Search Results (42)

The efficient recovery of rhenium (Re), a critical metal in high-tech industries, is essential to address its growing demand and reduce reliance on primary mining. In this study, we developed novel anion-exchange resins for the selective adsorption and recovery of Re(VII) ions from acidic solutions, simulating industrial by-products. The resins were synthesized from a vinylbenzyl chloride-co-divinylbenzene copolymer modified with aliphatic, heterocyclic, and aromatic weakly basic amines, selected from among bis(3-aminopropyl)amine (BAPA), 1-(2-pyrimidinyl)piperazine (PIP), thiosemicarbazide (TSC), 2-amino-3-hydroxypyridine (AHP), 1-(2-hydroxyethyl)piperazine (HEP), 4-amino-2,6-dihydroxypyrimidine (AHPI), and 2-thiazolamine (TA). The adsorption of Re on BAPA, PIP, and HEP resins obeyed the Langmuir model, and the resins exhibited high adsorption capacities, with maximum values reaching 435.4 mg Re g⁻¹ at pH 6. Furthermore, strong selectivity for ReO₄⁻ ions over competing species, including Mo, Cu, and V, was noted in solutions simulating the leachates of the by-products of Cu-Mo ores. Additionally, complete elution of Re was possible. The developed resins turned out to be highly suitable for the continuous-flow-mode adsorption of ReO₄⁻, revealing outstanding adsorption capacities before reaching column breakthrough. In this context, the novel anion-exchange resins developed offer a reference for further Re recovery strategies. Full article

Lost circulation during drilling has significantly hindered the safe and efficient development of oil and gas resources. Supramolecular polymer gel–based lost circulation materials have shown significant potential for application due to their unique molecular structures and superior performance. Herein, a high–performance supramolecular polymer gel was developed, and the influence of reservoir conditions on the performance of the supramolecular polymer gel was investigated in detail. The results identified an optimal formulation for the preparation of supramolecular polymer gel comprising 15 wt% acrylamide, 3 wt% 2-acrylamide-2-methylpropanesulfonic acid, 2.6 wt% divinylbenzene, 5 wt% polyvinyl alcohol, 0.30 wt% cellulose nanofibers, and 3 wt% laponite. The performance of the gel-forming suspension and the resulting supramolecular polymer gel was influenced by various factors, including temperature, density, pH, and the intrusion of drilling fluid, saltwater, and crude oil. Nevertheless, the supramolecular polymer gels consistently exhibited high strength under diverse environmental conditions, as confirmed by rheological measurements. Moreover, the gels exhibited strong plugging performance across various fracture widths and in permeable formations, with maximum breakthrough pressures exceeding 6 MPa. These findings establish a theoretical foundation and practical approach for the field application of supramolecular polymer gels in complex geological formations, demonstrating their effectiveness in controlling lost circulation under challenging downhole conditions. Full article

Strategic utilization of carbon dioxide as both a carbon mitigation tool and a sustainable C1 feedstock represents a pivotal pathway toward green chemistry. Although poly(ionic liquid)s (PILs) exhibit promise in CO₂ conversion, conventional divinylbenzene (DVB) cross-linked architectures are limited by reduced ionic density and limited accessibility of active sites. Herein, we reported a binuclear imidazolium-functionalized PIL catalyst (P-BVIMCl), synthesized through a simple self-polymerization process, derived from rationally designed ionic liquid monomers formed by quaternization of 1,4-bis(chloromethyl)benzene with N-vinylimidazole. The dual active sites in P-BVIMCl-quaternary ammonium cation (N⁺) and nucleophilic chloride anion (Cl⁻) synergistically enhanced CO₂ adsorption/activation and epoxide ring-opening. Under optimal catalyst preparation conditions (100 °C, 24 h, water/ethanol = 1:3 (v/v), 10 wt% AIBN initiator) and reaction conditions (100 °C, 2.0 MPa CO₂, 10 mmol epichlorohydrin, 6.7 wt% catalyst loading, 3.0 h), P-BVIMCl catalyzed the synthesis of glycerol carbonate (GLC) with a yield of up to 93.4% and selectivity of 99.6%, maintaining activity close to 90% after five cycles. Systematic characterization and density functional theory (DFT) calculations confirmed the synergistic activation mechanism. This work established a paradigm for constructing high-ionic-density catalysts through molecular engineering, advancing the development of high-performance PILs for industrial CO₂ valorization. Full article

