Concentrated Solutions Research Articles

Highly efficient visible light active iron oxide-based photocatalysts for both hydrogen production and dye degradation

Photocatalysis is essential for wastewater cleanup and clean energy, and in this current study, we have synthesized nanomaterials (iron oxide-based) for photocatalytic pollution degradation and hydrogen production. The performance of aluminium oxide/ferric oxide (Al2O3/Fe2O3), samarium oxide/ferric oxide (Sm2O3/Fe2O3) and yttrium oxide/ferric oxide (Y2O3/Fe2O3) were compared for the production of hydrogen (H2) and degradation of dye under natural sunlight. Various characterisation equipment was used to characterize these photocatalysts’ structure, morphology, elemental content, binding energy and band gap. The hydrogen recovery efficiency of iron oxide-based photocatalysts from sulphide-containing wastewater is assessed. Y2O3/Fe2O3 has shown the highest hydrogen production of 340 mL/h. The influence of operating factors such as sulphide ion concentration, catalyst quantity, and photocatalyst photolytic solution volume on hydrogen production is studied. The optimal values were 0.25 M, 0.2 g/L, and 1L, respectively. The developed photocatalyst passed multiple cycles of stability testing. Fe2O3 has shown the highest Rhodamine B (RhB) dye degradation efficiency of 94% under visible light.

Cluster Formation Induced by Local Dielectric Saturation in Restricted Primitive Model Electrolytes.

Experiments using the Surface Force Apparatus (SFA) have found anomalously long-ranged charge-charge underscreening in concentrated salt solutions. Meanwhile, theory and simulations have suggested ion clustering to be a possible origin of this behavior. The popular Restricted Primitive Model of electrolyte solutions, in which the solvent is represented by a uniform relative dielectric constant, εr, is unable to resolve the anomalous underscreening seen in experiments. In this work, we modify the Restricted Primitive Model to account for local dielectric saturation within the ion hydration shell. The dielectric "constant" in our model locally decreases from the bulk value to a lower saturated value at the ionic surface. The parameters for the model are deduced so that typical salt solubilities are obtained. Our simulations for both bulk and slit geometries show that our model displays strong cluster formation and these give rise to long-ranged density correlations between charged surfaces, at distances similar to what has been observed in SFA measurements. An electrolyte model wherein the dielectric constant remains uniform does not display similar clusters, even with εr equal to the low saturated value at ion contact. Hence, the observed behaviors are not simply due to an enhanced Coulomb interaction. In the latter case, cluster growth is counteracted by long-ranged repulsions between like-charged ions within clusters; this is an effect that is considerably reduced when the dielectric response drop is local. Our results imply that long-ranged interactions in these systems are mainly due to cluster-cluster correlations, rather than large electrostatic screening lengths.

Comment on "Binding Debye-Hückel theory for associative electrolyte solutions" [J. Chem. Phys. 159, 154503 (2023)

It is argued that the Binding Debye-Hückel (BiDH) model proposed by Naseri Boroujeni et al. [J. Chem. Phys. 159, 154503 (2023)] might not be appropriate for the description of Monte Carlo simulation data obtained for primitive model electrolytes. The first reason is that the original Debye-Hückel (DH) theory is of low accuracy for describing deviations from ideality in concentrated solutions of strong salts. The DH framework is thus a poor basis for building a model including association. The second reason is that the mean-spherical approximation, without assumption of association, apparently predicts Monte Carlo (MC) data for primitive electrolytes better than BiDH. Thus, the BiDH model seems to be simply a way of compensating for the deficiencies of DH theory by assuming association.

Thermo-rheological properties of xanthan solutions: from shear thinning to elasto-viscoplastic behavior.

The thermo-rheological behavior of xanthan solutions with concentrations spanning a wide range is investigated experimentally. After carefully identifying four distinct regimes of concentration we focused on highly concentrated xanthan solutions. By combining several rheological techniques, it is shown for the first time that such solutions belong to the broad class of elasto-viscoplastic materials by exhibiting both a yield stress and elasticity that manifests around the solid-fluid transition. The soft and weakly entangled structure responsible for the elasto-viscoplastic rheological behavior is controlled by two factors:imposed stress, temperature. Consequently, concentrated solutions of xanthan may yield to either imposed stress or temperature. The systematic analysis of the elasticity mediate solid-fluid transition at various operating temperatures revealed the presence of a novel state termed as "molten solid". A clear relationship between the rheological states and the molecular states (native, denaturated, re-naturated) is established.

