Search Results (205)

Photocatalytic CO₂ reduction holds great potential for sustainable solar fuel production, yet its practical application is often limited by inefficient charge separation and poor product selectivity. The photothermal effect presents a viable strategy to address these challenges by reducing activation energies and accelerating reaction kinetics. In this work, we report a rationally designed CN-B/Ti₃C₂ heterojunction that effectively leverages photothermal promotion for enhanced CO₂ reduction. The black carbon nitride (CN-B) framework, synthesized via a one-step calcination of urea and Phloxine B, exhibits outstanding photothermal conversion, reaching 131.4 °C under 300 mW cm⁻² illumination, which facilitates CO₂ adsorption and charge separation. Coupled with Ti₃C₂ MXene, the optimized composite (3:1) achieves remarkable CO and CH₄ production rates of 80.21 and 35.13 μmol g⁻¹ h⁻¹, respectively, without any cocatalyst—representing a 2.9-fold and 8.8-fold enhancement over CN-B and g-C₃N₄ in CO yield. Mechanistic studies reveal that the improved performance stems from synergistic effects: a built-in electric field prolongs charge carrier lifetime (3.15 ns) and reduces interfacial resistance, while localized heating under full-spectrum light further promotes CO₂ activation. In situ Fourier transform infrared (FTIR) spectroscopy confirms the accelerated formation of key intermediates (*COOH and *CO). The catalyst also maintains excellent stability over 24 h. This study demonstrates the promise of combining photothermal effects with heterojunction engineering for efficient and durable CO₂ photoreduction. Full article

Near-complete (>99%) dissolution of lithium and cobalt was achieved by the leaching of black mass from spent (end-of-life) lithium-ion batteries (LiBs) using 4 M H₂SO₄ or HCl at 60 °C. Raising the temperature to 90 °C did not increase the overall extraction of lithium or cobalt, but it increased the rate of extraction. At 60 °C, 2 M H₂SO₄ or 2 M HCl performed similarly to the 4 M H₂SO₄/HCl solution, although extractions were lower using 1 M H₂SO₄ or HCl (~95% and 98%, respectively). High extractions were also observed by leaching in low pulp density (15 g/L) at 60 °C with 2 M CH₂ClCOOH. Leaching was much slower with hydrogen peroxide reductant concentrations below 0.5 mol/L, with cobalt extractions of 90–95% after 3 h. Pulp densities of up to 250 g/L were tested when leaching with 4 M H₂SO₄ or HCl, with the stoichiometric limit estimated for each test based on the metal content of the black mass. Extractions were consistently high, above 95% for Li/Ni/Mn/Cu with a pulp density of 150 g/L, dropping sharply above this point because of insufficient remaining acid in the solution in the later stages of leaching. The final component of the test work used leaching parameters identified in the previous experiments as producing the largest extractions, and just sulphuric acid. A seven-stage semi-continuous sulphuric acid leach at 60 °C of black mass from LiBs that had undergone an oxidising roast (2h in a tube furnace at 500 °C under flowing air) to remove binder material resulted in high (93%) extraction of cobalt and near total (98–100%) extractions of lithium, nickel, manganese, and copper. Higher cobalt extraction (>98%) was expected, but a refractory spinel-type cobalt oxide, Co₃O₄, was generated during the oxidising roast as a result of inefficient aeration, which reduced the extraction efficiency. Full article

Viologens are promising candidates for next-generation electrochromic devices due to their reversible color changes, low operating voltages, and structural tunability. However, their practical performance is often constrained by limited color range, stability issues, and poor charge delocalization. In this study, we present a detailed density functional theory (DFT) and time-dependent DFT (TD-DFT) investigation of asymmetric viologens based on the Benzyl-4,4′-dipyridyl-R (BnV-R) framework. A series of electron-donating and electron-withdrawing substituents (CN, COOH, PO₃H₂, CH₃, OH, NH₂) were introduced via either benzyl or phenyl linkers. Geometry optimizations for neutral, radical cationic, and dicationic states were performed at the CAM-B3LYP/6-31+G(d,p) level with C-PCM solvent modeling. Electronic structure, frontier orbital distributions, and redox potentials were correlated with substituent type and linkage mode. Natural Bond Orbital analysis showed that electron-withdrawing groups stabilize reduced states, while electron-donating groups enhance intramolecular charge transfer and switching kinetics. TD-DFT calculations revealed significant bathochromic and hyperchromic shifts dependent on substitution patterns, with phenyl linkers promoting extended conjugation and benzyl spacers minimizing aggregation. Radical cation stability, quantified via ΔE_red and comproportionation constants, highlighted cyano- and amine-substituted systems as particularly promising. These insights provide predictive design guidelines for tuning optical contrast, coloration efficiency, and electrochemical durability in advanced electrochromic applications. Full article

