Self-Aggregation Control of Porphyrin for Enhanced Selective Covalent Organic Network Membranes.

Covalent organic networks (CONs) are considered ideal for precise molecular separation compared with traditional polymer membranes because their pores have a sharp molecular weight cut-off and a robust structure. However, challenges remain with regard to tuning pores as a prerequisite for facile membrane fabrication to a defect-free layer. Herein, a highly conjugated amino-porphyrin is used and exploited its tunable stacking behavior to fabricate porphyrin-based polyamide CONs with ordered structures through interfacial polymerization with acyl chlorides. Controlling the self-aggregation behavior of the porphyrin and the conformation of the acyl chlorides can create different covalent networks. Acid-triggered porphyrin protonation offsets stacking to reduce the pore in the network from mesopore to micropore, enabling selective molecule transport. Furthermore, different acyl chloride ligands are used to control the interlayer bonding in CONs. Accordingly, the tailored pore diameters (0.48-0.78 nm) are confirmed by the molecule rejections with performance stability over 25 days of operation, as well as under various conditions. This study leverages porphyrin chemistry and interfacial polymerization to fabricate a defect-free CON layer with a significantly lower molecular weight cut-off (< 330 Da) than previously reported porphyrin-based membranes (>800 Da). This will pave the way for the development of ideal topological membranes.

Two-Dimensional Interlayer Space Induced Horizontal Transformation of Metal-Organic Framework Nanosheets for Highly Permeable Nanofiltration Membranes.

Laminar membranes comprising graphene oxide (GO) and metal-organic framework (MOF) nanosheets benefit from the regular in-plane pores of MOF nanosheets and thus can support rapid water transport. However, the restacking and agglomeration of MOF nanosheets during typical vacuum filtration disturb the stacking of GO sheets, thus deteriorating the membrane selectivity. Therefore, to fabricate highly permeable MOF nanosheets/reduced GO (rGO) membranes, a two-step method is applied. First, using a facile solvothermal method, ZnO nanoparticles are introduced into the rGO laminate to stabilize and enlarge the interlayer spacing. Subsequently, the ZnO/rGO membrane is immersed in a solution of tetrakis(4-carboxyphenyl)porphyrin (H2 TCPP) to realize in situ transformation of ZnO into Zn-TCPP in the confined interlayer space of rGO. By optimizing the transformation time and mass loading of ZnO, the obtained Zn-TCPP/rGO laminar membrane exhibits preferential orientation of Zn-TCPP, which reduces the pathway tortuosity for small molecules. As a result, the composite membrane achieves a high water permeance of 19.0 L m-2  h-1  bar-1 and high anionic dye rejection (>99% for methyl blue).

Tough ion gels composed of coordinatively crosslinked polymer networks using ZIF-8 nanoparticles as multifunctional crosslinkers.

Constructing crosslinked polymer networks via reversible interactions is a promising approach to recover the mechanical strength of damaged gels. In addition, by designing effective reversible crosslinks, the mechanical strength of the gel can be enhanced through energy dissipation based on the destruction of the crosslinks by an applied force. In this study, we introduced zeolitic imidazole framework-8 nanoparticles (ZIF-8 NPs), which acted as multifunctional crosslinkers, to provide multipoint coordination bonding with a poly(N,N-dimethylacrylamide)-based polymer network in a gel containing an ionic liquid. The mechanical strength of the gel increased with an increase in the content of ZIF-8 NPs up to 6 wt%. It was confirmed that the energy loaded onto the gel was dissipated through the desorption of the polymer network from the surface of the ZIF-8 NPs. Owing to the reversible destruction and reconstruction of the coordinative crosslinking between the polymer network and ZIF-8 NPs, the mechanical strength of the damaged gel was almost fully recovered through annealing.

Energy dissipation via the internal fracture of the silica particle network in inorganic/organic double network ion gels.