Novel thermally regenerated flexible cellulose-based films

AbstractIn this work, cellulose powder obtained by acid hydrolysis of industrial Eucalyptus kraft pulp was dissolved in NaOH/Urea/H2O system (7/12/81 wt%) in a concentration of 6% (w/v). Cellulose films were prepared by spreading the dissolved cellulose over glass plates, followed by thermal regeneration – a novel approach reported here for the first time. To obtain final flexible films, plasticization was carried out by immersion in aqueous glycerol solutions of various concentrations (10 to 70 wt%) and hot-pressing (at 0.1 MPa and 105 ºC) was used to dry and compress the cellulose films. The resulting films were characterized by Attenuated Total Reflectance Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, X-ray diffraction, contact angle measurements, transparency analysis, and gas permeabilities (oxygen and water vapor). Highly flexible films containing up to 50 wt% of glycerol were successfully obtained, exhibiting no glycerol release upon manual handling. Overall, the produced films demonstrated dense and compact structure, good transparency, flexibility and malleability, and very low oxygen permeability.

A Method for Efficiently Predicting the Radial Distribution Function and Osmotic Coefficients of Aqueous Electrolyte Solutions.

The prediction of the structural and thermodynamic properties of electrolyte solutions is critical for a huge range of practical situations where these solutions play a vital role. Theoretical models, such as the continuum solvent model, attempt to explain the behavior of solutions using a coarse-grained description of the interactions of species in the solution, whereas molecular simulations aim to directly compute the behavior of the solution, including the interactions between all ions and molecules in the system. Both methods have limitations: theoretical models are generally less accurate because they rely on assumptions, while molecular simulations require significant computational resources, particularly if higher accuracy is desired. To address these issues, we propose an affordable and effective method that combines the advantages of the modified Poisson-Boltzmann equation (MPBE) with classical molecular dynamics (MD) simulations to predict the radial distribution functions and thermodynamic properties of electrolyte solutions. We demonstrate a method of using the MPBE to compute the short-range potential of mean force (PMF) from the radial distribution functions (RDFs) and vice versa. Furthermore, we provide insights into the relationship between the RDFs and the short-range PMF based on the MPBE. Our analysis reveals that the effective short-range PMFs can be approximately calculated using low concentration simulations but the short-range PMFs are slightly concentration-dependent in simulations at higher concentrations. Additionally, we demonstrate that for concentrated solutions, osmotic coefficients can be calculated in agreement with experiment using a virial approach. This is based on the effective short-range PMFs and RDFs obtained from the MPBE method. Our proposed MPBE can therefore accelerate the calculation of the structural and thermodynamic properties of electrolyte solutions.

Innovative process for sulphur recovery from waste incineration flue gases: production of marketable sodium bisulphite solution

ABSTRACT This study presents an innovative process for recovering sulphur from hazardous waste incineration flue gases, designed to produce a marketable sodium bisulphite solution while ensuring complete SO2 removal. This new process is characterized by a double absorption strategy at two different pH levels. The first step, at an acidic pH, generates the desired bisulphite solution, while the second step, at a basic pH, produces the sulphite solution for recycling into the first step and ensures total SO2 removal. The process’s performance and feasibility were evaluated on a laboratory scale using a batch reactor with synthetic gas. The parametric study focused on the initial sulphite concentration in the absorption solution and the reactor temperature. A removal efficiency exceeding 95% was achieved across all initial sulphite concentrations and temperature ranges, when the pH was maintained above 6. At pH 5, where bisulphites are the predominant sulphur species, the removal efficiency remained substantial at approximately 70%. The oxidation of sulphites/bisulphites by oxygen in the flue gases was minimal, with less than 5% conversion to sulphate. Additionally, pH-controlled experiments were conducted to optimize plant start-up procedures. For the basic reactor, starting with water and adjusting the pH to 8 during SO2 absorption effectively minimized sodium hydroxide consumption. In contrast, for the acidic reactor at pH 5, initiating the process with a concentrated sulphite solution resulted in more stable absorption rates. These findings underscore the process's potential for efficient sulphur recovery and highlight the importance of pH management in optimizing operational stability and chemical consumption.