Photocatalytic conversion of CO₂ to hydrocarbon fuels offers a promising pathway for sustainable renewable energy production. In this study, a ZnO/ZnFe₂O₄ composite featuring a Type-II heterojunction was synthesized through a facile one-step hydrothermal approach, significantly enhancing visible-light-driven CO₂ reduction activity. The optimized catalyst exhibits CH₄ and CO production rates that are 3.3 and 4.9 times higher, respectively, than those of pristine ZnFe₂O₄ over 6 h. This significant enhancement in photocatalytic performance is attributed to the Type-II band alignment, which not only broadens light absorption but also greatly promotes efficient charge separation. It is corroborated by a series of experimental evidence: a two-fold enhancement in photocurrent response, a 15.1% reduction in PL intensity, decreased electrochemical impedance, and an extended charge carrier lifetime. Furthermore, in situ FTIR spectroscopy confirms that the heterojunction facilitates the formation of key intermediates (specifically *COOH and HCOO⁻). This study highlights the importance of precise interface design based on a Type-II heterojunction in heterostructured composite catalysts and provides mechanistic insights for developing highly efficient CO₂ photoreduction systems. Full article

Alkaptonuria (AKU) is a rare metabolic disorder caused by homogentisate 1,2-dioxygenase (HGD) deficiency, leading to homogentisic acid (HGA) accumulation and ochronotic pigment deposition, which drug therapy cannot reverse. The process of pigment formation and deposition is still unclear. This study offers molecular insights into the polymeric structure, with the goal of developing future adjuvant strategies that can inhibit or reverse pigment formation, thereby complementing drug therapy in AKU. HGA polymerisation was examined under physiological, acidic, and alkaline conditions using liquid and solid phase nuclear magnetic resonance (NMR), electron paramagnetic resonance (EPR), and polyacrylamide gel electrophoresis. At physiological pH, HGA polymerised slowly, while alkaline catalysis accelerated pigment formation while retaining the HGA aromatic scaffold. During the process, EPR detected a semiquinone radical intermediate, consistent with an oxidative coupling mechanism. Reactivity profiling showed the diphenol ring was essential for polymerisation, while –CH₂COOH modifications did not impair reactivity. Pigments displayed a polydisperse molecular weight range (11–50 kDa) and a strong negative charge. Solid-state NMR has revealed the presence of phenolic ether and biphenyl linkages. Collectively, these identified structural motifs can serve as a foundation for future molecular targeting related to pigment formation. Full article

In this work, pCh-MWCNTs@Ag-TiO₂/S and pCh-MWCNTs@Ag-TiO₂ nanocomposites were synthesized through a combined phosphorylation and cross-linked polymerization method. The materials were thoroughly characterized using several analytical techniques, including SEM/EDS, FTIR, TGA, and BET analysis. SEM images revealed that the pCh-MWCNTs@Ag-TiO₂/S nanocomposite displayed a smooth, flake-like morphology with spherical, dark greenish particles. EDS analysis confirmed the presence of Si, S, P, and Ag as prominent elements, with Ti, C, and O showing the most intense peaks. The TGA curves indicated significant weight loss between 250–610 °C for pCh-MWCNTs@Ag-TiO₂ and 210–630 °C for pCh-MWCNTs@Ag-TiO₂/S, corresponding to the decomposition of organic components. FTIR spectra validated the existence of functional groups such as hydroxyl (-OH), carboxyl (-COOH), and carbonyl (-C=O) on the surface of the nanocomposites. Following characterization, the materials were evaluated for their capacity to adsorb Hg²⁺ at parts-per-billion (ppb) concentrations in contaminated water. Batch adsorption experiments identified optimal conditions for mercury removal. For pCh-MWCNTs@Ag-TiO₂, the best performance was observed at pH 4, with an adsorbent dose of 4.0 mg, initial mercury concentration of 16 ppb, and a contact time of 90 min. For pCh-MWCNTs@Ag-TiO₂/S, optimal conditions were at pH 6, a dosage of 3.5 mg, the same initial concentration, and a contact time of 100 min. Each parameter was optimized to determine the most effective conditions for Hg²⁺ removal. The nanocomposites showed high efficiency, achieving more than 95% mercury removal under these conditions. Kinetic studies indicated that the adsorption process followed a pseudo-second-order model, while the equilibrium data aligned best with the Langmuir isotherm, suggesting monolayer adsorption behavior. Overall, this research highlights the effectiveness of sulfur-modified chitosan-based nanocomposites as eco-friendly and efficient adsorbents for the removal of mercury from aqueous systems, offering a promising solution for water purification and environmental protection. Full article

