Search Results (87)

Rechargeable aqueous Zn-MnO₂ batteries are positioned as a highly promising candidate for next-generation energy storage, owing to their compelling combination of economic viability, inherent safety, exceptional capacity (with a theoretical value of ≈308 mAh·g⁻¹), and eco-sustainability. However, this system still faces multiple critical challenges that hinder its practical application, primarily including the ambiguous energy storage reaction mechanism (e.g., unresolved debates on core issues such as ion transport pathways and phase transition kinetics), dendrite growth and side reactions (e.g., the hydrogen evolution reaction and corrosion reaction) on the metallic Zn anode, inadequate intrinsic electrical conductivity of MnO₂ cathodes (≈10⁻⁵ S·cm⁻¹), active material dissolution, and structural collapse. This review begins by systematically summarizing the prevailing theoretical models that describe the energy storage reactions in Zn-Mn batteries, categorizing them into the Zn²⁺ insertion/extraction model, the conversion reaction involving MnO_x dissolution–deposition, and the hybrid mechanism of H⁺/Zn²⁺ co-intercalation. Subsequently, we present a comprehensive discussion on Zn anode protection strategies, such as surface protective layer construction, 3D structure design, and electrolyte additive regulation. Furthermore, we focus on analyzing the performance optimization strategies for MnO₂ cathodes, covering key pathways including metal ion doping (e.g., introduction of heteroions such as Al³⁺ and Ni²⁺), defect engineering (oxygen vacancy/cation vacancy regulation), structural topology optimization (layered/tunnel-type structure design), and composite modification with high-conductivity substrates (e.g., carbon nanotubes and graphene). Therefore, this review aims to establish a theoretical foundation and offer practical guidance for advancing both fundamental research and practical engineering of Zn-manganese oxide secondary batteries. Full article

Mineral oil-based lubricants contain harmful elements, such as sulfur and phosphorus, pose significant harm to the environment. In current research on the application of waste oils and fats in bio-based lubricants, most studies focus on single pretreatment processes or additive preparation, lacking systematic investigations into the combined use of composite pretreatment and additives on lubricant performance. Moreover, the decolorization efficiency of traditional physical adsorption methods for treating waste oils and fats is limited, making it difficult to meet the raw material requirements for bio-based lubricants. The purpose of this study is to conduct composite pretreatment processes on waste oils and fats, understand the impacts of parameters such as additive dosage and environmental factors on lubricant performance, establish an environmentally friendly and performance-compliant preparation process for bio-based lubricants, and provide a theoretical basis and technical support for its industrial application. Recent studies have shown that new decolorization processes for waste oil treatment significantly improve decolorization and recovery rates, as evidenced by research comparing new and traditional methods. Pretreatment with hydrogen peroxide, activated clay, and activated carbon significantly improved the color and odor of treated waste oil, meeting standards for bio-based lubricant production. The intercalation polymerization reaction between ethyl cellulose (EC) and montmorillonite (MMT) was employed to develop an additive (CTAB-MMT/KH560-EC). A thorough investigation was performed to analyze the impact of temperature, processing time, and additive concentration on the rheological behavior. The bio-based lubricant exhibited a kinematic viscosity of 200.3 mm²/s at 40 °C and 28.3 mm²/s at 100 °C, meeting the standard conditions as outlined in ASTM D2270-10e1. This lubricant achieved an improved low-temperature performance with a pour point of −22 °C, a friction coefficient of 0.081, and an average pitting diameter of 0.94 mm, indicating its suitability for a range of applications. These lubricants exhibit outstanding viscosity characteristics, meeting the relevant requirements for energy and environmental applications in green, eco-friendly, and biodegradable sustainable development strategies while expanding their application scope. Full article

CdS is a promising photocatalyst for solar-driven hydrogen production due to its favorable optical properties and electronic structure. However, rapid recombination of photogenerated carriers and photocorrosion significantly limit its practical application. In this study, we developed a sustainable strategy by constructing CdS/ReS₂ nanocomposites through hydrothermal interfacial engineering. On this basis, ReS₂ nanosheets were intercalated on the surface of CdS by the hydrothermal method for catalyst modification. The introduction of ReS₂ can effectively enhance the photoelectrochemical performance of CdS and accelerate the transfer of photogenerated carriers. The effects of different ReS₂ loadings on the photocatalytic activity of CdS were explored experimentally, and the data revealed that the photocatalytic hydrogen evolution efficiency reached 50 mmol g⁻¹ h⁻¹ when the loading amount of ReS₂ was 7 wt% and did not show any obvious attenuation during four cycles. This study provides a robust surface engineering strategy to enhance the catalytic efficiency of CdS photocatalysts and provides a theoretical basis for its application in photocatalytic hydrogen precipitation. This study also emphasizes the potential of abundant, non-precious metal materials for promoting scalable, environmentally friendly hydrogen production technologies that align with the principles of green chemistry and sustainable energy systems. Full article

A series of novel guanidino-aryl (GA) compounds containing phenanthrene, fluoranthene, fluorene, and naphthalene aromatic cores were synthesized to investigate their interactions with DNA, RNA, and G-quadruplex structures. Among the novel compounds, the phenanthrene-guanidino compound demonstrated the highest micromolar affinity for AT-DNA, possibly due to partial phenanthrene intercalation in addition to hydrogen bonding and electrostatic interactions of guanidine cation. All new guanidino-aryl GA compounds bind strongly to the Tel22 G-quadruplex structure with similar affinities regardless of aromatic core size. The 1:1 stoichiometric complex is stabilised by π-π stacking interactions with the top or bottom G-tetrad, together with strong electrostatic interactions of the guanidino cation. The guanidino-porphyrin PoGU displayed distinct binding stoichiometry, indicating possible sandwiching between two G-quadruplex structures. Within the GA compounds tested, guanidino-fluorene exhibited moderate antimetabolic activity against the HeLa cell line, without selectivity against the healthy cell line. Full article

Developing high-performance photocatalysts for solar hydrogen production requires the synergistic modulation of chemical composition, nanostructure, and charge carrier transport pathways. Herein, we report a Cs and P co-doped tubular graphitic carbon nitride (Cs/PTCN-x) photocatalyst synthesized via a strategy that integrates elemental doping with morphological engineering. Structural characterizations reveal that phosphorus atoms substitute lattice carbon to form P-N bonds, while Cs⁺ ions intercalate between g-C₃N₄ layers, collectively modulating surface electronic states and enhancing charge transport. Under visible-light irradiation (λ ≥ 400 nm), the optimized Cs/PTCN-3 catalyst achieves an impressive hydrogen evolution rate of 8.085 mmol·g⁻¹·h⁻¹—over 33 times higher than that of pristine g-C₃N₄. This remarkable performance is attributed to the multidimensional synergy between band structure tailoring and hierarchical porous tubular architecture, which together enhance light absorption, charge separation, and surface reaction kinetics. This work offers a versatile approach for the rational design of g-C₃N₄-based photocatalysts toward efficient solar-to-hydrogen energy conversion. Full article

Sodium-ion batteries (SIBs) have been considered as a promising alternative to lithium-ion batteries (LIBs) for large-scale energy storage. However, the commercial graphite anode is not suitable for SIBs due to its low Na⁺ ion storage capability. Currently, hard carbon has been considered a promising anode material for SIBs. Herein, the surface porousized hard carbon anode materials have been prepared by using hydrogen peroxide (H₂O₂) with a hydrothermal method (HC-HO) and utilized as the anode material for SIBs. The porous structure of HC-HO provides more storage space for Na⁺ ions and enhances the intercalation/deintercalation reversibility and diffusion rate of Na⁺ ions. Moreover, HC-HO can effectively alleviate the particle volume expansion and generate a thin and stable SEI film during charge/discharge processes. Thus, the HC-HO exhibits a high reversible capacity (314.4 mAh g⁻¹ with an ICE of 92.3% at 0.05 C), excellent rate performance (241.4 mAh g⁻¹ at 3 C), and outstanding cycling stability (a capacity retention of 78.6% after 500 cycles at 1 C). The preparation of porous hard carbon provides new ideas for the future development direction of hard carbon. Full article

