Department of Chemistry, The University of Alabama, Tuscaloosa, Alabama 35487-0336, United States.
Langmuir. 2012 Jul 17;28(28):10610-9. doi: 10.1021/la300858d. Epub 2012 Jul 3.
The present work reports the structural and electrochemical properties of carbon-modified nanostructured TiO(2) electrodes (C-TiO(2)) prepared by anodizing titanium in a fluoride-based electrolyte followed by thermal annealing in an atmosphere of methane and hydrogen in the presence of Fe precursors. The C-TiO(2) nanostructured electrodes are highly conductive and contain more than 1 × 10(10) /cm(2) of nanowires or nanotubes to enhance their double layer charge capacitance and electrochemical stability. Electrogenerated chemiluminescence (ECL) study shows that a C-TiO(2) electrode can replace noble metal electrodes for ultrasensitive ECL detection. Dynamic potential control experiments of redox reactions show that the C-TiO(2) electrode has a broad potential window for a redox reaction. Double layer charging capacitance of the C-TiO(2) electrode is found to be 3 orders of magnitude higher than an ideal planar electrode because of its high surface area and efficient charge collection capability from the nanowire structured surface. The effect of anodization voltage, surface treatment with Fe precursors for carbon modification, the barrier layer between the Ti substrate, and anodized layer on the double layer charging capacitance is studied. Ferrocene carboxylic acid binds covalently to the anodized Ti surface forming a self-assembled monolayer, serving as an ideal precursor layer to yield C-TiO(2) electrodes with better double layer charging performance than the other precursors.
本工作报道了通过在氟化物电解质中阳极氧化钛,然后在甲烷和氢气气氛中用铁前体制备的碳改性纳米结构 TiO(2)电极(C-TiO(2))的结构和电化学性能。C-TiO(2)纳米结构电极具有高导电性,并且含有超过 1×10(10)/cm(2)的纳米线或纳米管,以增强其双层充电电容和电化学稳定性。电致化学发光(ECL)研究表明,C-TiO(2)电极可以替代贵金属电极用于超灵敏 ECL 检测。氧化还原反应的动态电位控制实验表明,C-TiO(2)电极具有用于氧化还原反应的宽电位窗口。由于其高表面积和从纳米线结构表面有效收集电荷的能力,C-TiO(2)电极的双层充电电容比理想的平面电极高 3 个数量级。研究了阳极氧化电压、用于碳改性的铁前体表面处理、Ti 衬底和阳极氧化层之间的阻挡层对双层充电电容的影响。二茂铁羧酸通过共价键结合到阳极氧化的 Ti 表面,形成自组装单层,作为理想的前体层,可获得比其他前体更好的双层充电性能的 C-TiO(2)电极。