A note on versions:The version presented here may differ from the published version or from the version of record. If you wish to cite this item you are advised to consult the publisher's version. Please see the repository url above for details on accessing the published version and note that access may require a subscription. chlorometallate complexes we demonstrate the deposition of elemental Ga, In, Ge, Sn, Sb, Bi, Se, Te. In all cases, with the exception of Ga which is a liquid under the deposition conditions, the resulting deposits are characterised by scanning electron microscopy, energy dispersive X-ray analysis, X-ray diffraction and Raman. An advantage of this electrolyte system is that the reagents are all crystalline solids that are reasonably easy to handle and that are not highly water or oxygen sensitive. The results presented here significantly broaden the range of materials accessible by electrodeposition from supercritical fluid and open the future possibility to deposit binary or ternary alloys and compounds of the p-block.

Electrodeposition of Sn from supercritical difluoromethane has been performed into anodic alumina templates with pores down to 3 nm in diameter and into mesoporous silica templates with pores of diameter 1.5 nm. Optimized deposits have been characterized using X-ray diffraction, scanning electron microscopy, and scanning transmission electron microscopy (bright field, high-angle annular dark field, and energy-dispersive X-ray elemental mapping). Crystalline 13 nm diameter Sn nanowires have been electrodeposited in symmetric pore anodic alumina. Direct transmission electron microscopy evidence of sub 7 nm Sn nanowires in asymmetric anodic alumina has been obtained. These same measurements present indirect evidence for electrodeposition through 3 nm constrictions in the same templates. A detailed transmission electron microscopy study of mesoporous silica films after Sn deposition is presented. These indicate that it is possible to deposit Sn through the 1.5 nm pores in the mesoporous films, but that the nanowires formed are not stable. Suggestions of why this is the case and how such extreme nanowires could be stabilized are presented.

X-ray absorption spectroscopy reveals separately the structures of metal and oxide phases of iridium and ruthenium electrocatalysts containing both.

No abstract

In situ XAS measurements show that iridium oxide electrocatalysts manufactured by the polymeric precursor synthesis method contain a significant fraction of elemental iridium metal and that potential cycling only oxidises a thin layer of the elemental component of the composite.