A simple method has been developed for the simultaneous analysis of ibuprofen (acid drug), and salbutamol and atenolol (basic drugs) in urine samples at concentrations of 0.40 µg·mL⁻¹. Simultaneous chromatographic separation has been possible using hydrophilic interaction liquid chromatography (Kinetex HILIC^® column (2.1 mm × 150 mm, 2.6 μm particle size diameter and 100 Å pore size) combined with gradient elution by employing a mixture of acetonitrile–acetate buffer 5 mM at pH 6 (from 95:5 to 75:25 (v/v)) as the mobile phase. Detection was performed at 227 and 275 nm. The simultaneous preconcentration and cleaning of the sample has been possible by solid-phase extraction using the HLB ExtraBond^® polymeric-type sorbent (which is a pyrrolidone-modified divinylbenzene polystyrene type). It has provided recoveries between (63 ± 9)% for salbutamol, (74 ± 8)% for ibuprofen, and (96 ± 9)% for atenolol in 10 mL of synthetic urine containing 4.0 μg of each of the drugs analyzed. The detection limits were 0.025 µg·mL⁻¹ for ibuprofen, µg·mL⁻¹ for salbutamol, and 0.007 µg·mL⁻¹ for atenolol. The detection limits obtained allow the evaluation of the free forms of ibuprofen, atenolol, and salbutamol at the excreted concentration levels at the therapeutic doses usually administered. The coefficients of variation between days were in the range 4.5–10.9%. Full article

Background/Objectives: Biogenic volatile organic compounds (BVOCs), extensively studied in terrestrial plants with global emissions around 1 PgC yr⁻¹, are also produced by marine organisms. However, benthic species, especially seagrasses, are understudied despite their global distribution (177,000–600,000 km²). This study aims to examine BVOC emissions from key Mediterranean seagrass species (Cymodocea nodosa, Posidonia oceanica, Zostera noltei, and Zostera marina) in marine and coastal lagoon environments. Methods: BVOCs were collected using headspace solid-phase microextraction (HS-SPME) using divinylbenzene/carboxen/polydimethylsiloxane (DVB/CAR/PDMS) fibers and analyzed by gas chromatography–mass spectrometry (GC-MS). Results: An important chemical diversity was found with a total of 92 volatile compounds (61 for Z. noltei, 59 for C. nodosa, 55 for P. oceanica, and 51 for Z. marina), from different biosynthetic pathways (e.g., terpenoids, benzenoids, and fatty acid derivatives) and with several types of chemical functions (e.g., alkanes, esters, aldehydes, and ketones) or heteroatoms (e.g., sulfur). No differences in chemical richness or diversity of compounds were observed between species. The four species shared 29 compounds enabling us to establish a specific chemical footprint for Mediterranean marine plants, including compounds like benzaldehyde, benzeneacetaldehyde, 8-heptadecene, heneicosane, heptadecane, nonadecane, octadecane, pentadecane, tetradecane, and tridecanal. PLS-DA and Heatmap show that the four species presented significantly different chemical profiles. The major compounds per species in relative abundance were isopropyl myristate for C. nodosa (25.6%), DMS for P. oceanica (39.3%), pentadecane for Z. marina (42.9%), and heptadecane for Z. noltei (46%). Conclusions: These results highlight the potential of BVOCs’ emission from seagrass ecosystems and reveal species-specific chemical markers. Full article

