Are Hansen solubility parameters relevant in predicting the post-treatment effect on polyamide-based TFC membranes?

This study investigates the impact of solvent post-treatment on polyamide-based thin film composite (TFC) membranes, specifically examining the effect on commercial nanofiltration (NF) and reverse osmosis (RO) membranes. Na2SO4 rejection and increase in pure water permeance (PWP) were considered as the output parameters. The disparity in Hansen solubility parameters (HSP) between the post-treatment solution and the polyamide layer of the TFC membrane, denoted by Ra, is well adapted to understand the enhancement in water permeance through the membranes upon treatment. Aqueous solutions of dimethylformamide with a Ra value of 4, acetonitrile with a Ra value of 8.3, and ethanol with a Ra value of 12.7 were used as the post-treatment solutions. Our experimental design, based on the Box-Behnken design of Response Surface Methodology, incorporates variables such as the concentration of the solvent in the solution (% v/v), Ra value, and treatment time (s). Our findings demonstrate that the effect of post-treatment on the TFC membranes is not governed by the Ra value. Notably, while the post-treatment with the aqueous solution of acetonitrile, 80% v/v for 30 s, had considerable effects on NF membranes (124.5% enhancement in PWP; reduction of 3.5% in Na2SO4 rejection), its impact on RO membranes was negligible. Several factors explain this discrepancy, including the limitations of the HSP model for composite polymers, the inaccuracy of the PWP or salt rejection as a swelling indicator, variations in the HSP values of the polyamide layers for different membranes, and possible modifications in the interface between the support membrane and the polyamide layer. In summary, our study provides insights into the complex interactions between solvents and composite membranes, indicating that HSP alone is not a decisive factor in predicting post-treatment effects on polyamide-based TFC membranes.

Semiaromatic Polyamide-Based Membrane in Forward Osmosis: Molecular Insights.

Despite the increased interest in forward osmosis (FO) in recent years, the technology's advancement in commercial and industrial applications has been hampered by the absence of suitable FO membranes and ideal draw solutes, which demands the exploration of new membranes and novel draw solutes targeted for some specific applications. In this context, we considered a semiaromatic polyamide (SAPA) for an application where monovalent salt can be permeated but has high selectivity toward divalent salt and excellent water permeability. In this regard, we constructed an atomistic model for the membrane via a heuristic approach using an equilibrated mixture of hydrolyzed trimesoyl chloride and piperazine monomers and performed nonequilibrium molecular dynamics simulations on the SAPA membrane in the FO process to understand the structural properties and performance of the membrane at the atomistic level. We used pure water as the feed and Na2SO4 as the draw solution. It is observed that the SAPA membrane shows excellent water permeability and no reverse draw solute flux. To further test the dynamics of salt ions inside the membranes, we performed two distinct equilibrium simulations on systems consisting of either monovalent salt, such as NaCl, or divalent salt, such as Na2SO4. The atomistic details of the interactions between the functional groups of the membrane and salt ions provided in this work can inspire further experiments on SAPA membranes in the context of separation of monovalent and divalent salts, which have applications in the treatment of textile industry wastewater.

Nanoscale Ni-NiO-ZnO Heterojunctions for Switchable Dehydrogenation and Hydrogenation through Modulation of Active Sites.

Catalysts consisting of metal-metal hydroxide/oxide interfaces are highly in demand for advanced catalytic applications as their multicomponent active sites will enable different reactions to occur in close proximity through synergistic cooperation when a single component fails to promote it. To address this, herein we disclosed a simple, scalable, and affordable method for synthesizing catalysts consisting of nanoscale nickel-nickel oxide-zinc oxide (Ni-NiO-ZnO) heterojunctions by a combination of complexation and pyrolytic reduction. The modulation of active sites of catalysts was achieved by varying the reaction conditions of pyrolysis, controlling the growth, and inhibiting the interlayer interaction and Ostwald ripening through the efficient use of coordinated acetate and amide moieties of Zn-Ni materials (ZN-O), produced by the reaction between hydrazine hydrate and Zn-Ni-acetate complexes. We found that the coordinated organic moieties are crucial for forming heterojunctions and their superior catalytic activity. We analyzed two antagonistic reactions to evaluate the performance of the catalysts and found that while the heterostructure of Ni-NiO-ZnO and their cooperative synergy were crucial for managing the effectiveness and selectivity of the catalyst for dehydrogenation of aryl alkanes/alkenes, they failed to enhance the hydrogenation of nitro arenes. The hydrogenation reaction was influenced by the shape, surface properties, and interaction of the hydroxide and oxide of both zinc and nickel, particularly accessible Ni(0). The catalysts showed functional group tolerance, multiple reusabilities, broad substrate applicability, and good activity for both reactions.