A nitro-derivative of fenamic acid (4′–nitro–fenamic acid) was synthesized and used as ligand for the synthesis of four Co(II) complexes in the absence or presence of the N,N′-donors 2,2′–bipyridylamine, 1,10–phenanthroline and 2,9–dimethyl–1,10–phenanthroline. The characterization of the resultant complexes was performed with diverse techniques (elemental analysis, molar conductivity measurements, IR and UV-vis spectroscopy, single-crystal X-ray crystallography). The biological evaluation of the compounds encompassed (i) antioxidant activity via hydrogen peroxide (H₂O₂) reduction and free radical scavenging; (ii) antimicrobial screening against two Gram-positive and two Gram-negative bacterial strains; (iii) interactions with calf-thymus (CT) DNA; (iv) cleavage of supercoiled pBR322 plasmid DNA (pDNA), in the dark or under UVA/UVB/visible light irradiation; and (v) binding affinity towards bovine and human serum albumins. The antioxidant activity of the compounds against 2,2′–azinobis–(3–ethylbenzothiazoline–6–sulfonic acid) radicals and H₂O₂ is significant, especially in the case of H₂O₂. The complexes exhibit adequate antimicrobial activity against the strains tested. The complexes interact with CT DNA through intercalation with binding constants reaching a magnitude of 10⁶ M⁻¹. The compounds have a significantly enhanced pDNA-cleavage ability under irradiation, showing promising potential as photodynamic therapeutic agents. All compounds can bind tightly and reversibly to both albumins tested. Full article

Metal complexes of endogenous metals, such as iron, copper, and zinc, offer a biocompatible, cost-effective, and eco-friendly alternative to heavy metals for drug design. This study presents the synthesis, structural characterization, and evaluation of the biological activity of eight novel iron(III) complexes with substituted salicylaldehydes as ligands. The characterization of the complexes involved spectroscopic and physicochemical methods. The structures of two complexes were determined using single-crystal X-ray crystallography. The biological studies of the complexes focused on the interaction of calf-thymus DNA, the (photo)cleavage of pBR322 plasmid DNA (pDNA), the affinity for bovine and human serum albumins, and the antioxidant activity. The complexes interacted with calf-thymus DNA via intercalation with high DNA-binding constants. The complexes exhibited high pDNA-cleavage ability, which is significantly enhanced upon exposure to UVA or UVB irradiation. The complexes can bind tightly and reversibly to both serum albumins, and their binding locations were identified. Finally, the complexes showed moderate ability to scavenge 1,1-diphenyl-picrylhydrazyl and 2,2′-azinobis-(3-ethylbenzothiazoline-6-sulfonic acid) radicals with a high ability to reduce hydrogen peroxide. Full article

Molecular modeling calculations for the design and improvement of next-generation additives for motor oils have reached a level that can support and improve experimental results. The regulation of insoluble sludge nanoparticle aggregations within oil and on engine pistons is a critical performance metric for lubricant oil additives. There is a general agreement regarding the mechanism of deposit formation which is attributed to the self-aggregation of nano-sized carbon rich insoluble structures. Dispersants are a primary category of additives employed to inhibit aggregation in lubricant formulations. Along with the base oil, they are crucial in dispersing and stabilizing insoluble particles to manage the formation of deposits. In this study, multiscale modeling methods were used to elucidate molecular mechanism of deposit control via polyisobutylene-bis-succinimide (PIBSI) dispersants by using density functional theory (DFT), molecular dynamics (MD) simulations of cells constructed by statistical sampling of molecular configurations, and coarse-grained (CG) simulations. The aim of this study was to understand the role of different groups such as succinimide, amine center, and two polyisobutylene (PIB) tails in PIBSI dispersants. It was demonstrated that the mechanism of deposit control by the polymer-based PIBSI dispersant can be elucidated through the interactions among various constituents, including hydrogen bonding and hydrophilic–hydrophobic interactions. We showed that sludge type nanoparticle aggregation is mitigated by intercalation of polar amine central groups of dispersant between the nanoparticles followed by the extension of two hydrophobic PIB chains into the oil phase that decreases coalesce further by forming a hydrophobic repulsive layer. Full article

