Hydrophobic vitamin B_(12). Part 18. Preparation of a sol-gel modified electrode trapped with a vitamin B_(12) derivative and its photoelectrochemical reactivity

摘要

A vitamin B_(12) derivative, heptapropyl cobyrinate perchlorate, was readily trapped onto an indium tin oxide (ITO) electrode by a sol-gel reaction. The complex was physically retained in a silica gel film which is formed on an ITO electrode. The thickness of the film could be controlled by the withdrawing speed of the dip coating process. Formation of a sol-gel film was confirmed by SEM measurements, and the total amount of the complex in the film was determined by UV-VIS absorption spectra. The complex exhibits the Co~(II)/Co~I redox couple at -0.42 V vs. Ag-AgCl.The amount of the electroactive complex in the sol-gel film deduced from electrochemical measurements is 3.0 X 10~(-11) and 6.2 X 10~(-11) mol cm~(-2) for thicknesses of 170 and 330 nm, respectively. This electroactive complex shows a high reactivity towards organic halides, and the controlled-potential electrolysis of benzyl bromide using the sol-gel modified electrode at -1.20 V vs. Ag-Ag in aqueous solution containing 0.1 M KCl afforded dehalogenated products, bibenzyl and toluene, with a total turnover number of > 1000 for 1 h.