In order to realize the effective separation of palladium from high-level liquid waste (HLLW), a ligand-supported adsorbent (NTAamide(C8)/SiO₂-P) was prepared by the impregnation method in a vacuum. The SiO₂-P carrier was synthesized by in situ polymerization of divinylbenzene and styrene monomers on a macroporous silica skeleton. The NTAamide(C8)/SiO₂-P adsorbent was fabricated by impregnating an NTAamide(C8) ligand into the pore of a SiO₂-P carrier under a vacuum condition. The adsorption performance of NTAamide(C8)/SiO₂-P in nitric acid medium has been systematically studied. In a solution of 0.2 M HNO₃, the distribution coefficient of Pd on NTAamide(C8)/SiO₂-P was 1848 mL/g with an adsorption percentage of 90.24%. With the concentration of nitric acid increasing, the adsorption capacity of NTAamide(C8)/SiO₂-P decreases. Compared to the other 10 potential interfering ions in fission products, NTAamide(C8)/SiO₂-P exhibited excellent adsorption selectivity for Pd(II). The separation factor (SF_{Pd/other metals} > 77.8) is significantly higher than that of similar materials. The interference of NaNO₃ had a negligible effect on the adsorption performance of NTAamide(C8)/SiO₂-P, which maintained above 90%. The adsorption kinetics of Pd(II) adsorption on NTAamide(C8)/SiO₂-P fits well with the pseudo-second order model. The Sips model is more suitable than the Langmuir and Freundlich model for describing the adsorption behavior. Thermodynamic analysis showed that the adsorption of Pd(II) on NTAamide(C8)/SiO₂-P was a spontaneous, endothermic, and rapid process. NTAamide(C8)/SiO₂-P also demonstrated good reusability and economic feasibility. Full article

Rare earth elements (REEs) are crucial for green energy applications due to their unique properties, but their extraction poses sustainability challenges because the global supply of REEs is concentrated in a few countries, particularly China, which produces 70% of the world’s REEs. To address this, the study investigated TK221, a modified extraction chromatographic resin featuring diglycolamide (DGA) and carbamoyl methyl phosphine oxide (CMPO), as a promising adsorbent for REE recovery. The elemental composition and functional groups of DGA and CMPO on the polystyrene-divinylbenzene (PS-DVB) support of TK221 were confirmed using scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX), attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), and X-ray photoelectron spectroscopy (XPS). The adsorption kinetics of neodymium (Nd), yttrium (Y), cerium (Ce), and erbium (Er) followed the pseudo-second-order kinetic model and Langmuir isotherm, indicating monolayer chemisorption. Furthermore, iron (Fe) adsorption reached apparent equilibrium after 360 min, with consistent Fe adsorption observed at both 360 min and 1440 min. The inclusion of Fe in the study is due to its common presence as an impurity in most REE leachate solutions. The Fe adsorption isotherm results are better fitted with the Langmuir isotherm, implying chemisorption. Maximum adsorption capacities (q_max) of the resin were determined as follows: Nd (45.3 mg/g), Ce (43.1 mg/g), Er (35.1 mg/g), Y (15.6 mg/g), and Fe (12.3 mg/g). ATR-FTIR analysis after adsorption suggested that both C=O and P=O bands shifted from 1679 cm⁻¹ to 1618 cm⁻¹ and 1107 cm⁻¹ to 1142 cm⁻¹ for Y, and from 1679 cm⁻¹ to 1607 cm⁻¹ and 1107 cm⁻¹ to 1135 cm⁻¹ for Ce, implying possible coordination with REEs. These results suggest that TK221 has a huge potential as an alternative adsorbent for REE recovery, thus contributing to sustainable REE supply diversification. Full article

