MIL-101-NH2(Fe)-Coated Nylon Microfibers for Immobilized Photocatalysts in RhB and Cr(VI) Removal.

MIL-101-NH2(Fe) is one of the effective photocatalytic metal-organic frameworks (MOFs) working under visible light. However, its powder-type form inhibits reusability in practical applications. In this study, we immobilized MIL-101-NH2(Fe) on a polymeric microfiber mesh to improve reusability while minimizing the loss of catalytic performance. To overcome the lack of surface functionality of the nylon fibers, an atomic layer deposition Al2O3 layer and NH2-BDC linker were introduced to facilitate uniform coating of the MOF on the fiber surface. The reactions of the metal precursor to the nylon substrate and NH2-BDC ligand of the MOF allow chemical bonding from the core to the shell of the entire hybrid catalytic materials. The resulting fiber-immobilized MOFs (Nylon@Al2O3@MOF) demonstrated high photocatalytic performance in the removal of RhB and Cr(VI) as representatives of organic dyes and heavy metals, respectively, while retaining over 85% of its efficiency after five cycles.

Lanthanide and Ladder-Structured Polysilsesquioxane Composites for Transparent Color Conversion Layers.

Ladder-type polysilsesquioxanes (LPSQs) containing phenyl as a high refractive index unit and cyclic epoxy as a curable unit were found to be excellent candidates for a transparent color conversion layer for displays due to being miscible with organic solvents and amenable to transparent film formation. Therefore, the LPSQs were combined with luminescent lanthanide metals, europium Eu(III), and terbium Tb(III), to fabricate transparent films with various emission colors, including red, orange, yellow, and green. The high luminescence and transmittance properties of the LPSQs-lanthanide composite films after thermal curing were attributed to chelating properties of hydroxyl and polyether side chains of LPSQs to lanthanide ions, as well as a light sensitizing effect of phenyl side chains of the LPSQs. Furthermore, Fourier-transform infrared (FT-IR) and X-ray photoelectron spectroscopy and nanoindentation tests indicated that the addition of the nanoparticles to the LPSQs moderately enhanced the epoxy conversion rate and substantially improved the wear resistance, including hardness, adhesion, and insusceptibility to atmospheric corrosion in a saline environment. Thus, the achieved LPGSG-lanthanide hybrid organic-inorganic material could effectively serve as a color conversion layer for displays.

Feasible Detoxification Coating Material for Chemical Warfare Agents Using Poly(methyl methacrylate)-Branched Poly(ethyleneimine) Copolymer and Metal-Organic Framework Composites.

Defense against chemical warfare agents (CWAs) is regarded as a top priority for the protection of humanity, but it still depends on physical protection with severe limitations such as residual toxicity and post-treatment requirement. In this study, a strategically designed functional polymeric substrate was composited with a metal-organic framework catalyst to remove toxicity immediately. A series of PMMA-BPEI copolymers exhibited high processability as a coating and accelerated the catalytic activity of Zr(IV)-based metal-organic framework catalysts (UiO-66). Among them, PMB12_40 composite coating on a cotton fabric, containing a PMMA-BPEI copolymer (PMMA/BPEI = 1/2) and 40% of UiO-66 catalyst, can efficiently decompose nerve agent simulants (methyl-paraoxon) under both liquid phase (t1/2 = 0.14 h) and humidified (t1/2 = 4.8 h) conditions. Moreover, a real agent, GD, was decomposed 100% by PMB12_40 in 4 h at 25 °C and 65% relative humidity. On the basis of superior catalytic activity, the PMB composites are anticipated to be a potential material for active chemical protection coating.

Pore-size control of chitin nanofibrous composite membrane using metal-organic frameworks.

Herein, environmentally benign chitin nanofiber (ChNF) membranes were fabricated by regulating suspension behavior. The introduction of zeolitic imidazole frameworks (ZIF-8) into the composite membranes led to the domain formation of ChNF derived by coordinative interaction, resulting in pore size-tunable membranes. Based on the rheological, morphological, and structural characterizations, the driving force of pore-size control was studied in the aqueous suspension of ChNF and ZIF-8 according to the relative concentration. At critical concentration, the 30-ChNF membrane presents superior water permeance (40 LMH h-1) while maintaining a high rejection rate (>80% for all organic dyes). Moreover, the molecular size cut-off of the composite membranes for dyes can be controlled in the range of less than 1 nm to 2 nm. The experimental results provide a simple strategy for the preparation of pore tunable ChNF membranes using MOF with high mechanical strength, good durability, high flux, dye rejection, and antifouling ability.

Robust Nanocellulose/Metal-Organic Framework Aerogel Composites: Superior Performance for Static and Continuous Disposal of Chemical Warfare Agent Simulants.