Structural and dynamic behaviour of concentrated aqueous solutions of (poly)ethylene glycols: Insight into the impact of hydrophobicity, hydrogen bonding and chain length

Understanding the delicate interplay between hydrophobicity/hydrophilicity, hydrogen bonding ability and solute size in modulating the chemico-physical properties of aqueous solutions with increasing solute concentration is a challenging task. Here, we focus on how bulk properties, such as diffusion and aggregation behaviour, are affected by the different hydration patterns observed for differently concentrated aqueous solutions of (poly)ethylene glycols, and their corresponding methoxyethers, of various lengths. Using a combined experimental and computational approach, we analyse solutions of ethylene glycol (EG), dimethoxyethane (DME), polyethylene glycol with 4 repeating units capped with either hydroxyl (PEG200) or methoxyl (PEG250DME) tails, and polyethylene glycol with 9 repeating units (PEG400). By disentangling the contributions of hydrophobicity, hydrogen bonding ability, and chain length, we observe that for the smaller solutes electristriction and hydrophobic hydration are the main phenomena occurring. Instead, as the solute becomes larger, these effects give way to the non-trivial conformational flexibility that can either favour or disfavour intermolecular interactions which lead to the formation of water-rich regions excluded from the solute.

Multiple origins of extra electron diffractions in fcc metals.

Diffuse intensities in the electron diffraction patterns of concentrated face-centered cubic solid solutions have been widely attributed to chemical short-range order, although this connection has been recently questioned. This article explores the many nonordering origins of commonly reported features using a combination of experimental electron microscopy and multislice diffraction simulations, which suggest that diffuse intensities largely represent thermal and static displacement scattering. A number of observations may reflect additional contributions from planar defects, surface terminations incommensurate with bulk periodicity, or weaker dynamical effects.

Supersolubilization and Amorphization of a Weakly Acidic Drug, Flurbiprofen, by applying Acid-Base supersolubilization (ABS) principle

Improvement in drug solubility is a major challenge for developing pharmaceutical products. It was demonstrated earlier that aqueous solubilities of weakly basic drugs could be increased greatly by interaction with weak acids that would not form salts with the drugs, and the highly concentrated solutions thus produced converted to amorphous solids upon drying. The technique was called acid-base supersolubilization (ABS). The current investigation explored whether the ABS principle could also be applied to weakly acidic drugs. By taking flurbiprofen (pKa 4.09; free acid solubility 0.011 mg/mL) as the model weakly acidic drug and tromethamine, lysine, meglumine, and NaOH as bases, it was studied which of the bases would result in ABS. While in the presence of NaOH and tromethamine, flurbiprofen converted to salts having aqueous solubility of 11–19 mg/mL, the solubility increased to > 399 mg/mL with lysine and > 358 mg/mL with meglumine, producing supersolubilization. However, crystallization of lysine salt was observed with time, followed by some decrease in solubility after reaching maximum solubility with lysine. In contrast, the supersolubilization was maintained with meglumine, and no crystallization of meglumine salt was observed. Upon drying, flurbiprofen-meglumine solutions produced amorphous materials that dissolved rapidly and produced high drug concentrations in aqueous media. Thus, the ABS principle also applies to acidic drugs depending on the weak base used.

Longitudinal ultrasound measurements of polyethylene oxide across dilute to concentrated aqueous solutions

Measuring the properties of polymer solutions is crucial for understanding fundamental polymer physics. The longitudinal ultrasound measurement method offers a promising technique for characterizing these properties. In this study, we develop a mathematical model to correlate longitudinal ultrasonic signals with the material properties of polyethylene oxide (PEO) from dilute to concentrated aqueous solutions. After applying reflection and diffraction corrections, the accuracy of the measurement results improves to over 97%. Our findings reveal a positive correlation between the speed of sound, density, and longitudinal modulus with the mass concentration of PEO. Additionally, ultrasonic relaxation analysis reveals that PEO solutions exhibit at least one relaxation process in the frequency range of 3 to 7 MHz, independent of concentration and molecular weight. Compared to dilute solutions, the relaxation amplitude in concentrated solutions is larger and accompanied by strong nonlinearity, attributed to conformational changes caused by molecular entanglement in concentrated solutions.

