Amy Keirstead - 1-(3'-amino)propylsilatrane derivatives as covalent surface linkers to nanoparticulate metal oxide films for use in photoelectrochemical cells.

Version 1

      Publication Details (including relevant citation   information):

      Bradley Brennan,   Amy Keirstead,   Paul Liddell,   Sean Vail, Thomas Moore,   Ana Moore, Devens Gust

      Nanotechnology. 11/2009; 20(50):505203.




      A triethanolamine-protected silane, 1-(3'-amino)propylsilatrane,   was incorporated into the structure of porphyrin- and   ruthenium-based dyes and used to link them to transparent   semiconductor nanoparticulate metal oxide films. Silatrane reacts   with the metal oxide to form strong, covalent silyl ether bonds.   In this study, silatrane-functionalized dyes and analogous   carboxylate-functionalized dyes were used as visible light   sensitizers for porous nanoparticulate SnO(2) photoanodes. The   performance of the dyes was compared in photoelectrochemical   cells incorporating either non-regenerative or regenerative redox   components. The non-regenerative cell used NADH   (beta-nicotinamide adenine dinucleotide) as a sacrificial   electron donor and Hg(2)SO(4)/Hg as a sacrificial cathode,   whereas the regenerative cell used the iodide/triiodide redox   couple. Experiments showed that the silyl ether bonding gave the   electrodes increased stability toward sensitizer desorption   compared to carboxylate surface linkages. Porphyrin-silatrane   dyes also demonstrated similar or better performance than their   carboxylate analogs in photoelectrochemical cells. The   improvement correlates with the results from transient absorbance   spectroscopy, which show that the longer linker on the silatrane   porphyrins slows charge recombination between oxidized porphyrin   and the electrode surface. The improved photoelectrochemical cell   efficiency and stability of the silatrane-based dyes compared to   carboxylates demonstrate that silatranes are promising agents for   bonding organic molecules to metal oxide surfaces.

      Address (URL): http://