规整有机分子自聚集体对铜的高效缓蚀的研究

doi:10.11949/0438-1157.20191318

摘要/Abstract

摘要：

通过多步法合成了离子型含双苯并三氮唑环的目标分子，4，4'-{苯-1，3-二基二[(1E)-3-羰基丙-1-烯-1，3-二基]}二[2-(2H-苯并三唑-2-基)苯醇酸]二钾。在室温条件下，目标分子在3.5%（质量）NaCl/DMSO（二甲基亚枫）混合溶液（体积比：40/60）中能够发生分子自组装产生纳-微米级的自聚集体。通过傅里叶变换红外光谱（FT-IR）、拉曼光谱和X射线光电子能谱（XPS）的表征，证实了所形成的目标分子自聚集体能够对铜表面产生强烈的化学吸附作用，在铜表面形成自组装膜。利用电化学方法测定了目标分子自聚集体吸附在铜表面形成自组装膜后，在3.5%（质量）NaCl溶液中的缓蚀性能。结果表明目标分子自聚集体在NaCl溶液中能高效地抑制铜腐蚀。

关键词: 自聚集, 吸附, 铜, NaCl溶液, 腐蚀, 修复

Abstract:

This study presents synthesis of target ionic bistriazole rings-based molecule, 4,4'-{benzene-1,3-diylbis[(1E)-3-oxoprop-1-ene-1,3-diyl]}bis[2-(2H-benzotriazol-2-yl)phenolate] dipotassium (BDBD), through multi-step preparation route. At room temperature, the target molecule can self-assemble to produce nano-micron self-aggregates in a 3.5%(mass) NaCl / DMSO (dimethyl maple) mixed solution (volume ratio, 40/60). It is shown that the predominantly strong chemical adsorption of the formed molecular self-aggregates on the studied copper specimen leads to the yield of self-assembly film on copper surface, which is characterized by FT-IR, Raman and XPS spectroscopy. The corrosion inhibition performance of the stable self-aggregates adsorbed-copper specimens in 3.5%(mass) brine solution based on electrochemical method is surveyed. The results show that the target molecular self-aggregates can effectively inhibit copper corrosion in NaCl solution.

Key words: self-aggregation, adsorption, copper, NaCl solution, corrosion, repair

中图分类号:

TG 178

罗雪, 荆川, 黄海军, 李红茹, 王治永, 王震强, 高放, 张胜涛. 规整有机分子自聚集体对铜的高效缓蚀的研究[J]. 化工学报, 2020, 71(10): 4733-4749.

Xue LUO, Chuan JING, Haijun HUANG, Hongru LI, Zhiyong WANG, Zhenqiang WANG, Fang GAO, Shengtao ZHANG. Study on highly efficient corrosion inhibition of copper by regular self-aggregates of organic molecule[J]. CIESC Journal, 2020, 71(10): 4733-4749.

图/表 20

图1 目标分子BDBD的化学结构和合成路线

Fig.1 Chemical structure and synthesis route of the target molecule BDBD

图2 目标分子BDBD形成自聚集体并有效吸附在铜表面示意图

Fig.2 Schematic diagram of the formation of the target molecular BDBD aggregates efficiently adsorbed on copper surface

图3 目标分子BDBD自聚集体在浓度为5×10-4 mol/L条件下，在混合溶剂3.5% NaCl/DMSO溶液中（DMSO体积含量40%）聚集20 min后的扫描电镜图像(a)；1 h后的扫描电镜图像(b)；2 h后的扫描电镜图像(c)

Fig.3 SEM images of BDBD aggregates at 5×10-4 mol/L in the mixed 3.5% NaCl solution/DMSO (40% volume ratio of DMSO) at aggregation time course of 20 min (a)， 1 h (b)， 2 h (c), respectively

图4 自聚集时间2 h，在3.5% NaCl/ DMSO混合水溶液 (DMSO体积比为40%) 中，BDBD自聚集体浓度分别为1.0×10-4 mol/L（a）、3.0×10-4 mol/L(b)、5.0×10-4 mol/L（c）、7.0×10-4 mol/L（d）时, 样品的扫描电镜图

Fig.4 SEM images of the BDBD aggregates in the mixed 3.5% NaCl DMSO aqueous solution (40% DMSO volume ratio) at 2 h evolving time with diflerent BDBD concentration: 1.0×10-4 mol/L （a）, 3.0×10-4 mol/L (b), 5.0×10-4 mol/L （c）, 7.0×10-4 mol/L （d）

图5 铜表面的SEM表面形貌分析: 打磨好的铜试样的表面形貌 (a)；铜试样在3.0×10-4 mol/L(b)、5.0×10-4 mol/L(c)和7.0×10-4 mol/L(d)的BDBD自聚集体、3.5% NaCl/DMSO溶液浸泡3 h后的表面形貌

Fig.5 SEM micrographs of the studied Cu specimen surfaces: before the immersion in the 3.5% NaCl/DMSO aqueous solution containing the stable BDBD aggregates (a); after the immersion in the 3.5% NaCl/DMSO aqueous solution with 3.0×10-4 mol/L of the stable BDBD aggregates for 3 h (b); after the immersion in the 3.5% NaCl/DMSO aqueous solution with 5.0×10-4 mol/L of the stable BDBD aggregates for 3 h (c); after the immersion in the 3.5% NaCl/DMSO aqueous solution with 7.0×10-4 mol/L of the stable BDBD aggregates for 3 h (d)

图6 铜试样在5.0×10-4 mol/L稳定的BDBD自聚集体的3.5% NaCl/ DMSO溶液浸泡3 h后，取出浸泡于3.5% NaCl溶液14 d后的表面形貌图