Environment-friendly and robust nanocellulose/metal-organic framework aerogel composites were prepared for effective detoxification of chemical warfare agent simulants both in static and dynamic continuous flow systems. For this, we fabricated a durable porous composite of the UiO-66 catalyst and TEMPO-oxidized cellulose nanofibers (TOCN) to examine as a detoxification filter. Even with over 50 wt % UiO-66, the obtained cellulose aerogel composites exhibited high stability without leaking of UiO-66 for 4 weeks under an aqueous state. The cellulose aerogel composite with 54 wt % UiO-66 showed a quite high surface area (483 m2 g-1) despite the presence of TOCN, which caused fast degradation of methyl paraoxon (MPO), a nerve agent simulant, with a 0.7 min half-life in an aqueous solution with N-ethylmorpholine buffer. This aerogel composite was then examined as the detoxification filter in the continuous flow system under a 7.2 mL h-1 flow rate, which surprisingly decomposed 53.7 g of MPO within 1 h with 1 m2 of the effective area.

Decomposition of the Simulant 2-Chloroethyl Ethyl Sulfide Blister Agent under Ambient Conditions Using Metal-Organic Frameworks.

Metal organic frameworks (MOFs) have been suggested as promising materials for application in the degradation of chemical warfare agents, with the majority of studies to date focusing on nerve agents. One of the most prominent MOFs used in the detoxification of nerve agents is UiO-66, which is of interest as a future nerve agent decontaminant. However, blister agents, which constitute one of the most toxic and highly reactive categories of chemical agents, are yet to be examined as gas-phase decontamination targets using MOF structures. In this study, a novel type of UiO-66 with a smaller particle size, namely, UiO-66S, was used as a decontaminant for the blister agent simulant, 2-chloroethyl ethyl sulfide (2-CEES). The gas-phase chemical adsorption and decomposition of 2-CEES were demonstrated for the first time, with an estimated t1/2 of 1.34 h. This value is the highest reported value for an MOF in gas-phase reaction conditions. The obtained nontoxic degradation products were identified, and the reaction mechanism was studied using density functional theory calculations. Furthermore, the synthesized UiO-66S catalyst also exhibits superior catalytic ability toward nerve agent simulants (diisopropyl fluorophosphate).The results of the study provide a firm basis for the use of UiO-66S as a future decontaminant for both nerve and blister agents.

Continuous Flow Composite Membrane Catalysts for Efficient Decomposition of Chemical Warfare Agent Simulants.

Continuous and safe decomposition of chemical warfare agents (CWAs) is a critical requirement to protect both soldiers and citizens and to eliminate the stockpiles after the cold war. The Zr-based metal-organic framework (Zr-MOF) has been known as the most effective catalyst for decomposing CWAs, especially the most fatal nerve agents, however, its low processability due to the powder form limits its expansion to actual military applications. To this end, the composite membrane catalysts (CMCs) comprising the Zr-MOF (UiO-66 catalyst) and nylon 6 nanofiber (porous supporter) are developed by the simple integration of electrospray and electrospinning, resulting in selective immobilization of UiO-66 on the surface of the nylon 6 nanofibers. These strategical benefits of CMCs gave super catalytic durability including recyclability over five times without decreasing the catalytic activity for the decomposition of methyl paraoxon (MPO), a simulant of the nerve agent, in the presence of N-ethylmorpholine (N-EM), which was not achieved in the original particulate UiO-66. Because of the excellent physical and chemical stabilities of CMCs, the CMC with 56 wt % of UiO-66 (CMC56) decomposed 198 g of MPO within an hour in the continuous flow system with a flow rate of 21.6 mL h-1. This study highlights the important strategies in designing the feasible membrane-type catalysts with superior catalytic activity and robust durability for decomposing CWAs in the continuous flow system.

Organophosphorus hydrolase-poly-ß-cyclodextrin as a stable self-decontaminating bio-catalytic material for sorption and degradation of organophosphate pesticide.

A region suffering from an attack of a nerve agent requires not only a highly sorptive material but also a fast-acting catalyst to decontaminate the lethal chemical present. The product should be capable of high sorptive capacity, selectivity and quick response time to neutralize the long lasting harmful effects of nerve agents. Herein, we have utilized organophosphorus hydrolase (OPH) as a non-toxic bio-catalytic material held in with the supporting matrix of poly-ß-cyclodextrin (PCD) as a novel sorptive reinforced self-decontaminating material against organophosphate intoxication. OPH coated PCD (OPH-PCD) will not only be providing support for holding enzyme but also would be adsorbing methyl paraoxon (MPO) used as a simulant, in a host-guest inclusion complex formation. Sorption trend for PCD revealed preference towards the more hydrophobic MPO against para-nitrophenol (pNP). The results show sorption capacity of 1.26 mg/g of 100 µM MPO with PCD which was 1.7 times higher compared to pNP. The reaction rate with immobilized OPH-PCD was found to be 23% less compared to free enzyme. With the help of OPH-PCD, continuous hydrolysis (100%) of MPO into pNP was observed for a period of 24 h through packed bed reactor with good reproducibility and stability of enzyme. The long-term stability also confirmed its stable nature for the investigation period of 4 days where it maintained activity. Combined with its fast and reactive nature, the resulting self-decontaminating regenerating material provides a promising strategy for the neutralization of nerve agents and preserving the environment.

