Periodic organosilica hollow nanospheres as anode materials for lithium ion rechargeable batteries

Polymeric micelles with core-shell-corona architecture have been found to be the efficient colloidal templates for synthesis of periodic organosilica hollow nanospheres over a broad pH range from acidic to alkaline media. In alkaline medium, poly (styrene-b-[3-(methacryloylamino)propyl] trimethylammonium chloride-b-ethylene oxide) (PS-PMAPTAC-PEO) micelles yield benzene-silica hollow nanospheres with molecular scale periodicity of benzene groups in the shell domain of hollow particles. Whereas, an acidic medium (pH 4) produces diverse hollow particles with benzene, ethylene, and a mixture of ethylene and dipropyldisulfide bridging functionalities using poly(styrene-b-2-vinyl pyridine-b-ethylene oxide) (PS-PVP-PEO) micelles. These hollow particles were thoroughly characterized by powder X-ray diffraction (XRD), dynamic light scattering (DLS), thermogravimetric analysis (TG/DTA), Fourier transformation infrared (FTIR) spectroscopy, transmission electron microscopy (TEM), magic angle spinning-nuclear magnetic resonance ((29)Si MAS NMR and (13)CP-MAS NMR), Raman spectroscopy, and nitrogen adsorption/desorption analyses. The benzene-silica hollow nanospheres with molecular scale periodicity in the shell domain exhibit higher cycling performance of up to 300 cycles in lithium ion rechargeable batteries compared with micron-sized dense benzene-silica particles.     

The effect of cationic surfactant and some organic/inorganic additives on the morphology of mesostructured silica templated by pluronics

Tri-block copolymers (poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide), represented as EO_xPO_yEO_x), pluronics (F127 = EO₁₀₆PO₇₀EO₁₀₆, P65 = EO₂₀PO₃₀EO₂₀, P85 = EO₂₇PO₃₉EO₂₇, P103 = EO₁₇PO₅₅EO₁₇, and P123 = EO₂₀PO₇₀EO₂₀) and cationic surfactants (cethyltrimethylammonium bromide (CTAB)), two surfactant systems, form complex micelles that self-assemble into mesostructured particles with distinct morphology depending on the pluronic type, the concentration of the cationic surfactant and the organic–inorganic ingredients in a siliceous reaction media under acidic conditions. The CTAB–P65 and CTAB–P85 systems form spheres, CTAB–P103 and CTAB–P123 systems form wormlike particles, and CTAB–F127 system form single crystals of mesostructured silica particles under very similar conditions. However addition of various salts (such as KCl and NaNO₃) into a CTAB–P103 or CTAB–P123 solution system and cyclohexane and KCl into a CTAB–P85 solution system produces the mesostructured silica spheres and wormlike particles, respectively. By controlling the hydrophilic–hydrophobic character of the pluronics, core–corona interface, by means of additives, such as small organic molecules or salts, one could obtain the desired morphology that is dictated by the shape of the micelles of the pluronic–cationic surfactant complex. The effects of the additives and the formation mechanism of those morphologies have been discussed using spectroscopy (FT-IR and Raman), diffraction (XRD) and microscopy (POM and SEM) data.     

Characterization of surface-modified ceria oxide nanoparticles synthesized continuously in supercritical methanol

Surface-modified ceria oxide (CeO₂) nanoparticles were synthesized continuously in supercritical methanol at 400 °C, 30 MPa and a residence time of 40 s using a flow type reactor system. Oleic acid and decanoic acid were used as the surface modifiers. Transmission electron microscopy (TEM) showed that the surface modifiers changed drastically the shape and size of the nanoparticles. When 0.3 M of the surface modifiers were used, primary particles with diameter of 2–3 nm loosely aggregated and formed secondary particles with size of 30–50 nm. Wide angle X-ray diffraction (WAXD) analysis revealed that the surface-modified nanoparticles retained CeO₂ crystalline structure. The surface-modified CeO₂ nanoparticles had a very high surface area (140–193 m²/g) compared to the unmodified CeO₂ particles synthesized in supercritical water (8.5 m²/g). Fourier transform infrared (FT-IR) and thermogravimetric analysis (TGA) indicated that aliphatic, carboxylate and hydroxyl groups were chemically bounded on the surface of CeO₂ nanoparticles. Dispersability test using ultraviolet transmittance showed that most of the surface-modified CeO₂ nanoparticles were dispersed in ethylene glycol for 30 days while the unmodified CeO₂ particles synthesized in supercritical water or in supercritical methanol were precipitated after 7–15 days.     

