Journal of Molecular Liquids最新文献

The presence of diverse functionalities, tuneable pore size, and arrangements make block copolymers (BCPs) an effective choice for membrane technology. The self-assembly induces the development of different nanostructures enable the formation of different membranes with diverse porosity, like microfiltration membranes, nanofiltration membranes, etc. Thus, the fabrication of ultrathin membranes out of the BCPs enables its use in different fields like catalysis, water purification, molecular separation, air filtration, and dye degradation. Even though there are reviews on block copolymer membranes (BCMs) in water purification, there are no reviews on the applications of BCMs in biomedical applications and environmental remediation. Hence this review tries to bridge the gap by giving insights into the fabrication, properties, and applications of BCMs in different areas like environmental remediation, molecular separation, biomedical applications, and fuel cells. The review portrays the different synthesis methods followed for BCM fabrication like SNIPS, NIPS, solvent casting, and etching comprehensively. The properties of the BCMs and their size tunability are well-discussed to give more clarity to the researchers in this field. The review helps in identifying the suitable BCP, and the fabrication methods for tuning the properties, especially the size of pores for the judicious selection of BCMs for appropriate application. BCMs show better performance compared to conventional membranes but fouling, cost, scalability, stability, and complex synthesis limit their high-end applications. This drawback can be reduced up to a certain extent by surface functionalization and crosslinking of BCMs, and by introducing stimuli responsive characteristics. This review tries to address the limitations and put forward some new ideas for the successful utilization of BCMs for advanced applications. Thus, the review gives new insights to the researchers and scientists working in the field of membranes and their applications.

Merocyanine 540 (MC540) is a dye molecule that displays diverse photophysical features in varying environments. Micelle environments exert intriguing influences on the behavior of such molecules. This study’s primary objective is to examine the spectroscopic and thermodynamic consequences with different surfactants on the aggregation tendency of MC540. Interactions of MC540 with negatively charged sodium dodecyl sulphate (SDS), neutral triton X-100 (TX100) and positively charged hexadecyltrimethylammonium bromide (CTAB) surfactants were investigated by using molecular absorption spectroscopy. The interactions of MC540 with the SDS, CTAB, and TX100 under and above critical micelle concentration (CMC) were studied and H aggregate formation was observed under CMC. This H aggregate structure leaded to a shift towards monomer band above the CMC of SDS, TX100, CTAB according to the H aggregate-monomer equilibrium. Moreover, it was firstly observed that MC540 has trimer type aggregate structures as well with varying CTAB concentrations. In addition, by using temperature studies, thermodynamic function ΔH⁰_dis values, dimer and trimer structures, were calculated as 6.10 kcal/mol, and 8.94 kcal/mol, respectively, and ΔS⁰_dis values for dimer and trimer structures as −3.87 cal/Kmol, and −18.39 cal/Kmol, respectively. The calculated thermodynamic functions showed that disaggregation of aggregates is endothermic in nature and entropy is the driving force.

We report an easy process to prepare new anionic and zwitterionic surfactants to break water in Arabian heavy crude oil emulsions (W/O) with different compositions (10/90, 30/70 and 50/50 vol%). Surfactants were prepared in only two stages using simple methodology. Diethylenetriamine was interacted with three moles of glycidyl 4-nonyl ether followed by the interaction with 3 and 8 mol of 1,3-propanesultone to yield TNDTS-3 and TNDTS-8 respectively. FTIR and NMR spectroscopies were carried out to substantiate the chemical structures of surfactants. Relative solubility number (RSN), surface activity and solubility properties were determined. Demulsification efficiencies and interfacial tension (IFT) of the prepared surfactants were investigated. Our findings demonstrated that increasing propyl sulfonate groups in the surfactant structure improved water solubility, IFT activity and demulsification efficiency. TNDTS-8 achieved 100 % demulsification activities in all W/O emulsions (10/90, 30/70 and 50/50 vol%).

