CIESC Journal ›› 2020, Vol. 71 ›› Issue (10): 4733-4749.doi: 10.11949/0438-1157.20191318

• Surface and interface engineering • Previous Articles     Next Articles

Study on highly efficient corrosion inhibition of copper by regular self-aggregates of organic molecule

Xue LUO1(),Chuan JING1(),Haijun HUANG1,Hongru LI1,Zhiyong WANG1,Zhenqiang WANG1,2,Fang GAO1(),Shengtao ZHANG1   

  1. 1.School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044, China
    2.College of Chemistry, Chongqing Normal University, Chongqing 401331, China
  • Received:2019-11-11 Revised:2020-03-28 Online:2020-10-05 Published:2020-04-22
  • Contact: Fang GAO;;


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

CLC Number: 

  • TG 178


Chemical structure and synthesis route of the target molecule BDBD"


Schematic diagram of the formation of the target molecular BDBD aggregates efficiently adsorbed on copper surface"


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"


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)"


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)"


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"


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)"


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)"


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"


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"

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"

c (mol/L)Ecorr(SCE)/ Vjcorr/(A/cm2)βc/(V/dec)βa/(V/dec)ηj /%


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


Equivalent circuit models fitting the EIS experimental data in 3.5% NaCl solution"

Table 3

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

方法Kads/ (L/mol)吸附能/ (J/mol)


Representative 1H NMR spectrum of target molecule BDBD"


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"


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


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"


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


The possible chemical coordination mechanism of the target molecule BDBD with Cu (I)"

1 Fan H, Li S, