Preferential adsorption of selenium oxyanions onto {1 1 0} and {0 1 2} nano-hematite facets.

As the commercial use of nano metal oxides, including iron oxides, becomes more prevalent, there is a need to understand functionality as it relates to the inherent properties of the nanomaterial. Many applications of nanomaterials rely on adsorption, ranging from catalysis to aqueous remediation. In this paper, adsorption of selenium (Se), an aqueous contaminant, is used as a model sorbate to elucidate the relationships of structure, property, and (adsorptive) function of nano-hematite (nα-Fe2O3). As such, six nα-Fe2O3 particles were synthesized controlling for size, shape and surface area without capping agents. Sorbent characteristics of the six particles were then assessed for their impact on selenite (HSeO3-) and selenate (SeO42-) adsorption capacity and mechanism. Mechanism was assessed using in-situ attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy and extended X-ray absorption fine edge spectroscopy (EXAFS). Regression analyses were then performed to determine which characteristics best describe adsorption capacity and binding mechanisms of Se on nα-Fe2O3. The results demonstrate that crystal surface structure, specifically presence of the {0 1 2} facet promotes adsorption of Se and the presence of {0 1 2} facets promotes SeO42- sorption to a greater extent than HSeO3-. The data further indicates that {1 1 0} facets bind HSeO3- with binuclear complexes while {0 1 2} facets bind HSeO3- via mononuclear inner-sphere complexes. Specific nα-Fe2O3 facets also likely direct the ratio of inner to outer-sphere complexes in SeO42- adsorption.

Underlying mechanisms in size control of uniform nanoparticles.

Insights are given into underlying mechanisms for size control of uniform nanoparticles in liquid phases. At the outset, instead of the classical nucleation theories, which are hardly applicable to the size control of uniform particles, a fundamental equation for the nucleation of monodisperse particles, derived for their size control on the basis of the LaMer model, is introduced. This equation was derived on three assumptions: (1) There is a mass balance between the supply rate of solute and its consumption rate for nucleation and growth of the generated nuclei; (2) The supply rate of solute is independent of the subsequent precipitation events; (3) The nucleation rate is controlled only by the growth of the preformed nuclei at a fixed supply rate of solute. Thus, this nucleation theory is applicable to a system in which the precursor solute is supplied by slow irreversible generation in a closed system or by continuous feed from outside in an open system. However, it is inapplicable even if only one of these three assumptions is not fulfilled. Examples of applicable and inapplicable systems are listed, and finally discussion is focused on the underlying mechanisms of size control in some unique processes chosen from them, such as hydrolysis-induced precipitation of AgCl nanoparticles, double-jet precipitation of AgCl nanoparticles in a reverse micelle system to resolve the mechanism of particle formation in general reverse micelle systems, and a gel-sol process for the formation of nanoparticles of anatase TiO2.

Effects of the water content on the growth rate of AgCl nanoparticles in a reversed micelle system.

The effects of water content on the growth rate and the final particle size of AgCl nanoparticles in a reversed micelle (RM) system of polyoxyethylene (6) nonylphenyl ether (NP-6)/water/cyclohexane were investigated using a double-jet technique, in which RM solutions of AgNO(3) and KCl were added concurrently to a RM solution containing the excess concentration of chloride ion. As a result, the particle growth rate and the final particle size at a constant Rw ( identical with[water]/[surfactant]) below 5 were found to be in excellent agreement with our theoretical prediction based on a dynamic Ostwald ripening mechanism governed by the overall solubility of the solid and the diffusivity of the reversed micelles, whereas the final particle size was far beyond the size of the water pool of a reversed micelle. Thus, the dramatic reduction of the particle size in the RM system can be explained by the drastic reduction of the overall solubility of the solid and the small diffusivity of the bulky reversed micelles as a carrier of silver ion, and not by the size of the water pool of a reversed micelle as conventionally explained. Some additional contribution of a coagulation process was also suggested in a high Rw range above 5. Significant coagulation of AgCl particles was observed in a RM system with AOT in place of NP-6 even under the standard conditions for the NP-6 system.

Shape control of anatase TiO2 nanoparticles by amino acids in a gel-sol system.

Ellipsoidal anatase TiO2 nanoparticles of different aspect ratios were obtained by the gel-sol method in the presence of amino acids in which the resulting particles were basically single crystals, but highly rough surfaces or partly polycrystalline structures were observed with a high concentration of glutamic acid or aspartic acid.

Systematic control of size, shape, structure, and magnetic properties of uniform magnetite and maghemite particles.

