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Journal of Chinese Society for Corrosion and protection  2017, Vol. 37 Issue (5): 395-401    DOI: 10.11902/1005.4537.2017.086
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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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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 words:  scanning electrochemistry microscopy      gap control      feedback mode      approach curve      COMSOL simulation      EC reaction kinetic     
Received:  02 June 2017     
Fund: Supported by National Key Research and Development Program (2017YFB0702302), National Natural Science Foundation of China (51771174), Zhejiang Province Natural Science Foundation of China (LR16E 010001) and Fundamental Research Funds for the Central Universities (2017QNA3011)

Cite this article: 

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.

URL: 

https://www.jcscp.org/EN/10.11902/1005.4537.2017.086     OR     https://www.jcscp.org/EN/Y2017/V37/I5/395

Fig.1  Schematic description of feedback mode of SECM (a) and corresponding COMSOL geometry model (b) (In which, d is the gap, a is radius of tip and substrate, and other parametersare described in Table 1 in detail)
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
Table 1  Boundary conditions in the SECM simulation
Fig.2  Approach curves of 5 μm tip on 2 mm Pt and glass substrate respectively (The fitting curves are simulation results based on 2D axisymmetric model of COMSOL)
Fig.3  Simulation results of approach curves of 5 μm tip on the substrates with different regeneration rate constants based on 2D axisymmetric model of COMSOL
Fig.4  Calibration curves of typical approach and withdraw distances by stepper motor with real distance calculated by steady current of CV under two conditions of approaching to substrate (a) and withdrawing far away the substrate (b) (The moving speed of the tip is constant at 60 nm/s)
Fig.5  Approaching curves of 10 μm Pt tip (RG≈5) on Pt substrate, ZL104 aluminum alloy with fresh surface and native oxide film in 0.001 mol/L FcMeOH+ 0.1 mol/L NaCl aqueous solution
Fig.6  Collected currents of the tip and substrate for a EC reaction model (a), and corresponding collection efficiency and corrected distance (b)
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