Elucidating the mechanisms of CO₂ photocatalytic conversion systems is crucial for tackling the challenges of carbon neutrality. In this study, a series of Ag@g-C₃N₄ photocatalysts were constructed with metal particle size modulation as the core strategy to systematically reveal the modulation mechanism of Ag nanoparticles (Ag NPs) size variation on the selectivity of CO₂ photoreduction products. Systematic characterizations revealed that increasing Ag size enhanced visible light absorption, promoted charge separation, and improved CH₄ selectivity. Photocatalytic tests showed Ag_3.0%@CN achieved optimal activity and electron utilization. Energy band analyses indicated that Ag modification preserved favorable conduction band positions while increasing donor capacity. Further density-functional theory (DFT) calculations reveal that Ag NPs size variations significantly affect the adsorption stability and conversion energy barriers of intermediates such as *COOH, CO and CHO, with small-sized Ag₇ NPs favoring the CO pathway, while large-sized Ag NPs stabilize the key intermediates and drive the reaction towards the CH₄ pathway evolution. The experimental and theoretical results corroborate each other and clarify the dominant role of Ag NPs size in regulating the reaction path between CO and CH₄. This study provides mechanistic guidance for the selective regulation of the multi-electron reduction pathway, which is of great significance for the construction of efficient and highly selective CO₂ photocatalytic systems. Full article

With the development of the new energy industry in high-altitude regions, epoxy resin insulating materials in electrical equipment face severe challenges from prolonged exposure to strong radiation environments. Strong ultraviolet irradiation induces the generation of free radicals such as alkyl (CH₂), alkoxy (CH₂O), and peroxyl (CH₂OO), which continuously attack the cross-linking structure of epoxy resin, leading to its degradation. This study employs molecular dynamics simulations to evaluate the enhancing effect of graphene quantum dots (GQDs) on the radiation resistance of epoxy resin (EP), proposing cross-linking structural integrity as an evaluation criterion. It compares and analyses pure EP (EP/neat), hydrogen-terminated GQDs (EP/GQD_C₅₄H₁₈), and carboxyl-terminated GQDs (EP/GQD_COOH) under three types of free radicals. The results indicate that the unique sp² hybrid structure and hydrogen-donating ability of GQDs can effectively inhibit the activity of free radicals, and improve the integrity of the cross-linked structure by 8% to 16% compared to EP/neat. While both types of GQDs demonstrate comparable behavior in response to alkyl free radicals, EP/GQD_COOH exhibits superior performance under the influence of oxygen-containing free radicals. This enhanced performance can be attributed to its augmented hydrogen-donating capacity and an increased number of active sites. This study investigates the extent to which GQDs with different structures enhance the radiation resistance of epoxy resins, providing an important theoretical basis for the modification of epoxy resins for applications in high-radiation environments. Full article

Natural clinoptilolite from the Shankhanai deposit (Kazakhstan) was modified via acid and thermal treatments to improve its physicochemical and catalytic properties. The zeolite was activated using 10% nitric acid alone, nitric acid followed by thermal treatment (600 °C), and a mixed acid solution (10% HNO₃ + 5% CH₃COOH) followed by mild thermal treatment (280 °C). Structural, textural, and thermal changes were characterized by XRD, FTIR, BET, TGA, SEM, and EDX. Nitric acid treatment increased the BET surface area from 4.95 to 59.9 m²/g but reduced crystallinity, whereas the dual-acid approach enhanced porosity and acidity while preserving framework integrity. Preliminary catalytic testing in thiophene hydrodesulfurization (HDS) revealed improved conversion (up to 20.7%) in the absence of active metals, confirming the potential of modified clinoptilolite as a catalyst support. The dual-acid method presents a promising, eco-friendly pathway for producing thermally stable and catalytically active zeolitic materials, suitable for selective hydrodesulfurization of thiophene. Full article

