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Calcium phosphate nanofibers with a diameter of only a few nanometers and a cotton-ball-like aggregate morphology have been reported several times in the literature. Although fiber formation seems reproducible in a variety of conditions, the crystal structure and chemical composition of the fibers have been elusive. Using scanning transmission electron microscopy, low dose electron (nano)diffraction, energy-dispersive X-ray spectroscopy, and energy-filtered transmission electron microscopy, we have assigned crystal structures and chemical compositions to the fibers. Moreover, we demonstrate that the mineralization process yields true polymer/calcium phosphate hybrid materials where the block copolymer template is closely associated with the calcium phosphate.
Fully renewable pyridinium ionic liquids were synthesised via the hydrothermal decarboxylation of pyridinium zwitterions derived from furfural and amino acids in flow. The functionality of the resulting ionic liquid (IL) can be tuned by choice of different amino acids as well as different natural carboxylic acids as the counterions. A representative member of this new class of ionic liquids was successfully used for the synthesis of ionogels and as a solvent for the Heck coupling.
Ionic guest in ionic host
(2022)
Ionosilica ionogels, i.e. composites consisting of an ionic liquid (IL) guest confined in an ionosilica host matrix, were synthesized via a non-hydrolytic sol-gel procedure from a tris-trialcoxysilylated amine precursor using the IL [BMIM]NTf2 as solvent. Various ionosilica ionogels were prepared starting from variable volumes of IL in the presence of formic acid. The resulting brittle and nearly colourless monoliths are composed of different amounts of IL guests confined in an ionosilica host as evidenced via thermogravimetric analysis, FT-IR, and C-13 CP-MAS solid-state NMR spectroscopy. In the following, we focused on confinement effects between the ionic host and guest. Special host-guest interactions between the IL guest and the ionosilica host were evidenced by H-1 solid-state NMR, Raman spectroscopy, and broadband dielectric spectroscopy (BDS) measurements. The three techniques indicate a strongly reduced ion mobility in the ionosilica ionogel composites containing small volume fractions of confined IL, compared to conventional silica-based ionogels. We conclude that the ionic ionosilica host stabilizes an IL layer on the host surface; this then results in a strongly reduced ion mobility compared to conventional silica hosts. The ion mobility progressively increases for systems containing higher volume fractions of IL and finally reaches the values observed in conventional silica based ionogels. These results therefore point towards strong interactions and confinement effects between the ionic host and the ionic guest on the ionosilica surface. Furthermore, this approach allows confining high volume fractions of IL into self-standing monoliths while preserving high ionic conductivity. These effects may be of interest in domains where IL phases must be anchored on solid supports to avoid leaching or IL spilling, e.g., in catalysis, in gas separation/sequestration devices or for the elaboration of solid electrolytes for (lithium-ion) batteries and supercapacitors.
A new solid-state material, N-butyl pyridinium diiodido argentate(I), is synthesized using a simple and effective one-pot approach. In the solid state, the compound exhibits 1D ([AgI2](-))(n) chains that are stabilized by the N-butyl pyridinium cation. The 1D structure is further manifested by the formation of long, needle-like crystals, as revealed from electron microscopy. As the general composition is derived from metal halide-based ionic liquids, the compound has a low melting point of 100-101 degrees C, as confirmed by differential scanning calorimetry. Most importantly, the compound has a conductivity of 10(-6) S cm(-1) at room temperature. At higher temperatures the conductivity increases and reaches to 10(-4 )S cm(-1) at 70 degrees C. In contrast to AgI, however, the current material has a highly anisotropic 1D arrangement of the ionic domains. This provides direct and tuneable access to fast and anisotropic ionic conduction. The material is thus a significant step forward beyond current ion conductors and a highly promising prototype for the rational design of highly conductive ionic solid-state conductors for battery or solar cell applications.
A new solid-state material, N-butyl pyridinium diiodido argentate(I), is synthesized using a simple and effective one-pot approach. In the solid state, the compound exhibits 1D ([AgI2](-))(n) chains that are stabilized by the N-butyl pyridinium cation. The 1D structure is further manifested by the formation of long, needle-like crystals, as revealed from electron microscopy. As the general composition is derived from metal halide-based ionic liquids, the compound has a low melting point of 100-101 degrees C, as confirmed by differential scanning calorimetry. Most importantly, the compound has a conductivity of 10(-6) S cm(-1) at room temperature. At higher temperatures the conductivity increases and reaches to 10(-4 )S cm(-1) at 70 degrees C. In contrast to AgI, however, the current material has a highly anisotropic 1D arrangement of the ionic domains. This provides direct and tuneable access to fast and anisotropic ionic conduction. The material is thus a significant step forward beyond current ion conductors and a highly promising prototype for the rational design of highly conductive ionic solid-state conductors for battery or solar cell applications.
Advanced catalysis triggered by photothermal conversion effects has aroused increasing interest due to its huge potential in environmental purification.
In this work, we developed a novel approach to the fast degradation of 4-nitrophenol (4-Nip) using porous MoS2 nanoparticles as catalysts, which integrate the intrinsic catalytic property of MoS2 with its photothermal conversion capability.
Using assembled polystyrene-b-poly(2-vinylpyridine) block copolymers as soft templates, various MoS 2 particles were prepared, which exhibited tailored morphologies (e.g., pomegranate-like, hollow, and open porous structures).
The photothermal conversion performance of these featured particles was compared under near-infrared (NIR) light irradiation.
Intriguingly, when these porous MoS2 particles were further employed as catalysts for the reduction of 4-Nip, the reaction rate constant was increased by a factor of 1.5 under NIR illumination.
We attribute this catalytic enhancement to the open porous architecture and light-to-heat conversion performance of the MoS2 particles. This contribution offers new opportunities for efficient photothermal-assisted catalysis.
Thin films of ferroelectric beta-phase poly(vinylidene fluoride) (PVDF) were spin-coated from a solution that contained small amounts of the ionic liquid (IL) 1-ethyl-3-methylimidazolium nitrate. A remanent polarization of 60 mC/m(2) and a quasi-static pyroelectric coefficient of 19 mu C/m(2)K at 30 degrees C were observed in the films. It is suggested that the IL promotes the formation of the beta phase through dipolar interactions between PVDF chain-molecules and the IL. The dipolar interactions are identified as Coulomb attraction between hydrogen atoms in PVDF chains and anions in IL. The strong crystallinity increase is probably caused by the same dipolar interaction as well.
The iron-containing ionic liquid (IL) 1-butyl-3-methylimidazolium tetrachloroferrate(III) [Bmim][FeCl4] has been used as a building block in the synthesis of transparent, ion-conducting, and paramagnetic ionogels. UV/Vis spectroscopy shows that the coordination around the Fe(III) ion does slightly change upon incorporation of the IL into PMMA. The thermal stability of the PMMA increases significantly with IL incorporation. In particular, the onset weight loss observed at ca. 265 degrees C for pure PMMA is completely suppressed. The ionic conductivity shows a strong temperature dependence and increases with increasing IL weight fractions. The magnetic properties are similar to those reported for the pure IL and are not affected by the incorporation into the PMMA matrix. The resulting ionogel is thus an interesting prototype for soft, flexible, and transparent materials combining the mechanical properties of the matrix with the functionality of the metal-containing IL, such as magnetism.