A. Klaassen

Sorption‐Determined Deposition of Platinum on Well‐Defined Platelike WO3

The photodeposition of Pt nanoparticles from [PtCl6 ](2-) on platelike WO3 crystals occurs preferentially on the small, subordinate facets. Rather than the often-used explanation of preferred light-induced charge migration, we propose that this phenomenon is due to differences in the intrinsic surface charges of WO3 facets exposed to water; thus, the dark sorption of [PtCl6 ](2-) on positively charged facets/edges is preferred. This conclusion is based on 1)u2005(dark) impregnation studies, which showed Pt deposition to also be facet-specific, and 2)u2005aqueous-phase AFM studies, which suggest intrinsic surface charges to be in agreement with sorption-based Pt distributions.

Electroviscous Dissipation in Aqueous Electrolyte Films with Overlapping Electric Double Layers

We use dynamic atomic force microscopy (AFM) to investigate the forces involved in squeezing out thin films of aqueous electrolyte between an AFM tip and silica substrates at variable pH and salt concentration. From amplitude and phase of the AFM signal we determine both conservative and dissipative components of the tip sample interaction forces. The measured dissipation is enhanced by up to a factor of 5 at tip–sample separations of ≈ one Debye length compared to the expectations based on classical hydrodynamic Reynolds damping with bulk viscosity. Calculating the surface charge density from the conservative forces using Derjaguin–Landau–Verwey–Overbeek (DLVO) theory in combination with a charge regulation boundary condition we find that the viscosity enhancement correlates with increasing surface charge density. We compare the observed viscosity enhancement with two competing continuum theory models: (i) electroviscous dissipation due to the electrophoretic flow driven by the streaming current that is generated upon squeezing out the counterions in the diffuse part of the electric double layer, and (ii) visco-electric enhancement of the local water viscosity caused by the strong electric fields within the electric double layer. While the visco-electric model correctly captures the qualitative trends observed in the experiments, a quantitative description of the data presumably requires more sophisticated simulations that include microscopic aspects of the distribution and mobility of ions in the Stern layer.