The design of semiconductor heterostructures as the effective strategy are recognized to enhance the photocatalytic capacity of photocatalysts for the settlement of energy shortage and pollutant treatment. To efficiently utilize solar energy, the Bi₂O₃-Sn₃O₄ nanoparticles with the Z-scheme energy band structure were synthesized on TiO₂ nanotube arrays (TiO₂ NTs) by the solvothermal deposition method. The TiO₂ NTs/Bi₂O₃-Sn₃O₄ exhibited the outstanding photocatalytic dye degradation and Cr(VI) removal, which was much higher than those of single Bi₂O₃ or Sn₃O₄ sensitized samples. The H₂ evolution test indicated that the Bi₂O₃-Sn₃O₄ cosensitization dramatically enhanced the photocatalytic H₂ generation ability of TiO₂ NTs with the rate of 58.75 μmol·h⁻¹·cm⁻². The high photoelectric conversion was also confirmed, and the outstanding photocatalytic performance was further revealed by the contrast experiment. The plausible photocatalytic mechanism based on the ESR and capturing experiments indicated that the Z-scheme energy band structure induced the photoelectron separation and the generation of O₂ and OH radicals, which was the decisive role for the improved photocatalytic performance.

Octogen (HMX) is the most powerful military explosive in current use. However, the unclear thermodynamic molecular mechanisms severely limit the development of its production process. In this paper, the solubility of β-HMX in three binary mixed solvent systems (acetone + ethanol, acetone + dichloromethane, acetone + toluene) was measured via a dynamic method at temperature ranging from 283.15 to 313.15 K under atmospheric pressure. The experimental results reveal that the solubility of β-HMX in these binary mixed solvent systems is positively correlated with acetone molar fraction and temperature, and the solvent composition has a greater impact on its solubility compared with the temperature. Moreover, the solubility of β-HMX is further correlated with the Van’t Hoff equation, modified Apelblat equation, CNIBS/R-K model, Jouyban-Acree-Van’t Hoff model, Jouyban-Acree-Apelblat model and NRTL model, and the modified Apelblat equation can give better fitting result (ARD = 8.101 × 10⁻³, RMSD = 1.065 × 10⁻⁵). Finally, the microscopic mechanism of the thermodynamic properties of β-HMX in binary mixed solvents is revealed by investigating the types, intensity and interaction sites of interactions based on density functional theory (DFT) and molecular dynamic (MD) simulation. The results demonstrate that both acetone molecules and ethanol molecules can form certain intermolecular interactions with β-HMX molecules, which are the main driving force of solubilization. In contrast, solvent–solvent interactions have an antagonistic effect on the solubility of β-HMX in mixed solvents. This work can further be informative for researchers in the field of energetic material for the solubility evaluations and provide a reference for the industrial production and performance enhancement of HMX in the future.

Natural polymers are the most promising alternatives to petroleum-based plastics for developing biodegradable food packaging films. However, the brittleness and lack of active protection of films from most natural polymers pose a challenge to their practical application. The addition of plasticizers and natural extracts to these films is considered an effective solution to address these issues. In this study, the potential for the use of deep eutectic solvents (DESs) and DES extracts derived from Hibiscus sabdariffa in the production of chitosan films and their effects on their mechanical and antioxidant properties were examined. Initially, the extraction efficacy of DESs composed of choline chloride (ChCl) and various carboxylic acids (citric, lactic, tartaric, and oxalic acids) was evaluated in terms of phenolic and anthocyanin contents along with antioxidant activities. Optimal results were achieved with the utilization of ChCl-oxalic acid as the extraction medium. Subsequently, chitosan films were fabricated by introducing DESs and DES extracts as plasticizers and compared with glycerol-plasticized chitosan films. The incorporation of DESs and DES extracts into the film matrix led to a notable reduction (11.78–14.82%) in moisture content compared with glycerol (25.34%). Notably, using ChCl-tartaric acid improved the tensile strength, while ChCl-citric acid enhanced the film flexibility. Films containing ChCl-tartaric acid demonstrated exceptional light barrier properties. SEM analysis revealed an interaction between chitosan and DESs, which was further corroborated by FTIR and XRD. Additionally, DES extracts provided superior antioxidant activity to the films than their pure DESs. These findings suggest a significant potential for DES extracts from Hibiscus sabdariffa as bioactive agents and plasticizers in chitosan films.

Passivation treatment is the last key process to ensure the service life of copper foil for lithium-ion batteries. Although chromic anhydride commonly used in industry has an efficient passivation effect, it can threat human health and the environment. Herein, an environmentally friendly passivator is prepared from pomelo peel by a simple and economical solution extraction method, which makes copper foil have good anti-corrosion properties in air, chlorine-containing solution, and organic electrolyte. Electrochemical methods and X-ray photoelectron spectroscopy (XPS) confirm the potential of pomelo peel extractant (PP) to replace chromic anhydride as a passivating agent for copper foil. The interaction mechanism between PP and copper foil is analyzed by adsorption models, and the efficient passivation behavior of PP for copper foil is consistent with the Langmuir model. Density Functional Theory (DFT) calculations of the naringin (main component of PP) is performed to further reveal the protection mechanism of PP on copper foil. In addition, the copper foil treated by PP still has excellent electrochemical performance as lithium-ion battery current collector, indicating that the presence of PP not only protects the copper foil from corrosion, but also does not affect the conductivity of the copper foil. This research provides a new insight into the chrome-free passivation of copper foils, which is in line with the development concept of green production.