Narrow multi-walled carbon nanotubes produced by chemical vapor deposition using graphene layer encapsulated catalytic metal particles

The use of graphene layer encapsulated catalytic metal particles for the growth of narrower multi-walled carbon nanotubes (MWCNTs) has been studied using plasma-enhanced chemical vapor deposition and conventional thermal CVD. Ni–C or Fe–C composite nanoclusters were fabricated using the dc arc discharge technique with metal–graphite composite electrodes carrying a current of 100–200 A in a stainless-steel chamber filled with He and CH₄ mixture gas at 27 kPa. Nano-sized grains with diameters less than 10 nm were fabricated and deposited on a Si substrate, and were used as a catalyst for MWCNT growth. Structural analyses of the composite nanoclusters and MWCNTs were carried out using transmission electron microscopy. The results show that the diameters of the MWCNTs were reduced from 50–100 nm for a conventional Ni thin film-evaporated Si substrate to a minimum of roughly 2–4 nm in the present study.     

Mesoporous H3PW12O40-silica composite: Efficient and reusable solid acid catalyst for the synthesis of diphenolic acid from levulinic acid

Mesoporous H₃PW₁₂O₄₀-silica composite catalysts with controllable H₃PW₁₂O₄₀ loadings (4.0–65.1%) were prepared by a direct sol–gel–hydrothermal technique in the presence of triblock poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) copolymer. Powder X-ray diffraction (XRD) patterns and nitrogen sorption analysis indicate the formation of well-defined mesoporous materials. With H₃PW₁₂O₄₀ loading lower than 20%, the materials exhibit larger BET surface area (604.5–753.0 m² g⁻¹), larger and well-distributed pore size (6.1–8.6 nm), larger pore volume (0.75–1.2 cm³ g⁻¹), and highly dispersed Keggin unit throughout the materials. Raman scattering spectroscopy studies confirm that the primary Keggin structure remained intact after formation of the composites. As a novel kind of reusable solid acid catalyst, as-prepared H₃PW₁₂O₄₀-silica composite was applied for the synthesis of diphenolic acid (DPA) from biomass platform molecule, levulinic acid (LA), under solvent-free condition, and remarkably high catalytic activity and stability were observed.     

Microwave plasma chemical vapor deposition of cone-like structure of diamond/SiC/Si on Si (100)

Diamond deposition on 1 × 1 cm² Si (100) substrates with bias was carried out by microwave plasma chemical vapor deposition (MPCVD). Distribution of deposited diamonds has been significantly improved in uniformity over all the Si substrate surface area by using a novel designed dome-shaped Mo anode. The deposits were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and Raman analysis. SEM observations show that there is a high density of cone-like particles uniformly deposited on the surface of the substrate in short bias nucleation period. The average diameter, height and density of cone-like structure were increased with methane concentration in the bias stage. TEM reveals that the cone-like structure is actually composed of Si conic crystal covered with diamond. Between Si and diamond, a thin layer of cubic SiC is found in epitaxy with Si. Furthermore, for 3% CH₄ concentration, the range of diameter of cone-like structure was about 20–90 nm and the size of diamond was about 10–60 nm.     