In the present study, two chelating resins were prepared and used for simultaneous adsorption of toxic metal ions, i.e., Cr³⁺, Mn²⁺, Fe³⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺, and Pb²⁺ (M^X+). In the first step, chelating resins were prepared starting with styrene-divinylbenzene resin, a strong basic anion exchanger Amberlite IRA 402(Cl⁻) with two chelating agents, i.e., tartrazine (TAR) and amido black 10B (AB 10B). Key parameters such as contact time, pH, initial concentration, and stability were evaluated for the obtained chelating resins (IRA 402/TAR and IRA 402/AB 10B). The obtained chelating resins show excellent stability in 2M HCl, 2M NaOH, and also in ethanol (EtOH) medium. The stability of the chelating resins decreased when the combined mixture (2M HCl:EtOH = 2:1) was added. The above-mentioned aspect was more evident for IRA 402/TAR compared to IRA 402/AB 10B. Taking into account the higher stability of the IRA 402/TAR and IRA 402/AB 10B resins, in a second step, adsorption studies were carried out on complex acid effluents polluted with M^X+. The adsorption of M^X+ from an acidic aqueous medium on the chelating resins was evaluated using the ICP-MS method. The following affinity series under competitive analysis for IRA 402/TAR was obtained: Fe³⁺(44 µg/g) > Ni²⁺(39.8 µg/g) > Cd²⁺(34 µg/g) > Cr³⁺(33.2 µg/g) > Pb²⁺(32.7 µg/g) > Cu²⁺ (32.5 µg/g) > Mn²⁺(31 µg/g) > Co²⁺(29 µg/g) > Zn²⁺ (27.5 µg/g). While for IRA 402/AB 10B, the following behavior was observed: Fe³⁺(58 µg/g) > Ni²⁺(43.5 µg/g) > Cd²⁺(43 µg/g) > Cu²⁺(38 µg/g) > Cr³⁺(35 µg/g) > Pb²⁺(34.5 µg/g) > Co²⁺(32.8 µg/g) > Mn²⁺(33 µg/g) > Zn²⁺(32 µg/g), consistent with the decreasing affinity of M^X+ for chelate resin. The chelating resins were characterized using TG, FTIR, and SEM analysis. The obtained results showed that the chelating resins prepared have promising potential for wastewater treatment in the context of the circular economy approach. Full article

The immobilized cell fermentation technique (IMCF) has gained immense popularity in recent years due to its capacity to enhance metabolic efficiency, cell stability, and product separation during fermentation. Porous carriers used as cell immobilization facilitate mass transfer and isolate the cells from an adverse external environment, thus accelerating cell growth and metabolism. However, creating a cell-immobilized porous carrier that guarantees both mechanical strength and cell stability remains challenging. Herein, templated by water-in-oil (w/o) high internal phase emulsions (HIPE), we established a tunable open-cell polymeric P(St-co-GMA) monolith as a scaffold for the efficient immobilization of Pediococcus acidilactici (P. acidilactici). The porous framework’s mechanical property was substantially improved by incorporating the styrene monomer and cross-linker divinylbenzene (DVB) in the HIPE’s external phase, while the epoxy groups on glycidyl methacrylate (GMA) supply anchoring sites for P. acidilactici, securing the immobilization to the inner wall surface of the void. For the fermentation of immobilized P. acidilactici, the polyHIPEs permit efficient mass transfer, which increases along with increased interconnectivity of the monolith, resulting in higher _L-lactic acid yield compared to that of suspended cells with an increase of 17%. The relative _L-lactic acid production is constantly maintained above 92.9% of their initial relative production after 10 cycles, exhibiting both its great cycling stability and the durability of the material structure. Furthermore, the procedure during recycle batch also simplifies downstream separation operations. Full article

