ACS Appl Mater Interfaces. 2018 Apr 18;10(15):13211-13217. doi: 10.1021/acsami.8b01219. Epub 2018 Apr 6.
The immobilization of molecular species onto electrodes presents a direct route to modifying surface properties with molecular fidelity. Conventional methods include direct covalent attachment and physisorption of pyrene-appended molecular compounds to electrodes with aromatic character through π-π interactions. A recently reported hybrid approach extends the synthetic flexibility of the latter to a broader range of electrode materials. We report an application of this approach to immobilization of pyrene-appended ferrocene onto pyrene-functionalized indium tin oxide (ITO). The modified ITO surfaces were characterized using X-ray photoelectron spectroscopy, fluorescence spectroscopy, and electrochemical techniques. An electron-transfer rate constant ( k) of 100 ± 8 s was measured between the electrode and immobilized ferrocene using electrochemical methods. For comparison, a ferrocene-modified electrode using conventional covalent attachment of vinylferrocene was also prepared, and k was measured to be 9 ± 2 s.
将分子物种固定在电极上，为通过分子保真度来修饰表面性质提供了一条直接途径。常规方法包括通过π-π相互作用将带有芘基的分子化合物直接共价连接和物理吸附到具有芳香族特征的电极上。最近报道的一种混合方法将后者的合成灵活性扩展到更广泛的电极材料。我们报告了将芘基修饰的二茂铁固定在芘功能化的氧化铟锡（ITO）上的这种方法的应用。使用 X 射线光电子能谱、荧光光谱和电化学技术对修饰后的 ITO 表面进行了表征。通过电化学方法测量到电极和固定化二茂铁之间的电子转移速率常数（k）为 100 ± 8 s。为了进行比较，还使用常规的乙烯基二茂铁共价连接制备了一个二茂铁修饰的电极，并测量 k 值为 9 ± 2 s。