Inorganic/organic double network (DN) ion gels, which are composed of an inorganic silica particle network, an organic poly(N,N-dimethylacrylamide) (PDMAAm) network, and a large amount of ionic liquid, showed excellent mechanical strength of over 25 MPa compression fracture stress at an 80 wt% ionic liquid content. The excellent mechanical strength of these inorganic/organic DN ion gels was attributed to the energy dissipation of the inorganic/organic DN structure. It has been considered that the energy dissipation in inorganic/organic DN ion gels is caused by the internal fracture of the silica particle network, which is preferentially fractured by deformation. However, no studies aiming to investigate the internal fracture of the silica particle network in inorganic/organic DN ion gels have been conducted by direct approaches. In this study, the internal fracture of the silica particle network in the inorganic/organic DN ion gel was directly evaluated by a small angle X-ray scattering (SAXS) technique. The synchrotron SAXS measurements conducted under a uniaxial loading-unloading process demonstrated that the aggregation size of the silica particle network irreversibly decreased with uniaxial stretch. Based on these results, it was clarified that the energy dissipation of the inorganic/organic DN ion gels was attributed to the internal fracture of the silica particle network.

Inorganic/Organic Double-Network Ion Gels with Partially Developed Silica-Particle Network.

Tough inorganic/organic composite network gels consisting of a partially developed silica-particle network and a large amount of an ionic liquid, named micro-double-network (µ-DN) ion gel, are fabricated via two methods. One is a one-pot/one-step process conducted using a simultaneous network formation via sol-gel reaction of tetraethyl orthosilicate and free radical polymerization of N, N-dimethylacrylamide in an ionic liquid. When the network formation rates of the inorganic and organic networks are almost the same, the µ-DN structure is formed. The second method is simpler and involved the use of silica nanoparticles as the starting material. By controlling the dispersion state of the silica nanoparticles in an ionic liquid, the µ-DN structure is formed. In both µ-DN ion gels, silica nanoparticles partially aggregate and form network-like clusters. When a large deformation is induced in the µ-DN ion gels, the silica-particle clusters rupture and dissipate the loaded energy. The fracture stress and Young's modulus of the µ-DN ion gel increase as the size of the silica nanoparticles decreases. The increment in the mechanical strength would have been caused by the increase in the total van der Waals attraction forces and the total number of hydrogen bonding in the silica-particle networks.

Sucrose purification and repeated ethanol production from sugars remaining in sweet sorghum juice subjected to a membrane separation process.

The juice from sweet sorghum cultivar SIL-05 (harvested at physiological maturity) was extracted, and the component sucrose and reducing sugars (such as glucose and fructose) were subjected to a membrane separation process to purify the sucrose for subsequent sugar refining and to obtain a feedstock for repeated bioethanol production. Nanofiltration (NF) of an ultrafiltration (UF) permeate using an NTR-7450 membrane (Nitto Denko Corporation, Osaka, Japan) concentrated the juice and produced a sucrose-rich fraction (143.2 g L-1 sucrose, 8.5 g L-1 glucose, and 4.5 g L-1 fructose). In addition, the above NF permeate was concentrated using an ESNA3 NF membrane to provide concentrated permeated sugars (227.9 g L-1) and capture various amino acids in the juice, enabling subsequent ethanol fermentation without the addition of an exogenous nitrogen source. Sequential batch fermentation using the ESNA3 membrane concentrate provided an ethanol titer and theoretical ethanol yield of 102.5-109.5 g L-1 and 84.4-89.6%, respectively, throughout the five-cycle batch fermentation by Saccharomyces cerevisiae BY4741. Our results demonstrate that a membrane process using UF and two types of NF membranes has the potential to allow sucrose purification and repeated bioethanol production.

Development of an ion gel-based CO2 separation membrane composed of Pebax 1657 and a CO2-philic ionic liquid.

A tough ion gel membrane containing a CO2-philic ionic liquid, 1-ethyl-3-methylimidazolium tricyanomethanide ([Emim][C(CN)3]), was developed, and its CO2 permeation properties were evaluated under humid conditions at elevated temperatures. Pebax 1657, which is a diblock copolymer composed of a polyamide block and a polyethylene oxide block, was used as the gel network of the ion gel membrane to prepare a tough ion gel with good ionic liquid-holding properties. The polyamide block formed a semicrystalline structure in [Emim][C(CN)3] to toughen the ion gel membrane via an energy dissipation mechanism. The polyethylene oxide block exhibited good compatibility with [Emim][C(CN)3] and contributed to the retention of the ionic liquid in the ion gel. The developed ion gel membrane showed a good CO2 separation performance of 1677 barrer CO2 permeability and 37 CO2/N2 permselectivity under humid conditions of 75% relative humidity at an elevated temperature of 50 °C, which corresponds to an exhaust gas from a coal-fired power plant.

