Heterostructured Graphene@Silica@Iron Phenylphosphinate for Fire-Retardant, Strong, Thermally Conductive Yet Electrically Insulated Epoxy Nanocomposites.

The portfolio of extraordinary fire retardancy, mechanical properties, dielectric/electric insulating performances, and thermal conductivity (λ) is essential for the practical applications of epoxy resin (EP) in high-end industries. To date, it remains a great challenge to achieve such a performanceportfolio in EP due to their different and even mutually exclusive governing mechanisms. Herein, a multifunctional additive (G@SiO2@FeHP) is fabricated by in situ immobilization of silica (SiO2) and iron phenylphosphinate (FeHP) onto the graphene (G) surface. Benefiting from the synergistic effect of G, SiO2 and FeHP, the addition of 1.0 wt% G@SiO2@FeHP enables EP to achieve a vertical burning (UL-94) V-0 rating and a limiting oxygen index (LOI) of 30.5%. Besides, both heat release and smoke generation of as-prepared EP nanocomposite are significantly suppressed due to the condensed-phase function of G@SiO2@FeHP. Adding 1.0 wt% G@SiO2@FeHP also brings about 44.5%, 61.1%, and 42.3% enhancements in the tensile strength, tensile modulus, and impact strength of EP nanocomposite. Moreover, the EP nanocomposite exhibits well-preserved dielectric and electric insulating properties and significantly enhanced λ. This work provides an integrated strategy for the development of multifunctional EP materials, thus facilitating their high-performance applications.

Engineering Sulfur-Containing Polymeric Fire-Retardant Coatings for Fire-Safe Rigid Polyurethane Foam.

With the advantages of lightweight and low thermal conductivity properties, polymeric foams are widely employed as thermal insulation materials for energy-saving buildings but suffer from inherent flammability. Flame-retardant coatings hold great promise for improving the fire safety of these foams without deteriorating the mechanical-physical properties of the foam. In this work, four kinds of sulfur-based flame-retardant copolymers are synthesized via a facile radical copolymerization. The sulfur-containing monomers serve as flame-retardant agents including vinyl sulfonic acid sodium (SPS), ethylene sulfonic acid sodium (VS), and sodium p-styrene sulfonate (VSS). Additionally, 2-hydroxyethyl acrylate (HEA) and 4-hydroxybutyl acrylate are employed to enable a strong interface adhesion with polymeric foams through interfacial H-bonding. By using as-synthesized waterborne flame-retardant polymeric coating with a thickness of 600 µm, the coated polyurethane foam (PUF) can achieve a desired V-0 rating during the vertical burning test with a high limiting oxygen index (LOI) of >31.5 vol%. By comparing these sulfur-containing polymeric fire-retardant coatings, poly(VS-co-HEA) coated PUF demonstrates the best interface adhesion capability and flame-retardant performance, with the lowest peak heat release rate of 166 kW m-2 and the highest LOI of 36.4 vol%. This work provides new avenues for the design and performance optimization of advanced fire-retardant polymeric coatings.

Oxygen Vacancy-Mediated CuWO4/CuBi2O4 Samples with Efficient Charge Transfer for Enhanced Catalytic Activity toward Photodegradation of Pharmacologically Active Compounds.

Photocatalytic degradation is a promising method for controlling the increasing contamination of the water environment due to pharmacologically active compounds (PHACs). Herein, oxygen vacancy (OV)-modulated Z-scheme CuWO4/CuBi2O4 hybrid systems were fabricated via thermal treatment by loading of CuWO4 nanoparticles with OVs on CuBi2O4 surfaces. The synthesized CuWO4/CuBi2O4 hybrid samples exhibited an enhanced photodegradation ability to remove PHACs under visible-light irradiation. More importantly, an optimized sample (10 wt % CuWO4/CuBi2O4) exhibited superior catalytic activity and excellent recycling stability for PHAC photodegradation. In addition, possible degradation paths for PHAC removal over the CuWO4/CuBi2O4 hybrid systems were proposed. The enhanced photocatalytic performance could be attributed to the efficient separation and transfer of photoformed charge pairs via the Z-scheme mechanism. This Z-scheme mechanism was systematically analyzed using trapping experiments of active species, ultraviolet photoelectron spectroscopy, electron spin resonance, and the photodepositions of noble metals. The findings of this study can pave the way for developing highly efficient Z-scheme photocatalytic systems for PHAC photodegradation.

Construction of Enantioenriched Quaternary C-Cl Oxindoles through Palladium-Catalyzed Asymmetric Allylic Substitution with Chloroenolates.

