Film Permeation by Rotating Disk Voltammetry at Electrodes Modified with Electrochemically Inert Layers and Heterogeneous Composites
Film Permeation by Rotating Disk Voltammetry at Electrodes Modified with Electrochemically Inert Layers and Heterogeneous Composites
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通过转盘伏安法在电化学惰性层和异质复合材料修饰的电极上进行薄膜渗透
DOI：
10.1149/2.0241604jes
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发表时间：
2016
影响因子：
3.9
通讯作者：
Leddy, Johna
中科院分区：
文献类型：
--
作者：
Knoche, Krysti L.;Hettige, Chaminda;Zook-Gerdau, Lois Anne;Leddy, Johna
稳态转盘伏安法可对电极上的薄膜和层的渗透性进行出色的测量，因为转盘的流体动力学控制建立了垂直于电极的明确边界层。对于存在于溶液中并在层中预平衡的氧化还原探针，伏安法测量当探针从溶液传输、穿过薄膜并到达探针被电解的电极时探针的电解电流。诊断方程将稳态质量传输限制电流 i ss 与旋转速率 ω 联系起来。不可压缩层对于探针形式电势呈电惰性。诊断可用于单层、均匀的薄膜（Gough 和 Leypoldt）。均匀薄膜是均匀的，没有结构特征。这里提供了双层和多层均匀薄膜的诊断，其中多层包括离散和连续分级的薄膜。考虑垂直于电极的串行传质电阻可以对均匀的薄膜进行诊断。异质、微米和纳米结构层在电极平面上形成结构。将平行传质阻力视为层传质阻力的一部分可以对异质膜进行诊断。诊断结果经过文献数据的审查。指出了理论和实践的优点和局限性。
Steady state rotating disk voltammetry provides excellent measurement of permeability for films and layers on electrodes because the hydrodynamic control of rotating disks establishes well defined boundary layers normal to the electrode. For a redox probe present in solution and pre-equilibrated in the layer, voltammetry measures electrolysis current for the probe as the probe transports from solution, through the film, and to the electrode where the probe is electrolyzed. Diagnostic equations relate the steady state, mass transport limited current i ss to the rotation rate ω. The incompressible layer is electroinactive about the probe formal potential. Diagnostics are available for a single layer, uniform film (Gough and Leypoldt). Uniform films are homogeneous with no structural features. Here diagnostics are provided for bilayer and multilayer uniform films, where multilayers include discretely and continuously graded films. Consideration of serial mass transport resistances normal to the electrode allows diagnostics for uniform films. Heterogeneous, micro-and nano-structured layers are structured in the plane of the electrode. Consideration of parallel mass transport resistances as part of the layer mass transport resistance yields diagnostics for heterogeneous films. Diagnostics are vetted with literature data. Theoretical and practical advantages and limitations are noted.
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