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中国腐蚀与防护学报  2017, Vol. 37 Issue (5): 395-401    DOI: 10.11902/1005.4537.2017.086
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扫描电化学显微镜的数值模拟和距离控制及其应用
曹发和(),柳晓燕,朱泽洁,叶珍妮,刘盼,张鉴清
浙江大学化学系 杭州 310027
Mumeric Simulation and Gap Control of Scanning Electrochemical Microscopy and Its Application
Fahe CAO(),Xiaoyan LIU,Zejie ZHU,Zhenni YE,Pan LIU,Jianqing ZHANG
Department of Chemistry, Zhejiang University, Hangzhou 310027, China
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摘要: 

应用反馈模式,结合COMSOL数值模拟,分别考察了步进马达移动距离速率对真实距离、铝合金表面氧化膜状态对逼近曲线以及距离测试误差对典型电化学-化学耦合反应 (EC) 动力学测试结果的影响。结果表明,正负反馈效应与探针距基底电极距离有关,距离越小,反馈效应越强,同时也与基底电极再生动力学有关。步进马达控制的探针逼近和离开基底电极移动距离与探针真实移动距离的比例分别是0.843和0.568。铝合金表面氧化膜的状态影响逼近曲线从部分正反馈至完全负反馈的变化过程,而步进马达移动引入的距离误差导致EC反应中一级化学均相反应的动力学速率常数误差高达60%。精确距离控制是扫描电化学实验的最基本要求。

关键词 扫描电化学显微镜距离控制反馈模式逼近曲线COMSOL模拟EC反应动力学    
Abstract

Since the gap between the probe electrode and the substrate electrode of scanning electrochemical microscopy (SECM) is not easy to control and clear, based on the feedback model and the COMSOL numeric simulation, the effect of the moving distance of the step motor on the real distance is investigated. The effects of the oxidation film of aluminum alloy on the approaching curve and the test error of the distance on the kinetic parameters of electrochemical-chemical reaction are also investigated. The results show that the positive and negative feedback effect is related to the gap between the probe and the substrate electrode. The smaller the gap, the stronger the feedback effect, while the feedback effect is also impacted by the regeneration kinetics on the substrate electrode. The ratio of the step motor-controlled distance to the approaching and withdrawing distance from the substrate electrode to the actual moving distance of the tip is 0.843 and 0.568, respectively, which indicates when the stepper motor movement is labeled 1 μm, the actually distances are only 0.843 and 0.568 μm. The state of the oxide film on the surface of aluminum alloy affects the approaching curve from partial positive feedback to pure negative feedback, and the distance error of stepper motor movement leads to the error of chemical homogeneous reaction rate constant in EC reaction as high as 60%. Precise gap control is the fundamental for scanning electrochemical microscopy experiments.

Key wordsscanning electrochemistry microscopy    gap control    feedback mode    approach curve    COMSOL simulation    EC reaction kinetic
收稿日期: 2017-06-02     
基金资助:国家重点研发计划 (2017YFB0702302),国家自然科学基金 (51771174),浙江省自然科学基金杰出青年项目(LR16E010001) 和中央高校基本研究经费 (2017QNA3011)
作者简介: 曹发和,男,1979年生,博士

引用本文:

曹发和, 柳晓燕, 朱泽洁, 叶珍妮, 刘盼, 张鉴清. 扫描电化学显微镜的数值模拟和距离控制及其应用[J]. 中国腐蚀与防护学报, 2017, 37(5): 395-401.
Fahe CAO, Xiaoyan LIU, Zejie ZHU, Zhenni YE, Pan LIU, Jianqing ZHANG. Mumeric Simulation and Gap Control of Scanning Electrochemical Microscopy and Its Application. Journal of Chinese Society for Corrosion and protection, 2017, 37(5): 395-401.

链接本文:

https://www.jcscp.org/CN/10.11902/1005.4537.2017.086      或      https://www.jcscp.org/CN/Y2017/V37/I5/395

图1  SECM反馈模式和对应的COMSOL几何模型示意图
No z coordinate r coordinate Boundary condition
1 50 μm+d 0≤ra CO=0, DR?CR?z=-DO?CO?z
2 50 μm+d arrT1 DR?CR?z=-DO?CO?z=0
3 150-drT2-rT1×r+50+d×rT2-200×rT1rT2-rT1 rT1rrT2 DR?CR?z=-DO?CO?z=0
4 200 μm rT2r ≤200 μm CO=0, CR=CR*
5 50 μm 0≤ra' CO=0, DR?CR?z=-DO?CO?z=0
6 50 μm a'≤rrS1 DR?CR?z=-DO?CO?z=0
7 -50rS2-rS1×r+50×rS2rS2-rS1 rS1rrS2 DR?CR?z=-DO?CO?z=0
8 0 μm rS2r ≤200 μm CO=0, CR=CR*
9 0≤z ≤200 μm r =200 μm CO=0, CR=CR*
10 50 μm≤z ≤50 μm+d r =0 DR?CR?z=-DO?CO?z=0
表1  SECM模拟的边界条件
图2  半径为5 μm的探针在2 mm的Pt和玻璃基底上的逼近曲线,其中拟合曲线是基于COMSOL二维轴对称模型模拟获得
图3  半径为5 μm的探针在具有不同再生速率常数基底上的逼近曲线模拟结果
图4  典型的步进马达逼近和抬起距离与通过CV稳态电流获得的真实移动距离的校正曲线 (探针移动速率恒定为60 nm/s)
图5  Pt基底、ZL104铝合金新鲜表面和具有自然氧化膜表面的逼近曲线,其中探针为10 μm Pt (RG≈5),溶液为0.001 mol/L FcMeOH+0.1 mol/L NaCl
图6  EC反应模型下的探针和基底电流和对应的收集效率曲线
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