Unraveling agglomeration and deagglomeration in aqueous colloidal dispersions of very small tin dioxide nanoparticles.

HYPOTHESIS: Understanding deagglomeration, agglomerate formation and structure for very small nanoparticles (NPs), due to their more facile agglomeration, is critical for processing or tailoring agglomerates for nanostructured materials. We propose that by controlling and fine-tuning the interplay of agglomeration (colloidal interaction) and deagglomeration (hydrodynamic forces), the design of agglomerate size, microstructure and morphology is possible even for very small NPs. EXPERIMENTS: Here, we investigate very small SnO2 NPs (10 nm) generated in the gas phase as model system. Small-angle X-ray scattering (SAXS) and dynamic light scattering (DLS) are used to study dispersions in aqueous media across the entire pH range (2-12) at various NaCl concentrations treated with ultrasound. Parallel to size and size distribution, agglomerate morphology and microstructure are analyzed by means of the mass fractal dimension, dm and modeled with ab initio shape simulations. The critical coagulation concentration (CCC) is determined for the alkaline region where the SnO2 NPs are highly charged. FINDINGS: Quantitative analysis of SAXS and DLS data reveals that size and size distribution of the agglomerates depend similarly on the electrostatic interaction influenced by pH and salinity as observed by the zeta potential. In contrast dm is mainly influenced by the salt concentration. Ab initio shape simulations support these experimental findings.

Laser synthesis, structure and chemical properties of colloidal nickel-molybdenum nanoparticles for the substitution of noble metals in heterogeneous catalysis.

Platinum and iridium are rare and expensive noble metals that are used as catalysts for different sectors including in heterogeneous chemical automotive emission catalysis and electrochemical energy conversion. Nickel and its alloys are promising materials to substitute noble metals. Nickel based materials are cost-effective with good availability and show comparable catalytic performances. The nickel-molybdenum system is a very interesting alternative to platinum in water electrolysis. We produced ligand-free nickel-molybdenum nanoparticles by laser ablation in water and acetone. Our results show that segregated particles were formed in water due to the oxidation of the metals. X-ray diffraction shows a significant change in the lattice parameter due to a diffusion of molybdenum atoms into the nickel lattice with increasing activity in the electrochemical oxygen evolution reaction. Even though the solubility of molecular oxygen in acetone is higher than in water, there were no oxides and a more homogeneous metal distribution in the particles in acetone as seen by TEM-EDX. This showed that dissolved molecular oxygen does not control oxide formation. Overall, the laser ablation of pressed micro particulate mixtures in liquids offers a combinational synthesis approach that allows the screening of alloy nanoparticles for catalytic testing and can convert micro-mixtures into nano-alloys.

Interaction of L-Cysteine with ZnO: Structure, Surface Chemistry, and Optical Properties.

Zinc oxide (ZnO) nanoparticles (NPs) were stabilized in water using the amino acid l-cysteine. A transparent dispersion was obtained with an agglomerate size on the level of the primary particles. The dispersion was characterized by dynamic light scattering (DLS), pH dependent zeta potential measurements, scanning transmission electron microscopy (STEM), X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, Raman spectroscopy, photoluminescence (PL) spectroscopy, and X-ray absorption fine structure (EXAFS, XANES) spectroscopy. Cysteine acts as a source for sulfur to form a ZnS shell around the ZnO core and as a stabilizer for these core-shell NPs. A large effect on the photoluminescent properties is observed: the intensity of the defect luminescence (DL) emission decreases by more than 2 orders of magnitude, the intensity of the near band edge (NBE) emission increases by 20%, and the NBE wavelength decreases with increasing cysteine concentration corresponding to a blue shift of about 35 nm due to the Burstein-Moss effect.