Interfacial synthesis of large-area ultrathin polyimine nanofilms as molecular separation membrane.

Thin film membranes of covalent organic frameworks are promising for high-permeance molecular separation. However, their synthesis needs a high temperature or longer reaction time, unsuitable for large-scale fabrication of thin film composite membranes. The ultrathin film of porous organic polymers as a separation layer of the composite membrane could be a close alternative to COF membranes. Here we report transition metal ion-catalyzed room temperature fabrication of the ultrathin (≈12 nm) polyimine nanofilms via interfacial polymerization of melamine and triformylphloroglucinol onto hydrolyzed polyacrylonitrile support within a short reaction time. Composite membranes exhibit high water permeance (≈78 L m-2 h-1 bar-1), high rejection (99.6%) of brilliant blue R (825.9 g mol-1), low rejection of NaCl (≈1.8%) and Na2SO4 (≈17%), and enable efficient molecular separation. The role of metal ion catalysts for large-area fabrication of the ultrathin polyimine nanofilm membranes used for molecular separation is demonstrated.

Large Area Self-Assembled Ultrathin Polyimine Nanofilms Formed at the Liquid-Liquid Interface Used for Molecular Separation.

Separation membranes with higher molecular weight cut-offs are needed to separate ions and small molecules from a mixed feed. The molecular sieving phenomenon can be utilized to separate smaller species with well-defined dimensions from a mixture. Here, the formation of freestanding polyimine nanofilms with thicknesses down to ≈14 nm synthesized via self-assembly of pre-synthesized imine oligomers is reported. Nanofilms are fabricated at the water-xylene interface followed by reversible condensation of polymerization according to the Pieranski theory. Polyimine nanofilm composite membranes are made via transferring the freestanding nanofilm onto ultrafiltration supports. High water permeance of 49.5 L m-2 h-1 bar-1 is achieved with a complete rejection of brilliant blue-R (BBR; molecular weight = 825 g mol-1 ) and no more than 10% rejection of monovalent and divalent salts. However, for a mixed feed of BBR dye and monovalent salt, the salt rejection is increased to ≈18%. Membranes are also capable of separating small dyes (e.g., methyl orange; MO; molecular weight = 327 g mol-1 ) from a mixed feed of BBR and MO. Considering a thickness of ≈14 nm and its separation efficiency, the present membrane has significance in separation processes.

Water Transport through Ultrathin Polyamide Nanofilms Used for Reverse Osmosis.

Thin-film composite membranes comprising a polyamide nanofilm separating layer on a support material are state of the art for desalination by reverse osmosis. Nanofilm thickness is thought to determine the rate of water transport through the membranes; although due to the fast and relatively uncontrolled interfacial polymerization reaction employed to form these nanofilms, they are typically crumpled and the separating layer is reported to be ≈50-200 nm thick. This crumpled structure has confounded exploration of the independent effects of thickness, permeation mechanism, and the support material. Herein, smooth sub-8 nm polyamide nanofilms are fabricated at a free aqueous-organic interface, exhibiting chemical homogeneity at both aqueous and organic facing surfaces. Transfer of these ultrathin nanofilms onto porous supports provides fast water transport through the resulting nanofilm composite membranes. Manipulating the intrinsic nanofilm thickness from ≈15 down to 8 nm reveals that water permeance increases proportionally with the thickness decrease, after which it increases nonlinearly to 2.7 L m-2 h-1 bar-1 as the thickness is further reduced to ≈6 nm.

MEMBRANE FILTRATION. Sub-10 nm polyamide nanofilms with ultrafast solvent transport for molecular separation.

Membranes with unprecedented solvent permeance and high retention of dissolved solutes are needed to reduce the energy consumed by separations in organic liquids. We used controlled interfacial polymerization to form free-standing polyamide nanofilms less than 10 nanometers in thickness, and incorporated them as separating layers in composite membranes. Manipulation of nanofilm morphology by control of interfacial reaction conditions enabled the creation of smooth or crumpled textures; the nanofilms were sufficiently rigid that the crumpled textures could withstand pressurized filtration, resulting in increased permeable area. Composite membranes comprising crumpled nanofilms on alumina supports provided high retention of solutes, with acetonitrile permeances up to 112 liters per square meter per hour per bar. This is more than two orders of magnitude higher than permeances of commercially available membranes with equivalent solute retention.