In this work, zeolitic imidazolate frameworks (ZIF-8, ZIF-67, and ZC-ZIF) and their hybrid composites with carboxylate-functionalized carbon nanotubes (fCNTs) are synthesized through low-cost synthesis methods for enhanced physisorption-based hydrogen storage at room temperature. While both base and hybrid structures are designed to improve hydrogen uptake, the base materials exhibit the most notable performance compared to their carbon hybrid counterparts. The structural analysis confirms that all samples maintain high crystallinity and exhibit well-defined rhombic dodecahedral morphologies. The hybrid composites, due to the intercalation of fCNTs, show slightly larger particle sizes than their base materials. X-ray photoelectron spectroscopy reveals strong nitrogen–metal coordination in the ZIF structures, contributing to a larger specific surface area (SSA) and optimal microporous properties. A linear fit of SSA and hydrogen uptake indicates improved hydrogen transport at low pressures due to fCNT addition. ZIF-8 achieves the highest SSA of 2023.6 m²/g and hydrogen uptake of 1.01 wt. % at 298 K and 100 bar, with 100% reversible adsorption. Additionally, ZIF-8 exhibits excellent cyclic repeatability, with only 10% capacity reduction after five adsorption/desorption cycles. Kinetic analysis reveals that hydrogen adsorption in the ZIF materials is governed by a combination of surface adsorption, intraparticle diffusion, and complex pore filling. These findings underscore the potential of ZIFs as superior materials for room-temperature hydrogen storage. Full article

The pursuit of efficient and sustainable hydrogen production is essential in the fight against climate change. One important method for achieving this is the electrolysis of water, particularly through the oxygen evolution reaction (OER). Recent studies indicate that trimetallic layered double hydroxides (LDHs) can enhance OER performance compared to bimetallic LDHs. This improvement occurs because the third cation alters the electronic structures of the other two cations, thereby increasing the intermediates’ binding energies and enhancing electrical conductivity. This study proposes an approach enabling the modulation of the electronic structures of all three cations involved in the synthesis of the trimetallic LDHs. It suggested intercalating sodium dodecyl sulfate (SDS) into the interlayer of the trimetallic NiFe-La-LDH. A successful intercalation of SDS has been confirmed through the XRD, FT-IR, EDS, and XPS. This has expanded the interlayer distance which was beneficial for the electrical conductivity. Furthermore, SDS generated sulphur, which modulated the electronic structures of all three cations enriching the active sites and improving electrical conductivity and OER performance compared to its counterparts. This approach is beneficial: 1. The interlayer can be further enlarged by using different doping ratios of SDS. 2. Sulphur can enrich the active sites and improve the OER performance. Full article

Many properties of 2,4-dichlorophenoxyacetic acid (2,4-D) depend on its molecular environment, such as whether it is an isolated molecule, a dimer, or in a crystalline state. The molecular geometry, conformational analysis, and vibrational spectrum of 2,4-D were theoretically calculated using Density Functional Theory (DFT) methods. A new slightly more stable conformer was found, which is different to those previously reported. The most stable conformer shows a dimer by means of hydrogen bonds between the carboxylic groups of both molecules, which agrees with the experimental results. The crystal structure of 2,4-D was also calculated with 3D periodical boundary conditions at the DFT level. From the theoretical IR spectra, a vibrational analysis of this molecular species was accomplished, and the bands were reassigned. ¹H and ¹³C NMR in the dissolution and solid states, respectively, showed intramolecular hydrogen bonds between carboxylic acid groups. The dimer is more stable than the isolated molecule. All these results indicated that the dimer can also exist in the solid state, which could explain the low solubility of this compound. In addition, the intercalation of 2,4-D into the confined interlayer space of montmorillonite was also calculated, and it was found that the adsorption is energetically favourable. This result was experimentally confirmed. These findings predicted that these natural clay minerals, which are found in the environment, can be excellent adsorbents for the 2,4-D pollutant. Full article

Background: Melanoma is the most aggressive and lethal skin cancer that affects thousands of people worldwide. Ruthenium complexes have shown promising results as cancer chemotherapeutics, offering several advantages over platinum drugs, such as potent efficacy, low toxicity, and less drug resistance. Additionally, anthraquinone derivatives have broad therapeutic applications, including melanoma. Objectives: Thus, two new ruthenium complexes with 1-hydroxy-9,10-anthraquinone were obtained: trans-[Ru(HQ)(PPh₃)₂(bipy)]PF₆ (1) and cis-[RuCl₂(HQ)(dppb)] (2), where HQ = 1-hydroxy-9,10-anthraquinone, PPh₃ = triphenylphospine, bipy = 2,2′-bipyridine, PF₆ = hexafluorophosphate, and dppb = 1,4-bis(diphenylphosphine)butane. Methods: The complexes were characterized by infrared (IR), UV–vis, ¹H, ¹³C{¹H}, and ³¹P{¹H} NMR spectroscopies, molar conductivity, cyclic voltammetry, and elemental analysis. Furthermore, density functional theory (DFT) calculations were performed. Results: Compound (2) was determined by single-crystal X-ray diffraction, which confirms the bidentate coordination mode of HQ through the carbonyl and phenolate oxygens. Additionally, DNA-binding experiments yielded constants of 10⁵ M⁻¹ (Kb = 6.93 × 10⁵ for (1) and 1.60 × 10⁵ for (2)) and demonstrate that both complexes can interact with DNA through intercalation, electrostatic attraction, or hydrogen bonding. Conclusions: The cytotoxicity profiles of the compounds were evaluated in human melanoma cell lines (SK-MEL-147, CHL-1, and WM1366), revealing greater cytotoxic activity for (1) on the CHL-1 cell line with an IC₅₀ of 14.50 ± 1.09 µM. Subsequent studies showed that (1) inhibits the proliferation of CHL-1 cells and induces apoptosis, associated at least in part with the pro-oxidant effect and cell cycle arrest at the G1/S transition. Full article