Integrated interferometers as a new platform for low cost gas chromatography detection

Gas chromatography is a reference method for gas analysis. As part of efforts to miniaturize gas chromatography systems, the miniaturization of detectors is essential. In this work, we report a new integrated photonic platform for gas chromatography analyte detection. The fabricated silicon die integrates Mach-Zehnder interferometers into low dead volume microfluidic channels, with coherent cost-effective detection scheme with a fixed 850 nm wavelength laser. A proof of concept is demonstrated with the separation and detection of three volatile organic compounds: heptane, octane, and toluene. Peaks’ widths at half height range from 1 to 5 seconds. Peaks are very well resolved by our system, which acquires more than 100 points per second. From a heptane dilution range, we evaluate the limit of detection of our system to be the headspace of a 0.22% heptane concentration solution. To our knowledge, these are the first integrated Mach-Zehnder interferometers reported for gas chromatography detection. This work could open new strategies for fast low cost and low limit of detection specific gas chromatography silicon micro-detectors.

Nano-carbon octadecahedron: in situ carbonization of DTAB of aggregates in concentrated calcium chloride solution

Morphologies play an important role in carbon nanomaterials. Carbon nanomaterials with different morphologies have different applications in different fields. However, carbon nano-polyhedra have been rarely reported in literatures. Nano-carbon octadecahedron were prepared by the interaction of DTAB of aggregates with a concentrated solution of calcium chloride at 600 °C and with a size of about 700 nm. A series of characterizations, such as SEM, FT-IR, XPS, XRD, Raman, etc., proved that it conforms to the basic characteristics of carbon nanomaterials and may be doped with Ca and carbon. Successful preparation of carbon octadecahedron suggests that the use of in situ carbonization in a concentrated salt system is a new and worthwhile approach to explore.

Stress Corrosion Cracking of 304 Austenitic Stainless Steel in H2SO4/NaCl Media at Room Temperature

ABSTRACT The effects of Cl− ion concentration, H2SO4 concentration, the applied potential, and the strain rate on the stress corrosion cracking (SCC) of 304 stainless steel were investigated. The post-fracture SEM micrographs of the fractured surfaces revealed that solutions of high H2SO4 concentration combined with low Cl− ion concentration resulted in corrosion (active dissolution), while solutions of very low H2SO4 concentration combined with a relatively moderate Cl− ion concentration resulted in ductile failure. Solutions with moderate concentrations of H2SO4 and Cl− ions resulted in transgranular stress corrosion cracking (TGSCC). The susceptibility to SCC and the fracture surface morphology were found to depend on the [H2SO4]/[Cl−] ratio, the strain rate, and the applied potential. The average crack growth rate (ACGR) was found to depend on the strain rate and the applied potential. For specimens undergoing SCC at the open circuit potential (OCP), the ACGR increased with increasing the strain rate. For specimens undergoing SCC under applied potential in the active range, the ACGR increased with increasing the applied potential. The specimen eventually failed in a ductile manner when tested under an applied anodic potential in the passive range. The increase in the ACGR with increasing the strain rate and the applied anodic potential is attributed to the enhanced dissolution at the crack tip. Moreover, secondary cracks formed when relatively high strain rates were used. The secondary cracks are believed to propagate mainly along the slip planes. The fracture surface morphology shows the {110} planes are the preferred fracture planes, with the fracture surface consisting of parallel facets separated by steps. Finally, the results indicate that hydrogen may play an indirect role in SCC.

Dual Fluorescence and Phosphorescence Emissions from Dye-Modified (NCN)-Bismuth Pincer Thiolate Complexes.