A palladium-catalyzed asymmetric chloroenolate allylation with vinyl benzoxazinanones under mild reaction conditions has been developed, affording a series of optically active 3,3-disubstituted oxindoles exhibiting a chloro-group and a linear aryl amino side chain in good yields with up to 96% ee. Versatile functional group tolerance on the benzene ring has been demonstrated, and the utility of this method was probed by a scale-up synthesis and highlighted by product derivatizations.

Synthesis of gem-Difluoro-3,4-dihydro-2H-pyrans via a TfOH-Catalyzed [4 + 2] Annulation of Difluoroenoxysilanes with α-Cyano Chalcones.

Difluoroenoxysilane, a commonly used difluoroallylating reagent, has attracted considerable attention in recent years. However, its application in the annulation reaction for the construction of fluorinated heterocyclic compounds remains relatively limited. Presented here is the Brønsted acid-catalyzed efficient formal [4 + 2] annulation of difluoroenoxysilanes with α-cyano chalcones. The developed protocol demonstrates tolerance to various substituents under mild reaction conditions, providing a reliable approach to construct gem-difluoro-3,4-dihydro-2H-pyrans in good to excellent yields with high diastereoselectivities.

Ni-CoSe2 heterojunction coated by N-doped carbon for modified separators of high-performance Li-sulfur batteries.

Functional separators modified by transition metal compounds have been proven to be effective in suppressing the shuttle effect of polysulfides and accelerating sluggish electrode dynamics in lithium-sulfur batteries (LSBs). However, the behaviors of heterojunctions composed of transition metals and their compounds in LSBs are still rarely studied. Herein, we report a novel Ni-CoSe2 heterostructure coated with nitrogen-doped carbon. Compared to homogeneous cobalt diselenide, it exhibits much stronger adsorption and catalytic conversion abilities towards polysulfides. With the modified separators, the lithium-sulfur batteries exhibit significantly improved capacity retention and reduced polarization during cycling.

How the chemical structure of phosphoramides affect the fire retardancy and mechanical properties of polylactide?

Phosphoramides, as a kind of high-efficient fire retardants, have been designed in many structures and endowed exceptional fire retardancy to polylactide (PLA). However, due to ignorance of the structure-property correlation, the effect of phosphoramides' structure on the fire retardancy and mechanical properties of PLA is still unclear. Herein, a series of biobased phosphoramides (phosphoramide (V1), linear polyphosphoramide (V2) and hyperbranched polyphosphamide (V3)) were designed and incorporated into PLA, and the structural effect of phosphoramides on the fire-retardant and mechanical properties of PLA was deeply researched. Among three kinds of phosphoramides, the hyperbranched polyphosphoramide is more effective than the corresponding linear polyphosphoramide and phosphoramide in improving the fire-retardant and anti-dripping properties of PLA, and only linear polyphosphoramide shows a positive effect in the mechanical strength of PLA. This work provides a feasible strategy for creating mechanically robust and fire-retardant polymer composites by molecularly tailoring the structure of fire retardants and uncovering their structure-property relationship.

Largely enhanced thermal and mechanical properties of polymer nanocomposites via incorporating C60@graphene nanocarbon hybrid.

Although considerable progress has been achieved to create advanced polymer nanocomposites using nanocarbons including fullerene (C60) and graphene, it remains a major challenge to effectively disperse them in a polymer matrix and to fully exert their extraordinary properties. Here we report a novel approach to fabricate the C60@graphene nanocarbon hybrid (C60: ~47.9 wt%, graphene: ~35.1%) via three-step reactions. The presence of C60 on a graphene sheet surface can effectively prevent the aggregation of the latter which in turn helps the dispersion of the former in a polymer matrix during melt-processing. C60@graphene is found to be uniformly dispersed in a polypropylene (PP) matrix. Compared with pristine C60 or graphene, C60@graphene further improves the thermal stability and mechanical properties of PP. The incorporation of 2.0 wt% C60@graphene (relative to PP) can remarkably increase the initial degradation temperature by around 59 ° C and simultaneously enhance the tensile strength and Young's modulus by 67% and 76%, respectively, all of which are higher than those of corresponding PP/C60 (graphene) nanocomposites. These significant performance improvements are mainly due to the free-radical-trapping effect of C60, and the thermal barrier and reinforcing effects of graphene nanosheets as well as the effective stress load transfer. This work provides a new methodology to design multifunctional nanohybrids for creating advanced materials.

Z-scheme MnO2/Mn3O4 heterojunctions with efficient peroxymonosulfate activation for organic pollutant removal.

