New Journal of Chemistry最新文献

Iron–chromium redox flow batteries (ICRFBs) have attracted considerable attention due to their high safety, stability, and cost effectiveness. However, the commonly used Nafion-212 ion exchange membrane (IEM) suffers from high cost and low ion selectivity, which hinders its practical application. In this study, lignosulfonic acid (LSA) was synthesized from sodium lignosulfonate (SLS), a byproduct of the paper industry with abundant and renewable sources. Then we combined LSA with sulfonated poly (ether ether ketone) (SPEEK) to fabricate a green and low-cost composite membrane in a single cell. The abundant sulfonic and polar functional groups in LSA provided active sites for proton conduction while effectively suppressing the crossover of Fe³⁺ and Cr³⁺ ions. As a result, the membrane demonstrated excellent coulombic efficiency (CE: 99.67%) and energy efficiency (EE: 79.45%), surpassing those of the SPEEK IEM (CE: 97.24%, EE: 75.69%) after 100 cycles at a current density of 100 mA cm⁻², although its EE is slightly lower than that of the Nafion-212 IEM (CE: 95.96% and EE: 80.8%). In addition, the self-discharge time of the cell was extended to 45 h, significantly outperforming the cells using other two membranes. Our research provided a strategy of fabricating a green and cost-effective composite membrane for high-performance ICRFBs.

A one-dimensional Cr-doped chromium–zinc composite oxide nanowire desulfurizer was synthesized hydrothermally. This design was founded on the impurity doping theory of semiconductor metal oxides and the intrinsic structural advantages of one-dimensional nanostructures. As-prepared samples were characterised by scanning electron microscopy (SEM), X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET) method and X-ray photoelectron spectroscopy (XPS), enabling systematic evaluation of the influence of Cr doping concentration on the morphology, crystallinity, textural properties, and electronic structure of the nanomaterials. Furthermore, the influence of Cr doping on both the structural attributes and the desulphurisation performance was investigated in detail. The results revealed that the introduction of Cr induced the significant modifications in grain size, lattice parameters, crystal structure, and surface morphology, collectively enhancing desulfurization efficiency. Subsequent regeneration experiments demonstrated that excellent stability was maintained by the sorbent over multiple cycles. This enhanced regenerability was attributed to the ability of the one-dimensional nanowire structure to preserve its integrity under high-temperature regeneration conditions.

To further improve the efficiency and stability of quantum dot light-emitting diodes (QLEDs), it is essential to explore electron transport layers (ETLs) with superior properties. Metal oxide nanocrystals, featuring wide bandgaps, suitable energy level alignment and low cost, have been widely used as ETLs in QLEDs. In this study, we prepared oleic acid-capped TiO₂ nanocrystals with a narrow size distribution and high crystallinity. To enhance the charge transport capability of the TiO₂ ETL, these nanocrystals were chlorinated using thionyl chloride (SOCl₂), yielding alcohol-dispersible TiO₂ nanocrystals with good colloidal stability. Furthermore, a wide-bandgap CaMoO₄ interfacial layer was introduced between the ETL and the quantum dot emissive layer to suppress exciton quenching. Consequently, the optimized TiO₂-based QLEDs achieved a maximum external quantum efficiency of 11.38%, a peak luminance of 100 920 cd m⁻² and a current efficiency of 17.12 cd A⁻¹. This work provides a new strategy for the development of high-performance TiO₂-based QLEDs.

The Mn-catalyzed cross-coupling reaction of alcohols is an effective strategy for the synthesis of substituted quinolines. To understand the reaction mechanism, a density functional theory (DFT) study was carried out on the reaction of 2-aminobenzyl alcohol and 2-phenylethanol. The reaction is mainly composed of three processes: (1) the dehydrogenation of 2-aminobenzyl alcohol to produce 2-aminobenzyl aldehyde and catalyst regeneration, (2) the dehydrogenation of 2-phenylethanol to form 2-phenylacetaldehyde and catalyst regeneration, and (3) the C–N coupling of 2-aminobenzyl aldehyde and 2-phenylacetaldehyde to produce 3-substituted quinoline. For catalyst regeneration (processes 1 and 2), the 2-aminobenzyl alcohol-assisted dehydrogenation is more favorable compared to either direct dehydrogenation or 2-phenylethanol-assisted dehydrogenation. The proton transfer in process 3 was identified as the rate-controlling step, with an energy barrier of 23.9 kcal mol⁻¹. The solvent effects were also examined. The mechanistic insights gained in this study would be helpful in improving the current reaction system or designing new reactions.

A stable, water-soluble PEG–Fe(II) coordination micro-assembly achieves rapid, low-cost detection through efficient fluorescence quenching, covalent functionalization, and instant colorimetric readout. Engineered for simplicity and robustness, it enables affordable, field-ready diagnostics ideally suited for resource-limited settings and the urgent global need for scalable infectious-disease testing.

Understanding the role of open metal sites (OMS) in regulating guest-framework interactions is essential for the rational design of rare earth metal–organic frameworks (RE-MOFs) for sorption applications. Herein, we report a europium-based MOF, [Eu₂(TCPP)_1.5(DMF)₂(H₂O)]·DMF·H₂O (Eu-H₄TCPP), synthesized under solvothermal conditions. Single-crystal X-ray diffraction reveals a robust three-dimensional framework with one-dimensional channels, in which the Eu³⁺ centres are partially coordinated by labile solvent molecules. Eu-H₄TCPP exhibits high chemical stability over a wide pH range and thermal stability up to 250 °C. Variable-temperature in situ powder X-ray diffraction demonstrates that the framework remains intact during activation, accompanied by the stepwise removal of coordinated DMF and H₂O molecules to generate accessible OMS. Gas sorption measurements using N₂ and water vapour reveal that the activation-induced coordinatively unsaturated Eu³⁺ centres serve as primary binding sites, dominating the initial water uptake through direct metal-water interactions. Water vapor sorption tests demonstrate that the activated Eu-MOF delivers a prominent water uptake capacity of 0.29 g g⁻¹, which is nearly twice that of the pristine non-activated counterpart. Moreover, the activated Eu-MOF maintains stable water adsorption performance for at least three consecutive sorption–desorption cycles, showing competitive water capture capability among state-of-the-art RE-MOFs. These results highlight the crucial role of OMS accessibility in modulating water adsorption behaviour in RE-MOFs.

The coupling of environmental remediation and advanced material preparation through plant cells, also called bioreactors, is of great significance for achieving the waste valorization of pollutants. However, elucidating the intricate interactions among metal ions within bioreactors and subsequent products remains a critical challenge. Herein, a strategy of bimetallic synergistic metabolism utilizing Lemna cells to construct phase-controllable carbon-based composites for the anode of Li-ion batteries has been proposed. By systematically tuning the ratio of Fe³⁺ to Co²⁺/Ni²⁺ in simulated wastewater, the modulation of inorganic phase composition within derived-carbon can be achieved. The competitive allocation of phosphate ions by distinct metal species within bioreactors serves as a pivotal factor governing the phase evolution of metal precursors. Sulfurization effectively converts adjacent metal compounds into bimetallic sulfides. Owing to the engineered bimetallic synergy and phase architecture, the resulting composites exhibit superior “fast-charging” performance, among which the capacity of Lm-FeNi11-S remains almost unchanged (∼230 mAh g⁻¹) after 1600 cycles at a current density of 1 A g⁻¹, and still maintains a specific capacity of 185 mAh g⁻¹ at a high current density of 10 A g⁻¹. This work underscores the potential of this biometabolic pathway for converting hazardous wastewater streams into high-value energy storage materials.

