On the mechanism of metal nanoparticle synthesis in the brust-schiffrin method

Brust-Schiffrin synthesis (BSS) of metal nanoparticles has emerged as a major breakthrough in the field for its ability to produce highly stable thiol functionalized nanoparticles. In this work, we use a detailed population balance model to conclude that particle formation in BSS is controlled by a new synthesis route: continuous nucleation, growth, and capping of particles throughout the synthesis process. The new mechanism, quite different from the others known in the literature (classical LaMer mechanism, sequential nucleation-growth-capping, and thermodynamic mechanism), successfully explains key features of BSS, including size tuning by varying the amount of capping agent instead of the widely used approach of varying the amount of reducing agent. The new mechanism captures a large body of experimental observations quantitatively, including size tuning and only a marginal effect of the parameters otherwise known to affect particle synthesis sensitively. The new mechanism predicts that, in a constant synthesis environment, continuous nucleation-growth-capping mechanism leads to complete capping of particles (no more growth) at the same size, while the new ones are born continuously, in principle leading to synthesis of more monodisperse particles. This prediction is validated through new experimental measurements.

Simulation of precipitation reactions in reverse micelles

Precipitation involving mixing of two sets of reverse micellar solutions-containing a reactant and precipitant respectively-has been analyzed. Particle formation in such systems has been simulated by a Monte Carlo (MC) scheme (Li, Y.; Park, C. W. Langmuir 1999, 15, 952), which however is very restrictive in its approach. We have simulated particle formation by developing a general Monte Carlo scheme, using the interval of quiescence technique (IQ). It uses Poisson distribution with realistic, low micellar occupancies of reactants, Brownian collision of micelles with coalescence efficiency, fission of dimers with binomial redispersion of solutes, finite nucleation rate of particles with critical number of molecules, and instantaneous particle growth. With the incorporation of these features, the previous work becomes a special case of our simulation. The present scheme was then used to predict experimental data on two systems. The first is the experimental results of Lianos and Thomas (Chem. Phys. Lett. 1986, 125, 299, J. Colloid Interface Sci. 1987, 117, 505) on formation of CdS nanoparticles. They reported the number of molecules in a particle as a function of micellar size and reactant concentrations, which have been predicted very well. The second is on the formation of Fe(OH)(3) nanoparticles, reported by Li and Park. Our simulation in this case provides a better prediction of the experimental particle size range than the prediction of the authors. The present simulation scheme is general and can be applied to explain nanoparticle formation in other systems.

Synthesis of nanocrystalline alpha-Al2O3 by ultrasonic flame pyrolysis

Nanocrystalline alpha-alumina was synthesized in an indigenously built ultrasonic flame pyrolysis (UFP) setup. This paper describes the technical aspects of the apparatus and particle formation in the flame. Ultrasonically atomized aluminium nitrate dissolved in methanol-water mixture was pyrolyzed in an oxy-propane flame for yielding nanocrystalline alpha-alumina. The formation of nanophase alumina was confirmed by powder XRD analysis. Scanning electron microscopy (SEM) analysis was carried out to study particulate morphology. (C) 2003 Elsevier Science Ltd. All rights reserved.

Optical Properties Study of S40Se60-xSbx Bulk Alloys

Bulk samples of S40Se60-xSbx (with x=10, 20, 30, 40 at. %) were prepared from high purity S, Se and Sb by melt quenching method. XRD studies revealed that all the samples have poly-crystalline phase. The variation in optical properties with composition has been investigated by XPS and Raman spectroscopy. The intensity of XPS core level spectra changes with addition of Sb clearly interprets the optical properties change due to compositional variation. The Raman shift and new peak formation in these samples clearly shows the structural modifications due to Sb addition.

Compositional dependence properties change in S40Se60-x,Sb-x alloys

Bulk samples of S40Se60,Sb-x (with x=10, 20, 30 and 40 at. %) were prepared from high purity chemicals by melt quenching technique. The samples compositions were confirmed by using energy dispersive analysis of X-rays. X-ray diffraction studies revealed that all the samples have poly-crystalline phase. The variation in optical properties with compositional has been investigated by X-ray photoelectron spectroscopy and Raman spectroscopy. The optical band gap of the thin films is found to be decreased with composition. Increasing Sb content was found to affect the structural and optical properties of bulk samples. The intensity of core level spectra changes with the addition of Sb clearly interprets the optical properties change due to compositional variation. The Raman shift and new peak formation in these samples clearly show the structural modifications due to Sb addition.

