A simple approach to prepare monodisperse mesoporous silica nanospheres with adjustable sizes

A new and facile approach has been developed to prepare monodisperse mesoporous silica nanospheres (MMSNs) with controlled particle sizes and pore structures. In our approach, MMSNs were synthesized simply in a sodium acetate solution without adding any other alkali or alcohol additives. MMSNs have a spherical shape and uniform particle sizes, which can be adjusted from 50 to 110 nm by increasing the reaction temperature from 40 to 80 °C. By performing a subsequent hydrothermal treatment (HT) under basic condition (pH=~11.5) at 130 °C, the mesoporous pore volume and surface area can be enhanced, while keeping the mono-dispersion characteristics and the mesopore size almost unchanged. The pore sizes of MMSNs can be adjusted from 2.8 to 4.0 nm under acidic solutions by changing the HT temperature from 100 to 130 °C. The formation process of MMSNs has been investigated by transmission electron microscopy (TEM) and attenuated total reflection Fourier transform infrared (ATR-FTIR) techniques. A spherical micelle templating mechanism is proposed to explain the formation of MMSNs in our system, which is different from that of traditional highly ordered mesoporous silica nanoparticles (MCM-41).     

Synthesis of fluorescent silica-coated gibbsite platelets

We describe the fluorescent labeling of gibbsite particles. Gibbsite particles are first stabilized with polyvinyl pyrrolidone. Subsequently the particles are covered with a silica layer in which a fluorescent dye is incorporated. Both fluorescein and rhodamine dyes have been used. The fluorescent labeling is applicable to gibbsite particles of various sizes. Particles are transferred to dimethyl formamide by vacuum distillation after dialysis. These particles are used for confocal scanning laser microscopy and confocal fluorescence-recovery after photobleaching.     

Sedimentation and phase transitions of colloidal gibbsite platelets

We study the competition between sedimentation, gelation, and liquid crystal formation in suspensions of colloidal gibbsite platelets of five different sizes at three ionic strengths. For large particles (with diameters of 350, 420, and 570 nm) sedimentation is initially the most important factor determining the macroscopic behavior. Only after the main part of the sample has sedimented in an amorphous phase, phase separation takes place. For the smallest particles (diameter 210 and 270 nm), it is the other way around: fast (within one week) phase separation or gelation takes place, after which sedimentation determines the final macroscopic appearance. We distinguish six different scenarios within this two-fold scheme and interpret these on the basis of the previously obtained phase diagram of colloidal gibbsite platelets (van der Beek, D.; Lekkerkerker, H. N. W. Langmuir 2004, 20, 8582).     

Seeded polymerization as a method for producing hollow monodisperse microspheres

Crosslinked hollow monodisperse microspheres with diameters of 1.9–5.9 μm and one- or two-layer shells, with the layers being based on polymers of different natures, are produced by one- and two-stage seeded copolymerization of styrene and/or methyl methacrylate with ethylene glycol dimethacrylate or allyl methacrylate as crosslinking agents. Factors determining the morphology and dispersity of the microspheres are revealed. It is shown that, when, at the final stage of the synthesis, the content of a crosslinking agent in the reaction mixture is at least 50 wt %, the produced microspheres retain their size and morphology after exposure in toluene and dimethylformamide.     

Seeded polymerization of vinyl acetate using monodisperse poly(vinyl acetate) latex particles

The seeded polymerizations of vinyl acetate, using monodisperse poly(vinyl acetate) latex particles prepared in the absence of emulsifiers with potassium persulfate, have been investigated at 70°C with potassium persulfate as an initiator. New small particles were formed in the system containing a small amount of seed particles, but were not observed in the system containing a large amount of seed particles. The size of the secondary particles increased, and their number decreased, with an increase in the seed particle number. The minimum diameter of PVAc particles, which are stabilized by the sulfate ion groups bound at the end of polymer chains during polymerization, was determined to be 0.12 μm diameter from the limiting total surface area of seed particles which prevented further secondary nucleation. The minimum diameter of the particles increased as the speed of the stirrer increased. The new small particle number calculated using this value agreed well with that formed in the seeded polymerization.     

Seeded growth of two-dimensional dendritic gold nanostructures

We show that seeded growth can be applied to creating two-dimensional (2D) dendritic Au nanostructures on sample grids, which can be directly characterized by transmission electron microscopy (TEM). The 2D synthesis of highly consistent structures offers a novel mechanistic perspective on the aggregation of colloidal Au nanocrystals on a surface.     

