Li Xiuting, Lin Chuhong, Batchelor-McAuley Christopher, Laborda Eduardo, Shao Lidong, Compton Richard G
Department of Chemistry, Physical & Theoretical Chemistry Laboratory, Oxford University , Oxford OX1 3QZ, United Kingdom.
Departamento de Química Física, Facultad de Química, Universidad de Murcia , 30100 Murcia, Spain.
J Phys Chem Lett. 2016 Apr 21;7(8):1554-8. doi: 10.1021/acs.jpclett.6b00448. Epub 2016 Apr 12.
The reductive redox behavior of oxygen in aqueous acid solution leading first to adsorbed superoxide species at single palladium coated multiwalled carbon nanotubes (of length ca. 5 μm and width 130 nm) is reported. The small dimensions of the electroactive surface create conditions of high mass-transport permitting the resolution of electrode kinetic effects. In combination with new theoretical models, it is shown that the physical location of the formed product within the double layer of the electrode profoundly influences the observed electron transfer kinetics. This generically important result gives new physical insights into the modeling of the many electrochemical processes involving adsorbed intermediates.
据报道，在酸性水溶液中，氧气的还原氧化还原行为首先导致在单个钯包覆的多壁碳纳米管（长度约5μm，宽度130nm）上吸附超氧物种。电活性表面的小尺寸创造了高质量传输的条件，从而能够解析电极动力学效应。结合新的理论模型表明，所形成产物在电极双层中的物理位置对观察到的电子转移动力学有深远影响。这一具有普遍重要性的结果为涉及吸附中间体的许多电化学过程的建模提供了新的物理见解。
