Molecular simulation of osmometry in aqueous solutions of the BMIMCl ionic liquid: a potential route to force field parameterization of liquid mixtures.

Despite widespread development and use of ionic liquids (ILs) in both academic and industrial research, computational force fields (FFs) for most of those are not available for a precise description of inter-species interactions in aqueous environments. In the scope of this study, by means of molecular simulations, the osmotic coefficient of an aqueous solution of an IL is calculated and used as a basis to reparameterize popular IL-FFs existing in the literature. We first calculate the osmotic coefficients (at 298.15 K and 1 atm pressure) of aqueous solutions of 1-butyl-3-methylimidazolium chloride (BMIMCl), a generic IL, popularly used in biomass processing and the subsequent conversion to value-added intermediates. The performance of two popular atomic, nonpolarizable FFs developed for BMIMCl, one by Lopes, Pádua, and coworkers (FF-LP) and the other by Sambasivarao, Acevedo, and coworkers (FF-SA), when mixed with the SPC/E water model, is tested with respect to their ability to reproduce the experimental osmotic coefficient data. Interestingly, the osmotic coefficient is found to be increasing with a gradual increase in IL molality within the concentration range of our investigation, which is contrary to the experimental trend reported in the literature for the same IL-water mixture. Henceforth, necessary corrections to the nonbonded ion-ion and ion-water interactions are made to match the experimental osmotic coefficient. To further assess the reliability of the new FF, we extensively explore the thermodynamic (density, isothermal compressibility, and thermal expansion coefficient), dynamic (diffusivity and viscosity), and association/dissociation properties (rationalized with the help of radial distribution functions) with both the original and reparameterized FF for a wider range of concentrations up to a molality of 18.50 mol kg-1. The calculated quantities are compared against experimental data wherever available. The modified FF parameters exhibit significant improvements in terms of its ability to match experimental solution properties, such as density, viscosity, association/dissociation, etc. We report that excessive dissociation of BMIMCl in water is responsible for the shortcomings observed in the original FFs and improved prediction of physicochemical properties could be achieved using the modified FFs.

High-Performance Polyacrylic Acid-Grafted PVDF Nanofiltration Membrane with Good Antifouling Property for the Textile Industry.

In the textile industry, a high-efficiency dye removal and low-retention of salt is demanded for recycling wastewater. In this study, polyvinylidene fluoride (PVDF) ultrafiltration membrane was transformed to a negatively charged loose nanofiltration (NF) membrane through UV-grafting of acrylic acid. At the optimal exposure of PVDF membrane in UV light for 5 min, the membrane had a high dye recovery above 99% (Congo red and Eriochrome® Black T) and a low sodium chloride (NaCl) rejection of less than 15% along with pure water flux of 26 L∙m-2∙h-1∙bar-1. Its antifouling and oleophobicity surface properties were verified using fluorescent- bovine serum albumin (BSA) and underwater mineral oil contact angle, respectively. According to the fluorescent microscopic images, the modified membrane had ten times lower adhesion of protein on the surface than the unmodified membrane. The underwater oil contact angle was raised from 110° to 155°. Moreover, the salt rejection followed this sequence: Na2SO4 > MgSO4 > NaCl > MgCl2, which agreed with the typical negatively charged NF membrane. In addition, the physicochemical characterization of membranes was further investigated to understand and link to the membrane performance, such as surface functional group, surface elements analysis, surface roughness/morphology, and surface hydrophilicity.

Zwitterionic Polymer Brush Grafted on Polyvinylidene Difluoride Membrane Promoting Enhanced Ultrafiltration Performance with Augmented Antifouling Property.

Superhydrophilic zwitterions on the membrane surface have been widely exploited to improve antifouling properties. However, the problematic formation of a <20 nm zwitterionic layer on the hydrophilic surface remains a challenge in wastewater treatment. In this work, we focused on the energy consumption and time control of polymerization and improved the strong hydrophilicity of the modified polyvinylidene difluoride (PVDF) membrane. The sulfobetaine methacrylate (SBMA) monomer was treated with UV-light through polymerization on the PVDF membrane at a variable time interval of 30 to 300 s to grow a poly-SBMA (PSBMA) chain and improve the membrane hydrophilicity. We examined the physiochemical properties of as-prepared PVDF and PVDF-PSBMAx using numeric analytical tools. Then, the zwitterionic polymer with controlled performance was grafted onto the SBMA through UV-light treatment to improve its antifouling properties. The PVDF-PSBMA120s modified membrane exhibited a greater flux rate and indicated bovine serum albumin (BSA) rejection performance. PVDF-PSBMA120s and unmodified PVDF membranes were examined for their antifouling performance using up to three cycles dynamic test using BSA as foulant. The PVDF-modified PSBMA polymer improved the antifouling properties in this experiment. Overall, the resulting membrane demonstrated an enhancement in the hydrophilicity and permeability of the membrane and simultaneously augmented its antifouling properties.

Zwitterion Co-Polymer PEI-SBMA Nanofiltration Membrane Modified by Fast Second Interfacial Polymerization.

Nanofiltration membranes have evolved as a promising solution to tackle the clean water scarcity and wastewater treatment processes with their low energy requirement and environment friendly operating conditions. Thin film composite nanofiltration membranes with high permeability, and excellent antifouling and antibacterial properties are important component for wastewater treatment and clean drinking water production units. In the scope of this study, thin film composite nanofiltration membranes were fabricated using polyacrylonitrile (PAN) support and fast second interfacial polymerization modification methods by grafting polyethylene amine and zwitterionic sulfobutane methacrylate moieties. Chemical and physical alteration in structure of the membranes were characterized using methods like ATR-FTIR spectroscopy, XPS analysis, FESEM and AFM imaging. The effects of second interfacial polymerization to incorporate polyamide layer and 'ion pair' characteristics, in terms of water contact angle and surface charge analysis was investigated in correlation with nanofiltration performance. Furthermore, the membrane characteristics in terms of antifouling properties were evaluated using model protein foulants like bovine serum albumin and lysozyme. Antibacterial properties of the modified membranes were investigated using E. Coli as model biofoulant. Overall, the effect of second interfacial polymerization without affecting the selectivity layer of nanofiltration membrane for their potential large-scale application was investigated in detail.

Hydrolysis of microcrystalline cellulose using functionalized Bronsted acidic ionic liquids - A comparative study.

Cellulose conversion to platform chemicals is required to meet the demands of increasing population and modernization of the world. Hydrolysis of microcrystalline cellulose was studied with SO3H, COOH and OH functionalized imidazole based ionic liquid using 1-butyl-3-methylimidazolium chloride [BMIM]Cl as a solvent. The influence of temperature, time, acidity of ionic liquids and catalyst loading was studied on hydrolysis reaction. The maximum %TRS yield 85%, was obtained at 100°C and 90min with 0.2g of SO3H functionalized ionic liquid. UV-vis spectroscopy using 4-nitro aniline as an indicator was performed to find out the Hammett function of ionic liquid and acidity trends are as follows: SO3H>COOH>OH. Density functional theory (DFT) calculations were performed to optimize the ionic liquid and their conjugate bases at B3LYP 6-311G++ (d, p) level using Gaussian 09 program. Theoretical findings are in agreement with the experimental results.