Facile one-pot synthesis of PEGylated monodisperse mesoporous silica nanoparticles with controllable particle sizes

In this work, we describe the one-pot synthesis of PEGylated mesoporous silica nanoparticles （MSNs） with uniform shape, tunable sizes, and narrow size distributions. The size of these nanoparticles can be controlled from 49 nm to 98 nm by simply varying the concentration oftriethanolamine during the base- catalyzed sol-gel reaction. Particles were characterized by transmission electron microscopy, dynamic light scattering, Fourier transform infrared spectrometry, thermogravimetric analysis, and nitrogen adsorption-desorption measurements. These PEGylated MSNs exhibited excellent long-term stability in biological media, which ensures their potential applications in drug delivery.     

Porous gadolinia-doped ceria with adjustable pore sizes using PI-b-PEO copolymer as the structure-directing agent

In this study, we report that by coupling the kinetics of both hydrolysis and condensation of the oxide precursors and the kinetics of self-assembly process of the block copolymer, we can synthesize both mesoporous and macroporous gadolinia-doped ceria (GDC) with one chemical composition but different processing conditions. Our process uses poly(isoprene-b-ethylene oxide) as the structure-directing agent and cerium and gadolinium acetylacetonates as the precursors for the sol?Cgel synthesis of GDC. By controlling the extent of the hydrolysis and condensation of the oxide precursor before mixing with the copolymer, we can adjust the hydrophilic domain size from nanometers to micrometers. As a result, highly crystalline porous GDC with dominant mesopores (15?nm?<?d?<?50?nm) or macropores (50?nm?<?d?<?5???m) are produced after removal of the copolymer via a two-step calcination treatment. The discovery of this study offers a facile and viable approach to produce meso- and macro-porous materials, in a ??one-pot?? synthesis with one chemical composition but different processing conditions to control pore sizes.     

Seeded growth of submicron Au colloids with quadrupole plasmon resonance modes

A modified seeded growth process has been used for the controlled synthesis of quasispherical, CTAB-stabilized gold nanoparticles from 12 up to 180 nm with narrow size distributions. The UV-visible spectra of the aqueous colloids show distinct bands corresponding to dipole and quadrupole plasmon modes, for diameters above 100 nm, in close agreement with predictions based on Mie theory. The assignment of the modes is demonstrated by calculation of near field enhancement maps based on the boundary element method. Apart from other applications, since absorption is drastically reduced above 600 nm, while scattering is largely increased, these particles open new possibilities for construction of highly efficient photonic structures.     

Hydrothermal process of synthetic gibbsite and the characteristics of Na in gibbsite crystal

The presence of Na in synthetic gibbsite was studied by several modern testing methods such as X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy and inductively coupled plasma. Results show that Na is located between gibbsite crystals and is not present as sodium aluminosilicate hydrate in synthetic gibbsite. Synthetic gibbsite crystal can be transformed into boehmite under the hydrothermal condition of 210 °C for 60 min. During the reaction process, synthetic gibbsite crystal particles break up into small fragments and form boehmite. During the process, impurities are released and the Na can be removed by washing. Over 90% of Na can be removed during the hydrothermal transformation process. This technology can be applied in the production process of high-purity alumina.     

Magnetic properties of monodisperse NiHx nanoparticles and comparison to those of monodisperse Ni nanoparticles

We produced, for the first time, monodisperse NiH(x) nanoparticles with particle diameters of 7.0 nm and investigated their magnetic properties. We also produced monodisperse Ni nanoparticles with nearly the same particle diameters as those of NiH(x) nanoparticles as a comparison. The magnetic properties of NiH(x) nanoparticles were quite different from those of Ni nanoparticles. We observed two compositional phases in NiH(x) nanoparticles, similar to bulk material: one is the nearly pure Ni phase with the blocking temperature (T(B)) of 11 K and the other is the hydride phase. We observed T(B) of 40 K in Ni nanoparticles.     

Synthesis and characterization of (Mo72Fe30)-coated large hexagonal gibbsite gamma-Al(OH)3 platelets

The polyoxometalates or POMs (clusters comprising at least two metal and many oxygen atoms) have recently gained significant interest owing to their versatile architecture and especially their catalytic activities. Due to their high catalytic activity but low surface area, there is always a demand for making high surface area POMs. This work demonstrates the attachment of the anionic (Mo72Fe30) POMs to gibbsite nanoplatelets with a residual positive charge to form large surface area composites. The resulting composite reported here has been characterized using cryo-TEM imaging, EDX/STEM (elemental) analysis, ATR-IR spectroscopy, SAXS, electrophoretic mobility determination and XRD. The composite reported here could find application in catalysis.     