Engineering phase-selective gel composites presents a promising route to enhance both CO₂ adsorption and conversion efficiency in photocatalytic systems. In this work, Cu₉S₅/TiO₂ gel composites were synthesized via a hydrazine-hydrate-assisted hydrothermal method, using TiO₂ derived from a microwave-assisted sol–gel process. The resulting materials exhibit a porous gel-derived morphology with highly dispersed Cu₉S₅ nanocrystals, as confirmed by XRD, TEM, and XPS analyses. These structural features promote abundant surface-active sites and interfacial contact, enabling efficient CO₂ adsorption. Among all samples, the optimized 0.36Cu₉S₅/TiO₂ composite achieved a methane production rate of 34 μmol·g⁻¹·h⁻¹, with 64.76% CH₄ selectivity and 88.02% electron-based selectivity, significantly outperforming Cu₉S₈/TiO₂ synthesized without hydrazine hydrate. This enhancement is attributed to the dual role of hydrazine: facilitating phase transformation from Cu₉S₈ to Cu₉S₅ and modulating the interfacial electronic environment to favor CO₂ capture and activation. DFT calculations reveal that Cu₉S₅/TiO₂ effectively lowers the energy barriers of critical intermediates (*COOH, *CO, and *CHO), enhancing both CO₂ adsorption strength and subsequent conversion to methane. This work demonstrates a gel-derived composite strategy that couples efficient CO₂ adsorption with selective photocatalytic reduction, offering new design principles for adsorption–conversion hybrid materials. Full article

Many industries release untreated synthetic dye effluents into water bodies, harming ecosystems and human health. Therefore, an economical and sustainable solution for treating dye-contaminated water must be developed. In this study, mulberry leaves (Morus nigra L.), as a cost-effective and sustainable adsorbent, were prepared to remove Basic Yellow 28 (BY28) and Basic Blue 3 (BB3) cationic dyes from industrial dye wastewater using adsorption. Batch experiments with key variables such as initial dye concentration, adsorbent dosage, contact time, temperature, stirring speed, and pH were conducted to find optimal conditions. The effectiveness of mulberry leaves as an adsorbent after multiple regeneration cycles was examined. The adsorbent was characterized through various instrumental methods, including FTIR, SEM, XRD, and BET analysis. Adsorption performance was analyzed using the Langmuir and Freundlich isotherm models. The results showed that the mulberry leaf adsorbent best fits the Langmuir model, with R² values of 0.999 for BY28 and 0.973 for BB3. The maximum adsorption capacities were 0.15 mg/g for BY28 and 7.19 mg/g for BB3, indicating their upper limits for dye uptake. The optimal conditions achieving removal efficiencies of over 99% were 1.5 g, 50 mL, 15 min, 180 rpm, and 10 mg/L at 30 °C for BY28 in neutral pH (7) and 1.5 g, 50 mL, 45 min, 100 rpm, and 30 mg/L at 40 °C for BB3 in basic pH (10). The regeneration of mulberry leaves as an adsorbent through acid treatment with 0.1 M HCl and 0.1 M CH₃COOH solutions maintained a high performance, achieving up to 98% dye removal efficiency after two regeneration cycles. It has been observed that successful results can be achieved in terms of reusability. Additionally, the removals of BB3 and BY28 performed in an ultrasonic-bath-assisted environment successfully achieved removal efficiencies of 84.87% and 75.41%, respectively. According to the results, mulberry leaves can effectively be used in wastewater treatment to remove dyes, can be reused multiple times, and thus serve as an environmentally friendly and sustainable adsorbent. Full article

This study evaluated the inhibitory efficacy of sulphur dioxide, hydrogen peroxide, copper sulphate pentahydrate, chlorine-based formulations, a chlorine-free formulation, ethanol, and acetic acid against Cladosporium cladosporioides, Aspergillus niger, and Penicillium expansum. An in vitro inhibition test was employed to investigate the inhibitory properties. The results demonstrated different sensitivities of filamentous fungi to the inhibitors. All tested substances displayed fungicidal properties. Sulphur dioxide (40% NH₄HSO₃ solution) inhibited growth at a 4% v/v concentration. No minimum effective concentration was established for H₂O₂; only a 30% w/v solution inhibited P. expansum. CuSO₄·5H₂O completely inhibited fungal growth at 5% w/v solution, with 2.5% w/v also proving effective. For the chlorine-based product, 40% w/v solution (48 g∙L⁻¹ active chlorine) had the most substantial effect, though it only slowed growth, and NaClO solution completely inhibited growth at 2.35 g NaClO per 100 g of product (50% w/v solution). FungiSAN demonstrated fungicidal effects; however, the recommended dose was insufficient for complete inhibition. Ethanol exhibited the lowest efficacy, while the inhibitory threshold for CH₃COOH was found to be a 5% v/v solution. The findings of this study may serve as a basis for informed decision-making when selecting the most suitable product, depending on specific application conditions. Full article