We report the synthesis, characterization, and photophysical properties of four new dye-modified (NCN)Bi pincer complexes with two mercaptocoumarin or mercaptopyrene ligands. Their photophysical properties were probed by UV/vis spectroscopy, photoluminescence (PL) studies, and time-dependent density functional theory (TD-DFT) calculations. Absorption spectra of the complexes are dominated by mixed pyrene or coumarin π → π*/n(pS) → pyrene or coumarin π* transitions. While unstable toward reductive elimination of the corresponding disulfide under irradiation at room temperature, the complexes provide stable emissions at 77 K. Under these conditions, coumarin complexes 2 and 4 exhibit exclusively green phosphorescence at 508 nm. In contrast, the emissive properties of pyrene complexes 1 and 3 depend on the excitation wavelength and on sample concentration. Irradiation into the lowest-energy absorption band exclusively triggers red phosphorescence from the pyrenyl residues at 640 nm. At concentrations c < 1 μM, excitation into higher excited electronic states results in blue pyrene fluorescence. With increasing c (1-100 μM), the emission profile changes to dual fluorescence and phosphorescence emission, with a steady increase of the phosphorescence intensity, until at c ≥ 1 mM only red phosphorescence ensues. Progressive red-shifts and broadening of steady-state excitation spectra with increasing sample concentration suggest the presence of static excimers, as we observe it for concentrated solutions of pyrene. Crystalline and powdered samples of 1 indeed show intermolecular association through π-stacking. TD-DFT calculations on model dimers and a tetramer of 1 support the idea of aggregation-induced intersystem crossing (AI-ISC) as the underlying reason for this behavior.

Fabricating Large-Area Thin Films of 2D Conductive Metal-Organic Frameworks.

ConspectusRecent years have witnessed significant interest in two-dimensional metal-organic frameworks (MOFs) due to their unique properties and promising applications across various fields. These materials offer distinct advantages, including high porosity and excellent charge transport properties. Their tunability allows precise control over various factors, including the electronic structure adjustments and local reactivity modulation, facilitating a wide range of properties and applications, such as material sensing and spin dynamics control. Moreover, the precise crystal structure of 2D MOFs supports rational design and mechanism studies, providing insights into their potential applications and enhancing their utility in various scientific and technological endeavors.To fully unveil the latent capabilities of 2D MOFs and advance their applications across diverse fields, thin film synthesis is crucial. Thin films provide a platform for investigating the intrinsic electrical properties of 2D MOFs with anisotropic structures, enabling the exploration of their unique characteristics comprehensively. Additionally, thin films offer the advantage of minimizing interference at contacts and junctions, thereby enhancing the performance of 2D MOFs for various applications. Furthermore, the properties of thin films can vary with thickness, presenting an opportunity to tailor their characteristics based on specific requirements.In this Account, we present an overview of our research focusing on the synthesis of 2D conductive MOF thin films encompassing two primary methods: chemical vapor deposition and solution processing. The chemical vapor deposition method allows for one-step, all-vapor-phase processes resulting in MOFs with edge-on orientation, controllable film thicknesses ranging from 55 to 662.7 nm, and smooth, homogeneous surfaces. On the other hand, solution-processing introduces a novel MOF, Cu3(HHTATP)2, by reducing interlayer interactions through the addition of pendent Brønsted bases on a ligand, enabling spin coating for thin film synthesis. This method yields a concentrated 2D MOF solution, enabling spin coating for thin film synthesis, where reversible electrical conductivity changes occur through doping with an acid and dedoping with a base. Additionally, we discuss various other synthesis methods, such as interfacial synthesis, layer-by-layer assembly, and microfluidic-assisted synthesis, offering versatile approaches for fabricating large-area thin films with tailored properties. Finally, we address ongoing challenges and potential strategies for further advancement in 2D conductive MOF thin film synthesis. We hope that this Account provides insights for selecting synthesis methods tailored to specific purposes, contributes to the development of varied synthesis techniques, and facilitates the exploration of diverse applications, unlocking the full potential of 2D conductive MOFs for next-generation technologies.

Fabrication of a family of porous azo polymers with multifunctional adsorption and separation performances

In this paper, a class of porous organic polymers (POPs) of p-hydroxy azobenzene with a mesoporous structure was designed and synthesized by a –NN– coupling reaction of tetraamino-metal phthalocyanine (MTAPc, where M = Co, Ni or Cu) with hydroquinone (namely Azo-MHQ, where M = Co, Ni or Cu). The Azo-MHQ materials possessed good thermal stabilities, excellent dispersibilities in water, polar and non-polar organic solvents, as well as excellent chemical stabilities. Among them, Azo-CuHQ showed an outstanding iodine trapping ability in an iodine solution and vapor with saturated adsorption capacities of 1347.47 mg g−1 and 118 wt%. In addition, Azo-CuHQ also showed a high adsorption capacity for methylene blue (MB) with the adsorption amount of 191.21 mg g−1. Furthermore, by loading Azo-CuHQ onto polyethersulfone (PES) membrane, the water permeability of the obtained membranes reached 147.03 L m−2 h−1 bar−1, and the retention rate of Ag in a very low concentration solution of 20 ppm was 56.8 %. Additionally, a thorough analysis of the Azo-CuHQ adsorption and separation mechanism was conducted. A novel approach to the design and synthesis of a class of materials with multifunctional adsorption and separation capabilities is presented in this research.