In recent years, hydrogel contact lenses used as ocular drug-delivery platforms have received extensive attention in the medical field. However, they suffer from limited drug-loading capacity and rapid release profiles, typically achieving complete release within 1–2 hours, which makes it difficult to maintain long-term therapeutic efficacy. Additionally, conventional hydrogel contact lenses exhibit insufficient oxygen permeability, and long-term wear of drug-loaded lenses may lead to corneal hypoxia and increase the risk of ocular surface infections. In this study, a novel silicone hydrogel corneal contact lens loaded with hollow silica nanoparticles (HSN-SCL) was prepared using an immersion method. Levofloxacin was used as a model drug to evaluate the drug-loading capacity and release behavior of the HSN-SCL. The results showed that the drug-loading capacity of HSN-SCL reached 253.2 µg per lens with a nanoparticles content of 2 wt%. Meanwhile, the lenses exhibited an oxygen permeability of 98 Barrer while maintaining stable water content and mechanical properties. Therapeutically meaningful drug delivery was achieved under in vitro conditions. Cytotoxicity tests indicated no obvious adverse effects. These results suggest that HSN-SCL lenses can enhance drug loading while maintaining essential lens properties, providing guidance for nanoparticle-functionalized hydrogel design.

In this study, aminophenol-formaldehyde resin hollow spheres (H-APF) are directly prepared through a facile one-pot sol–gel process, which adopts the strategy of manipulating the polymerization degree of the polymer products, followed by their in situ selective dissolution. The characterization results verify the well-defined hollow architecture and abundant amine groups of the synthesized products. After carbonization, the porous N-doped carbon hollow spheres are obtained. Through a suitable reduction depositing method, gold or platinum nanoparticles are anchored onto the surface of polymer hollow spheres, exhibiting excellent activity in the selective hydrogenation of o-nitrochlorobenzene. In addition, Fe- and Co-doped H-APF hybrids with metal species embedded in their carbonaceous shells are synthesized via this facile one-pot process by introducing the corresponding precursors into the synthetic system. Compared to the metal-free sample, the metal-doped carbon hollow spheres are more efficient in the ORR process. This work demonstrates the facile synthesis of N-doped carbonaceous spheres with a hollow architecture, which have been proven to be versatile in the fields of heterogeneous catalysis and electrochemical processes.

Rational design of gold-based nanocarriers for neurotherapeutics requires atomic-scale understanding of drug-material interactions. Density functional theory calculations were performed to investigate levodopa (L-DOPA) adsorption on small gold clusters (Au₂–Au₄) with cationic, neutral, and anionic charges, with additional validation on a larger Au₁₀ cluster using multiple low-energy isomers. Binding free energies (ΔG_bind), charge transfer, and electronic descriptors were determined in gas and aqueous phases. Adsorption strength is strongly dependent on cluster charge. Cationic clusters exhibit the strongest binding, with ΔG_bind ranging from −59.7 to −41.7 kcal mol⁻¹ in the gas phase and −46.6 to −27.4 kcal mol⁻¹ in water, driven by high electrophilicity and significant ligand-to-metal charge transfer (0.66–0.82 e). Neutral clusters show moderate and adaptable binding (ΔG_bind = −28.3 to −11.1 kcal mol⁻¹), with coordination switching between Au–N and Au–O depending on ligand protonation state. Anionic clusters exhibit weak or unfavourable interactions (ΔG_bind = +1.8 to +5.0 kcal mol⁻¹). These charge-dependent trends are preserved across cluster sizes and solvation environments, and are further supported by the Au₁₀ validation, indicating robustness of the observed behaviour. The computed binding energies fall within reported ranges for amino acid adsorption on gold surfaces. From these results, three design principles emerge: (i) cationic or electronically soft gold clusters maximize binding stability; (ii) neutral clusters enable tunable adsorption behaviour; and (iii) anionic clusters are unfavourable for stable conjugation. By elucidating the electronic determinants of Au–L-DOPA interactions, this work provides fundamental insights into charge-controlled binding mechanisms that can guide the rational design of gold-based nanocarriers for neurotherapeutic applications.