Molybdenum-Doped PdPt@Pt Core-Shell Octahedra Supported by Ionic Block Copolymer-Functionalized Graphene as a Highly Active and Durable Oxygen Reduction Electrocatalyst.

Development of highly active and durable electrocatalysts that can effectively electrocatalyze oxygen reduction reactions (ORR) still remains one important challenge for high-performance electrochemical conversion and storage applications such as fuel cells and metal-air batteries. Herein, we propose the combination of molybdenum-doped PdPt@Pt core-shell octahedra and the pyrene-functionalized poly(dimethylaminoethyl methacrylate)-b-poly[(ethylene glycol) methyl ether methacrylate] ionic block copolymer-functionalized reduced graphene oxide (Mo-PdPt@Pt/IG) to effectively augment the interfacial cohesion of both components using a tunable ex situ mixing strategy. The rationally designed Mo-PdPt@Pt core-shell octahedra have unique compositional benefits, including segregation of Mo atoms on the vertexes and edges of the octahedron and 2-3 shell layers of Pt atoms on a PdPt alloy core, which can provide highly active sites to the catalyst for ORR along with enhanced electrochemical stability. In addition, the ionic block copolymer functionalized graphene can facilitate intermolecular charge transfer and good stability of metal NPs, which arises from the ionic block copolymer interfacial layer. When the beneficial features of the Mo-PdPt@Pt and IG are combined, the Mo-PdPt@Pt/IG exhibits substantially enhanced activity and durability for ORR relative to those of commercial Pt/C. Notably, the Mo-PdPt@Pt/IG shows mass activity 31-fold higher than that of Pt/C and substantially maintains high activities after 10 000 cycles of intensive durability testing. The current study highlights the crucial strategies in designing the highly active and durable Pt-based octahedra and effective combination with functional graphene supports toward the synergetic effects on ORR.

Rational Design of Multiamphiphilic Polymer Compatibilizers: Versatile Solubility and Hybridization of Noncovalently Functionalized CNT Nanocomposites.

The design of amphiphilic polymer compatibilizers for solubility manipulation of CNT composites was systematically generalized in this study. Structurally tailored multiamphiphilic compatibilizer were designed and synthesized by applying simple, high-yield reactions. This multiamphiphilic compatibilizer was applied for noncovalent functionalization of CNTs as well as provided CNTs with outstanding dispersion stability, manipulation of solubility, and hybridization with Ag nanoparticles (NPs). With regard to the dispersion properties, superior records in maximum concentration (2.88-3.10 mg/mL in chloroform), and mass ratio of the compatibilizer for good CNT dispersion (36 wt %) were achieved by MWCNTs functionalized with a multiamphiphilic block copolymer compatibilizer. In particular, the solubility limitations of MWCNT dispersion in solvents ranging from toluene (nonpolar) to aqueous solution (polar) are surprisingly resolved by introducing this multiamphiphilic polymer compatibilizer. Furthermore, this polymer compatibilizer allowed the synthesis of the hybrid CNT nanocomposites with Ag nanoparticles by an in situ nucleation process. As such, the multiamphiphilic compatibilizer candidate as a new concept for the noncovalent functionalization of CNTs can extend their use for a wide range of applications.

Tailor-made polyamide membranes for water desalination.

Independent control of the extrinsic and intrinsic properties of the polyamide (PA) selective layer is essential for designing thin-film composite (TFC) membranes with performance characteristics required for water purification applications besides seawater desalination. Current commercial TFC membranes fabricated via the well-established interfacial polymerization (IP) approach yield materials that are far from ideal because their layer thickness, surface roughness, polymer chemistry, and network structure cannot be separately tailored. In this work, tailor-made PA-based desalination membranes based on molecular layer-by-layer (mLbL) assembly are presented. The mLbL technique enables the construction of an ultrathin and highly cross-linked PA selective layer in a precisely and independently controlled manner. The mLbL-assembled TFC membranes exhibit significant enhancements in performance compared to their IP-assembled counterparts. A maximum sodium chloride rejection of 98.2% is achieved along with over 2.5 times higher water flux than the IP-assembled counterpart. More importantly, this work demonstrates the broad applicability of mLbL in fabricating a variety of PA-based TFC membranes with nanoscale control of the selective layer thickness and roughness independent of the specific polyamide chemistry.