Using Reverse Osmosis Membrane at High Temperature for Water Recovery and Regeneration from Thermo-Responsive Ionic Liquid-Based Draw Solution for Efficient Forward Osmosis.

Forward osmosis (FO) membrane process is expected to realize energy-saving seawater desalination. To this end, energy-saving water recovery from a draw solution (DS) and effective DS regeneration are essential. Recently, thermo-responsive DSs have been developed to realize energy-saving water recovery and DS regeneration. We previously reported that high-temperature reverse osmosis (RO) treatment was effective in recovering water from a thermo-responsive ionic liquid (IL)-based DS. In this study, to confirm the advantages of the high-temperature RO operation, thermo-sensitive IL-based DS was treated by an RO membrane at temperatures higher than the lower critical solution temperature (LCST) of the DS. Tetrabutylammonium 2,4,6-trimethylbenznenesulfonate ([N4444][TMBS]) with an LCST of 58 °C was used as the DS. The high-temperature RO treatment was conducted at 60 °C above the LCST using the [N4444][TMBS]-based DS-lean phase after phase separation. Because the [N4444][TMBS]-based DS has a significantly temperature-dependent osmotic pressure, the DS-lean phase can be concentrated to an osmotic pressure higher than that of seawater at room temperature (20 °C). In addition, water can be effectively recovered from the DS-lean phase until the DS concentration increased to 40 wt%, and the final DS concentration reached 70 wt%. From the results, the advantages of RO treatment of the thermo-responsive DS at temperatures higher than the LCST were confirmed.

Inorganic/organic nanocomposite ion gels with well dispersed secondary silica nanoparticles.

We have previously reported tough inorganic/organic nanocomposite (NC) ion gels composed of silica particles and poly(N,N-dimethylacrylamide) (PDMAAm) networks and a large amount of ionic liquid. In this study, the network structure and toughening mechanism of NC ion gels were investigated. The NC ion gels showed characteristic mechanical properties; i.e. the stress was significantly increased at a highly elongated state. In addition, the NC ion gels showed an almost elastic mechanical property, which was completely different from that of our other developed inorganic/organic tough ion gels named double-network (DN) ion gels. It was found from structural observation that secondary silica nanoparticles dispersed well in the NC ion gel. It was also found that some of the secondary silica nanoparticles had a ring-like structure which would incorporate PDMAAm chains. From the silica particle content dependency on stress-strain curves of inorganic/organic NC ion gels, it was inferred that the secondary silica particles could serve as a movable cross-linker of PDMAAm chains in the NC ion gel.

Gas Permeation Characteristics of TiO2-ZrO2-Aromatic Organic Chelating Ligand (aOCL) Composite Membranes.

Methyl gallate (MG) and ethyl ferulate (EF) with a benzene ring were separately used as aromatic organic chelating ligands (aOCLs) to prepare two versions of TiO2-ZrO2-aOCL composite sols via hydrolysis and polycondensation reactions with titanium(IV) isopropoxide (Ti(OC3H7)4) and zirconium(IV) butoxide (Zr(OC4H9)4). Thermogravimetric and FT-IR analysis of dry gels revealed that aromatic rings were present in the residual organic matter when the gel was fired under nitrogen at 300 °C. In X-ray diffraction (XRD) measurements, the TiO2-ZrO2 composite material prepared using these two aOCLs showed an amorphous structure with no crystalline peaks for TiO2 and ZrO2. In N2 adsorption/desorption measurements at 77 K, the TiO2-ZrO2 samples using the aOCLs as a template appeared porous with a larger specific surface area than TiO2-ZrO2 without aOCL. TiO2-ZrO2-aOCL composite membranes were prepared by coating and firing TiO2-ZrO2-aOCL sol onto a SiO2 intermediate layer using an α-alumina porous tube as a substrate. Compared with the TiO2-ZrO2 membrane, the TiO2-ZrO2-aOCL membranes had higher gas permselectivity. The TiO2-ZrO2-EF membrane showed a He permeance of 2.69 × 10-6 mol m-2 s-1 Pa-1 with permeance ratios of He/N2 = 10.6 and He/CF4 = 163, while the TiO2-ZrO2-MG membrane revealed a bit less He permeance at 8.56 × 10-7 mol m-2 s-1 Pa-1 with greater permeance ratios of He/N2 = 61.7 and He/CF4 = 209 at 200 °C. A microporous TiO2-ZrO2 amorphous structure was obtained by introducing aOCL. The differences in the side chains of each aOCL could possibly account for the differences in the microporous structures of the resultant TiO2-ZrO2-aOCL membranes.