Facile synthesis of nanocrystalline magnesium oxide with high surface area

Nanocrystalline magnesium oxide with high surface area has been synthesized by precipitation method using ammonium hydroxide and polyvinyl alcohol as precipitant and polymeric surfactant, respectively. The results show that the polymeric surfactant (PVA) has a significant effect on the synthesis of MgO nanocrystals. The specific surface area of the MgO powder decreases from 123 m²g^− 1 to 61 m²g^− 1and the crystallite size on the (200) plane increases from 12.2 nm to 14.2 nm with increasing temperature from 600 °C to 800 °C. Transmission electron microscopy (TEM) and N₂ adsorption/desorption isotherm also show a nanostructure consisting of aggregates or agglomerates of particles forming slit shaped pores (plates or edged particles like cubes).     

Preparation of waterborne polyurethanes using an amphiphilic diol for breathable waterproof textile coatings

The application of polyurethanes (PUs) on breathable waterproof fabric coatings requires a balance of water vapor permeability (WVP) and water resistance which can be achieved by tailoring hydrophilic and hydrophobic segments. PU prepolymers were prepared from isophorone diisocyanate, dimethylol butanoic acid, and a mixture of various ratios of amphiphilic PPG2050 (copolymer of ethylene oxide and propylene oxide with –OH end groups) and hydrophobic poly(tetramethylene ether glycol) (PTMEG). After neutralization with triethylamine, the prepolymers were chain-extended with ethylene diamine/1,4-butanediol (1:1 by molar). The WVP values of the fabric coatings prepared using various waterborne PUs were very similar (910–990 g/m² × 24 h). When waterborne PUs prepared using a mixture of PPG2050 and PTMEG were employed for the textile coatings, the resulting PU-coated textiles exhibited excellent waterproof properties (>10,000 mm H₂O). The textile coatings prepared from PPG2050/PTMEG-based waterborne PUs were significantly more waterproof than those prepared from poly(ethylene glycol) (PEG)/poly(propylene glycol) (PPG)/PTMEG-based waterborne PU. This is probably due to a more even distribution of hydrophobic segments in the PUs, even though the WVP values of the PEG/PPG/PTMEG-based PU coatings were considerably smaller than those of the PPG2050/PTMEG-based PU coatings.     

The synthesis of Al-MCM-41 from volclay — A low-cost Al and Si source

The alkaline fusion of volclay (a low-cost sodium exchanged smectite) was used as source to generate the Si and Al components which were effectively transformed into mesoporous Al-MCM-41 depending on hydrothermal condition. The Al-MCM-41 materials were investigated by powder X-ray diffraction (XRD), N₂ adsorption–desorption measurements and both scanning electron microscopy (SEM) and environmental scanning electron microscopy (ESEM). The volclay which converted into a silicon and an aluminium source allowed the formation of well ordered mesoporous Al-MCM-41 materials with high aluminium content (roughly 4 times higher than a Al-MCM-41 produced by a standard method), a high specific surface area (1060 m²/g), a pore volume of 0.8 cm³/g (for pore width < 7.1 nm) with an mono-modal pore distribution with a maximum in the mesoporous pore size of 3.8 nm in pore width.     

In situ synthesis of iron oxide nanoparticles on poly(ethylene oxide) nanofibers through an electrospinning process

Iron oxide nanoparticle coated poly(ethylene oxide) nanofibers as organic–inorganic hybrids with 200–400‐nm diameters were prepared by the in situ synthesis of iron oxide nanoparticles on poly(ethylene oxide) nanofibers through the electrospinning of a poly(ethylene oxide) solution having Fe²⁺ and Fe³⁺ ions in a gaseous ammonia atmosphere. Transmission electron microscopy analysis proved the presence of iron oxide nanoparticles on the polymer nanofibers. The thermal properties of the nanofiber mat were also studied with differential scanning calorimetry and thermogravimetric analysis techniques. X‐ray diffraction showed that the formed iron oxide nanoparticles were maghemite nanoparticles. The results were compared with those of the electrospinning of a poly(ethylene oxide) solution having Fe²⁺ and Fe³⁺ ions and a pure poly(ethylene oxide) solution in an air atmosphere. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Synthesis of high surface area nanocrystalline MgO by pluronic P123 triblock copolymer surfactant

