Priority Organization for Innovation and Excellence, Kumamoto University, Chuo-ku, Kumamoto, Japan.
Phys Chem Chem Phys. 2013 Aug 14;15(30):12504-9. doi: 10.1039/c3cp50797a.
The stability and phase transitions of adlayers of two cobalt(II) porphyrins, 5,10,15,20-tetraphenyl-21H,23H-porphine cobalt(II) (CoTPP) and 2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphine cobalt(II) (CoOEP), formed on Au(100) were investigated under electrochemical conditions. In situ scanning tunneling microscopy (STM) was employed to investigate the structure of CoTPP and CoOEP adlayers in 0.1 M HClO4. The CoTPP and CoOEP adlayer structures were varied with the modification time and the concentration. The in situ STM observations showed that the underlying reconstructed atomic structure was lifted to a (1 × 1) atomic arrangement by either the adsorption of CoTPP/CoOEP during modification in a benzene solution or positive potential manipulation in 0.1 M HClO4. Ordered CoTPP arrays with two different hexagonal and square packing arrangements were found on an Au(100)-(1 × 1) surface, along with characteristic Au islands. The CoOEP molecules also formed a close-packed hexagonal structure on an Au(100)-(hex) surface; CoOEP molecules were arranged in a semi-square structure on the Au(100)-(1 × 1) surface by the lifting of reconstruction. The results of this study showed that the interaction between the cobalt porphyrins and the Au(100) substrate depended on the modification conditions and the electrochemical potential.
两种钴(II)卟啉，5,10,15,20-四苯基-21H,23H-卟啉钴(II)（CoTPP）和 2,3,7,8,12,13,17,18-辛基-21H,23H-卟啉钴(II)（CoOEP）在 Au(100)上形成的吸附层的稳定性和相转变在电化学条件下进行了研究。原位扫描隧道显微镜（STM）用于研究 0.1 M HClO4 中 CoTPP 和 CoOEP 吸附层的结构。CoTPP 和 CoOEP 吸附层结构随修饰时间和浓度而变化。原位 STM 观察表明，在苯溶液中修饰期间或在 0.1 M HClO4 中施加正电势时，基底的重构原子结构被吸附的 CoTPP/CoOEP 提升到（1 × 1）原子排列。在 Au(100)-(1 × 1)表面上发现了具有两种不同的六边形和正方形堆积排列的有序 CoTPP 阵列，以及特征性的 Au 岛。CoOEP 分子也在 Au(100)-(hex)表面上形成了紧密堆积的六边形结构；CoOEP 分子通过重构的提升在 Au(100)-(1 × 1)表面上排列成半正方形结构。这项研究的结果表明，钴卟啉与 Au(100)基底之间的相互作用取决于修饰条件和电化学势。
