The influence of external electrical fields on local concentration distributions and the mass transport of ionic background (buffer) species, as well as eluting co- and counterionic tracer molecules, was investigated in a fixed bed of native glass beads by confocal laser scanning microscopy and numerical simulations. Due to the negative surface charge of the porous glass beads and significant electrical double layer overlap, the intraparticle mesopore space becomes ion-permselective. This cation selectivity and the externally superimposed electrical fields induce concentration polarization in the bulk electrolyte solution adjacent to the particles. At the anodic hemisphere of a bead, the actual interplay of convection, diffusion, and electromigration leads to the formation of a convective-diffusion boundary layer with reduced ion concentrations relative to the bulk solution. At the opposite, cathodic hemisphere where counterions leave a bead in the direction of the applied field, electrolyte concentrations increase generating an enriched concentration polarization zone. Complementary data from quantitative confocal laser scanning microscopy and numerical simulations provide insight into the spatial variations of chemical and electrical potential gradients in the hierarchically structured material, including molar flux densities of the background ionic species, and reveal the elution dynamics of co- and counterionic analytes. These results demonstrate that concentration polarization in the external fluid domain, as well as the magnitude and sign of electrophoretic with respect to electroosmotic mobility in the ion-permselective domain, are major local contributions to coupled mass and charge transport, reflecting analyte retention, migration, and dispersion on a macroscopic scale.

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The dynamic operating behaviour of the direct methanol fuel cell (DMFC) is governed by several physico-chemical phenomena which occur simultaneously: double layer charging, electrode kinetics, mass transport inside the porous structures, reactant distributions in the anode and cathode flowbeds etc. Therefore it is essential to analyse the interactions of these phenomena in order to fully understand the DMFC. These phenomena were initially analysed independently by systematic experiments and model formulations. Electrode kinetics were determined by fitting models of varying complexity to electrochemical impedance spectroscopy (EIS) measurements. Reaction intermediates adsorbed on the catalyst seem to play a key role here. To describe mass transport across the DMFC a onedimensional model was formulated applying the generalised Maxwell-Stefan equations for multi-component mass transport and a Flory-Huggins model for the activities of mobile species inside the membrane (PEM). Also swelling of the PEM as well as heat production and transport were considered. Finally, the anode flowbed was analysed by observing flow patterns in different flowbed designs and measuring residence time distributions (RTDs). Detailed CFD models as well as simpler CSTR network representations were used to compare to the experimental results. Even the simpler models showed good agreement with the experiments. After these investigations the results were combined: the electrode kinetics model was implemented in the mass transport model as well as in the CSTR network flowbed model. In both cases, good agreement, even to dynamic experiments, was obtained. List of SymbolsMolar concentration d (m) Thickness i (mA cm )2 ) Current density n (mol m )2 s )1 ) Overall molar flux density r (mol m )3 s )1 ) Reaction rate t (s)

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