Nanocrystalline magnesium oxide with high surface area was prepared by a simple precipitation method using pluronic P123 triblock copolymer (Poly(ethylene glycol)-block, Poly(propylene glycol)-block, Poly(ethylene glycol)) as surfactant. The prepared samples were characterized by X-ray Diffraction (XRD), N₂ adsorption (BET), Fourier transform infrared spectroscopy (FTIR), Thermal, differential thermal gravimetric and differential thermal analyses (TG/DTG/DTA) and Scanning electron microscopy (SEM). The obtained results revealed that the addition of surfactant is effective to prepare magnesium oxide with high surface area and affects the morphology of the prepared samples. The results showed that the magnesium oxide calcined at different temperatures ranging from 600 to 800 °C possessed a high surface area in the range of 133.9–78.1 m² g^?1. In addition, the magnesium oxide prepared with the addition of surfactant showed a narrower pore size distribution compared to the sample prepared without the addition of a surfactant.     

Organic/Inorganic Hybrid Composite Films from Polyimide and Organosilica: Effect of the Type of Organosilica Precursors

We report the influence of the type of organosilica precursors on the growth of organosilica domains and the interfacial interaction between polyimide (PI) and organosilica in PI/organosilica hybrid composite films. The organosilica precursors used are tetraethoxysilane (TEOS), triethoxy(ethyl)silane (TEES), and 1,2-bis(triethoxysilyl)ethane (BTSE). The hybrid composite films were prepared by thermal imization of the precursor films that were made via sol-gel process of the mixture of poly(4,4’-oxydianiline benzenetetracarboxamic acid) (PMDA-ODA PAA) and organosilica precursors. The hybrid composite films were characterized using Fourier transform infrared (FT-IR) spectra, ²⁹Si cross polarization (CP) MAS-NMR spectra, field emission-scanning electron microscopy (FE-SEM), UV-visible spectra, small angle x-ray scattering (SAXS), dynamic mechanical analysis (DMA), and thermogravimetric analysis (TGA). The results showed that the TEES precursor was more pronounced in improving the interaction of corresponding organosilica with PI than other precursors.     

The use of CTAB to improve the crystallinity and dispersibility of ultrafine magnesium hydroxide by hydrothermal route

The high-dispersed lamellar ultrafine magnesium hydroxide was obtained at relatively low hydrothermal temperature in the presence of cationic surfactant, cetyl trimethyl ammonium bromide (CTAB). The procedure described in this study is attractive since proper amount of CTAB could promote the dissolution and precipitation of magnesium hydroxide in hydrothermal system, resulting in the well-defined morphology, narrow size distribution and good crystallinity of ultrafine particles. The resultant magnesium hydroxide was characterized by X-ray powder diffraction (XRD), thermogravimetric analysis-differential scanning calorimetry (TGA-DSC), field-emission scanning electron microscopy (FESEM) and laser diffusion analysis. The method led to the production of particles with mean size of 400 nm and a thickness of 60 nm. The optimal conditions of preparation were hydrothermal treatment at 150 °C for 6 h at pH 11 with Mg²⁺/CTAB molar ratio of 80.     

Crosslinked particles of poly[n-(1-phenylethyl)acrylamide]: Preparation and application as chromatographic stationary phases

Crosslinked particles of poly [N-(1-phenylethyl)acrylamidel have been successfully prepared by suspension polymerization of N-(1-phenylethyl) acrylamide and ethylene dimethacrylate in water using poly(vinyl alcohol) as dispersant. The particle morphology is investigated by optical microscope and scanning electron microscope (SEM). The pressure resistance of the crosslinked particles, evaluated after packing as stationary phases of high-performance liquid chromatography (HPLC), increases from 7 to 20 kg/cm² as the mole percent of ethylene dimethacrylate increases from 10% to 30%. The particles were sieved into four sieve fractions, i.e. 37–63 m, 63–88 m, 88–105 m, and 105–149 m, and packed into HPLC columns, respectively. The chromatographic performances of these columns have been investigated in HPLC system thoroughly, using benzene as solute and mixtures ofn-hexane and 2-propanol as eluents. The crosslinked particles show potential application as stationary phases for HPLC.     