Controlled surface trap state photoluminescence from CdS QDs impregnated in poly(methyl methacrylate).

A method of microwave (MW) assisted synthesis was employed to prepare cadmium sulfide (CdS) quantum dots (QDs) in dimethylformamide in the presence of poly(methyl methacrylate) (PMMA). The MW irradiation was carried out for a fixed time of 20-30 s and the size of QDs varied from 2.9-5.5 nm. Before each irradiation the solution was cooled down to ambient temperature and the irradiation process was repeated six times. An increase in the intensity and red shift of the characteristic UV-vis absorption peak originating from CdS QDs were observed with repeated MW irradiation, suggesting that the amount of generated CdS QDs increased within the PMMA network and aggregated with repeated MW irradiation. MW irradiation could influence selectively the nucleation and growing rates of PMMA-CdS QDs systems. The broadness and large Stokes shift of the emission from Cd(2+)-rich PMMA-CdS QDs was due to the surface trap state photoluminescence. The recombination of shallow trapped electrons and shallow trapped holes has been considered as the primary source of the surface trap state photoluminescence in Cd(2+)-rich PMMA-CdS QDs. The photoluminescence lifetime was observed to be decreased sharply when the amount of QDs was less, showing the emission decay was dependent on the surface property of PMMA-CdS QDs. The origin of the longer lifetime was due to the involvement of surface trap states and dependent on the amount of CdS QDs present within PMMA and its environment. The effect of the concentration of Cd(2+), S(2-) and PMMA on the generation of CdS QDs within PMMA and the effect of repeated MW irradiation on the optical properties was studied and the results are discussed in this article.

Ultrafast viscous permeation of organic solvents through diamond-like carbon nanosheets.

Chemical, petrochemical, energy, and environment-related industries strongly require high-performance nanofiltration membranes applicable to organic solvents. To achieve high solvent permeability, filtration membranes must be as thin as possible, while retaining mechanical strength and solvent resistance. Here, we report on the preparation of ultrathin free-standing amorphous carbon membranes with Young's moduli of 90 to 170 gigapascals. The membranes can separate organic dyes at a rate three orders of magnitude greater than that of commercially available membranes. Permeation experiments revealed that the hard carbon layer has hydrophobic pores of ~1 nanometer, which allow the ultrafast viscous permeation of organic solvents through the membrane.

Synthesis of thiol capped CdS nanocrystallites using microwave irradiation and studies on their steady state and time resolved photoluminescence.

Synthesis of cadmium sulfide (CdS) nanocrystallites has been performed through the microwave (MW) assisted reaction of cadmium acetate with thiourea in N,N-dimethylformamide (DMF) in the presence of two capping agents, 1-butanethiol and 2-mercaptoethanol. Attempts were made to control the size and size distribution of the thiol capped CdS nanocrystallites by controlling the number of MW irradiations/exposures for a fixed time (duration). The prepared nanocrystallites have been characterized by UV-vis spectroscopy, FTIR, XRD, FESEM and TEM. The peak position of the absorption band of the 1-butanethiol caped CdS nanocrystals in DMF solution shifted towards longer wavelength with the increasing number of MW exposures indicating the growth of particle size. In contrast, the peak position of absorption band for the 2-mercaptoethanol capped CdS nanocrystals remained nearly at the same wavelength and only the intensity of the absorption band increased with the increasing number of MW exposures. The observed steady state photoluminescence (visible range) of the 1-butanethiol capped CdS nanocrystals in DMF solution shifted towards higher wavelength, showing a decrease in intensity, with the increase in the number of MW exposures. Whereas in the case of 2-mercaptoethanol capped CdS nanocrystals in DMF solution, the photoluminescence peak remained nearly at the same position showing a decrease in intensity with increase in the number of MW exposures. The interesting results on the size-dependent steady state and time resolved photoluminescence (PL) of the CdS nanocrystallites are discussed in the present article. Possible application of such studies in the area of biotechnology has been mentioned.

Ultrathin nanofibrous films prepared from cadmium hydroxide nanostrands and anionic surfactants.

