Pt/IrO x -pH超微电化学传感器性能探究及其在铜/不锈钢电偶腐蚀研究中的应用

doi:10.11902/1005.4537.2023.107

中国腐蚀与防护学报

2023, Vol. 43

Issue (6): 1264-1272 CSTR: 32134.14.1005.4537.2023.107 DOI: 10.11902/1005.4537.2023.107

研究报告

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Pt/IrO _x -pH超微电化学传感器性能探究及其在铜/不锈钢电偶腐蚀研究中的应用

张勤号¹, 朱泽洁², 蔡浩冉¹, 李鑫冉¹, 孟宪泽¹, 李昊¹, 伍廉奎¹, 罗荘竹¹, 曹发和¹(

)

^1.中山大学材料学院深圳 518107
^2.中国计量大学材料与化学学院杭州 310018

Performance of Pt/IrO _x -pH Ultra-micro Electrochemical Sensor and its Application in Study of Galvanic Corrosion of Copper/Stainless Steel

ZHANG Qinhao¹, ZHU Zejie², CAI Haoran¹, LI Xinran¹, MENG Xianze¹, LI Hao¹, WU Liankui¹, LUO Zhuangzhu¹, CAO Fahe¹(

)

^1.School of Materials, Sun Yat-sen University, Shenzhen 518107, China
^2.School of Materials and Chemistry, China Jiliang University, Hangzhou 310018, China

引用本文:

张勤号, 朱泽洁, 蔡浩冉, 李鑫冉, 孟宪泽, 李昊, 伍廉奎, 罗荘竹, 曹发和. Pt/IrO _x -pH超微电化学传感器性能探究及其在铜/不锈钢电偶腐蚀研究中的应用[J]. 中国腐蚀与防护学报, 2023, 43(6): 1264-1272.
Qinhao ZHANG, Zejie ZHU, Haoran CAI, Xinran LI, Xianze MENG, Hao LI, Liankui WU, Zhuangzhu LUO, Fahe CAO. Performance of Pt/IrO _x -pH Ultra-micro Electrochemical Sensor and its Application in Study of Galvanic Corrosion of Copper/Stainless Steel[J]. Journal of Chinese Society for Corrosion and protection, 2023, 43(6): 1264-1272.

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摘要:

通过在直径10 μm铂超微电极表面电化学沉积一层氧化铱薄膜，获得具有pH响应的全固态铂/氧化铱 (Pt/IrO _x ) 电化学微传感器，分析了其线性响应、瞬时响应、稳定性和抗典型离子干扰能力。结果表明，制备的Pt/IrO _x -pH微传感器电极在pH=1.00~13.00的范围内呈现优异的线性响应性能 (R²=0.999)；在短期 (20000 s内) 和长期 (110 d内) 均具有较高的稳定性；在溶液pH发生变化时，Pt/IrO _x -pH传感器电位能瞬间响应；在溶液中加入Fe²⁺、Cu²⁺和Cl^-时，线性响应不变，抗干扰能力强，但Ti³⁺的存在会影响检测的准确性。进一步将制备的Pt/IrO _x -pH超微传感器电极应用于铜和304不锈钢在pH=2.00的3.5% NaCl溶液中电偶腐蚀行为研究，SECM面扫描和线扫描结果结合OCP的变化，表明Cu和304 SS在开始发生电偶腐蚀时，Cu为阴极，304不锈钢为阳极，而当浸泡至12 h时，发生阴阳极极性反转，此时Cu为阳极，而304不锈钢为阴极，且Cu表面pH更低。

