铂电极上自组装铁原卟啉单分子层的表面增强振动光谱初探(英文)

应用现场表面增强拉曼光谱和衰减全反射表面增强红外光谱初步研究了0.1mol·L-1HClO4溶液中Pt电极表面铁原卟啉(FePP)自组装单层的电化学和结构特性.以514nm波长为激发线,得到了增强因子约为40的粗糙Pt电极上FePP在不同电位下的表面增强拉曼光谱.分析0.5～-0.3V(SCE)区间内谱峰变化,得到近似的吸附等温式,由此可估算出Fe3+/Fe2+的式量电位大约为-0.2V.原位表面增强红外光谱的测试结果表明,FePP分子主要以斜立方式吸附在Pt膜电极表面,其中一个环外羧酸根与电极表面相接触,而另一羧酸基团以氢键与相邻的FePP分子相连.这样的吸附结构在-0.1～0.9V(SCE)的电位区间内并没有显著的变化.

Preliminary Investigation of Iron Protoporphyrin SAMs on Platinum Electrodes by Surface Enhanced Vibrational Spectroscopies

In situ SERS and ATR-SEIRAS were applied to investigate the electrochemical and structural properties of iron protoporphyrin IX (FePP) self-assembled monolayers (SAMs) on Pt electrodes in 0. 1 mol· L -1 HClO4. The potential dependent SERS spectra of the FePP SAM on a roughened Pt electrode with the enhancement factor of ca. 40 were acquired with the excitation line of 514 nm. Analyses of SERS data over the potential region from 0. 5 to -0. 3 V enabled to obtain potential dependent adsorption isotherms,from which the formal redox potential could be estimated to be ca. - 0. 2 V. Up-tilted orientation of FePP SAM on Pt film electrode involving one peripheral propionate group attached to the surface and one propionic acid group hydrogenbonded with adjacent FePP,was deduced based on in situ ATR-SEIRAS results,without significant structural change over the potential region from -0. 1 to 0. 9 V.