The exploration of efficient heterogeneous catalysts for persistent organic pollutant removal is extremely attractive. In the present work, MnO2/Mn3O4 photo-Fenton catalysts were designed by a facile hydrothermal route to activate peroxymonosulfate (PMS) under visible light irradiation for organic pollutant degradation. The optimized MnO2/Mn3O4 heterojunction shows excellent Rhodamine B (RhB) removal efficiency, whose apparent kinetic constant is 11.9 and 5.36 times as high as the MnO2 and Mn3O4. Meanwhile, there is a neglectable attenuation in catalytic performance after 5 recycling runs. Based on the active species trapping experiments, the non-radical process contributes more than the radical process during RhB degradation. Moreover, factors including the dosage of PMS, initial RhB concentration, initial pH, the presence of various anions, different organic pollutants, and water sources are investigated. Systematical characterizations reveal that the enlarged specific surface areas and the efficient charge separation aroused from the Z-scheme mechanism are attributed to the enhanced photo-Fenton performance. The present work contributes to the construction of the Mn-based photo-Fenton catalyst with efficient PMS activation capacity for environmental remediation.

An Anisotropic Hydrogel by Programmable Ionic Crosslinking for Sequential Two-Stage Actuation under Single Stimulus.

As one of the most important anisotropic intelligent materials, bi-layer stimuli-responsive actuating hydrogels have proven their wide potential in soft robots, artificial muscles, biosensors, and drug delivery. However, they can commonly provide a simple one-actuating process under one external stimulus, which severely limits their further application. Herein, we have developed a new anisotropic hydrogel actuator by local ionic crosslinking on the poly(acrylic acid) (PAA) hydrogel layer of the bi-layer hydrogel for sequential two-stage bending under a single stimulus. Under pH = 13, ionic-crosslinked PAA networks undergo shrinking (-COO-/Fe3+ complexation) and swelling (water absorption) processes. As a combination of Fe3+ crosslinked PAA hydrogel (PAA@Fe3+) with non-swelling poly(3-(1-(4-vinylbenzyl)-1H-imidazol-3-ium-3-yl)propane-1-sulfonate) (PZ) hydrogel, the as-prepared PZ-PAA@Fe3+ bi-layer hydrogel exhibits distinct fast and large-amplitude bidirectional bending behavior. Such sequential two-stage actuation, including bending orientation, angle, and velocity, can be controlled by pH, temperature, hydrogel thickness, and Fe3+ concentration. Furthermore, hand-patterning Fe3+ to crosslink with PAA enables us to achieve various complex 2D and 3D shape transformations. Our work provides a new bi-layer hydrogel system that performs sequential two-stage bending without switching external stimuli, which will inspire the design of programmable and versatile hydrogel-based actuators.

Synthesis of Fluoro 3(2H)-Furanones via a TFA-Catalyzed Dehydrofluorinative Cyclization of 2,2-Difluoro-3-hydroxy-1,4-diketones.

A TFA-catalyzed dehydrofluorinative cyclization of 2,2-difluoro-3-hydroxy-1,4-diketones has been developed in the presence of amines under mild conditions in which the difluorinated substrates are readily prepared according to our reported literature. This protocol provides a rapid construction of fluoro 3(2H)-furanones in good to excellent yields with good functional group tolerance. Easy scale-up synthesis also shows a practical advantage.

Facile synthesis of Si/Ge/graphite@C composite with improved tap density and electrochemical performance.

Nanoengineering is one of the most effective methods to promote the lithium storage performance of silicon material, which suffers from huge volume changes and poor reaction kinetics during cycling. However, the commercial application of nanostructured silicon is hindered by its high manufacturing cost and low tap density. Herein, a Si/Ge/graphite@C composite was successfully synthesized by ball-milling with subsequent calcination. By introducing Ge, graphite and an amorphous carbon coating, both tap density and electrochemical performance are improved significantly. Benefiting from the synergetic effects of the above components, the Si/Ge/graphite@C composite delivers a reversibility capacity of 474 mA h g-1 at 0.2 A g-1 and stable capacity retention.

Bioinspired, Highly Adhesive, Nanostructured Polymeric Coatings for Superhydrophobic Fire-Extinguishing Thermal Insulation Foam.

Lightweight polymeric foam is highly attractive as thermal insulation materials for energy-saving buildings but is plagued by its inherent flammability. Fire-retardant coatings are suggested as an effective means to solve this problem. However, most of the existing fire-retardant coatings suffer from poor interfacial adhesion to polymeric foam during use. In nature, snails and tree frogs exhibit strong adhesion to a variety of surfaces by interfacial hydrogen-bonding and mechanical interlocking, respectively. Inspired by their adhesion mechanisms, we herein rationally design fire-retardant polymeric coatings with phase-separated micro/nanostructures via a facile radical copolymerization of hydroxyethyl acrylate (HEA) and sodium vinylsulfonate (VS). The resultant waterborne poly(VS-co-HEA) copolymers exhibit strong interfacial adhesion to rigid polyurethane (PU) foam and other substrates, better than most of the current adhesives because of the combination of interfacial hydrogen-bonding and mechanical interlocking. Besides a superhydrophobic feature, the poly(VS-co-HEA)-coated PU foam can self-extinguish a flame, exhibiting a desired V-0 rating during vertical burning and low heat and smoke release due to its high charring capability, which is superior to its previous counterparts. Moreover, the foam thermal insulation is well-preserved and agrees well with theoretical calculations. This work offers a facile biomimetic strategy for creating advanced adhesive fire-retardant polymeric coatings for many flammable substrates.

