Quentel Francois, Mirceski Valentin, L'Her Maurice
Laboratoire de Chimie Analytique, UMR-CNRS 6521, Université de Bretagne Occidentale, 6, avenue Victor Le Gorgeu, C.S. 93837, 29238 BREST Cedex, France.
J Phys Chem B. 2005 Jan 27;109(3):1262-7. doi: 10.1021/jp045914c.
The redox properties of lutetium bis(tetra-tert-butylphthalocyaninato) (LBPC) have been studied in nitrobenzene that is deposited as a microfilm on the surface of highly oriented pyrolytic graphite electrodes. The behavior of the modified electrode, which is immersed in an aqueous electrolyte solution, is typical for the three-phase electrode (Scholz, F.; Komorsky-Lovrić, S.; Lovrić, M. Electrochem. Comm. 2000, 2, 112-118). LBPC can be both oxidized and reduced in one electron reversible processes. The oxidation and the reduction of LBPC at the graphite/nitrobenzene interface is accompanied by the transfer of anion or cation, respectively, from the aqueous phase into the organic layer. Thus, using LBPC as a redox probe for the three-phase electrode, the transfer of both anions and cations across the water/nitrobenzene interface can be studied in a single experiment. The hydrophobicity of LBPC is so high that it enables inspection of cations and anions with Delta (nb)(w) (G)(theta)(Cat+) < or = 43 kJ/mol and Delta (nb)(w) (G)(theta)(X-) < or = 50 kJ/mol, respectively. The direct transfer of Na(+) and Li(+) from water to nitrobenzene, mutually saturated, is achieved for the first time at a macroscopic water/nitrobenzene interface.
已在以微膜形式沉积于高度取向热解石墨电极表面的硝基苯中研究了双（四叔丁基酞菁）镥（LBPC）的氧化还原性质。浸入水性电解质溶液中的修饰电极的行为对于三相电极而言是典型的（朔尔茨，F.；科莫尔斯基 - 洛弗里奇，S.；洛弗里奇，M.《电化学通讯》，2000年，2卷，112 - 118页）。LBPC可在单电子可逆过程中被氧化和还原。LBPC在石墨/硝基苯界面处的氧化和还原分别伴随着阴离子或阳离子从水相转移到有机层中。因此，使用LBPC作为三相电极的氧化还原探针，在单个实验中就可以研究阴离子和阳离子跨水/硝基苯界面的转移。LBPC的疏水性非常高，以至于它能够分别检测Δ(nb)(w)(G)(θ)(Cat+)≤43 kJ/mol和Δ(nb)(w)(G)(θ)(X-)≤50 kJ/mol的阳离子和阴离子。首次在宏观的水/硝基苯界面实现了Na(+)和Li(+)从水到相互饱和的硝基苯的直接转移。