As an application of the gel-sol method especially developed for the synthesis of general monodisperse particles in large quantities, uniform hematite (alpha-Fe2O3), magnetite (Fe3O4), and maghemite (gamma-Fe2O3) particles, precisely controlled in size, aspect ratio, and internal structure, have been prepared. For the synthesis of uniform ellipsoidal single-crystal particles of alpha-Fe2O3, a highly condensed suspension of fine beta-FeOOH particles doped with a prescribed amount of PO4(3-) ion in their interiors was aged at 140 degrees C for 24 h with seed particles of alpha-Fe2O3 in an acidic medium containing optimum concentrations of HCl and NaNO3. Systematic control of the aspect ratio and mean size was achieved by regulating the concentration of PO4(3-) ion incorporated into the beta-FeOOH particles and the number of seeds added. The resulting hematite particles were converted into magnetite by reduction in a H2 stream at 330 degrees C for 6 h; the magnetite was then oxidized to maghemite in an air stream at 240 degrees C for 2 h. Magnetite and maghemite thus prepared retained the original shape of the hematite. On the other hand, polycrystalline hematite particles of different sizes and aspect ratios were also prepared by aging a condensed Fe(OH)3 gel in the presence of different concentrations of SO4(2-) ion and seeds. The polycrystalline hematite particles were similarly converted into magnetite and then maghemite. The magnetic properties of these magnetite and maghemite particles were analyzed as a function of their mean particle volume, aspect ratio, and internal structure.

Organic-inorganic hybrid liquid crystals: hybridization of calamitic liquid-crystalline amines with monodispersed anisotropic TiO2 nanoparticles.

A novel organic-inorganic hybrid thermotropic liquid crystal (LC) is developed by the hybridization of an organic amine with a mesogenic core and an acicular anisotropic TiO2 particle through the adsorption of the amino group to the surfaces of the TiO2. The hybrid LC shows nematic phases in wide ranges of temperatures. Variable-temperature small-angle X-ray measurements reveal that the formation of the one-dimensional nematic order of the acicular particles on a submicrometer scale induces thermotropic liquid crystallinity. This technique would lead to induction of dynamic functions in inorganic particles.

Synthesis of uniform anatase TiO2 nanoparticles by gel-sol method. 3. Formation process and size control.

Uniform anatase-type TiO(2) nanoparticles were prepared by the gel-sol process from a condensed Ti(OH)(4) gel preformed by the hydrolysis of a Ti-triethanolamine (TEOA) complex. The particle size of the anatase TiO(2) was increased from ca. 5 to 30 nm with pH increasing from 0.6 to 12 by aging the Ti(OH)(4) gel at 140 degrees C for 72 h, while the yield of the anatase TiO(2), 100% below pH 9.6, started to decrease from pH 10, to 67% at pH 11.5 and only 9% at pH 12.2. These results reveal a significant reduction of the nucleation rate of the anatase TiO(2) with increasing pH, as is explained by the reduction of the concentration of a precursor complex, Ti(OH)(3)(+), and the adsorption of hydroxide ion onto the embryos of TiO(2). Triethanolamine appeared to enhance the pH effect on the nucleation rate of anatase TiO(2) particles by adsorption onto their embryos, leading to the wide range of the size control. Triethanolamine was also found to act as a shape controller of the anatase TiO(2) particles for yielding ellipsoidal particles from Ti(OH)(4) gel at a relatively high pH above 11. The particle size was also controlled by seeding of anatase TiO(2). Moreover, the seeding experiment suggested that the rate-determining step of the gel-sol process was not the dissolution of the hydroxide gel, but the deposition of the monomeric precursor from the solution phase.

Synthesis of uniform anatase TiO2 nanoparticles by gel-sol method. 4. Shape control.

Uniform anatase-type TiO(2) nanoparticles of different shapes have been formed by phase transformation of a Ti(OH)(4) gel matrix in the presence of shape controllers. For example, triethanolamine (TEOA) was found to change the morphology of TiO(2) particles from cuboidal to ellipsoidal at pH above 11. The shape control can be explained in terms of the specific adsorption of TEOA onto the crystal planes parallel to the c-axis of the tetragonal system in the alkaline range, as supported by the observation of preferential adsorption of TEOA onto the crystal planes parallel to the c-axis at pH 11.5 and by the pH dependence of the adsorption onto ellipsoidal particles. Diethylenetriamine (DETA) also modified the particle shape to ellipsoidal above pH 9.5 and the aspect ratio was much higher than with TEOA. The mechanism of the shape control could be explained in the same way as with TEOA, since analogous specific adsorption was observed with DETA as well. Similar shape control to yield ellipsoidal particles of a high aspect ratio was also achieved with other primary amines, such as ethylenediamine (ED), trimethylenediamine (TMD), and triethylenetetramine (TETA). However, secondary amines, such as diethylamine, and tertiary amines, such as trimethylamine and triethylamine, acted as a complexing agent of Ti(IV) ions to promote the growth of ellipsoidal particles of a low aspect ratio, rather than a shape controller to produce ellipsoids of a high aspect ratio. Sodium oleate and sodium stearate were found to modify the particle shape from round-cornered cubes to sharp-edged cubes. The mechanism was explained in terms of the reduction of the specific surface energies of the [001] and [100] planes of the tetragonal crystal system by the preferential adsorption of oleate or stearate ion onto these planes, based on the adsorption experiment using ellipsoidal and cubic particles.

