Quaternarized chitosan nanofiber and ZIF aerogel composites for synergetic CO cycloaddition catalysis.

Chemical upcycling of CO, a major greenhouse gas, is attracting significant attention as a crucial strategy to combat global warming. The production of cyclic carbonate using metal-organic frameworks and their composites using nanofibrous carbohydrate polymer are promising ways to convert CO into valuable products. However, the current role of fibrous polymers is restricted to serving as physical substrates.

Multifunctional and Hierarchical Porous ZIF-8: Amine and Thiol Tagged via Mixed Multivariate Ligand Strategies for Enhanced CO and Iodine Adsorption.

This study demonstrated a simple and innovative way of using the direct de novo synthesis to fabricate the mesoporous structure and diverse functionality of ZIF-8 for environmental cleanup and gas storage applications. By introducing different ligands, we have developed a version of ZIF-8 that could better capture carbon dioxide (CO) and iodine. The ZIF-8 was successfully designed to have the hierarchical and mesoporous structure with the functional groups of amine and thiol groups by adjusting the pKa values (from 8 to 12) of ligand instead of the original ligand, 2-methyl imidazole (Hmim, pK~14.

Robust and highly reactive membranes for continuous disposal of chemical warfare agents: Effects of nanostructure and functionality in MOF and nanochitin aerogel composites.

Developing appropriate disposal of stockpiles of chemical warfare agents (CWAs) has gained significant attention as their lethal toxicity seriously harms humanity. In this study, a novel green-fabrication method with UiO-66 catalysts and amine-functionalized chitin nanofibers (ChNFs) was suggested to prepare durable and highly reactive membranes for decomposing chemical warfare agents (CWAs) in the continuous flow system. The strong interaction between ChNFs and the UiO-66 led to stable loading of the UiO-66 on the continuous nano-porous channel of the ChNF reactive membrane even with high loading of UiO-66 (70 wt% of UiO-66 in the ChNF substrate).

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

MIL-101-NH(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-NH(Fe) on a polymeric microfiber mesh to improve reusability while minimizing the loss of catalytic performance.

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.

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).

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.

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.

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.

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.

Organophosphorus hydrolase-poly-β-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-β-cyclodextrin (PCD) as a novel sorptive reinforced self-decontaminating material against organophosphate intoxication.

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.

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).

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.

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.

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.

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.

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.