微型金属氧化物<strong>pH</strong>电极的制备及腐蚀防护应用进展

doi:10.11902/1005.4537.2022.333

中国腐蚀与防护学报

2023, Vol. 43

Issue (5): 971-982 CSTR: 32134.14.1005.4537.2022.333 DOI: 10.11902/1005.4537.2022.333

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微型金属氧化物pH电极的制备及腐蚀防护应用进展

顾玉慧¹^,², 董亮¹(

), 宋沁峰¹

^1.常州大学石油与天然气工程学院江苏省油气储运技术重点实验室常州 213164
^2.中国石化润滑油有限公司江苏销售分公司南京 210003

Preparation of Micro Metal Oxide pH Electrode and Its Application in Corrosion and Protection

GU Yuhui¹^,², DONG Liang¹(

), SONG Qinfeng¹

^1.Jiangsu Key Laboratory of Oil & Gas Storage and Transportation Technology, School of Petroleum and Natural Gas Engineering, Changzhou University, Changzhou 213164, China
^2.Sinopec Lubricants Co., Ltd. Sales Branch, Nanjing 210003, China

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摘要:

归纳总结了铱/氧化铱、钛基、钨/氧化钨和氧化锰pH电极的响应机理、性能参数及其研究进展。其中，铱氧化物pH电极稳定性好、响应斜率高 (-59.5~-74.91 mV/pH)，应用最为广泛。介绍了电化学沉积法、电化学生长法、热氧化法和溶胶-凝胶法等微型pH电极的常用制备方法，对制备方法中不同工艺参数对电极性能的影响进行分析总结。其中，电化学沉积法应用前景广阔、成本低，制备的电极响应斜率高、响应速率快，但在长期使用过程中的电位漂移问题尚待解决。针对金属pH电极的电位漂移、老化时间久等问题，阐述了水合、热处理及水热处理等后处理工艺对电极性能的改善作用及应用机制。总结了金属氧化物pH微电极在点蚀、电偶腐蚀和应力腐蚀等局部腐蚀与阴极保护方面的应用，包括使用微型金属氧化物pH电极、复合双管pH电极以及将pH电极与扫描电化学显微镜技术 (SECM) 相结合等应用模式。金属氧化物pH电极具有易于微型化、响应快速、性能稳定等特点，使其在监测因局部阳极腐蚀或阴极还原反应形成的金属/介质界面微区环境pH值变化的过程中表现出良好的效果。最后对微型金属氧化物pH电极制备工艺的优缺点进行了总结，并展望了其制备工艺优化及应用趋势。

关键词 ：微型pH电极, 金属/金属氧化物pH电极, 制备, 腐蚀防护, 局部腐蚀, 阴极保护

Abstract：

Metal oxide electrode is widely used for pH examination in food, biology and medical industries due to its characteristics of wide pH response range (pH measurement range can reach 2-12, even 0-14) and easy to be miniaturized. It can be used for in situ measurement of pH value at the vicinity of metal/electrolyte interface, thus providing important parameters for deducing the possible electrochemical reactions, explaining specific corrosion behavior and revealing the relevant corrosion mechanism. In this paper, the response performance, performance parameters and the research progress of metal oxide electrodes made of iridium, manganese, titanium, tungsten and the relevant oxides were summarized. Among which, the iridium oxide electrode was most widely used as a pH detector for its stability and high response slope (-59.5 - -74.91 mV/pH). The commonly used preparation methods for micro metal oxide pH electrodes such as electrochemical deposition method, thermal oxidation method, sol-gel method, screen printing method, etc. as well as the effect of different process parameters were also summarized. The electrochemical deposition method had a broad application prospect, and with which the prepared electrodes had the characteristics of low cost, high response slope and fast response rate, but their potential drift for the long-term service needed to be solved. Aiming at the matter of potential drift and long aging time of metal pH electrodes, the effect of post-treatment processes such as hydration, heat treatment and hydrothermal treatment on the electrode performance were introduced. The applications of metal oxide pH micro-electrodes for the examination of pitting corrosion, galvanic corrosion, stress corrosion and other local corrosion, as well as for the monitoring cathodic protection were reviewed, including the micro metal oxide pH electrode, composite double-tube pH electrode and the combination of pH electrode and scanning electrochemical microscopy technology (SECM), etc. The metal oxide electrode was easy to be miniaturized and had a stable response, which made it show good response performance in the process of monitoring the change of pH value nearby the metal/electrolyte interface formed during local anodic corrosion or cathodic reduction reaction. Lastly, the preparation technology and application trend of the micro metal oxide electrode were also prospected.

Key words： micro pH electrode metal/metal oxide pH electrode preparation technology corrosion and protection local corrosion cathodic protection

收稿日期: 2022-10-28 32134.14.1005.4537.2022.333

ZTFLH:

TG174

基金资助:国家自然科学基金(51401017);江苏省研究生科研与实践创新计划(SJCX21_1269)

通讯作者: 董亮，E-mail: dongliang@cczu.edu.cn，研究方向为金属材料的腐蚀与防护

Corresponding author: DONG Liang, E-mail: dongliang@cczu.edu.cn

作者简介: 顾玉慧，女，1998年生，硕士生

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引用本文:

顾玉慧, 董亮, 宋沁峰. 微型金属氧化物pH电极的制备及腐蚀防护应用进展[J]. 中国腐蚀与防护学报, 2023, 43(5): 971-982.
GU Yuhui, DONG Liang, SONG Qinfeng. Preparation of Micro Metal Oxide pH Electrode and Its Application in Corrosion and Protection. Journal of Chinese Society for Corrosion and protection, 2023, 43(5): 971-982.

链接本文:

https://www.jcscp.org/CN/10.11902/1005.4537.2022.333 或 https://www.jcscp.org/CN/Y2023/V43/I5/971

图1 铱氧化物电极在700，750，800和870 ℃下加热不同时间后的表面形貌 [48]

图2 未使用和使用水合处理后的氧化铱电极表面形貌图[37]

图3 原始和超临界处理的氧化铱电极的Ir 4f精细XPS谱图[51]

表1 电极制备方法及性能汇总

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