Alberto Pimpinelli

Molecular transport through nanofluidic structures exhibits properties that are unique at the nanoscale. The high surface-to-volume ratio of nanometer-sized confined spaces renders particle interactions with the surface of central importance. The electrical double layer (EDL) at the solid-liquid interface of charged surfaces, generates an enrichment of counterions and the exclusion of co-ions that lead to a change in their diffusivity. In addition, the diffusive transport is altered by steric and hydrodynamic interactions between fluid molecules and the boundaries. An extensive body of literature investigates molecular transport at the nanoscale. However, most studies account for ionic species as point charges, severely limiting the applicability of results to ‘large’ nanofluidic systems. Moreover, and even more importantly, the change of pH in the nanoconfined region inside nanochannels has been completely overlooked. Corroborated by experimental data, here we present an all-encompassing analysis of molecular diffusion from the micro- to the ultra-nanoscale. While accounting for finite-size ions, we compute self-consistently the pH inside the channels. Surprisingly, we found that the concentration of ions + can change by more than 2 orders of magnitude compared to the bulk, hugely affecting molecular transport. Further, we found that counterions exhibit both enrichment and exclusion, depending on the size of nanochannels. Achieving a greater understanding of the effective transport properties of fluids at the nanoscale will fill the gap in knowledge that still limits the development of innovative systems for medicine and industrial applications alike.

Gas transport across nanoscale pores is determinant in molecular exchange in living organisms as well as in a broad spectrum of technologies. Here, we report an unprecedented theoretical and experimental analysis of gas transport in a consistent set of confining nanochannels ranging in size from the ultra-nanoscale to the sub-microscale. A generally applicable theoretical approach quantitatively predicting confined gas flow in the Knudsen and transition regime was developed. Unlike current theories, specifically designed for very simple channel geometries, our approach can be applied to virtually all geometries, for which the probability distribution of path lengths for particle–interface collisions can be computed, either analytically or by numerical simulations. To generate a much needed benchmark experimental model, we manufactured extremely reproducible membranes with two-dimensional nanochannels. Channel sizes ranged from 2.5 to 250 nm, and angstrom level of size control and interface tolerances were achieved using leading-edge nanofabrication techniques. We then measured gas flow in the Knudsen number range from 0.2 to 20. Excellent agreement between theoretical predictions and experimental data was found, demonstrating the validity and potential of our approach.

Ionic transport through nanofluidic systems is a problem of fundamental interest in transport physics and has broad relevance in desalination, fuel cells, batteries, filtration, and drug delivery. When the dimension of the fluidic system approaches the size of molecules in solution, fluid properties are not homogeneous and a departure in behavior is observed with respect to continuum-based theories. Here we present a systematic study of the transport of charged and neutral small molecules in an ideal nanofluidic platform with precise channels from the sub-microscale to the ultra-nanoscale (<5 nm). Surprisingly, we find that diffusive transport of nano-confined neutral molecules matches that of charged molecules, as though the former carry an effective charge. Further, approaching the ultra-nanoscale molecular diffusivities suddenly drop by up to an order of magnitude for all molecules, irrespective of their electric charge. New theoretical investigations will be required to shed light onto these intriguing results.

In studies of epitaxial growth, analysis of the distribution of the areas of capture zones (i.e. proximity polygons or Voronoi tessellations with respect to island centers) is often the best way to extract the critical nucleus size i. For non-random nucleation the normalized areas s of these Voronoi cells are well described by the generalized Wigner distribution (GWD) Pβ(s) = as^β exp(-bs²), particularly in the central region 0.5 < s < 2 where data are least noisy. Extensive Monte Carlo simulations reveal inadequacies of our earlier mean field analysis, suggesting β = i + 2 for diffusion-limited aggregation (DLA). Since simulations generate orders of magnitude more data than experiments, they permit close examination of the tails of the distribution, which differ from the simple GWD form. One refinement is based on a fragmentation model. We also compare island-size distributions. We compare analysis by island-size distribution and by scaling of island density with flux. Modifications appear for attach-limited aggregation (ALA). We focus on the experimental system para-hexaphenyl on amorphous mica, comparing the results of the three analysis techniques and reconciling their results via a novel model of hot precursors based on rate equations, pointing out the existence of intermediate scaling regimes between DLA and ALA.

Aqueous solutions containing light-absorbing nanoparticles have recently been shown to produce steam at high efficiencies upon solar illumination, even when the temperature of the bulk fluid volume remains far below its boiling point. Here we show that this phenomenon is due to a collective effect mediated by multiple light scattering from the dispersed nanoparticles. Randomly positioned nanoparticles that both scatter and absorb light are able to concentrate light energy into mesoscale volumes near the illuminated surface of the liquid. The resulting light absorption creates intense localized heating and efficient vaporization of the surrounding liquid. Light trapping-induced localized heating provides the mechanism for low-temperature light-induced steam generation and is consistent with classical heat transfer.