A novel phosphorus-containing sorbent (CyP(Ph)4–DVB) was prepared by copolymerizing divinylbenzene (DVB) with bis α,β-unsaturated phosphorylated cyclohexene (CyP(Ph)4). ATR-FT-IR indicated that the phosphinoyl group was introduced into the sorbent structure. The thermal properties of the sorbent were investigated using a differential scanning calorimeter (DSC), which revealed that (CyP(Ph)4–DVB) is more stable than poly(DVB). The CyP(Ph)4–DVB was applied for cationic dye removal, such as C.I. Basic Yellow 2 (BY2) and C.I. Basic Blue 3 (BB3). Batch adsorption tests suggested that the Freundlich isotherm model seemed to be the better one for the description of equilibrium sorption data at equilibrium, rather than the Langmuir or Temkin models. The Freundlich constants concerning the adsorption capacity of CyP(Ph)4–DVB, k_F, were calculated as 14.2 mg^1−1/nL^1/n/g for BY2 and 53.7 mg^1−1/nL^1/n/g for BB3. Full article

Modular connectors are applied by computer users, and they can be metallic secondary sources containing metals such as gold and copper. Because gold is a micro-component, the solution obtained after the pin digestion contains a low concentration of gold(III) ions, and efficient and selective sorbent should be used for gold(III) ion recovery. The selective removal of small amounts of gold(III) from 0.001–6 M hydrochloric acid solutions using pure and solvent-impregnated macroporous polystyrene crosslinked with divinylbenzene sorbents (Purolite MN 202 and Cyanex 272) is presented. Gold(III) ions were recovered effectively from the chloride solution after the digestion of the modular connector RJ 45 (8P8C) using Purolite MN 202 after the impregnation process. The dependence of the recovery percentage (R%) of gold(III) on the contact time was determined. The highest value of gold(III) ion sorption capacity (259.45 mg·g⁻¹) was obtained in 0.001 M HCl for Purolite MN202 after the Cyanex 272 impregnation. The results can be applied to gold recovery from e-waste. The presented method of gold recovery does not generate nitrogen oxides and does not require the use of cyanides. Full article

The aim of this study was to produce several flavor esters via esterification of octanoic acid with different commercial short-chain alcohols (methanol, propanol, isoamyl alcohol, hexanol and benzyl alcohol) and fusel oil in solvent-free systems. Lipase Eversa^® Transform 2.0 immobilized via mechanism of interfacial activation on poly(styrenene-divinylbenzene) (PSty-DVB) beads was used as heterogeneous biocatalyst and its catalytic performance was compared with that of the soluble lipase. The heterogeneous biocatalyst was prepared by employing 5 mmol·L⁻¹ buffer sodium acetate at pH 5.0 and 25 °C using an initial protein loading of 40 mg·g⁻¹. The maximum amount of immobilized protein reached was 31 mg·g⁻¹, corresponding to an immobilization yield of 80%. Mass transfer studies demonstrated that the lipase was preferentially adsorbed inside the pores of the support, which was confirmed by scanning electron microscopy analysis. Lipase immobilization can be described by a pseudo-first-order kinetic model via a physisorption process. When used as biocatalysts of the target reactions, the highest conversion percentage (between 65% and 85% of acid conversion after 60–90 min of reaction) values were achieved for esterification reactions catalyzed by immobilized lipase. Reusability tests revealed high retention of the original activity of the immobilized lipase after six successive batch reactions using isoamyl alcohol (47%) and fusel oil (72%). The proposed reaction systems can be considered green processes (EcoScale score above 80), with exception of methanol medium, classified as an acceptable green process (EcoScale score of 68). These results show that the heterogeneous biocatalyst prepared can be an economic and sustainable option for flavor esters production on an industrial scale. Full article