Design of a new static micromixer having simple structure and excellent mixing performance.

A novel micromixer with simple construction and excellent mixing performance is developed. The micromixer is composed of two stainless steel tubes with different diameters: one is an outer tube and another is an inner tube which fits in the outer tube. In this micromixer, one reactant fluid flows in the mixing zone from the inner tube and the other flows from the outer tube. The excellent mixing performance is confirmed by comparing the results of a Villermaux/Dushman reaction with those for the other micromixers. The developed micromixer has a mixing cascade with multiple means and an asymmetric structure to achieve effective mixing. The excellent mixing performance of the developed micromixer suggests that serial addition of multiple phenomena for mixing will give us an efficient micromixing.

Tough and stretchable inorganic/organic double network ion gel containing gemini-type ionic liquid as a multiple hydrogen bond cross-linker.

Tough and stretchable inorganic/organic double network ion gels containing gemini-type ionic liquids with two OH groups in the di-cation, which can work as multiple hydrogen bond-based weak cross-linkers of the gel networks, are developed.

Fabrication of Stacked Graphene Oxide Nanosheet Membranes Using Triethanolamine as a Crosslinker and Mild Reducing Agent for Water Treatment.

Two-dimensional (2D) nanosheets show promise for the development of water treatment membranes with extraordinary separation properties and the advantages of atomic thickness with micrometer-sized lateral dimensions. Stacked graphene oxide (GO)-based membranes can demonstrate unique molecular sieving properties with fast water permeation. However, improvements to the structural stability of the membranes in water to avoid problems such as swelling, disruption of the ordered GO layer and decreased rejection are crucial issues. This study reports the fabrication of stacked GO nanosheet membranes by simple vacuum filtration using triethanolamine (TEOA) as a crosslinker and mild reducing agent for improved structural stability and membrane performance. Results show that GO membranes modified with TEOA (GO-TEOA membranes) have a higher structural stability in water than unmodified GO membranes, resulting in improved salt rejection performance. Furthermore, GO-TEOA membranes show stable water permeance at applied pressures up to 9 bar with Na2SO4 rejection of 85%, suggesting the potential benefits for water treatment applications.

Inorganic/Organic Double-Network Gels Containing Ionic Liquids.

Highly robust ion gels, termed double-network (DN) ion gels, composed of inorganic/organic interpenetrating networks and a large amount of ionic liquids (ILs), are fabricated. The DN ion gels with an 80 wt% IL content show extraordinarily high mechanical strength: more than 28 MPa of compressive fracture stress. In the DN ion gel preparation, a brittle inorganic network of physically bonded silica nanoparticles and a ductile organic network of polydimethylacrylamide (PDMAAm) are formed in the IL. Because of the different reaction mechanisms of the inorganic/organic networks, the DN ion gels can be formed by an easy and free-shapeable one-pot synthesis. They can be prepared in a controllable manner by manipulating the formation order of the inorganic and organic networks via not only multistep but also single-step processes. When silica particles form a network prior to the PDMAAm network formation, DN ion gels can be prepared. The brittle silica particle network in the DN ion gel, serving as sacrificial bonds, easily ruptures under loading to dissipate energy, while the ductile PDMAAm network maintains the shape of the material by the rubber elasticity. Given the reversible physical bonding between the silica particles, the DN ion gels exhibit a significant degree of self-recovery by annealing.