Fig.6 SEM micrographs of the studied Cu specimen surface absorbed with 5.0×10-4 mol/L of the stable BDBD aggregates for 3 h in 3.5% NaCl/ DMSO, which was take out and immersed in the 3.5% NaCl for 14 d

图7 BDBD粉末的FT-IR光谱图(a)；稳定的BDBD自聚集体吸附在铜表面后的FT-IR光谱图(b)；稳定的BDBD自聚集体吸附在铜表面后的拉曼光谱图(c)

Fig.7 FT-IR spectrum of the BDBD powder (a); FT-IR spectrum of the stable BDBD aggregates adsorbed on the studied copper specimen surfaces (b); Raman spectra of stable BDBD aggregates adsorbed on the studied copper specimen surfaces (c)

图8 在3.5% NaCl/DMSO (DMSO/H2O，体积比40/60) 混合溶液中浸泡3 h后铜表面的Cu 2p (a)； O 1s (b)； C 1s (c) XPS谱图

Fig.8 Cu 2p (a), O 1s (b), C 1s (c) XPS spectra and the fitted curves measured on the studied copper specimens that were immersion in the mixed 3.5% NaCl DMSO aqueous solution for 3 h (DMSO/H2O: 40/60, volume ratio)

图9 铜片在含有浓度为5.0×10-4 mol/L稳定的BDBD自聚集体的3.5% NaCl/ DMSO溶液 (DMSO/H2O，体积比40/60) 中浸泡3 h后的铜表面的Cu 2p (a)； C 1s (b)； O 1s (c)和N 1s (d) XPS谱图

Fig.9 Cu 2p (a)， C 1s (b)； O 1s (c)， N 1s (d) XPS spectra and the fitted curves measured on the studied copper specimens after 3 h of immersion in the mixed 3.5% NaCl DMSO aqueous solution (DMSO/H2O: 40/60, volume ratio) containing the stable BDBD aggregates of 5.0 ×10-4 mol/L

图10 空白铜片和吸附了不同浓度的稳定BDBD自聚集体的铜片在3.5% NaCl溶液中的动电位极化曲线jpeak——Tafel曲线腐蚀峰的最大电流密度；jmin—Tafel曲线腐蚀峰最小电流密度

Fig.10 Potentiodynamic polarization curves in 3.5 % NaCl solution for the studied naked copper electrodes, and for the studied stable BDBD-aggregates of different concentrations covered copper electrodes

表1 空白铜和吸附了不同浓度的稳定的BDBD自组装体的铜在3.5% NaCl溶液中的极化曲线参数

Table 1 Polarization parameters for the studied copper specimens covered without and with the stable BDBD aggregates of different concentrations in 3.5% NaCl solution

缓蚀剂	极化曲线参数
缓蚀剂	c (mol/L)	E_corr(SCE)/ V	j_corr/(A/cm²)	β_c/(V/dec)	β_a/(V/dec)	η_j/%
空白	—	-0.221	5.233×10^-6	-0.1667	0.04305	—
BDBD自聚集体	1.0×10^-4	-0.237	1.349×10^-6	-0.1331	0.1153	74.22
	3.0×10^-4	-0.265	9.35×10^-7	-0.1382	0.1192	82.14
	5.0×10^-4	-0.269	2.22×10^-7	-0.1471	0.2025	95.76
	7.0×10^-4	-0.251	4.78×10^-7	-0.1425	0.1393	90.87

图11 空白铜片和吸附了不同浓度的稳定的BDBD自聚集体的铜片在3.5% NaCl溶液中的Nyquist图

Fig.11 Nyquist plots for the studied naked copper electrodes and the stable BDBD aggregates of different concentrations covered copper electrodes in 3.5% NaCl solution

图12 在3.5% NaCl溶液中拟合EIS实验数据的等效电路图

Fig.12 Equivalent circuit models fitting the EIS experimental data in 3.5% NaCl solution

表3 在298 K下，稳定的BDBD自聚集体于3.5% NaCl溶液中的吸附热力学参数

Table 3 Thermodynamic parameters for the adsorption of stable BDBD aggregates in 3.5% NaCl solution at 298 K

方法	K_ads/ (L/mol)	吸附能/ (J/mol)
Polarization	4.9×10⁴	-6730
EIS	4.5×10⁴	-36510

图A1 目标分子BDBD的1H NMR核磁氢谱图

Fig.A1 Representative 1H NMR spectrum of target molecule BDBD

图A2 目标分子BDBD自聚集体在浓度为5×10-4 mol/L条件下在混合溶剂3.5% NaCl 溶液/DMSO (DMSO体积占比为40%)中聚集6 h后的扫描电镜图像

Fig.A2 SEM images of the BDBD aggregates of 5.0×10-4 mol/L in the mixed 3.5% NaCl DMSO aqueous solution (40% DMSO volume ratio) at 6 h evolving time

图A3 空白铜试样浸泡于3.5% NaCl溶液14 d后的表面形貌图

Fig.A3 SEM micrographs of the studied blank Cu specimen surface immersed in the 3.5% NaCl for 14 d

图A4 吸附了稳定的BDBD自聚集体的铜在3.5% NaCl溶液中的Langmuir吸附等温线

Fig.A4 Langmuir adsorption isotherms of the stable BDBD aggregates covered on the studied copper specimen surfaces in 3.5 % NaCl solution (yp to potentiodynamic polarization and yE to electrochemical impedance spectroscopy

图A5 经结构优化后目标分子BDBD的稳定构型、HOMO和LUMO前线轨道以及Mulliken电荷分布

Fig.A5 Optimized geometric structure, electron cloudy density distribution of HOMO and LUMO and Mulliken charge of the target molecule BDBD

图A6 目标分子BDBD与铜离子（I）可能的化学络合机制

Fig.A6 The possible chemical coordination mechanism of the target molecule BDBD with Cu (I)

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