Design of High-Performance Molecular Imprinted Magnetic Nanoparticles-Loaded Hydrogels for Adsorption and Photodegradation of Antibiotics from Wastewater

A hydrogel formulation of 2-hydroxy ethyl methacrylate (HEMA) containing covalently linked magnetite nanoparticles was developed to actively facilitate the selective removal and photocatalytic degradation of antibiotics. To this purpose, the hybrid materials were molecularly imprinted with Lomefloxacin (Lome) or Ciprofloxacin (Cipro), achieving a selectivity of 60% and 45%, respectively, starting from a solution of XX concentration. After the adsorption, the embedded magnetite was used with the double function of (i) magnetically removing the material from water and (ii) triggering photo-Fenton (PF) reactions assisted by UVA light and H2O2 to oxidize the captured antibiotic. The success of the material design was confirmed by a comprehensive characterization of the system from chemical–physical and morphological perspectives. Adsorption and degradation tests demonstrated the material’s ability to efficiently degrade Lome until its complete disappearance from the electrospray ionization (ESI) mass spectra. Regeneration tests showed the possibility of reusing the material for up to three cycles. Ecotoxicological tests using algae Rapidocelis subcapitata, crustaceans Daphnia magna, and bacteria Vibrio fischeri were performed to evaluate the ecosafety of our synthesized materials.

Comparative analysis of multi-effect evaporators in an ammonium acetate concentration process for L-methionine production

The process of treating an acetic acid aqueous solution generated during L-methionine production with ammonia and recovering a highly concentrated ammonium acetate aqueous solution using a multi-effect evaporator process was studied. The electrolyte non-random two-liquid model was applied to calculate the activity in the electrolyte solution, and the Hayden-O’Connell model was used to consider the dimerization reaction of acetic acid in the vapor phase. The dissociation equilibrium constant of acetic acid was modeled based on experimental values, and all other thermodynamic property models and parameters were used as implemented in the Aspen Plus software. Economic evaluation was carried out with various sensitivity tests, considering the loss of acetic acid and ammonia, as well as the steam cost. Evaporator operation was found to be more economical when the molar ratio of acetic acid to ammonia was equal, feed concentration was high, feed flow rate was low, and evaporator temperature was low. These results were confirmed in actual plant operations, with significant correlations between the feed flow rate and evaporator temperature. Our findings have significant implications for the development of sustainable and economical L-methionine production methods that enable the recycling of ammonium acetate.

Preparation of Graphene Oxide (GO) incorporated-Polyvinylidene Fluoride (PVDF) Nanofiltration Membrane with Alkaline Post-Treatment for Textile Wastewater Treatment

The purpose of this research is to study the potential of polyvinylidene fluoride (PVDF) polymer incorporated with graphene oxide (GO), following with the alkaline etching post-treatment process for dye waste water treatment. Its anti-oxidation properties of PVDF, have led to its choice as a host polymer due to its high thermal stability, great organic selectivity, and excellent chemical and mechanical resistance. In addition, the post-treatment with a NaOH solutions of varied concentration ranging from 0 M to 0.2 M for 30 minutes was conducted in alter the morphology of the fabricated membrane with the aim to increase the perm-selectivity of the membranes. Besides, the fabricated membranes were further characterized in terms of the chemical and physical properties using Fourier-Transform Infrared Spectroscopy (FTIR), Contact Angle (CA), Ultraviolet Visible spectroscopy (UV-Vis), Atomic Microscopy (AFM) and Scanning Electron Microscopy (SEM). The experimental results showed that the post-treatment has decreased the membrane flux of dye wastewater. Based on the obtained result, as the concentration of NaOH solution increased, the permeability increased. While the overall dye rejection of the membrane remained of above 90 %.