By in situ generation of hydrazone bonds, a composite hydrogel that combines poly(N-isopropylacrylamide) and carboxymethyl cellulose and is reinforced with PDA nanoparticles was successfully prepared for injectable use, and was employed to treat metal ions in aqueous solutions. The composite hydrogels presented desirable compressive strength and anti-fatigue performance. The adsorption capacities of Cu²⁺, Pb²⁺ and Cd²⁺ reached high values of 193.8, 168.8 and 112.6 mg/g, respectively, in a single-ion adsorption system, due to the plentiful adsorptive sites on the hydrogels. The adsorption kinetics followed the Pseudo-second-order model, while the adsorption isotherm adhered to the Langmuir model. Besides, the hydrogels showed slightly higher selectivity for Cu²⁺ in an adsorption system involving multiple ions, and exhibited good reusability, enabling it to be employed repeatedly as a recyclable adsorbent. The analysis of the mechanism indicated that ion exchange, electrostatic interaction, chemical adsorption and coordination effect might occurred between metal ions and functional groups in hydrogel matrix and PDA nanopartiles. Moreover, the Cu²⁺-adsorbed hydrogels could act as a scaffold for the on-site generation of Cu nanoparticles. With the Cu nanoparticles, the hydrogels showed catalytic activity of ∼ 80 % conversion of 4-nitrophenol (1 mmol) to 4-aminophenol in 30 min, validating the dual functional properties for both adsorption and catalytic purposes in the treatment of wastewater.

Specialty oils and fats play a crucial role in enhancing the texture and flavor of foods. The findings revealed that the emulsion-filled gels containing sinapine exhibited a more uniform and consistent distribution of oil droplets and proteins, with an average particle size that was better aligned across the samples. These emulsion-filled gels also exhibited higher stability, up to 95 % oil binding capacity, 3 N higher hardness and 0.2 mJ higher adhesion compared to proanthocyanidins (PC) and catechins (EC). Additionally, they demonstrated better spread-ability. In terms of the rheological properties of the oleogel prepared with sinapine, the apparent viscosity was high and the thixotropy was good. However, the softness was poor. The groups involved in the binding of various species of polyphenols are essentially identical, and the primary non-covalent driving force in this system is hydrogen bonding along with double bonding. With a thiobarbituric acid reactant (TBARS) value of 4.5 µg/mL, sinapine is more effective at maintaining the stability of emulsion-filled gels. It also enhances the oleogel’s oil-holding capacity and antioxidant capacity. In addition, the cookies with increased levels of SPI and sinapine exhibited greater hardness and were more well-received by the public. This information will help expand the application of polyphenol-modified protein-based emulsion-filled gels in food systems.

Despite their low cost and intrinsic safety, aqueous rechargeable zinc-ion batteries suffer from rapid performance deterioration originating from parasitic reactions and inhomogeneous deposition on the Zn anode. Halogen bonds share similarities with hydrogen bonds, yet their unique directionality, strength tunability, and hydrophobicity provide a promising approach for enhancing the reversibility of Zn anodes. Herein, a systematic comparison of ionic liquids with different anions, acetate (Ac⁻) and chloride (Cl⁻), is performed to explore the non-covalent interactions in regulating ion solvation and dynamic behaviors of electrolytes. Different from the Ac⁻ possessing a strong capacity to form hydrogen bonds with water, the Cl⁻-water halogen bonds not only enable the structural diffusion of Zn²⁺ with better diffusion efficiency but also reduce the Zn²⁺ de-solvation energy barrier to promote uniform Zn nucleation. Consequently, the accelerated ions diffusion and homogeneous Zn deposition work in synergy to ensure high reversibility of Zn anode. These fundamental insights highlight the importance of hydrogen and halogen bonds in determining the dynamics and electrochemical behavior of electrolytes, providing theoretical guidance for the rational design of high-performance electrolytes.