高等学校化学学报 ›› 2019, Vol. 40 ›› Issue (1): 96.doi: 10.7503/cjcu20180589
马玉聪1, 樊保民1(), 郝华2, 吕金玉1, 冯云皓3, 杨彪1
收稿日期:
2018-08-23
出版日期:
2019-01-10
发布日期:
2018-12-20
作者简介:
联系人简介: 樊保民, 男, 博士, 副教授, 主要从事超分子化学与腐蚀电化学方面的研究. E-mail:
基金资助:
MA Yucong1, FAN Baomin1,*(), HAO Hua2, LÜ Jinyu1, FENG Yunhao3, YANG Biao1
Received:
2018-08-23
Online:
2019-01-10
Published:
2018-12-20
Contact:
FAN Baomin
E-mail:fanbaomin@btbu.edu.cn
Supported by:
摘要:
应用分子动力学模拟明确了以β-环糊精(β-CyD)为主体、 十八胺(ODA)为客体的分子组装体(CDDA)的最优空间构型, 并采用动态失重、 电化学极化与阻抗测试结合扫描电子显微镜、 原子力显微镜、 接触角、 X射线光电子能谱(XPS)与衰减全反射红外光谱(ATR-FTIR)等表面分析手段, 研究了CDDA对Q235碳钢在蒸汽凝结水中的缓蚀机理. 结果显示, CDDA的4种构型可共存于组装体系内; 35 ℃下, 添加1 mmol/L CDDA对碳钢的缓蚀率达94.1%; 添加CDDA不改变腐蚀机理, 但可同时抑制电化学反应的阴、 阳极过程, 并显著提升极化阻抗, 属于阳极抑制为主的混合型缓蚀剂. XPS和ATR-FTIR结果均表明, CDDA在碳钢/溶液界面释放客体ODA, 并由其自发吸附组装形成疏水膜, 吸附过程符合Langmuir等温式. 分子动力学模拟与量子化学计算结果支持上述ODA释放并于金属表面组装成膜的推断.
中图分类号:
TrendMD:
马玉聪, 樊保民, 郝华, 吕金玉, 冯云皓, 杨彪. 十八胺基分子组装体在碳钢表面的作用机理与模拟. 高等学校化学学报, 2019, 40(1): 96.
MA Yucong,FAN Baomin,HAO Hua,LÜ Jinyu,FENG Yunhao,YANG Biao. Experimental and Theoretical Studies of Action Mechanism of an Octadecylamine-based Molecular Assembly on Mild Steel†. Chem. J. Chinese Universities, 2019, 40(1): 96.
pH | Conductivity/ (μS·cm-1) | Concentration of dissolved oxygen/(mg·L-1) | Concentration of Na+/ (μg·L-1) | Concentration of Cl-/ (μg·L-1) |
---|---|---|---|---|
5.89 | 108.32 | 2.11 | 66.13 | 129.19 |
Table 1 Water parameters of the sampled condensate water at 25 ℃
pH | Conductivity/ (μS·cm-1) | Concentration of dissolved oxygen/(mg·L-1) | Concentration of Na+/ (μg·L-1) | Concentration of Cl-/ (μg·L-1) |
---|---|---|---|---|
5.89 | 108.32 | 2.11 | 66.13 | 129.19 |
Fig.2 Calculated energies of CDDA for different configurations(A) Wide towards narrow; (B) wide towards wide; (C) narrow towards narrow; (D) narrow towards wide.
