一种环保型缓蚀剂利拉利汀对紫铜在硫酸中的缓蚀机理研究

doi:10.11902/1005.4537.2023.144

中国腐蚀与防护学报

2023, Vol. 43

Issue (5): 1031-1040 CSTR: 32134.14.1005.4537.2023.144 DOI: 10.11902/1005.4537.2023.144

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一种环保型缓蚀剂利拉利汀对紫铜在硫酸中的缓蚀机理研究

董红梅¹, 李宝毅¹, 冉博元²^,³, 王琦¹, 牛宇岚¹, 丁莉峰¹(

), 强玉杰²^,³(

)

^1.太原工业学院化学与化工系太原 030008
^2.北京科技大学国家材料服役安全科学中心北京 100083
^3.吉县英才博士工作站临汾 042200

Corrosion Inhibition Mechanism of the Eco-friendly Corrosion Inhibitor Linagliptin on Copper in Sulfuric Acid

DONG Hongmei¹, LI Baoyi¹, RAN Boyuan²^,³, WANG Qi¹, NIU Yulan¹, DING Lifeng¹(

), QIANG Yujie²^,³(

)

^1.Department of Chemistry and Chemical Engineering, Taiyuan Institute of Technology, Taiyuan 030008, China
^2.Nation Center for Materials Service Safety, University of Science and Technology Beijing, Beijing 100083, China
^3.Talented Doctoral Workstation of Ji Xian, Linfen 042200, China

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摘要:

使用电化学阻抗技术、失重法等研究了一种被用于治疗人类糖尿病且价格低廉的利拉利汀 (LNLP) 药物在0.5 mol/L硫酸溶液中对Cu的缓蚀作用和缓蚀机理。结果表明，LNLP能够有效抑制Cu在硫酸中的腐蚀，是一种绿色环保型缓蚀剂。电化学阻抗测试显示该物质能够增大Cu表面的膜电阻和电荷转移电阻，降低膜电容和双电层电容来减缓Cu在0.5 mol/L硫酸溶液中的腐蚀速率。当LNLP浓度仅为1 mmol/L时，其缓蚀效率高达99.95%。动电位极化曲线测试结果表明，LNLP是一种谦逊的混合型缓蚀剂，能够有效地抑制Cu表面的阴阳极反应。利用吸附等温曲线和理论计算探究了LNLP与Cu表面的相互作用和LNLP分子结构与缓蚀性能之间的构效关系。结果表明，LNLP在Cu表面的吸附是一种平行吸附形态，最大程度地为Cu提供了保护。LNLP分子在Cu表面的吸附主要是以分子内的氮、氧杂原子和共轭的环状官能团为活性吸附中心，通过物理和化学吸附的协同作用，在Cu表面形成了单分子层膜，隔绝了腐蚀介质与Cu表面的接触。

关键词 ： Cu, 缓蚀剂, 硫酸, 腐蚀防护, 理论计算

Abstract：

Developing high-efficiency and eco-friendly corrosion inhibitors to replace traditional toxic and harmful ones is necessary to protect the ecological environment. Based on these premises, we employed electrochemical impedance techniques, gravimetric methods, and others to investigate the corrosion inhibition and mechanism of a low-cost drug, liraglutide (LNLP), used for human diabetes treatment, on copper in 0.5 mol/L sulfuric acid solution. The findings demonstrate that LNLP is a green, eco-friendly type of corrosion inhibitor, and is effective in inhibiting the corrosion of copper in sulfuric acid. The electrochemical results show that LNLP could slow down the corrosion rate of copper in 0.5 mol/L H₂SO₄ solution by increasing the film and charge transfer resistance and reducing the film and double-layer capacitance. When the concentration of LNLP is only 1 mmol/L, the η is as high as 99.95%. Potentiodynamic polarization curves results indicate that LNLP is a modest mixed-type inhibitor that can inhibit the anodic and cathodic reactions of copper. Based on the adsorption curve and theoretical calculation, the interaction between LNLP and the copper surface and the structure-performance relationship of LNLP molecule are revealed. The relevant results show that the adsorption of LNLP on the copper surface is parallel, providing max protection for copper. The adsorption of LNLP molecules on the copper is mainly through the nitrogen, oxygen heteroatoms, and conjugated ringy functional groups within the molecules, forming a single-molecule film through the synergistic effect of physical and chemical adsorption, isolating corrosive media from the copper surface.

Key words： Cu corrosion inhibitor sulfuric acid corrosion protection theoretical calculation

收稿日期: 2023-05-08 32134.14.1005.4537.2023.144

ZTFLH:

TG174

基金资助:山西省高等学校科技创新项目(2021L552);第8届中国科协青年人才托举工程(YESS20220689)

通讯作者: 丁莉峰，E-mail: dinglf@tit.edu.cn，研究方向为金属表面防护处理；强玉杰，E-mail: qiangyujie@ustb.edu.cn，研究方向为功能防护涂层与缓蚀剂

Corresponding author: DING Lifeng, E-mail: dinglf@tit.edu.cn;QIANG Yujie, E-mail: qiangyujie@ustb.edu.cn

作者简介: 董红梅，女，1989年生，博士生

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引用本文:

董红梅, 李宝毅, 冉博元, 王琦, 牛宇岚, 丁莉峰, 强玉杰. 一种环保型缓蚀剂利拉利汀对紫铜在硫酸中的缓蚀机理研究[J]. 中国腐蚀与防护学报, 2023, 43(5): 1031-1040.
DONG Hongmei, LI Baoyi, RAN Boyuan, WANG Qi, NIU Yulan, DING Lifeng, QIANG Yujie. Corrosion Inhibition Mechanism of the Eco-friendly Corrosion Inhibitor Linagliptin on Copper in Sulfuric Acid. Journal of Chinese Society for Corrosion and protection, 2023, 43(5): 1031-1040.

链接本文:

https://www.jcscp.org/CN/10.11902/1005.4537.2023.144 或 https://www.jcscp.org/CN/Y2023/V43/I5/1031

图1 利拉利汀的分子结构示意图

图2 Cu在含不同浓度LNLP的0.5 mol/L H2SO4溶液中的Nyquist图和对应的Bode图

图3 用于拟合EIS数据的等效电路

表1 Cu在含有不同浓度LNLP硫酸溶液中的EIS参数

表2 不同缓蚀剂对Cu在0.5 mol/L硫酸溶液中的缓蚀性能

图4 Cu在含有不同浓度LNLP硫酸溶液中的Tafel曲线

表3 Cu在含有不同浓度LNLP硫酸溶液中的Tafel参数

图5 Cu的质量损失结果和对应的吸附曲线

图6 Cu在不含和含有1 mmol/L LNLP硫酸溶液中的腐蚀形貌和EDS

图7 铜在不含和含有1 mmol/L LNLP硫酸溶液中的3D腐蚀形貌

图8 LNLP分子的几何优化构型，以及LUMO和HOMO电子云分布

图9 LNLP分子的密立根电荷分布

图10 LNLP分子在Cu表面的平衡吸附构型

图11 Cu在硫酸溶液中的腐蚀机理示意图和LNLP对Cu的缓蚀机理示意图

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