Seeded growth of titania colloids with refractive index tunability and fluorophore-free luminescence

Titania is an important material in modern materials science, chemistry, and physics because of its special catalytic, electric, and optical properties. Here, we describe a novel method to synthesize colloidal particles with a crystalline titania, anatase core and an amorphous titania-shell structure. We demonstrate seeded growth of titania onto titania particles with accurate particle size tunability. The monodispersity is improved to such an extent so that colloidal crystallization of the grown microspheres becomes feasible. Furthermore, seeded growth provides separate manipulation of the core and shell. We tuned the refractive index of the amorphous shell between 1.55 and 2.3. In addition, the particles show luminescence when trace amounts of aminopropyl-triethoxysilane are incorporated into the titania matrix and are calcined at 450 °C. Our novel colloids may be useful for optical materials and technologies such as photonic crystals and optical trapping.     

Facile access to monodisperse ultralarge rings

A facile access to monodisperse ultralarge rings counting 126, 174, and 294 ring atoms is described. It follows a reaction sequence that is well suited for the preparation of [2]catenanes but altered just in the sequence of the two steps cyclization and carbonate formation. The carbonate acts as a covalent template that is easily formed and later cleaved. The obtained monocyclic products are constitutional isomers of the catenanes.     

Kinetics and hydrothermal transformation of gibbsite

The transformation of gibbsite have been studied under hydrothermal influence. Results of the X-ray diffraction analysis of the samples heated at different temperatures from 170°C to 265°C are also discussed in detail. The percentage of the boehmite phase formed, due to the transformation of the gibbsite, have been determined by comparing the intensity of the most strongest reflection of the boehmite phase with a fully transformed sample. The activation energy value calculated form X-ray diffractograms is almost comparable with the value calculated from main DTA endotherm of gibbsite.Es wurde die Umwandlung von Gibbsit unter hydrothermalem Einfluß untersucht. Weiterhin werden auch Ergebnisse der Röntgendiffraktionsanalyse an den bei verschiedenen Temperaturen zwischen 170°C und 265°C erhitzten Proben besprochen. Durch Vergleich der Intensität der stärksten Reflexion der Böhmitphase mit einer vollständig umgewandelten Probe wurde der prozentuelle Anteil der während der Umwandlung von Gibbsit gebildeten Böhmitphase bestimmt. Der Wert für die Aktivierungsenergie, berechnet aus den Röntgendiffraktogrammen ist annähernd vergleichbar mit dem aus der DTA von Gibbsit berechneten Wert.

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RRL Contribution No. 2028.     

Supramolecular crystal growth in concentrated suspensions of charged monodisperse spherical silica particles

Concentrated suspensions of charged monodisperse spherical silica particles (MSSP) stabilized by alkalis or ammonia are able to crystallize at a certain destabilization. Crystal structures with the particles fixed at certain distances from each other show an isotropic normal mechanism of continuous growth with a rough phase boundary. The crystallization is determined by three parameters,víz. the concentration of particles, temperature, the thickness of the ion atmosphere around the particles and the concentration of counterions. The crystallization of MSSP suspensions is considered as a model of the supramolecular crystallization in the field of synthesis of mesoporous structures.     

Determination of nanocrystal sizes: a comparison of TEM, SAXS, and XRD studies of highly monodisperse CoPt3 particles

One of the most fundamental tasks in nanoscience is the accurate determination of particle sizes. Various methods have been developed to elucidate the mean particle diameter and the standard deviation for an ensemble of nanocrystals. However, good agreement between the results from different methods is not always encountered in the literature. In this study, we investigate colloidally prepared, highly monodisperse CoPt3 nanoparticles by transmission electron microscopy (TEM), small-angle X-ray scattering (SAXS), and powder X-ray diffraction (XRD). The results are compared in order to examine to which extent agreement is obtained by the different techniques when applied to small nanocrystals in the size range below 10 nm. In particular, the applicability of the simple Scherrer formula for size determination from the broadening of XRD reflections is checked. When the different techniques are correctly applied, the results from all methods are in good agreement.