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

doi:10.11902/1005.4537.2023.107

Journal of Chinese Society for Corrosion and protection

2023, Vol. 43

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

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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

Cite this article:

ZHANG Qinhao, ZHU Zejie, CAI Haoran, LI Xinran, MENG Xianze, LI Hao, WU Liankui, LUO Zhuangzhu, CAO Fahe. Performance of Pt/IrO _x -pH Ultra-micro Electrochemical Sensor and its Application in Study of Galvanic Corrosion of Copper/Stainless Steel. Journal of Chinese Society for Corrosion and protection, 2023, 43(6): 1264-1272.

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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

Received: 13 April 2023 32134.14.1005.4537.2023.107

ZTFLH:

TG172

Fund: National Natural Science Foundation of China(52001301);National Natural Science Foundation of China(52071347);National Natural Science Foundation of China(52201096);National Natural Science Foundation of China(52201097);China Postdoctoral Science Foundation(2022M723574)

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

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	Articles by authors
	ZHANG Qinhao
	ZHU Zejie
	CAI Haoran
	LI Xinran
	MENG Xianze
	LI Hao
	WU Liankui
	LUO Zhuangzhu
	CAO Fahe

URL:

https://www.jcscp.org/EN/10.11902/1005.4537.2023.107 OR https://www.jcscp.org/EN/Y2023/V43/I6/1264

Fig.1 CV curve of diameter 10 μm Pt UME in 1 mmol/L FcMeOH+0.1 mol/L KNO₃ solution (a), and optical photo of electrode surface after deposition of IrO _x (b)

Fig.2 Response potential and fitting curve of Pt/IrO _x -pH micro-sensor electrode at different pH (a), instantaneous response curve of the Pt/IrO _x -pH electrode to pH change (b), short-term stability of the Pt/IrO _x -pH electrode in 0.01 mol/L HCl solution (c) and long-term stability of the Pt/IrO _x -pH electrode when placed in air (d)

Fig.3 OCP (a) and linear relationship between response potential and pH and its fitting curve of Pt/IrO _x -pH sensor in 3.5% NaCl solution with different pH value (b), OCP of Pt/IrO _x -pH sensor in 3.5% NaCl solution (pH=2.00) containing 5 mmol/L Ti³⁺, Fe²⁺ and Cu²⁺, respectively (c), electrode potential of Pt/IrO _x -pH sensor in 5 mmol/L Fe²⁺ or Cu²⁺ solution and its fitting curve (d)

Fig.4 Surface scanning diagram of Cu electrode in 3.5% NaCl solution with pH=2.00 after immersion for 0 h (a), 6 h (b), 12 h (c), and comparison of surface scanning of Pt/IrO _x -pH microsensor electrode on Cu surface with distance of 5 μm in the three immersion times (d)

Fig.5 Surface scanning of 304 stainless steel in 3.5% NaCl solution with pH=2.00 after immersion for 0 h (a), 6 h (b), 12 h (c), and comparison of surface scanning of Pt/IrO _x -pH microsensor electrode on 304 stainless steel with distance of 5 μm in the three immersion times (d)

Fig.6 Surface scanning of Cu (a-d) and 304 stainless steel (e-h) galvanic corrosion under different immersion times in 3.5% NaCl solution with pH=2.00, in which results of surface scans at 0 h (a, e), 6 h (b, f), 12 h (c, g), and comparison of surface scanning of Pt/IrO _x -pH microsensor electrode on sample surface with distance of 5 μm in the three immersion times (d, f)

Fig.7 Line scanning curves of Pt/IrO _x -pH electrode on Cu/304 stainless steel surface with distance of 5 μm in 3.5% NaCl solution with pH=2.00

Fig.8 OCP of Cu and 304 stainless steel under different immersion times with galvanic corrosion in 3.5%NaCl solution with pH=2.00: (a) 0 h, (b) 6 h, (c) 12 h

