Universidad de Santiago de Chile (USACH), Faculty of Chemistry and Biology, Department of Chemistry of the Materials, Soft Matter Research and Technology Center, SMAT-C. Av. Libertador B. O'Higgins 3363, Box 40, Correo 33, Santiago 9170022, Chile.
Instituto de Química, Pontificia Universidad Católica de Valparaíso, Valparaíso 2374631, Chile.
Molecules. 2021 Mar 15;26(6):1631. doi: 10.3390/molecules26061631.
Current selective modification methods, coupled with functionalization through organic or inorganic molecules, are crucial for designing and constructing custom-made molecular materials that act as electroactive interfaces. A versatile method for derivatizing surfaces is through an aryl diazonium salt reduction reaction (DSRR). A prominent feature of this strategy is that it can be carried out on various materials. Using the DSRR, we modified gold surface electrodes with 4-aminebenzene from 4-nitrobenzenediazonium tetrafluoroborate (NBTF), regulating the deposited mass of the aryl film to achieve covering control on the electrode surface. We got different degrees of covering: monolayer, intermediate, and multilayer. Afterwards, the ArNO end groups were electrochemically reduced to ArNH and functionalized with Fe(II)-Phthalocyanine to study the catalytic performance for the oxygen reduction reaction (ORR). The thickness of the electrode covering determines its response in front of ORR. Interestingly, the experimental results showed that an intermediate covering film presents a better electrocatalytic response for ORR, driving the reaction by a four-electron pathway.
当前的选择性修饰方法，加上通过有机或无机分子的功能化，对于设计和构建作为电活性界面的定制分子材料至关重要。一种用于衍生表面的通用方法是通过芳基重氮盐还原反应（DSRR）。该策略的一个突出特点是它可以在各种材料上进行。我们使用 DSRR 将 4-硝基苯重氮四氟硼酸盐（NBTF）中的 4-胺苯修饰到金表面电极上，调节芳基膜的沉积质量以实现对电极表面的覆盖控制。我们得到了不同程度的覆盖：单层、中间层和多层。然后，ArNO 端基被电化学还原为 ArNH，并与 Fe(II)-酞菁功能化，以研究其对氧还原反应（ORR）的催化性能。电极覆盖的厚度决定了它在 ORR 面前的响应。有趣的是，实验结果表明，中间覆盖膜对 ORR 呈现出更好的电催化响应，通过四电子途径驱动反应。