This review explores the removal of textile dyes from wastewater using advanced polymer/clay composites. It provides an in-depth analysis of the chemical and physical properties of these composites, emphasizing how the combination of polymers and clays creates a synergistic effect that significantly improves the efficiency of dye removal. The structural versatility of the composites, derived from the interaction between the layered clay sheets and the flexible polymer matrices, is detailed, showcasing their enhanced adsorption capacity and catalytic properties for wastewater treatment. The review outlines the key functional groups present in both polymers and clays, which are crucial for binding and degrading a wide range of dyes, including acidic, basic, and reactive dyes. The role of specific interactions, such as hydrogen bonding, ion exchange, and electrostatic attractions between the dye molecules and the composite surface, is highlighted. Moreover, the selection criteria for different types of clays such as montmorillonite, kaolinite, and bentonite and their modifications are examined to demonstrate how structural and surface modifications can further improve their performance in composite materials. Various synthesis methods for creating polymer/clay composites, including in situ polymerization, solution intercalation, and melt blending, are discussed. These fabrication techniques are evaluated for their ability to control particle dispersion, optimize interfacial bonding, and enhance the mechanical and chemical stability of the composites. Furthermore, the review introduces advanced characterization techniques, such as X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR), and thermogravimetric analysis (TGA), to help researchers assess the morphological, structural, and thermal properties of the composites, aligning these features with their potential application in dye removal. Additionally, the review delves into the primary mechanisms involved in the dye removal process, such as adsorption, photocatalytic degradation, and catalytic reduction. It also provides an overview of the kinetic and thermodynamic models commonly used to describe the adsorption processes in polymer/clay composites. The environmental and operational factors influencing the efficiency of dye removal, such as pH, temperature, and composite dosage, are analyzed in detail, offering practical insights for optimizing performance under various wastewater conditions. In conclusion, this review not only highlights the promising potential of polymer/clay composites for textile dye removal but also identifies current challenges and future research directions. It underscores the importance of developing eco-friendly, cost-effective, and scalable solutions to address the growing concerns related to water pollution and sustainability in wastewater management. Full article

Seawater electrolysis represents a promising green energy technology with significant potential for efficient energy conversion. This study provides an in-depth examination of the key scientific challenges inherent in the seawater-electrolysis process and their potential solutions. Initially, it analyzes the potential issues of precipitation and aggregation at the cathode during hydrogen evolution, proposing strategies such as self-cleaning cathodes and precipitate removal to ensure cathode stability in seawater electrolysis. Subsequently, it addresses the corrosion challenges faced by anode catalysts in seawater, introducing several anti-corrosion strategies to enhance anode stability, including substrate treatments such as sulfidation, phosphidation, selenidation, and LDH (layered double hydroxide) anion intercalation. Additionally, this study explores the role of regulating the electrode surface microenvironment and forming unique coordination environments for active atoms to enhance seawater electrolysis performance. Regulating the surface microenvironment provides a novel approach to mitigating seawater corrosion. Contrary to the traditional understanding that chloride ions accelerate anode corrosion, certain catalysts benefit from the unique coordination environment of chloride ions on the catalyst surface, potentially enhancing oxygen evolution reaction (OER) performance. Lastly, this study presents the latest advancements in the industrialization of seawater electrolysis, including the in situ electrolysis of undiluted seawater and the implementation of three-chamber dual anion membranes coupled with circulating electrolyte systems. The prospects of seawater electrolysis are also explored. Full article