Cadmium is one of the many toxic elements for humans even at low concentrations, and it could exist in the environment for a long time. The ion imprinting technique has gained much attention due to its selective recognition performance. In this study, a cadmium ion imprinted maleic acid-co-acrylonitrile polymeric microsphere (Cd-I-MA-co-AN) was synthesized via precipitation polymerization using Cd(II) as a template ion, acrylonitrile and maleic acid as functional monomers, divinylbenzene as a cross-linker, and potassium persulfate as an initiator. UV–vis, SEM and FTIR were used for characterization, and the adsorption conditions were observed and optimized. The adsorption capacity and selectivity of Cd-I-MA-co-AN for Cd(II) were analyzed by flame atomic absorption spectrometry (FAAS). The results documented that the optimal pH, flow rate and eluent were 6, 2 mL min⁻¹ and 1 mol L⁻¹ nitric acid, respectively. Compared with the non-ion imprinted maleic acid-co-acrylonitrile polymeric microsphere (NI-MA-co-AN), Cd-I-MA-co-AN had a higher adsorption capacity. The saturated adsorption capacities of Cd-I-MA-co-AN and NI-MA-co-AN were 20.46 mg g⁻¹ and 7.64 mg g⁻¹, respectively. The adsorption behavior of Cd-I-MA-co-AN fitted with the Freundlich isotherm model. The relative selectivity coefficients of Cd-I-MA-co-AN for Cd(II) in the presence of Cu(II), Mn(II), Ni(II) and Pb(II) were 3.79, 3.39, 3.90 and 3.31, respectively. The Cd-I-MA-co-AN showed good selectivity for Cd(II). In addition, a reusability study showed that Cd-I-MA-co-AN can be recycled ten times and has high recovery in natural water samples. Full article

The practice of odorant analysis can often be very challenging because odorants are usually composed of a host of volatile organic compounds (VOCs) at low concentrations. Preconcentration with solid phase microextraction (SPME) is a conventional technique for the enrichment of these volatile compounds before analysis by headspace gas chromatography-mass spectrometry (GC-MS). However, commercially available SPME products usually bear the defects of weak mechanical strength and high cost. In this work, novel SPME fibers were prepared by a one-pot synthesis procedure from divinylbenzene (DVB), porous carbon powder (Carbon) and polydimethylsiloxane (PDMS). Factors that influence the extraction efficiency, such as extraction temperature, extraction time, salting effects, pH, stirring rate, desorption temperature and time, were optimized. VOCs in landfills pose a great threat to human health and the environment. The new SPME fibers were successfully applied in the analysis of VOCs from the leachate of a cyanobacteria landfill. Quantification methods of major odor contributors were established, and a good linearity (r > 0.998) was obtained, with detection limits in the range of 0.30–0.50 ng/L. Compared to commercial SPME fibers, the new material has higher extraction efficacy and higher precision. Hence, it is suitable for the determination of hazardous odorants of various sources. Full article

Nowadays, ibuprofen and ketoprofen are widely used over-the-counter medications to treat inflammation, fever, or pain. Their high consumption and improper disposal cause them to get into the environment and often pollute surface water. In this study, the new polymeric porous microspheres based on 4-vinylpyridine (4VP) are presented as effective sorbents for ibuprofen and ketoprofen preconcentration and removal. The porous microspheres were obtained via seed swelling polymerization with the use of two types of methacrylate crosslinkers, i.e., trimethylolpropane trimethacrylate (TRIM) and 1,4-dimethacryloiloxybenzene (14DMB). Additionally, as a reference sorbent, a copolymer of styrene and divinylbenzene was obtained. Porous structure investigations showed that the microspheres possess a specific surface area of about 100 m²/g, but noticeable differences were observed in their internal topography depending on the type of crosslinker used. Moreover, the porous structure of dry and swollen microspheres differs significantly. Swollen copolymers reveal the presence of micropores. The 4VP microspheres are characterized by high thermal stability; their initial decomposition temperature is about 300 °C. The performance of the 4VP copolymers as sorbents in aqueous solutions of drugs was evaluated in static and dynamic modes at three pH values of 3, 7, and 11. The highest sorption efficiency was obtained for ibuprofen and ketoprofen in pH 3. Both 4VP copolymers indicate the high sorption capacity in a static sorption as follows: towards ketoprofen of about 40 mg/g whereas towards ibuprofen of about 90 mg/g and 75 mg/g on copolymer crosslinked with trimethylolpropane trimethacrylate and 1,4-dimethacryloiloxybenzene, respectively. The recovery of ibuprofen and ketoprofen after dynamic sorption experiments was higher than 90%. Full article