethyl-3-methylbenzamide were also calculated via thermogravimetric analysis and high-performance liquid chromatography with diode array detection. The highest thermal diffusion rates and concentrations were observed for the material with Al₂O₃ (up to 148.3∙10⁻⁹ mol at 200 °C), and lower values for ZrO₂ and SiO₂-phenyl (up to 15.2∙10⁻⁹ mol and 34.3∙10⁻⁹ mol at 200 °C, respectively). The heat flux parameter J_f was also calculated according to Onsager’s theory and Fourier’s law. The release of repellent from polymeric materials can be achieved by applying less heat than that required to reach the boiling point of N,N-diethyl-3-methylbenzamide. Full article

Anaerobically digested liquid pig manure (LPM) is enriched with nutrients and thus can be used as an alternative nutrient source and substitute for chemical fertilizer (CF) in rice (Oryza sativa L.) farming. However, there are concerns regarding the contamination of the surrounding water due to the discharge of ponding water containing dissolved organic carbon (DOC), nitrogen (N), and phosphorus (P) from rice paddies fertilized using LPM. This study investigated the effects of the co-application of fly ash (FA) and zeolite (Z) amendments (FAZ amendments) on the concentration of DOC, N, and P in the ponding water of rice paddies fertilized with LPM at two different rates (standard (LPM_S) and double (LPM_D) at 11 and 22 g N m⁻², respectively). Rice was cultivated using four nutrient treatments, including no input, CF (11 g N m⁻²), LPM_S, and LPM_D, with or without FAZ amendments. When FAZ was not amended, LPM_S and LPM_D application increased the DOC concentration by 32% and 41%, respectively, compared to CF treatments (11 g N m⁻²), reflecting a high DOC concentration in LPM. The total N and P concentrations in the ponding water were lower in LPM_S treatment (by 5 and 8%, respectively) but higher (by 94% and 47%, respectively) in LPM_D treatment compared to CF treatments in the absence of FAZ, indicating a high potential for water pollution with a double LPM application rate. With a given nutrient treatment, FAZ amendments decreased DOC by 15–39%, supporting the immobilization of DOC by Z. FAZ consistently decreased the NH₄⁺ concentration by 6–51% across the nutrient treatments, likely via the sorption of NH₄⁺ onto the negatively charged sites of Z, but its effect on total N concentration was not consistent. Unexpectedly, total P concentration increased (by 77–167%) following the FAZ amendment. FAZ amendments tended to increase rice biomass and grain yield for LPM treatments, but these rice growth parameters were poor compared to CF regardless of FAZ amendment. Our results show that the application of LPM as a complete replacement for CF may hamper rice yield while increasing the likelihood of water pollution with DOC and P, although the co-application of FAZ may help to reduce rice yield loss and decrease DOC and NH₄⁺ concentrations. Full article

The HERMES project investigates the utilization of surplus wind and solar energy to produce renewable fuels such as hydrogen, methane, and methanol for seasonal storage, thereby supporting carbon neutrality and the energy transition. This initiative aims to create a closed-loop, zero-emission energy system with efficiencies of up to 65%, employing a low-pressure (≤30 bar) synthesis process—specifically, sorption-enhanced methanol synthesis—integrated into the power system. Excess renewable electricity is harnessed for chemical synthesis, beginning with electrolysis to generate hydrogen, which is then converted into methanol using CO₂ sourced from a biogas plant. This methanol, biomethane, or a hybrid fuel blend powers a supercritical gas turbine, providing a flexible and reliable energy supply. Optimization analysis indicates that a combined wind and photovoltaic system can meet 62% of electricity demand, while the proposed storage system can handle over 90%. Remarkably, liquid methanol storage requires a compact 313 m³ tank, significantly smaller than storage requirements for hydrogen or methane in gas form. The project entails a total investment of 105 M EUR and annual operation and maintenance costs of 3.1 M EUR, with the levelized cost of electricity expected to decrease by 43% in the short term and 69% in the long term as future investment costs decline. Full article