Structural characterisation of proton-exchanged zeolites, prepared using ion-transfer at the liquid–liquid interface, is reported. Specifically, electrochemical exchange of protons for sodium with zeolites X and A is described: the structural integrity of the resultant materials was probed by solid-state NMR spectroscopy and temperature-dependent powder X-ray diffraction. It is shown that replacement of ca. 40 % of the Na + can be achieved using this approach for both zeolites; however, the results indicate that exchange is accompanied by significant structural degradation in the case of zeolite A, with proton exchange occurring at the amorphous regions of the sample. In contrast, zeolite X retains its structure, and the level of proton exchange is comparable with the highest levels reported using conventional chemical methods, highlighting the utility of the electrochemical approach.

The voltammetric response of a bipolar cell is described where the cell is applied to electroless deposition processes. The method is illustrated with copper deposition on gold surfaces, driven by the oxidation of dimethylamine borane.

The modification of the liquid/liquid interface with membranes of silicalite, a neutral framework zeolite, is used to extend the potential window. This feature allows the observation of the transfer of extremely hydrophilic ions, due to the size-exclusion of organic ions from the interior of the zeolitic framework. Similarly, volume exclusion effects are shown to affect facilitated ion transfer processes involving alkali metal cations. In contrast, proton transfer is largely unaffected by the presence of the zeolite, which is suggestive of more rapid diffusion processes within the interior of the framework. The technique of liquid/liquid electrochemistry should allow the measurement of solution phase transport parameters for ions within microporous hosts.

The modification of the water/organic interface with size-selective membranes is presented as a means to elucidate the mechanism of facilitated ion transfer processes. In particular, an interfacial or organic phase complexation reaction is observed for the transfer of Cu2+ ions facilitated by dibenzo-18-crown-6, whereas the complexation process for the 1,4,7,10-tetrathiacyclododecane facilitated transfer of the same ion is suggested to occur within the aqueous phase. The contrasting transfer mechanism is discussed in terms of the solution phase behaviour of the thio-ether ligand.

The adsorption, desorption, and stability of the powerful chiral modifier precursors R- and S- naphthylethylamine (NEA) on the {111}, {211}, {331}, {643}(R), and "polycrystalline" platinum surfaces have been examined by cyclic voltammetry. NEA is effectively irreversibly adsorbed at room temperature to a saturation coverage that corresponds to occupancy of similar to80% of the available metal area and there is no detectable transport of adsorbate between the various adsorption sites present. Most importantly, the molecule adsorbs indiscrimminately and with essentially equal rates at terrace and step sites, and in the case of the chiral {643}(R) surface, the adsorption behavior of the enantiomers R- and S-NEA is the same. Specifically, the intrinsically chiral kink, sites neither fa or nor disfavor the adsorption of either enantiomer. In every case, desorption of NEA occurs under electro-reducing conditions with {100} facets showing an enhanced desorption rate on die {643}(R), {211}, and polycrystalline surfaces. The implications of these findings for our understanding of heterogeneous enantioselective hydrogenation at platinum surfaces are discussed.