1-[4-(Difluoro-meth-oxy)phen-yl]-N-(3,4-dimeth-oxy-phen-yl)-1H-1,2,4-triazole-3-carboxamide.

Two crystallographically independent mol-ecules, A and B, with similar conformations are present in the asymmetric unit of the title compound, C(18)H(16)F(2)N(4)O(4). In mol-ecule A, the plane of the 1,2,4-triazole ring is tilted relative of the 4-difluoro-meth-oxy-substituted and the 3,4-dimeth-oxy-substituted benzene rings by 6.5 (2) and 16.4 (1)°, respectively. The -CHF(2) group is twisted away from the plane of the benzene ring, with a dihedral angle between the O-C bond of the OCHF(2) group and the plane of the adjacent phenyl ring of 38.6 (3)°. The corresponding parameters for mol-ecule B are 7.7 (1), 9.5 (2) and 25.2 (2)°. In both mol-ecules, the conformations are stabilized by intra-molecular N-H⋯N and C-H⋯O hydrogen bonds. There are also C-H⋯π contacts between the methyl groups and the benzene rings, and π-π stacking inter-actions between the benzene rings of adjacent parallel A mol-ecules [centroid-centroid distance = 3.8942 (17) Å]. π-π inter-actions are also observed between the triazole ring and one of the benzene rings of parallel B mol-ecules [centroid-centroid distance = 3.7055 (16) Å].

Direct Z-scheme 1D/2D WO2.72/ZnIn2S4 hybrid photocatalysts with highly-efficient visible-light-driven photodegradation towards tetracycline hydrochloride removal.

There are increasing environmental concerns of serious pollution from emission of antibiotic wastewater. Herein, a series of direct Z-scheme WO2.72/ZnIn2S4 (WOZIS) hybrid photocatalysts composed of one-dimensional (1D) WO2.72 (WO) nanorods and two-dimensional (2D) ZnIn2S4 (ZIS) nanosheets have been designed and constructed for tetracycline hydrochloride (TCH) degradation without presence of solid-state electron mediators. The crystalline phase, chemical composition, morphology, optical properties and photocatalytic activity of the as-prepared samples were characterized by the XRD, XPS, SEM, HRTEM, BET, UV-vis DRS, and PL. Obviously, all the WOZIS hybrid photocatalysts exhibited significantly enhanced photocatalytic activity towards TCH degradation. Meanwhile, WOZIS-1 sample with WO/ZIS molar ratio of 1:1 showed the highest photocatalytic activity. The significantly enhanced photoactivity of WOZIS hybrid photocatalyst was due to Z-scheme charge separation mechanism based on the build of tight interfacial contacts between WO nanorods and ZIS nanosheets, thereby driving efficient charge separation. Moreover, the high photocatalytic stability of as-prepared WOZIS-1 hybrid sample was revealed through seven successive cycling reactions.

1-[4-(Difluoromethoxy)phenyl]-N-(2,3-dimethylphenyl)-1H-1,2,4-triazole-3-carboxamide.

In the mol-ecule of the title compound, C(18)H(16)F(2)N(4)O(2), the 1,2,4-triazole ring forms dihedral angles of 3.6 (2) and 14.9 (6)° with the 4-difluoro-meth-oxy-substituted benzene ring and the 2,3-dimethyl-substituted benzene ring, respectively. The OCHF(2) group is twisted away from the plane of the benzene ring, as shown by the C-O-C-C torsion angle of 145.8 (2)°. The conformation is stabilized by an inter-molecular N-H⋯N hydrogen bond. In the crystal, short C-H⋯O inter-actions lead to chains of mol-ecules.

Ruthenium-catalyzed decarboxylative C-S cross-coupling of carbonothioate: synthesis of allyl(aryl)sulfide.

A novel ruthenium-catalyzed decarboxylative cross-coupling of carbonothioate is disclosed. This method provides straightforward access to the corresponding allyl(aryl)sulfide derivatives in generally good to excellent yields under mild conditions and features a broad substrate scope, wide group tolerance and in particular, no need to use halocarbon precursors.