Well-defined fluorescent particles of ZnS:Cu. 1. Preparation and effects of annealing.

As an application of the gel-sol procedure for the synthesis of monodispersed particles in large quantities, uniform particles of ZnS:Cu were prepared by different methods from concentrated Zn-chelate solutions of nitrilotriatic acid (NTA) with thioacetamide (TAA), in which the dopant copper ion was introduced as a coexisting mixed chelate with Zn-NTA (Method A), a Cu-NTA complex in a separate solution continuously added to a system of Zn-NTA and TAA (Method B), or a Cu(NO3)2 solution infiltrated into a dry powder of ZnS prepared by Method A (Method C). All powders thus prepared were annealed before the test of fluorescent properties. The main roles of annealing were to remove the grain boundaries of such particles as nonradiative recombination centers of excited electrons and holes and to achieve uniform distribution of dopants. However, the initial intraparticle distribution of the dopant, controlled by the different methods, decisively affected the fluorescent particles, even after the conversion of the polycrystalline particles to single-crystal particles by annealing.

Synthesis of uniform anatase TiO2 nanoparticles by gel-sol method. 1. Solution chemistry of Ti(OH)(4-n)+(n) complexes.

The mole fractions of hydroxo complexes of titanium(IV) ion in an aqueous solution with 0.10 mol dm(-3) NaClO4 at 25 degrees C have been determined as a function of pH by a newly developed analytical procedure based on UV spectrophotometry, using a metastable homogeneous solution of 1.25 x 10(-4) mol dm(-30 in total concentration of Ti(IV). Also, the total concentration of the hydroxo complexes in equilibrium with Ti(OH)4 solid, or the solubility of Ti(OH)4 solid in an inhomogeneous system, has been obtained by ICP measurement for the solution phase. A combination of these data yielded the absolute concentration of each complex species in equilibrium with Ti(OH)4 solid. Finally, Ti(OH)+3 complex has been assigned to the precursor for the formation of anatase TiO2 nanoparticles transformed from Ti(OH)4 gel from a comparison between the above equilibrium data and a kinetic study on the formation rate of the anatase TiO2 particles in the gel-sol system.

Synthesis of uniform anatase TiO2 nanoparticles by the gel-sol method 2. Adsorption of OH- Ions to Ti(OH)4 gel and TiO2 particles.

The pH value in the gel-sol system for the preparation of uniform anatase TiO2 nanoparticles, as a decisive factor for controlling the size and shape of the final product, was found to be significantly changed during the formation process of the anatase TiO2 particles from a condensed Ti(OH)4 gel. The dramatic evolution of pH with the progress of the synthetic process has clearly been explained in terms of the adsorption and desorption of a hydroxide ion (OH-) ora proton (H+) on the solids transforming with time. The adsorption and desorption of OH- or H+ were enhanced by the presence of an inert electrolyte such as NaClO4, as explained by its shielding effect on the electrical interactions between the electrically charged precipitates and free OH- and H+ ions. The electrolyte also hampered the phase transformation of Ti(OH)4 precipitate to anatase TiO2. This effect of electrolytes was explained in terms of the inhibited nucleation of anatase TiO2 by enhanced adsorption of OH- ions toTiO2 embryos. The points of zero charge (PZC) of the amorphous Ti(OH)4 precipitate and the anatase TiO2 particles at 25 degrees C were obtained from the change in pH associated with the adsorption and desorption of OH- or H+, i.e., 4.6 for Ti(OH)4 precipitate and 6.0 for anatase TiO2 in the presence of 0.1 mol dm(-3) NaClO4. The PZCof the Ti(OH)4 precipitate measured at 25 degrees C after additional aging at 100 degrees C for 30 min was shifted to 4.1, owing to the promoted adsorption of OH-.