Adsorption and Catalytic Activity of Gold Nanoparticles in Mesoporous Silica: Effect of Pore Size and Dispersion Salinity.

The assembled state of nanoparticles (NPs) within porous matrices plays a governing role in directing their biological, electronic, and catalytic properties. However, the effects of the spatial confinement and environmental factors, such as salinity, on the NP assemblies within the pores are poorly understood. In this study, we use adsorption isotherms, spectrophotometry, and small-angle neutron scattering to develop a better understanding of the effect of spatial confinement on the assembled state and catalytic performance of gold (Au) NPs in propylamine-functionalized SBA-15 and MCM-41 mesoporous silica materials (mSiO2). We carry out a detailed investigation of the effect of pore diameter and ionic strength on the packing and spatial distribution of AuNPs within mSiO2 to get a comprehensive insight into the structure, functioning, and activity of these NPs. We demonstrate the ability of the adsorbed AuNPs to withstand aggregation under high salinity conditions. We attribute the observed preservation of the adsorbed state of AuNPs to the strong electrostatic attraction between oppositely charged pore walls and AuNPs. The preservation of the structure allows the AuNPs to retain their catalytic activity for a model reaction in high salinity aqueous solution, here, the reduction of p-nitrophenol to p-aminophenol, which otherwise is significantly diminished due to bulk aggregation of the AuNPs. This fundamental study demonstrates the critical role of confinement and dispersion salinity on the adsorption and catalytic performance of NPs.

Divergence of the third harmonic stress response to oscillatory strain approaching the glass transition.

The leading nonlinear stress response in a periodically strained concentrated colloidal dispersion is studied experimentally and by theory. A thermosensitive microgel dispersion serves as well-characterized glass-forming model, where the stress response at the first higher harmonic frequency (3ω for strain at frequency ω) is investigated in the limit of small amplitude. The intrinsic nonlinearity at the third harmonic exhibits a scaling behavior which has a maximum in an intermediate frequency window and diverges when approaching the glass transition. It captures the (in-) stability of the transient elastic structure. Elastic stresses in-phase with the third power of the strain dominate the scaling. Our results qualitatively differ from previously derived scaling behavior in dielectric spectroscopy of supercooled molecular liquids. This might indicate a dependence of the nonlinear response on the symmetry of the external driving under time reversal.

Colloidal Plastic Crystals in a Shear Field.

We study the structure and viscoelastic behavior of 3D plastic crystals of colloidal dumbbells in an oscillatory shear field based on a combination of small-angle neutron scattering experiments under shear (rheo-SANS) and Brownian dynamics computer simulations. Sterically stabilized dumbbell-shaped microgels are used as hard dumbbell model systems which consist of dumbbell-shaped polystyrene (PS) cores and thermosensitive poly(N-isopropylacrylamide) (PNIPAM) shells. Under increasing shear strain, a discontinuous transition is found from a twinned-fcc-like crystal to a partially oriented sliding-layer phase with a shear-molten state in between. In the novel partially oriented sliding-layer phase, the hard dumbbells exhibit a small but finite orientational order in the shear direction. We find that this weak correlation is sufficient to perturb the nature of the nonequilibrium phase transition as known for hard sphere systems. The discontinuous transition for hard dumbbells is observed to be accompanied by a novel yielding process with two yielding events in its viscoelastic shear response, while only a single yielding event is observed for sheared hard spheres. Our findings will be useful in interpreting the shear response of anisotropic colloidal systems and in generating novel colloidal crystals from anisotropic systems with applications in colloidal photonics.

Polyelectrolyte as solvent and reaction medium.

A poly(ionic liquid) with a rather low glass transition temperature of -57°C was synthesized via free radical polymerization of an acrylate-type ionic liquid monomer. It exhibits fluidic behavior in a wide temperature range from room temperature to the threshold of the thermal decomposition. We demonstrate that it could act as a unique type of macromolecular solvent to dissolve various compounds and polymers and separate substances. In addition, this polyelectrolyte could serve successfully as reaction medium for catalysis and colloid particle synthesis. The synergy in the solvation and stabilization properties is a striking character of this polymer to downsize the in situ generated particles.

Synthesis and characterization of monodisperse thermosensitive dumbbell-shaped microgels.

Monodisperse thermosensitive dumbbell-shaped core-shell microgels are fabricated, which consist of a polystyrene core with a cross-linked poly (N-isopropylacrylamide) shell. The morphology of the microgels was investigated through cryogenic transmission electron microscopy and depolarized dynamic light scattering. The effective volume fraction and aspect ratio of the system could be adjusted through the swelling of the thermosensitive shell. We observe a phase transition of the microgels to an ordered, crystal-like state, which is apparent through Bragg-reflections in the visible range. These observations are further supported by rheological measurements where the shear-melting of the crystal phase is clearly detected.