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Hartmann, Pascal,Lee, Doh-Kwon,Smarsly, Bernd M.,Janek, Juergen American Chemical Society 2010 ACS NANO Vol.4 No.6
<P>This paper describes a systematic comparison of the photoelectrochemical properties of mesoporous TiO<SUB>2</SUB> films prepared by the two most prevalent templating methods: The use of preformed, crystalline nanoparticles is generally considered advantageous compared to the usage of molecular precursors such as TiCl<SUB>4</SUB>, since the latter requires a separate heat treatment at elevated temperature to induce crystallization. However, our photoelectrochemical experiments clearly show that sol−gel derived mesoporous TiO<SUB>2</SUB> films cause an about 10 times higher efficiency for the water splitting reaction than their counterparts obtained from crystalline TiO<SUB>2</SUB> nanoparticles. This result indicates that for electrochemical applications the performance of nanoparticle-based metal oxide films might suffer from insufficient electronic connectivity.</P><P><B>Graphic Abstract</B> <IMG SRC='http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/ancac3/2010/ancac3.2010.4.issue-6/nn1004765/production/images/medium/nn-2010-004765_0008.gif'></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/nn1004765'>ACS Electronic Supporting Info</A></P>
Lee, Doh-Kwon,Fischer, Claus C.,Valov, Ilia,Reinacher, Jochen,Stork, Alexandra,Lerch, Martin,Janek, Juergen The Royal Society of Chemistry 2011 Physical chemistry chemical physics Vol.13 No.3
<P>The mobility and electrochemical activity of nitrogen inside and/or at the surface of ionic compounds is of fundamental, as well as of possibly practical, relevance. In order to better understand the role of nitrogen anions in solid electrolytes, we measured the transference number of nitrogen in yttria-stabilized zirconia (YSZ) by a concentration cell technique as a function of oxygen activity at different temperatures in the range of 1023 ≤<I>T</I>/<I>K</I>≤ 1123. YSZ doped with 1.9 wt% of N (YSZ:N) turned out to have an appreciable nitrogen transference number, which increased from 0 to 0.1 with decreasing oxygen activity in the range of −20 < log<I>a</I><SUB>O<SUB>2</SUB></SUB> < −14. The stability of N in YSZ:N, however, has yet to be elucidated under oxidizing conditions.</P> <P>Graphic Abstract</P><P>Solid state electrochemistry with (di-)nitrogen? EMF measurements with a zirconium oxide nitride (N-doped YSZ) solid electrolyte under reducing conditions reveal a significant transference number of nitrogen anions. <IMG SRC='http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/image/GA?id=c003991h'> </P>