High quality oxide-free metallic nanoparticles: a strategy for synthesis through laser ablation in aqueous medium

The paper explores the synthesis of oxide-free nanoparticles of Ag and Cu through laser ablation of pure targets under aqueous medium and tuning the quality and size through addition of Polyvinylpyrrolidone (PVP) in the medium. The size distribution of nanoparticles reduces from 37 +/- 30 nm and 13 +/- 5 nm to 32 +/- 12 nm and 4 +/- 1 nm for Ag and Cu with changes in PVP concentration from 0.00 to 0.02 M, respectively. Irregular shaped particles of Ag with Ag2O phase and a Cu-Cu2O core-shell particles form without the addition of PVP, while oxide layer is absent with 0.02 M of PVP. The recent understanding of the mechanism of particle formation during laser ablation under liquid medium allows us to rationalize our observation.

On the Two-Step Mechanism for Synthesis of Transition-Metal Nanoparticles

The two-step particle synthesis mechanism, also known as the Finke-Watzky (1997) mechanism, has emerged as a significant development in the field of nanoparticle synthesis. It explains a characteristic feature of the synthesis of transition metal nanoparticles, an induction period in precursor concentration followed by its rapid sigmoidal decrease. The classical LaMer theory (1950) of particle formation fails to capture this behavior. The two-step mechanism considers slow continuous nucleation and autocatalytic growth of particles directly from precursor as its two kinetic steps. In the present work, we test the two-step mechanism rigorously using population balance models. We find that it explains precursor consumption very well, but fails to explain particle synthesis. The effect of continued nucleation on particle synthesis is not suppressed sufficiently by the rapid autocatalytic growth of particles. The nucleation continues to increase breadth of size distributions to unexpectedly large values as compared to those observed experimentally. A number of variations of the original mechanism with additional reaction steps are investigated next. The simulations show that continued nucleation from the beginning of the synthesis leads to formation of highly polydisperse particles in all of the tested cases. A short nucleation window, realized with delayed onset of nucleation and its suppression soon after in one of the variations, appears as one way to explain all of the known experimental observations. The present investigations clearly establish the need to revisit the two-step particle synthesis mechanism.

An Optimizing Code Generator for a Class of Lattice-Boltzmann Computations

The Lattice-Boltzmann method (LBM), a promising new particle-based simulation technique for complex and multiscale fluid flows, has seen tremendous adoption in recent years in computational fluid dynamics. Even with a state-of-the-art LBM solver such as Palabos, a user has to still manually write the program using library-supplied primitives. We propose an automated code generator for a class of LBM computations with the objective to achieve high performance on modern architectures. Few studies have looked at time tiling for LBM codes. We exploit a key similarity between stencils and LBM to enable polyhedral optimizations and in turn time tiling for LBM. We also characterize the performance of LBM with the Roofline performance model. Experimental results for standard LBM simulations like Lid Driven Cavity, Flow Past Cylinder, and Poiseuille Flow show that our scheme consistently outperforms Palabos-on average by up to 3x while running on 16 cores of an Intel Xeon (Sandybridge). We also obtain an improvement of 2.47x on the SPEC LBM benchmark.

Quantitative In Situ Analysis of Deformation in Sliding Metals: Effect of Initial Strain State

Using in situ, high-speed imaging of a hard wedge sliding against pure aluminum, and image analysis by particle image velocimetry, the deformation field in sliding is mapped at high resolution. This model system is representative of asperity contacts on engineered surfaces and die-workpiece contacts in deformation and machining processes. It is shown that large, uniform plastic strains of 1-5 can be imposed at the Al surface, up to depths of 500 mu m, under suitable sliding conditions. The spatial strain and strain rate distributions are significantly influenced by the initial deformation state of the Al, e.g., extent of work hardening, and sliding incidence angle. Uniform straining occurs only under conditions of steady laminar flow in the metal. Large pre-strains and higher sliding angles promote breakdown in laminar flow due to surface fold formation or flow localization in the form of shear bands, thus imposing limits on uniform straining by sliding. Avoidance of unsteady sliding conditions, and selection of parameters like sliding angle, thus provides a way to control the deformation field. Key characteristics of the sliding deformation such as strain and strain rate, laminar flow, folding and prow formation are well predicted by finite element simulation. The deformation field provides a quantitative basis for interpreting wear particle formation. Implications for engineering functionally graded surfaces, sliding wear and ductile failure in metals are discussed.