High yield preparation of all-organic raspberry-like particles by heterocoagulation via hydrogen bonding interaction

We describe here a straightforward strategy towards the high yield preparation of raspberry-like all-organic particles. Poly(acrylic acid)-b-poly(butyl acrylate) core–shell nanoparticles (D ∼ 80 nm) and larger poly(ethylene oxide)-b-poly(butyl acrylate) core–shell (D ∼ 230 nm), synthesized by RAFT emulsion polymerization, were mixed at high solids content (23 wt%) at room temperature without any particular precaution (no dropwise addition, no pH adjustment). Raspberry-like particles constituted of one central PEO-b-PBA particle surrounded by about thirty PAA-b-PBA particles were successfully obtained, with no coagulum formation. The heteroaggregation process is probably driven by the hydrogen-bond interactions between the PAA and the PEO shells of the particles. The raspberry-like particles were characterized using electron microscopy (TEM and cryo-TEM), dynamic light scattering (DLS), chromatography (HDC) and calorimetry (ITC), demonstrating the selectivity of the process.     

Encapsulation of magnetic nickel nanoparticles via inverse miniemulsion polymerization

In this work, the encapsulation of magnetic nickel nanoparticles in polyacrylamide particles was performed via inverse miniemulsion polymerization. The dispersion of nickel nanoparticles was characterized in polar solvents including water, ethanol, and dimethyl sulfoxide using different stabilizers. The best results were obtained when the nonionic stabilizer poly(ethylene glycol) octadecyl ether (Brij 76) was used to stabilize the nickel nanoparticles in dimethyl sulfoxide. In addition, the block copolymer poly(ethylene‐co‐butylene)‐b‐poly(ethylene oxide) was used as a surfactant to create inverse miniemulsions while minimizing the coalescence of the miniemulsion droplets. Different types of salts such as zinc, nickel, and sodium nitrates were tested as lipophobes to retard Ostwald ripening. Transmission electron microscopy images of polyacrylamide/nickel particles synthesized with zinc and nickel salts as lipophobes indicate that nickel nanoparticles are embedded in the polyacrylamide matrix. Magnetization curves show that the saturation magnetization of polyacrylamide/nickel particles is only slightly below that of the pure nickel nanoparticles. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Characteristics of Gallium-Substituted Hexagonal Mesoporous Silica: Effects of Gallium Content

Gallium-substituted hexagonal mesoporous silicas (Ga-HMS) with various Si/Ga ratios in the range of 15 and 200 were prepared at ambient temperature by neutral surfanctant templating pathway. The materials were synthesized by using dodecylamine as a template and tetraethylorthosilicate as a silicon source. They were characterized by energy dispersive X-ray spectroscopy, powder X-ray diffraction (XRD), N₂ adsorption-desorption, thermogravimetric analysis, differential scanning calorimetry, scanning electron microscopy, transmission electron microscopy, Fourier-transform infrared absorption spectroscopy and ultraviolet-visible absorption spectroscopy. Ga-HMS samples had high surface areas and uniform mesoporous channels, which are similar to MCM-41. However, they differed from MCM-41 in presenting only a single peak in XRD patterns. They also possessed other characters of larger framework wall thickness, small crystallite domain sizes, and complementary textural mesoporosities in comparison with M41S materials. Ga-HMS materials had micropores and the hysteresis loops were obvious. These small crystallite size and complementary textural mesoporosity provided better access of the framework-confined mesopores. These mesoporous Ga-HMS samples exhibited irregularly shaped mesoscale fundamental particles which aggregated into larger particles. They also demonstrated better thermal stability than MCM-41. The textural pore volumes of Ga-HMS specimens could be up to 20 times as large as the framework volumes. The surfactant could be removed completely by calcination at 650^∘C. An absorption band of FT-IR at ca. 960 cm^–1 was assigned to the vibration of Si–O–Ga linkages. These samples also showed an absorbance band at 255 nm and 250 nm in UV-vis spectra. The results show that gallium was incorporated into the structure of HMS. The efforts in preparing Ga-HMS specimens by neutral-template synthesis route had led to new mesoporous silica molecular sieves with catalytically active gallium centers.     

