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Ramasamy, Easwaramoorthi,Jo, Changshin,Anthonysamy, Arockiam,Jeong, Inyoung,Kim, Jin Kon,Lee, Jinwoo American Chemical Society 2012 Chemistry of materials Vol.24 No.9
<P>Ordered mesoporous titanium nitride-carbon (denoted as OM TiN-C) nanocomposite with high surface area (389 m<SUP>2</SUP> g<SUP>–1</SUP>) and uniform hexagonal mesopores (ca. 5.5 nm) was facilely synthesized via the soft-template method. As a structure-directing agent, Pluronic F127 triblock copolymer formed an ordered structure with inorganic precursors, resol polymer, and prehydrolyzed TiCl<SUB>4</SUB>, followed by a successive heating at 700 °C under nitrogen and ammonia flow. In this study, the amorphous carbon within the parent OM TiO<SUB>2</SUB>-C acted as a rigid support, preventing structural collapse during the conversion process of TiO<SUB>2</SUB> nanocrystals to TiN nanocrystals. The OM TiN-C was then successfully applied as counter electrode material in dye-sensitized solar cells (DSCs). The organic electrolyte disulfide/thiolate (T<SUB>2</SUB>/T<SUP>–</SUP>) was introduced to study the electrocatalytic property of the OM TiN-C nanocomposite. Because of the existence of TiN nanocrystals and the defect sites of the amorphous carbon, the DSCs using OM TiN-C as a counter electrode showed 6.71% energy conversion efficiency (platinum counter electrode DSCs: 3.32%) in the organic electrolyte system (T<SUB>2</SUB>/T<SUP>–</SUP>). Furthermore, the OM TiN-C counter electrode based DSCs showed an energy conversion efficiency of 8.41%, whereas the DSCs using platinum as a counter electrode showed a conversion efficiency of only 8.0% in an iodide electrolyte system. The superior performance of OM TiN-C counter electrode resulted from the low charge transfer resistance, enhanced electrical conductivity, and abundance of active sites of the OM TiN-C nanocomposite. Moreover, OM TiN-C counter electrode showed better chemical stability in organic electrolyte compared with the platinum counter electrode.</P><P>Ordered mesoporous titanium nitride-carbon (OM TiN-C) nanocomposites were synthesized, for the first time, using a simple soft-template method. The iodine-free organic electrolyte dye-sensitized solar cells using OM TiN-C nanocomposite counter electrodes exhibited high efficiency (6.71%), that is, a performance 2-fold greater than that of conventional Pt counter electrode DSCs (fill factor: 0.33, efficiency: 3.32%).</P><P><B>Graphic Abstract</B> <IMG SRC='http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/cmatex/2012/cmatex.2012.24.issue-9/cm203672g/production/images/medium/cm-2011-03672g_0012.gif'></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/cm203672g'>ACS Electronic Supporting Info</A></P>
Moon, Hong Chul,Anthonysamy, Arockiam,Kim, Jin Kon American Chemical Society 2011 Macromolecules Vol.44 No.7
<P>We have demonstrated a facile synthetic route for well-defined poly(3-hexylthiophene)-<I>block</I>-poly(methyl methacrylate) copolymer (P3HT-<I>b</I>-PMMA) by anionic coupling reaction. For successful coupling reaction, newly generated anions should be more stable (less reactive) than initial anions of reactants. In this study, we chose α-phenyl acrylate (PA)-capped P3HTs for successful coupling with living PMMA anions because the anions at PA group are more stable than living PMMA anions. We found that all of the PA groups located at the end of P3HT were completely coupled with living PMMA anions having slightly excess amount (1.5 equiv relative to PA-capped P3HT). The unreactive PMMA homopolymers in crude product were completely removed by using column chromatography, resulting in narrow molecular weight distribution of pure P3HT-<I>b</I>-PMMA. The optical property and thin film morphology of the P3HT-<I>b</I>-PMMA were investigated by using UV−vis spectra and atomic force microscopy, respectively.</P><P><B>Graphic Abstract</B> <IMG SRC='http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/mamobx/2011/mamobx.2011.44.issue-7/ma200171m/production/images/medium/ma-2011-00171m_0004.gif'></P>
Jeong, Inyoung,Jo, Changshin,Anthonysamy, Arockiam,Kim, Jung-Min,Kang, Eunae,Hwang, Jongkook,Ramasamy, Easwaramoorthi,Rhee, Shi-Woo,Kim, Jin Kon,Ha, Kyoung-Su,Jun, Ki-Won,Lee, Jinwoo Wiley-VCH 2013 ChemSusChem Vol.6 No.2
<P>A disulfide/thiolate (T(2)/T(-)) redox-couple electrolyte, which is a promising iodine-free electrolyte owing to its transparent and noncorrosive properties, requires alternative counter-electrode materials because conventional Pt shows poor catalytic activity in such an electrolyte. Herein, ordered mesoporous tungsten suboxide (m-WO(3-x)), synthesized by using KIT-6 silica as a hard template followed by a partial reduction, is used as a catalyst for a counter electrode in T(2)/T(-)-electrolyte-based dye-sensitized solar cells (DSCs). The mesoporous tungsten suboxide, which possesses interconnected pores of 4 and 20 nm, provides a large surface area and efficient electrolyte penetration into the m-WO(3-x) pores. In addition to the advantages conferred by the mesoporous structure, partial reduction of tungsten oxide creates oxygen vacancies that can function as active catalytic sites, which causes a high electrical conductivity because of intervalence charge transfer between the W(5+) and W(6+) ions. m-WO(3-x) shows a superior photovoltaic performance (79 % improvement in the power conversion efficiency) over Pt in the T(2)/T(-) electrolyte. The superior catalytic activity of m-WO(3-x) is investigated by using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and Tafel polarization curve analysis.</P>