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中国腐蚀与防护学报  2018, Vol. 38 Issue (4): 381-390    DOI: 10.11902/1005.4537.2017.053
  研究报告 本期目录 | 过刊浏览 |
分子动力学模拟水溶液中席夫碱基表面活性剂在Zn表面的吸附行为
刘峥(), 李海莹, 王浩, 赵永, 谢思维, 张淑芬
桂林理工大学化学与生物工程学院 广西电磁化学功能物质重点实验室 桂林 541004
Molecular Dynamics Simulation of Adsorption Behavior of Schiff Base Surfactants on Zn Surface in Aqueous Solution
Zheng LIU(), Haiying LI, Hao WANG, Yong ZHAO, Siwei XIE, Shufen ZHANG
Guangxi Key Laboratory of Electrochemical and Magneto-chemical Functional Materials, College of Chemical and Biological Engineering, Guilin University of Technology, Guilin 541004, China
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摘要: 

合成了3种聚乙二醇 (400) 月桂酸单酯席夫碱基表面活性剂 (M1,M2和M3),并进行了结构表征。采用分子动力学模拟研究了M1,M2和M3在Zn表面的吸附行为和席夫碱基表面活性剂分子中基团对吸附性能的影响,探讨了其吸附机理。利用失重法、电化学阻抗谱和SEM研究了3种表面活性剂对碱性Zn电极的缓蚀性能。结果表明,M3的缓蚀性能最好,当其浓度达到1.0 mmol/L时,缓蚀率达92%。席夫碱基表面活性剂分子基本平行吸附在Zn表面,形成致密吸附分子膜。3种表面活性剂分子吸附能大小依次为：M3>M2>M1,吸附速率顺序为：M3>M2>M1;相比于M2和M1,M3对碱性Zn电极具有更好的缓蚀性能。
关键词 ： 表面活性剂,  吸附行为,  分子动力学模拟,  Zn表面,  缓蚀性能    
Abstract：

Three polyethylene glycol (400) lauric acid monoester Schiff base surfactants (M1, M2 and M3) were synthesized and characterized. The adsorption behavior and the effect of the group of surfactant molecules on the adsorption properties about M1, M2, M3 on the metal Zn surface were investigated by means of molecular dynamics simulation method. While the corrosion inhibition performance of the three surfactants on alkaline Zn-electrode was assessed by means of mass loss method, electrochemical impedance spectroscopy and scanning electron microscopy. It showed that M3 exhibited the best corrosion inhibition, and the corrosion inhibition efficiency was 92% when the concentration reached 1.0 mmol/L. The Schiff base surfactant molecules adsorbed on Zn surface parallelly to form a dense molecular adsorption film. What's more, the ranking of the adsorption energy of the three surfactants was M3>M2>M1, and that of the adsorption rate was M3>M2>M1. M3 had better corrosion inhibition performance for alkaline zinc electrode, and had better inhibition effect on zinc dendrite.
Key words： surfactant    adsorption behavior    molecular dynamics simulation    zinc surface    corrosion inhibition performance
收稿日期: 2017-04-13     
ZTFLH:  O643.12  
基金资助:国家自然科学基金 (21266006),广西省自然科学基金 (2016GXNSFAA380109) 和广西特聘专家专项经费(NO2401007012)
作者简介:

作者简介 刘峥,女,1962年生,教授
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引用本文:

刘峥, 李海莹, 王浩, 赵永, 谢思维, 张淑芬. 分子动力学模拟水溶液中席夫碱基表面活性剂在Zn表面的吸附行为[J]. 中国腐蚀与防护学报, 2018, 38(4): 381-390.
Zheng LIU, Haiying LI, Hao WANG, Yong ZHAO, Siwei XIE, Shufen ZHANG. Molecular Dynamics Simulation of Adsorption Behavior of Schiff Base Surfactants on Zn Surface in Aqueous Solution. Journal of Chinese Society for Corrosion and protection, 2018, 38(4): 381-390.

链接本文:

https://www.jcscp.org/CN/10.11902/1005.4537.2017.053      或      https://www.jcscp.org/CN/Y2018/V38/I4/381

图1  3种席夫碱基表面活性剂的合成路线图
图2  3种表面活性剂的分子结构图
Surfactant ConcentrationmmolL-1 ΔWg ηw% Dwg / m2h
Blank --- 3.6×10-2 --- ---
M1 0.4 1.4×10-2 62.0 1.89
0.7 7.7 ×10-3 79.0 1.06
1.0 6.3×10-3 82.0 0.87
1.3 6.1×10-3 82.8 0.85
1.6 6.0×10-3 83.3 0.82
M2 0.4 9.7×10-3 73.0 1.34
0.7 6.0×10-3 83.0 0.83
1.0 4.0×10-3 88.8 0.55
1.3 3.9×10-3 89.1 0.54
1.6 3.7×10-3 89.6 0.51
M3 0.4 8.3×10-3 77.0 1.15
0.7 5.0×10-3 86.0 0.69
1.0 2.8×10-3 92.2 0.38
1.3 2.5×10-3 93.0 0.34
1.6 2.3×10-3 93.6 0.31
表1  Zn片在添加不同浓度表面活性剂碱液中的失重实验数据
图3  Zn在含不同表面活性剂的溶液中的Nyquist曲线图及其等效电路图
Surfactant Concentration / mmolL-1 R1 / Ωcm2 R2 / Ωcm2 Cd / Fcm-2 η / %
Blank --- 0.31 52.82 1.2×10-2 ---
M1 0.4 0.57 108.71 4.1×10-4 51.41
0.7 0.58 147.44 1.1×10-3 64.18
1.0 0.62 224.60 1.0×10-2 76.47
M2 0.4 0.51 271.48 8.4×10-3 80.54
0.7 0.53 316.92 7.8×10-3 83.33
1.0 0.59 412.02 6.6×10-3 87.18
M3 0.4 0.62 480.30 5.9×10-3 89.00
0.7 0.65 519.53 7.7×10-3 89.83
1.0 0.64 672.02 4.686×10-3 92.14
表2  Zn电极在添加不同浓度表面活性剂饱和ZnO的6 mol/L KOH溶液中的电化学参数以及缓蚀率
图4  Zn电极在未加入与加入3种表面活性剂的饱和ZnO的 6 mol/L KOH溶液中浸泡50 h后的SEM像
图5  3种表面活性剂吸附在Zn表面的温度和能量平衡曲线图
图6  表面活性剂在Zn (1 1 0)表面吸附前后的构型图
Molecular Emolecule+surface / (kcalmol-1) Emolecule / (kcalmol-1) Esurface / (kcalmol-1) Eadsorption / (kcalmol-1)
M1 -34470 -38.19 -34023 -408.81
M2 -34484 -16.48 -34023 -444.52
M3 -34496 -16.93 -34023 -456.07
表3  3种表面活性剂分子在Zn (1 1 0)表面的吸附能
图7  3种表面活性剂分子吸附到Zn (1 1 0)表面的均方位移图
图8  吸附前后3种表面活性剂的两种基团之间的距离变化
图9  3种表面活性剂的特征基团原子和H2O与Zn表面之间的距离变化
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