A mesoporous composite template composed of self-assembled silica nanotube and multi-walled carbon nanotube

The multi-walled carbon nanotubes (MWNTs) were successfully embedded in the hexagonally-arranged silica tubular structure by the self-organization of two surfactant systems providing a MWNT-incorporated silica nancomposite template. The anionic surfactant (sodium dodecyl sulfate, SDS) adsorbed on the MWNT surfaces allowed the MWNTs to interact with the outer surface of the self-assembled non-ionic surfactant, poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide) (PEO–PPO–PEO) triblock copolymer. Due to the hydrophilic–hydrophilic interaction between the PEO blocks and the sulfate group of SDS, the MWNTs were most possibly surrounded by the outer wall of the SBA-15 hexagonal tubes aligning in the longitudinal and transverse directions to the silica tube direction. According to the interplanar distances, electron microscopy images, and N₂ adsorption–desorption isotherms, the synthesized SBA-15/MWNT system exhibited the structural integrity of silica-tube arrangement and structural characteristics of MWNTs in terms of BET surface area and micropore volume. This work made it clear that the developed SBA-15/MWNT template could be used to synthesize various MWNT-incorporated 2-D replicas.     

Synthesis of water dispersible magnetite nanoparticles in the presence of hydrophilic polymers

Water dispersible magnetite nanoparticles (Fe₃O₄) were synthesized by thermal decomposition of iron (III) acetylacetonate (Fe(acac)₃) in the presence of carboxylic acid-terminated poly(ethylene glycol) (mPEG acid), poly(vinyl alcohol) and NH₂-containing polyether. Crystal structure was investigated using X-ray diffractometry (XRD) and it showed that the as-synthesized particles had high crystallinity with distinct lattices. Particle size of the nanoparticles was investigated using XRD (15.32 nm), transmission electron microscopy (18.8 nm) and photo correlation spectroscopy (32 nm) techniques. Vibrating sample magnetometry indicated that magnetite nanoparticles exhibited superparamagnetic behavior at room temperature. Influence of each functional group on magnetic properties of the particles was also examined. These magnetite nanoparticles remained dispersible in aqueous dispersions with only 5% particles aggregating after 1 month of preparing.     

Periodic mesoporous hybrid monolith with hierarchical macro–mesopores

We describe the synthesis of hybrid monolith with hierarchically macro–mesoporous structure by a sol–gel process from the mixture of 1,4-bis(triethoxysilyl)benzene (BTEB) and tetraethoxysilane (TEOS) using poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) (P123) as structure directing agent under acid medium. The ordered mesoporous structure is embedded in the skeleton of the well-defined co-continuous macropore of the hybrid monolith. The influence of aging condition, acidic concentration, P123/Si ratio and TMB/P123 ratio on the macro- and meso-structure of the resultant monolith was investigated in details. The three-successive aging processes are necessary for the mesostructural order of the monolith to survive the surfactant removing process. The well-defined co-continuous macropore could be formed with the aid of TMB, which probably delays the phase separation rate during the sol–gel process through enhancing the interaction between the hydrophobic BTEB with P123 surfactant micelles. The macro–mesoporous hybrid monolith with phenylene bridged in the mesoporous framework may have potential application as a novel kind of stationary phase for high performance liquid chromatography (HPLC).