Gold nanorods in aqueous solution are generally surrounded by surfactants or capping agents. This is crucial for anisotropic growth during synthesis and for their final stability in solution. When CTAB is used, a bilayer has been evidenced from analytical methods even though no direct morphological characterization of the precise thickness and compactness has been reported. The type of surfactant layer is also relevant to understand the marked difference in further self-assembling properties of gold nanorods as experienced using 16-EO(1)-16 gemini surfactant instead of CTAB. To obtain a direct measure of the thickness of the surfactant layer on gold nanorods synthesized by the seeded growth method, we coupled TEM, SAXS, and SANS experiments for the two different cases, CTAB and gemini 16-EO(1)-16. Despite the strong residual signal from micelles in excess, it can be concluded that the thickness is imposed by the chain length of the surfactant and corresponds to a bilayer with partial interdigitation.
A complex between cetyltrimethylammonium bromide (CTAB) surfactant and silver bromide (CTASB) is recognized by NMR and X-ray photoelectron spectroscopy (XPS) to be the entity at the surface of gold nanorods, resulting from an in situ formation in the classical scheme of synthesis. It can thus be introduced directly along with the initial reactants in place of silver(I) salt to produce a new effective synthesis of these objects. Complementary XPS and quartz crystal microbalance (QCM) measurements on macroscopic gold surfaces confirm a strong adsorption of CTASB that is higher than that of CTAB and any other CTAX surfactants. The role of CTASB as a rod inducing agent by surface complexation is stressed.
The growth of gold nanorods has been followed by small
angle X-ray
scattering and X-ray absorption. The synthesis is performed at high
concentration of 3.5 mM in gold using in situ generation of seeds.
It is shown that the growth occurs at constant number density of nanoparticles
after the initial nucleation of seeds and that the final step of reduction
of Au(I) to Au(0) occurs only at the surface of the growing nanorods.
Anisotropy is acquired during the growth with a ratio of longitudinal
to basal growth rates measured at 12. The final aspect ratio is only
limited by the available amount of material and the experiment of
overgrowth was allowed to reach a final aspect ratio of 5 instead
of the initial 3.6.
A quantitative analysis of object populations obtained by TEM images is performed for the classical scheme of aqueous seedless synthesis of nanorods. Using an effective way to represent nanoparticle size distributions, we unravel that spheres, usually considered to be a side-product, are in fact coming from a competing route during nanorod formation. The differentiation between spheres and rods appears above a critical size of 5 nm and is due to different growth rates between faces. The initial repartition of faces on nuclei or on the nanoparticles at the critical size can be the source for the final differentiation between globules and rods. The efficiency of the selection is strongly influenced by the production of the initial seeds and, in particular, by the amount of borohydride added in the present scheme.
A specific methodology was developed to refine the complex clay mineralogy commonly encountered in soil environments. The soil examined was a Cambisol developed into a ferralitic paleosol. The sample was split into four sub-fractions of different particle sizes (<0.05, 0.05-0.1, 0.1-0.2, and 0.2-2 µm), and their respective mass contributions to the overall <2 µm clay fraction were determined. For each sub-fraction, X-ray diffraction (XRD) patterns were modeled using a trial-and-error approach based on the direct comparison of experimental and calculated profiles. Quantitative information derived from the fitting procedure for the different sub-fractions allowed for the determination of the complex mineralogy of the <2 µm clay fraction through the identification and quantification of eight clay phases. The results show that the finest and most reactive clay fraction (<0.05 µm) was totally hidden in the XRD pattern of the <2 µm fraction, the fraction commonly considered in soil mineralogical analyses. Similarly, this procedure revealed the presence of illite-smectite-chlorite and kaolinite-illite mixed-layer minerals seldom described in soil literature using classical methods. The use of this methodology improved our understanding of the pedogenesis of this soil through the identification and quantification of clay phases structural properties. The analysis of the evolution of structural parameters with particle size allowed for the detection of local modifications in the interlayer composition of expandable and hydroxy-interlayered vermiculite layers. Following this approach, key information can be derived to determine subtle changes in clay mineralogical composition that are related to microorganism and/or plant activity.
Three particle size fractions of sodium-saturated vermiculite (10-20, 1-2 and 0.1-0.2 μm), differing only in their ratios of external-to-total sorption sites, were used to probe the nature of the sites involved in desorption of cesium ions. The sorption was investigated for initial aqueous concentrations of cesium ranging from 5.6×10(-4) to 1.3×10(-2) mol/L, and the cesium desorption was probed by exchange with ammonium ions. The results showed that (1) the amounts of desorbed cesium were strongly dependent on the particle size for a given initial aqueous cesium concentration and (2) the amounts of desorbed cations (Na(+) and Cs(+)) strongly decreased with increasing initial cesium aqueous concentration, irrespective of the particle size investigated. Quantitative analysis of these results suggested that cesium ions sorbed on external (edge+basal) sorption sites can be desorbed by ammonium ions. As a contrast, most of cesium ions sorbed on interlayer sites remain fixed due to the collapse of the structure under aqueous conditions. This study provides important information, such as the nature of the sites involved in the exchange process, when the thermodynamic formalism is considered to describe the ion-exchange process involving cesium and high-charge swelling clay minerals in polluted soil environments.
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