关键词 ：扫描电化学显微镜, pH微传感器, 抗离子干扰能力, 电偶腐蚀

Abstract：

The ion selective electrode technology (ISET) based on scanning electrochemical microscopy (SECM) enables in situ monitoring of non-electrochemically active substances at both micron and submicron scales of the metal/solution interface. However, the research on the stability, potential response time, and anti-ion interference ability of ISET is obviously insufficient. In this paper, an all-solid platinum/iridium oxide (Pt/IrO _x ) electrochemical microsensor with pH response was prepared by deposing an iridium oxide thin film on the surface of a 10 μm diameter platinum ultra-microelectrode. Its linear response, instantaneous potential response, stability and anti-ion interference ability were analyzed. The results showed that the prepared Pt/IrO _x -pH microsensor electrode exhibited excellent linear response performance in the range of pH=1.00-13.00 (R²=0.999) and high stability in both the short term (within 20000 s) and the long term (within 110 d). When the pH value of the solution changed, the potential of the Pt/IrO _x -pH microsensor could change instantaneously, namely the sensor responds quickly to the solution pH value. Moreover, after adding Fe²⁺, Cu²⁺ and Cl^- into the solution, the linear response and stability of the sensor remain unchanged with high anti-interference ability. However, the addition of Ti³⁺ could affect the accuracy of the microsensor detection. The prepared Pt/IrO _x -pH microsensor was further applied to investigate the galvanic corrosion of copper and 304 stainless steel in 3.5% NaCl solution with pH=2.00. The results of SECM surface and line scanning images combined with OCP results showed that when the galvanic corrosion of Cu and 304 stainless steel began, Cu acted as the cathode and 304 stainless steel was the anode. However, after 12 h immersion, the polarity of anode and cathode was reversed, that is, Cu was the anode and 304 stainless steel was the cathode, and the surface pH value of Cu was lower.

Key words： scanning electrochemical microscope pH microsensor anti-ionic interference ability galvanic corrosion

收稿日期: 2023-04-13 32134.14.1005.4537.2023.107

ZTFLH:

TG172

基金资助:国家自然科学基金(52001301);国家自然科学基金(52071347);国家自然科学基金(52201096);国家自然科学基金(52201097);中国博士后科学基金(2022M723574)

通讯作者: 曹发和，E-mail: caofh5@mail.sysu.edu.cn，研究方向为材料电化学，腐蚀与防护

Corresponding author: CAO Fahe, E-mail: caofh5@mail.sysu.edu.cn

作者简介: 张勤号，男，1988年生，助理研究员，博士

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https://www.jcscp.org/CN/10.11902/1005.4537.2023.107 或 https://www.jcscp.org/CN/Y2023/V43/I6/1264

图1 直径10 μm Pt UME在1 mmol/L FcMeOH+0.1 mol/L KNO3溶液中CV曲线及沉积IrO x 后电极端面光学形貌

图2 Pt/IrO x -pH超微传感器在不同pH下的响应电位及其拟合曲线，对pH变化的瞬时响应时间曲线，在0.01 mol/L HCl溶液中短期稳定性曲及在空气中放置时长期稳定性

图3 Pt/IrO x -pH传感器在不同pH的3.5% NaCl溶液中OCP和响应电位与pH的线性关系及其拟合曲线，Pt/IrO x -pH传感器在含有5 mmol/L Fe2+，Cu2+和Ti3+的3.5 % NaCl溶液 (pH=2.00) 中的OCP以及Pt/IrO x -pH传感器在含5 mmol/L Fe2+或Cu2+溶液中的电极电位及其拟合曲线

图4 Cu在pH=2.00的3.5% NaCl溶液中不同浸泡时间面扫描结果及3个时间面扫描对比图

图5 304不锈钢在pH=2.00的3.5% NaCl溶液中不同浸泡时间面扫描结果及3个时间的面扫描对比图

图6 Cu和304 不锈钢在3.5% NaCl溶液中 (pH=2.00) 发生电偶腐蚀时，不同浸泡时间下面扫图对比图

图7 Pt/IrO x -pH电极在3.5% NaCl溶液中Cu/304不锈钢表面线扫描曲线

图8 Cu/304不锈钢在pH=2.00的3.5%NaCl溶液中浸泡不同时间发生电偶腐蚀的各自OCP

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