Prolonged drought and soil degradation severely affect soil fertility and limit crop productivity. Superabsorbent hydrogels offer an effective solution for improving water retention in soil and supporting plant growth. In this work, we examined the performance of superabsorbent hydrogels based on sodium alginate, acrylic acid (AA), and poly (ethylene oxide) (PEO) cross-linked with 12.5 kGy using e-beam irradiation. The hydrogels were assessed in various aqueous environments by examining network characteristics, swelling capacity, and swelling kinetics to evaluate the impact of water’s electrical conductivity (which ranges from 0.05 to 321 μS/cm). Morphological and chemical structure changes were evaluated using SEM and FTIR techniques. The results demonstrated that water conductivity significantly affected the physicochemical properties of the hydrogels. Swelling behavior showed notable sensitivity to electrical conductivity variations, with swelling degrees reaching 28,400% at 5 μS/cm and 14,000% at 321 μS/cm, following first-order and second-order kinetics. FTIR analysis confirmed that structural modifications correlated with water conductivity, particularly affecting the O–H, C–H, and COOH groups sensitive to the ionic environment. SEM characterization revealed a porous morphology with an interconnected microporous network that facilitates efficient water diffusion. These hydrogels show exceptional swelling capacity and are promising candidates for sustainable agriculture applications. Full article

The study at the Peggy Guggenheim Collection in Venice highlights critical interactions between indoor air quality, visitor dynamics, and microclimatic conditions, offering insights into preventive conservation of modern artworks. By analyzing pollutants such as ammonia, formaldehyde, and organic acids, alongside visitor density and environmental data, the research identified key patterns and risks. Through three seasonal monitoring campaigns, the concentrations of SO₂ (sulphur dioxide), NO (nitric oxide), NO₂ (nitrogen dioxide), NO_x (nitrogen oxides), HONO (nitrous acid), HNO₃ (nitric acid), O₃ (ozone), NH₃ (ammonia), CH₃COOH (acetic acid), HCOOH (formic acid), and HCHO (formaldehyde) were determined using passive samplers, as well as temperature and relative humidity data loggers. In addition, two specific short-term monitoring campaigns focused on NH₃ were performed to evaluate the influence of visitor presence on indoor concentrations of the above compounds and environmental parameters. NH₃ and HCHO concentrations spiked during high visitor occupancy, with NH₃ levels doubling in crowded periods. Short-term NH₃ campaigns confirmed a direct correlation between visitor numbers and the above indoor concentrations, likely due to human emissions (e.g., sweat, breath) and off-gassing from materials. The indoor/outdoor ratios indicated that several pollutants originated from indoor sources, with ammonia and acetic acid showing the highest indoor concentrations. By measuring the number of visitors and microclimate parameters (temperature and humidity) every 3 s, we were able to precisely estimate the causality and the temporal shift between these quantities, both at small time scale (a few minute delay between peaks) and at medium time scale (daily average conditions due to the continuous inflow and outflow of visitors). Full article

The present work reports the synthesis and structural design of three novel Zn(II) complexes [Zn(L¹)(CH₃COO)(H₂O)] (1), [Zn(L²)₂] (2), and [Zn(L³)₂] (3) with carbazate ligands, 2-acetylpyridine-methylcarbazate (HL¹), 2-acetylpyridine-ethylcarbazate (HL²), and 2-acetylpyridine-benzylcarbazate (HL³). All compounds were characterized by spectroscopic methods, and the crystal structures of the complexes were elucidated by single-crystal X-ray. Based on the analysis, distorted square pyramid geometry is suggested for complex (1) and an octahedral geometry is suggested for complexes (2) and (3) with the ligands exhibiting an NNO-donor system. The 3D Hirshfeld surface and the 2D fingerprint plot were used to study the non-covalent interactions in the crystal structures. The in vitro antibacterial investigation of the free ligands and their complexes was performed against different strains of periodontopathogen bacteria. The Zn(II) complexes showed more potent antibacterial activity than the free ligand. Molecular docking studies showed the metal complexes as promising candidates for further therapeutic exploration, particularly in targeting the ATP-binding cassette transporter with peptidase domain of the cariogenic bacteria S. mutans (PDB code 5XE9) and the prolyl tripeptidyl aminopeptidase from P. gingivalis anaerobic bacteria (PDB code 2EEP) inhibition. Full article