We developed a simple fabrication method of ultrathin nanofibrous films from the dispersion of cadmium hydroxide nanostrands and anionic surfactants. The nanostrands were prepared in a dilute aqueous solution of cadmium chloride by using 2-aminoethanol. They were highly positively charged and gave bundlelike fibers upon mixing an aqueous solution of anionic surfactant. The nanostrand/surfactant composite fibers were filtered on an inorganic membrane filter. The resultant nanofibrous film was very uniform in the area of a few centimeters square when the thickness was not less than 60 nm. The films obtained with sodium tetradecyl sulfate (STS) had a composition close to the electroneutral complex, [Cd37(OH)68(H2O)n] x 6(STS), as confirmed by energy dispersive X-ray analysis. They were water-repellent with a contact angle of 117 degrees, and the value slightly decreased with the alkyl chain length of anionic surfactants. Ultrathin nanofibrous films were stable enough to be used for ultrafiltration at pressure difference of 90 kPa. We could effectively separate Au nanoparticles of 40 nm at an extremely high filtration rate of 14000 L/(h m2 bar).

Power spectral density analysis and photoconducting behavior in copper(II) phthalocyanine nanostructured thin films.

Surface morphology of copper(II) phthalocyanine (CuPc) nanostructured thin films deposited on polished silicon surface was characterized by using atomic force microscopy (AFM). Characteristic topographic parameters like fractals contribute substantially to the thin film morphology, which directly or indirectly influences the physical and optical properties. Fractal geometry and scaling concepts can concisely as well as more effectively describe the complex rough surface morphology. The power values of power spectral density (PSD) for the AFM digital data were determined by the fast Fourier transform (FFT) algorithms instead of the root-mean-square (rms) and peak-to-valley value. The PSD provides a more reliable description to the topography than the rms roughness and imparts some useful information of the surface, including fractal contributions. Fractal analyses, including area-perimeter and PSD methods, have been used to evaluate surface morphology of a vacuum deposited CuPc thin film surface formed under various film deposition temperatures. Film deposition temperature has affected the microstructural and related morphological evolutions very differently. The PSD plots are successfully approximated by the k-correlation model. The film growth is interpreted by the bulk and surface diffusion using parameter C of the k-correlation model. The dark and photoconductivity of CuPc nanostructures in Si/CuPc/Ag configuration at different temperatures have been studied and their changes with roughness and temperature have been discussed. A significantly higher value of the rectification ratio (RR) and photoswitching behavior in such configuration have been noticed.

Nanostructured organic-inorganic photodiodes with high rectification ratio.

High quality organic-inorganic heterojunction photodiodes based on nanostructured copper (II) phthalocyanine (CuPc) and intrinsic zinc oxide (i-ZnO) have been fabricated. The i-ZnO thin films/layers were grown by RF magnetron sputtering on clean indium tin oxide (ITO) coated glass substrates. These films have been characterized by optical absorption and field emission scanning electron microscopy (FESEM). CuPc thin films deposited at room temperature on i-ZnO have exhibited a change in their surface morphology with the post-deposition annealing temperature under normal atmosphere. The electrical dark conductivity and the photoconductivity of ITO/i-ZnO/CuPc/Au sandwich structures have been measured under various photoexcitation intensities using a xenon light source. The devices have shown excellent reproducibility of their electrical characteristics and high rectification ratios. The highest rectification ratio is nearly 831 calculated above the threshold voltage at room temperature for the sample annealed at 250 °C (i.e. Pc 250). The effects of the annealing temperature of CuPc on the surface morphology, rectification ratio, and optical properties have been discussed.

A two-dimensional coordination compound as a zinc ion selective luminescent probe for biological applications.

A 2D coordination compound {[Cu2(HL)(N3)]ClO4}infinity (1; H3L = 2,6-bis(hydroxyethyliminoethyl)-4-methyl phenol) was synthesized and characterized by single-crystal X-ray diffraction to be a polymer in the crystalline state. Each [Cu2(HL)(N3)]+ species is connected to its adjacent unit by a bridging alkoxide oxygen atom of the ligand to form a helical propagation along the crystallographic a axis. The adjacent helical frameworks are connected by a ligand alcoholic oxygen atom along the crystallographic b axis to produce pleated 2D sheets. In solution, 1 dissociates into [Cu2(HL)2(H3L)]2H2O (2); the monomer displays high selectivity for Zn2+ and can be used in HEPES buffer (pH 7.4) as a zinc ion selective luminescent probe for biological application. The system shows a nearly 19-fold Zn2+-selective chelation-enhanced fluorescence response in the working buffer. Application of 2 to cultured living cells (B16F10 mouse melanoma and A375 human melanoma) and rat hippocampal slices was also studied by fluorescence microscopy.