Department of Chemistry, Emory University, Atlanta, Georgia 30322, USA.
J Am Chem Soc. 2011 May 11;133(18):6922-5. doi: 10.1021/ja2013664. Epub 2011 Apr 19.
We have characterized the covalent binding of the CO(2) reduction electrocatalyst ReC0A (Re(CO)(3)Cl(dcbpy) (dcbpy =4,4'-dicarboxy-2,2'-bipyridine)) to the TiO(2) rutile (001) surface. The analysis based on sum frequency generation (SFG) spectroscopy and density functional theory (DFT) calculations indicates that ReC0A binds to TiO(2) through the carboxylate groups in bidentate or tridentate linkage motifs. The adsorbed complex has the dcbpy moiety nearly perpendicular to the TiO(2) surface and the Re exposed to the solution in a configuration suitable for catalysis.
我们已经对 CO(2)还原电催化剂 ReC0A（Re(CO)(3)Cl(dcbpy)（dcbpy=4,4'-二羧酸-2,2'-联吡啶））与 TiO(2)金红石（001）表面的共价结合进行了表征。基于和频发生（SFG）光谱和密度泛函理论（DFT）计算的分析表明，ReC0A 通过二齿或三齿配位模式的羧酸盐基团与 TiO(2)结合。吸附的配合物具有 dcbpy 部分几乎垂直于 TiO(2)表面，Re 暴露在溶液中的构型适合催化。