1	Wang L W, Li X G, Du C W, et al. Recent advances in local electrochemical measurement techniques and applications in corrosion research [J]. J. Chin. Soc. Corros. Prot., 2010, 30: 498
	王力伟, 李晓刚, 杜翠薇等. 微区电化学测量技术进展及在腐蚀领域的应用 [J]. 中国腐蚀与防护学报, 2010, 30: 498
2	Xu D, Yang X J, Li Q, et al. Review on corrosion test methods and evaluation techniques for materials in atmospheric environment [J]. J. Chin. Soc. Corros. Prot., 2022, 42: 447
	徐迪, 杨小佳, 李清等. 材料大气环境腐蚀试验方法与评价技术进展 [J]. 中国腐蚀与防护学报, 2022, 42: 447
3	Bai Y H, Zhang H, Zhu Z J, et al. Research progress of monitoring ion concentration variation of micro-areas in corrosion crevice interior [J]. J. Chin. Soc. Corros. Prot., 2023, 43: 828
	白一涵, 张航, 朱泽洁等. 缝隙腐蚀内部微区离子浓度监测的研究进展 [J]. 中国腐蚀与防护学报, 2023, 43: 828 doi: 10.11902/1005.4537.2022.325
4	Li H, Zhang S T, Qiang Y J. Corrosion retardation effect of a green cauliflower extract on copper in H₂SO₄ solution: Electrochemical and theoretical explorations [J]. J. Mol. Liq., 2021, 321: 114450 doi: 10.1016/j.molliq.2020.114450
5	Li H, Qiang Y J, Zhao W J, et al. 2-mercaptobenzimidazole-inbuilt metal-organic-frameworks modified graphene oxide towards intelligent and excellent anti-corrosion coating [J]. Corros. Sci., 2021, 191: 109715 doi: 10.1016/j.corsci.2021.109715
6	Zhu Z J, Zhang Q H, Liu P, et al. Application of microelectrochemical sensors in monitoring of localized interface pH [J]. J. Chin. Soc. Corros. Prot., 2019, 39: 367
	朱泽洁, 张勤号, 刘盼等. 微型电化学传感器在界面微区pH监测中的应用 [J]. 中国腐蚀与防护学报, 2019, 39: 367 doi: 10.11902/1005.4537.2019.136
7	Gerlach G, Guenther M, Sorber J, et al. Chemical and pH sensors based on the swelling behavior of hydrogels [J]. Sensor. Actuat. B-Chem., 2005, 111/112B: 555
8	Matsuura K, Asano Y, Yamada A, et al. Detection of Micrococcus luteus biofilm formation in microfluidic environments by pH measurement using an ion-sensitive field-effect transistor [J]. Sensors, 2013, 13: 2484 doi: 10.3390/s130202484 pmid: 23429511
9	Takeshita Y, Martz T R, Johnson K S, et al. Characterization of an ion sensitive field effect transistor and chloride ion selective electrodes for pH measurements in seawater [J]. Anal. Chem., 2014, 86: 11189 doi: 10.1021/ac502631z pmid: 25325617
10	Glanc-Gostkiewicz M, Sophocleous M, Atkinson J K, et al. Performance of miniaturised thick-film solid state pH sensors [J]. Sens. Actuators, 2013, 202A: 2
11	Gu Y H, Dong L, Song Q F. Preparation of micro metal oxide pH electrode and its application in corrosion and protection [J]. J. Chin. Soc. Corros. Prot., 2023, 43: 971
	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, 2023, 43: 971
12	Sardarinejad A, Maurya D K, Alameh K. The pH sensing properties of RF sputtered RuO₂ thin-film prepared using different Ar/O₂ flow ratio [J]. Materials, 2015, 8: 3352 doi: 10.3390/ma8063352
13	Maurya D K, Sardarinejad A, Alameh K. High-sensitivity pH sensor employing a sub-micron ruthenium oxide thin-film in conjunction with a thick reference electrode [J]. Sensor. Actuat. B-Chem., 2013, 203: 300
14	Kuo L M, Chen K N, Chuang Y L, et al. A flexible pH-sensing structure using WO₃/IrO₂ junction with Al₂O₃ encapsulation layer [J]. ECS Solid State Lett., 2012, 2: P28 doi: 10.1149/2.004303ssl
15	Chen D C, Wang Z, Zheng J S, et al. Preparation of W/WO₃ pH electrode with a method of sol-gel and its surface film micro-analysis [J]. J. Funct. Mater., 2004, 35 (suppl.) : 1003
	陈东初, 王哲, 郑家燊等. W/WO₃ pH电极的制备以及表面膜微观分析研究 [J]. 功能材料, 2004, 35 (增刊) : 1003
16	Ha Y, Wang M. Capillary melt method for micro antimony oxide pH electrode [J]. Electroanalysis, 2006, 18: 1121 doi: 10.1002/elan.v18:11
17	Ghalwa N A, Hamada M, Abu-Shawish H M, et al. Using of Ti/Co₃O₄/PbO₂/ (SnO₂+Sb₂O₃) modified electrode as indicator electrode in potentiometric and conductometric titration in aqueous solution [J]. J. Electroanal. Chem., 2012, 664: 7 doi: 10.1016/j.jelechem.2011.10.005
18	Zhang Q H, Ye Z N, Zhu Z J, et al. Separation and kinetic study of iron corrosion in acidic solution via a modified tip generation/substrate collection mode by SECM [J]. Corros. Sci., 2018, 139: 403 doi: 10.1016/j.corsci.2018.05.021
19	Zhang Q H, Liu P, Zhu Z J, et al. Quantitative analysis of the polarization behavior of iron in an aerated acidic solution using SECM [J]. Electrochem. Commun., 2018, 93: 143 doi: 10.1016/j.elecom.2018.07.007
20	Zhang Q H, Liu P, Zhu Z J, et al. The study of the H₂O₂ during oxygen reduction process on typically corroding metal surface using tip generation-substrate collection mode of SECM [J]. Corros. Sci., 2020, 164: 108312 doi: 10.1016/j.corsci.2019.108312
21	Liu P, Zhang Q H, Zhang J Q, et al. Rapid synthesis of highly oriented hydrophobic silicalite-1 zeolite films on alloy steel at lower temperature for corrosion protection [J]. Chem. Eng. J., 2022, 430: 133173 doi: 10.1016/j.cej.2021.133173
22	Bard A J, Mirkin M V. Scanning Electrochemical Microscopy [M]. 2nd ed. Boca Raton: CRC Press, 2012
23	Zhu Z J, Liu X Y, Ye Z N, et al. A fabrication of iridium oxide film pH micro-sensor on Pt ultramicroelectrode and its application on in-situ pH distribution of 316L stainless steel corrosion at open circuit potential [J]. Sensor. Actuat. B-Chem., 2018, 255B: 1974
24	Zhu Z J, Ye Z N, Zhang Q H, et al. Novel dual Pt-Pt/IrO _x ultramicroelectrode for pH imaging using SECM in both potentiometric and amperometric modes [J]. Electrochem. Commun., 2018, 88: 47 doi: 10.1016/j.elecom.2018.01.018

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