Configuration | Et/(kJ·mol-1) | Ep/(kJ·mol-1) | En/(kJ·mol-1) |
---|---|---|---|
Wide towards narrow | 3820.59 | 2534.28 | 2444.70 |
Wide towards wide | 3828.99 | 2562.72 | 2420.12 |
Narrow towards narrow | 3830.92 | 2497.26 | 2464.99 |
Narrow towards wide | 3815.06 | 2518.11 | 2402.59 |
Table 2 Equilibrium values of total energy(Et), potential energy(Ep) and non-bond energy(En) for different spatial configurations of CDDA
Configuration | Et/(kJ·mol-1) | Ep/(kJ·mol-1) | En/(kJ·mol-1) |
---|---|---|---|
Wide towards narrow | 3820.59 | 2534.28 | 2444.70 |
Wide towards wide | 3828.99 | 2562.72 | 2420.12 |
Narrow towards narrow | 3830.92 | 2497.26 | 2464.99 |
Narrow towards wide | 3815.06 | 2518.11 | 2402.59 |
Temperature/℃ | c(CDDA)/(mol·L-1) | |||||
---|---|---|---|---|---|---|
0 | 0.05 | 0.1 | 0.3 | 0.6 | 1 | |
35 | 0.118 | 0.021(82.2) | 0.013(89.0) | 0.011(90.7) | 0.009(92.4) | 0.007(94.1) |
45 | 0.153 | 0.030(80.4) | 0.021(86.3) | 0.016(89.5) | 0.013(91.5) | 0.010(93.5) |
55 | 0.202 | 0.055(72.8) | 0.044(78.2) | 0.028(86.1) | 0.021(89.6) | 0.018(91.1) |
65 | 0.210 | 0.064(69.5) | 0.052(75.2) | 0.041(80.5) | 0.030(85.7) | 0.022(89.5) |
75 | 0.233 | 0.082(64.8) | 0.061(73.8) | 0.048(79.4) | 0.040(82.8) | 0.033(85.8) |
Table 3 Corrosion rates(g·m-2·h-1) of Q235 steel with various concentrations of CDDA in condensate water under preset temperatures along with the corresponding corrosion efficiencies(ηw, %) in the brackets
Temperature/℃ | c(CDDA)/(mol·L-1) | |||||
---|---|---|---|---|---|---|
0 | 0.05 | 0.1 | 0.3 | 0.6 | 1 | |
35 | 0.118 | 0.021(82.2) | 0.013(89.0) | 0.011(90.7) | 0.009(92.4) | 0.007(94.1) |
45 | 0.153 | 0.030(80.4) | 0.021(86.3) | 0.016(89.5) | 0.013(91.5) | 0.010(93.5) |
55 | 0.202 | 0.055(72.8) | 0.044(78.2) | 0.028(86.1) | 0.021(89.6) | 0.018(91.1) |
65 | 0.210 | 0.064(69.5) | 0.052(75.2) | 0.041(80.5) | 0.030(85.7) | 0.022(89.5) |
75 | 0.233 | 0.082(64.8) | 0.061(73.8) | 0.048(79.4) | 0.040(82.8) | 0.033(85.8) |
c(CDDA)/(mmol·L-1) | Ecorr/mV | Jcorr/(μA·cm-2) | βa/(mV·dec-1) | βc/(mV·dec-1) | ηp(%) |
---|---|---|---|---|---|
0 | -538.02 | 29.89 | 69.28 | -504.45 | —— |
0.05 | -495.82 | 4.90 | 222.47 | -462.29 | 83.6 |
0.1 | -490.06 | 2.36 | 253.04 | -484.93 | 92.1 |
0.3 | -492.89 | 2.01 | 252.97 | -481.25 | 93.3 |
0.6 | -478.53 | 1.94 | 258.49 | -478.06 | 93.5 |
1 | -462.73 | 1.88 | 251.29 | -479.89 | 93.7 |
Table 4 Electrochemical parameters and inhibition efficiencies for Q235 steel derived from cathodic and anodic polarization measurements
c(CDDA)/(mmol·L-1) | Ecorr/mV | Jcorr/(μA·cm-2) | βa/(mV·dec-1) | βc/(mV·dec-1) | ηp(%) |
---|---|---|---|---|---|
0 | -538.02 | 29.89 | 69.28 | -504.45 | —— |
0.05 | -495.82 | 4.90 | 222.47 | -462.29 | 83.6 |
0.1 | -490.06 | 2.36 | 253.04 | -484.93 | 92.1 |
0.3 | -492.89 | 2.01 | 252.97 | -481.25 | 93.3 |
0.6 | -478.53 | 1.94 | 258.49 | -478.06 | 93.5 |
1 | -462.73 | 1.88 | 251.29 | -479.89 | 93.7 |
Fig.4 Impedance spectra for Q235 steel in the condensate water at 35 ℃ without(A) and with(B) various concentrations of CDDA in Nyquist form along with the equivalent electric circuit(C)WE: working electrode; RE: reference electrode.