Tunable solubility parameter of poly(3-hexyl thiophene) with hydrophobic side-chains to achieve rubbery conjugated films.

A highly π-conjugated nanofibrillar network of poly(3-hexyl thiophene) (P3HT) embedded in polydimethylsiloxane (PDMS) elastomer films on SiO2 dielectrics was facilely developed via solution-blending of an ultrasound-assisted dilute P3HT solution with a PDMS precursor followed by spin-casting and curing. In contrast, simple blending without ultrasonication against the dilute P3HT solution yielded large agglomerates in cast films owing to a great difference in solubility parameter (δ) values (P3HT = 9.5 cal(1/2) cm(-3/2), PDMS = 7.3 cal(1/2) cm(-3/2)). In the ultrasound-assisted 0.1 vol % P3HT solutions, the π-conjugated polymer could develop crystalline nanofibrils surrounded by nonpolar hexyl side chains with the same δ value as that of PDMS, yielding homogeneously dispersed 10 wt % loaded P3HT/PDMS blend films. Spun-cast P3HT/PDMS blend films could yield high electrical properties in organic field-effect transistor, including mobilities of up to 0.045 cm(2) V(-1) s(-1) and on/off current ratios of >5 × 10(5), as well as excellent environmental stability owing to the outer PDMS layer.

Fouling-tolerant nanofibrous polymer membranes for water treatment.

Nafion/polyvinylidene fluoride (PVDF) nanofibrous membranes with electrostatically negative charges on the fiber surface were fabricated via electrospinning with superior water permeability and antifouling behaviors in comparison with the conventional microfiltration membranes. The fiber diameter and the resultant pore size in the nanofibrous membranes were easily controlled through tailoring the properties of the electrospinning solutions. The electrospun Nafion/PVDF nanofibrous membranes revealed high porosities (>80%) and high densities of sulfonate groups on the membrane surface, leading to praiseworthy water permeability. Unexpectedly, the water permeability was observed as proportional to the fiber diameter and pore size in the membrane. The presence of sulfonate groups on the membrane improved the antifouling performance against negatively charged oily foulants.

Molecular layer-by-layer assembled thin-film composite membranes for water desalination.

Molecular layer-by-layer (mLbL) assembled thin-film composite membranes fabricated by alternating deposition of reactive monomers on porous supports exhibit both improved salt rejection and enhanced water flux compared to traditional reverse osmosis membranes prepared by interfacial polymerization. Additionally, the well-controlled structures achieved by mLbL deposition further lead to improved antifouling performance.

Novel polymer nanowire crystals of diketopyrrolopyrrole-based copolymer with excellent charge transport properties.

The first demonstration of polymer nanowire (PNW) crystals based on a diketopyrrolopyrrole-based copolymer (i.e., PDTTDPP), and their application to field-effect transistors (FETs) is reported. Remarkably, transmission electron microscopy and selected area electron diffraction analyses of the PNW reveal its single-crystalline (SC) nature. FETs fabricated of a SC PNW exhibit a maximal charge carrier mobility of ≈7.00 cm(2) V(-1) s(-1) , which is almost one order of magnitude higher than that of the thin-film transistors made of the same polymer (PDTTDPP).

A new, higher yielding synthetic route towards dodecaphenyl cage silsesquioxanes: synthesis and mechanistic insights.

Cage dodecaphenylsilsesquioxane (T12-Phenyl) was synthesized in a one batch, mildly basic aqueous solution under room temperature conditions using a trialkoxysilane precursor. Significant improvements in synthetic yield (>95%) were observed compared with previous reports. Kinetic studies of the hydrolysis of phenyltrimethoxysilane were conducted and the condensation was monitored by (29)Si NMR which revealed the presence of a transient, intermediary T1 species as the pathway to dodecaphenylsilsesquioxane spherulites, and the tendency for T12 structures over T8, T10, and other substructures was explained through MM2 simulations.

Polymer catalysts from polymerization catalysts: direct encapsulation of metal catalyst into star polymer core during metal-catalyzed living radical polymerization.

Star polymers containing ruthenium complex in the core were prepared by ruthenium-catalyzed living radical polymerization, where the metal catalysts were directly encapsulated on linking reactions of living poly(MMA) in the presence of ethylene glycol dimethacrylate as a linker and diphenyl-4-styrylphosphine as a ligand incorporated in the core. The products were characterized by SEC/MALLS, UV-vis, NMR, AFM, TEM, and ICP-AES and were employed as polymer catalysts for the oxidation reaction of alcohol.