An amino acid ionic liquid-based tough ion gel membrane for CO2 capture.

A tough and thin double-network gel membrane containing amino acid ionic liquids as a CO2 carrier exhibited superior CO2 permeability and stability under pressurized conditions.

Effects of water concentration on the free volume of amino acid ionic liquids investigated by molecular dynamics simulations.

Amino acid ionic liquids (AAILs) are gaining attention because of their potential in CO2 capture technology. Molecular dynamics simulations of AAILs tetramethylammonium glycinate ([N1111][Gly]), tetrabutylammonium glycinate ([N4444][Gly]), and 1,1,1-trimethylhydrazinium glycinate ([aN111][Gly]) and their corresponding mixtures with water were performed to investigate the effect of water concentration on the cation-anion interactions. The water content significantly influenced the free volume (FV) and fractional free volume (FFV) of the AAILs that varied with the hydrophobic and hydrophilic nature of the ion pairs. Under dry conditions, the FFV increased with increasing cation molecular sizes, indicative of proportional adsorption of any inert gases, such as N2, as consistent with experimental observations. Furthermore, the polarity of the cation played an important role in FFV and hence the diffusion of the AAILs. Density functional theory calculations suggested that hydrophilic [aN111][Gly] featured stronger interactions in the presence of water, whereas the hydrophobic IL showed weaker interactions. The carboxylate group of glycinate displayed stronger interactions with water than the cation. The computational study provided qualitative insight into the role of FV of the AAILs on CO2 and N2 absorption and suggests that [aN111][Gly] has CO2 adsorption capacity in the presence of water superior to that of other studied AAILs.

Amino acid ionic liquid-based facilitated transport membranes for CO2 separation.

Supported liquid membranes incorporating amino acid ionic liquids remarkably facilitate CO(2) permeation under dry and low humid conditions.

Microcapsules with macroholes prepared by the competitive adsorption of surfactants on emulsion droplet surfaces.

We demonstrate a simple, unique method for preparing microcapsules with holes in their shells. Cross-linked polymelamine microcapsules are prepared by the phase-separation method. The holey shell of each microcapsule is synthesized on the surface of an oil-in-water (O/W) emulsion droplet where a water-soluble polymeric surfactant and an oil-soluble surfactant are competitively adsorbed. The water-soluble polymeric surfactant provides a reaction site for shell formation. The oil-soluble surfactant molecules seem to self-assemble while the shells are being formed, so holes appear where they assemble. The critical degree of surface coverage of an emulsion droplet by the water-soluble polymeric surfactant needed to form the holey shells is determined to be 0.90 from theoretical calculations in which competitive adsorption is considered. Theoretical consideration suggests that the size and quantity of the holes in the microcapsule shells are controlled by the composition of the surfactants adsorbed on the surface of an emulsion droplet. This theoretical consideration is confirmed by experiments. The prepared microcapsule with controllable macroholes in its shell has the potential to be used for controlled release applications and can be used to fabricate a microcapsule that encapsulates hydrophilic compounds.

Investigation of alternative compounds to poly(E-MA) as a polymeric surfactant for preparation of microcapsules by phase separation method.

Various water-soluble polymers were used to examine an alternative emulsifier for poly(ethylene-alt-maleic anhydride), used in the preparation of crosslinked polyurea microcapsules. Microcapsules were successfully prepared by using the water-soluble polymers with large molecular weight alternating copolymers, namely poly(olefin-maleic anhydride), poly(olefin-maleic acid), and poly(acrylic acid). On the other hand, no microcapsule resulted from olefin-maleic acid with small molecular weight alternating copolymers. From these results, the following guidelines were obtained for the selection of polymeric surfactants suitable for crosslinked polyurea microcapsule. A polymeric surfactant must have maleic acid or a carboxyl group in order to form a crosslinked polyurea microcapsule membrane. Furthermore, to form a stronger capsule membrane it is desirable to have a maleic anhydride group. It is also important for membrane formation that the polymeric surfactant has a suitable molecular weight.