c(CDDA)/(mmol·L-1) | Rp/(Ω·cm2) | Cdl/(μF·cm-2) | n | ηE(%) | |
---|---|---|---|---|---|
0 | 255.21 | 223.53 | 0.79 | 243.93 | —— |
0.05 | 1589.18 | 83.55 | 0.82 | 1598.41 | 84.7 |
0.1 | 1999.30 | 72.18 | 0.77 | 2003.76 | 87.8 |
0.3 | 2060.62 | 50.49 | 0.80 | 2079.39 | 88.3 |
0.6 | 2265.85 | 30.42 | 0.81 | 2289.16 | 89.3 |
1 | 2330.47 | 27.40 | 0.83 | 2358.32 | 89.7 |
Table 5 Impedance parameters for Q235 steel in the condensate water with various concentrations of CDDA
c(CDDA)/(mmol·L-1) | Rp/(Ω·cm2) | Cdl/(μF·cm-2) | n | ηE(%) | |
---|---|---|---|---|---|
0 | 255.21 | 223.53 | 0.79 | 243.93 | —— |
0.05 | 1589.18 | 83.55 | 0.82 | 1598.41 | 84.7 |
0.1 | 1999.30 | 72.18 | 0.77 | 2003.76 | 87.8 |
0.3 | 2060.62 | 50.49 | 0.80 | 2079.39 | 88.3 |
0.6 | 2265.85 | 30.42 | 0.81 | 2289.16 | 89.3 |
1 | 2330.47 | 27.40 | 0.83 | 2358.32 | 89.7 |
Fig.5 EDX spectra(A1—C1) and surface morphologies(A2—C2) of Q235 steel before and after immersion in condensate water for 72 h (A1, A2) Without CDDA; (B1, B2) with 1 mmol/L CDDA; (C1, C2) freshly polished.
Fig.6 Two-dimension AFM images(A1—C1) and sectional analyses(A2—C2) of Q235 steel surface before and after immersion in condensate water at 35 ℃ for 72 h(A1, A2) Without inhibitor; (B1, B2) with 1 mmol/L CDDA; (C1, C2) freshly polished.
Fig.7 Variation of contact angles for Q235 steel after immersion in condensate water containing 1 mmol/L CDDA with different time(A) and under different pH values after 72 h immersion(B)
Fig.8 XPS deconvoluted spectra of major elements on Q235 steel after immersion in condensate water with 1 mmol/L CDDA at 35 ℃ for 72 h(A) C1s; (B) N1s; (C) O1s.
Atom | Atom | ||||
---|---|---|---|---|---|
C1 | 0.019 | 0.004 | C11 | 0.022 | 0.005 |
C2 | 0.010 | 0 | C12 | 0.023 | 0.008 |
C3 | 0.019 | 0.001 | C13 | 0.030 | 0.011 |
C4 | 0.024 | 0.002 | C14 | 0.031 | 0.017 |
C5 | 0.028 | 0 | C15 | 0.032 | 0.025 |
C6 | 0.027 | 0.002 | C16 | 0.059 | 0.038 |
C7 | 0.027 | 0.001 | C17 | 0.091 | 0.058 |
C8 | 0.026 | 0.002 | C18 | 0.121 | 0.223 |
C9 | 0.013 | 0.003 | N19 | 0.015 | 0.367 |
C10 | 0.022 | 0.004 |
Table 6 Condensed Fukui indices of ODA*
Atom | Atom | ||||
---|---|---|---|---|---|
C1 | 0.019 | 0.004 | C11 | 0.022 | 0.005 |
C2 | 0.010 | 0 | C12 | 0.023 | 0.008 |
C3 | 0.019 | 0.001 | C13 | 0.030 | 0.011 |
C4 | 0.024 | 0.002 | C14 | 0.031 | 0.017 |
C5 | 0.028 | 0 | C15 | 0.032 | 0.025 |
C6 | 0.027 | 0.002 | C16 | 0.059 | 0.038 |
C7 | 0.027 | 0.001 | C17 | 0.091 | 0.058 |
C8 | 0.026 | 0.002 | C18 | 0.121 | 0.223 |
C9 | 0.013 | 0.003 | N19 | 0.015 | 0.367 |
C10 | 0.022 | 0.004 |
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