Self-assembly of three new coordination complexes: Formation of 2-D square grid, 1-D chain and tape structures

Three distinct coordination complexes, viz., [Co(imi)(2)(tmb)(2)] (1) [where imi = imidazole], {[Ni(tmb)(2)(H2O)(3)]center dot 2H(2)O}(n) (2) and [Cu-2(mu-tmb)(4)(CH3OH)(2)] (3), have been synthesized hydrothermally by the reactions of metal acetates,2,4,6-trimethylbenzoic acid (Htmb) and with or without appropriate amine. The Ni analogue of 1 and the Co analogue of 2 have also been synthesized. X-ray single-crystal diffraction suggests that complex 1 represents discrete mononuclear species and complex 2 represents a 1D chain coordination polymer in which the Ni(H) ions are connected by the bridging water molecules. Complex 3 represents a neutral dinuclear complex. In 1, the central metal ions are associated by the carboxylate moiety and imidazole ligands, whereas the central metal atom is coordinated to the carboxylate moiety and the respective solvent molecules in 2 and 3. In 3, the four 2,4,6-trimethylbenzoate moieties act as a bridge connecting two copper (11) ions and the 0 atoms of methanol coord geometry, with the methanol molecule at the apical position. In all the three structures the central metal atom sits on a crystallographic inversion centre. In all the cases, the coordination entities are further organized via hydrogen bonding interactions to generate multifarious supramolecular networks. Complexes 1, 2 and 3 have also been characterized by spectroscopic (UV/Vis and IR) and thermal analysis (TGA). In addition, the complexes were found to exhibit antimicrobial activity. The magnetic susceptibility measurements, measured from 8 to 300 K, revealed antiferromagnetic interactions between the Co(II) ions in compound 1 and the Ni(II) ions in la, respectively.

The illustrative use of thiosulfate in the formation of new three-dimensional hybrid structures

Examples of 3D cadmium thiosulfate based inorganic-organic hybrid compounds have been shown to be active photocatalysts using sunlight.

Reversible cation/anion extraction from K2La2Ti3O10: Formation of new layered titanates, KLa2Ti3O9.5 and La2Ti3O9

A new soft-chemical transformation of layered perovskite oxides is described wherein K2O is sequentially extracted from the Ruddlesden-Popper (R-P) phase, K2La2Ti3O10 (I), yielding novel anion-deficient KLa2Ti3O9.5 (II) and La2Ti3O9 (III). The transformation occurs in topochemical reactions of the R-P phase I with PPh4Br and PBu4Br (Ph = phenyl; Bu = n-butyl). The mechanism involves the elimination of KBr accompanied by decomposition of PR4+ (R = phenyl or n-butyl) that extracts oxygen from the titanate. Analysis of the organic products of decomposition reveals formation of Ph3PO, Ph3P, and Ph-Ph for R = phenyl, and Bu3PO, Bu3P along with butane, butene, and octane for R = butyl. The inorganic oxides II and III crystallize in tetragonal structures (II: P4/mmm, a = 3.8335(1) angstrom, c = 14.334(1) angstrom; III: /4/ mmm, a = 3.8565(2) angstrom, c = 24.645(2) angstrom) that are related to the parent R-P phase. II is isotypic with the Dion-Jacobson phase, RbSr2Nb3O10, while III is a unique layered oxide consisting of charge-neutral La2Ti3O9 anion-deficient perovskite sheets stacked one over the other without interlayer cations. Interestingly, both II and III convert back to the parent R-P phase in a reaction with KNO3. While transformations of the R-P phases to other related layered/three-dimensional perovskite oxides in ion-exchange/metathesis/dehydration/reduction reactions are known, the simultaneous and reversible extraction of both cations and anions in the conversions K2La2Ti3O10 reversible arrow KLa2Ti3O9.5 reversible arrow La2Ti3O9 is reported here for the first time.

Synthesis and characterization of barium bis(citrato) oxozirconate(iv) tetrahydrate--A new molecular precursor for fine particle BaZrO3

Barium metazirconate (BaZrO3) fine powder has been produced by thermally decomposing a molecular precursor, barium bis(citrato)oxozirconate(IV) tetrahydrate at about 700-degrees-C. The precursor, Ba[ZrO(C6H6O7)2] . 4H2O (BZO) has been synthesized and characterized by employing a combination of spectroscopic and thermoanalytical techniques. The precursor undergoes thermal decomposition in three major stages: (i) dehydration to give an anhydrous barium zirconyl citrate, (ii) decomposition of the anhydrous citrate in a multistep process to form an ionic oxycarbonate intermediate, Ba2Zr2O5CO3, and (iii) decomposition of the oxycarbonate to produce BaZrO3 fine powder. The particle size of the resultant BaZrO3 is about 0.2 mum, and the surface area is found to be 4.0 m2 g-1.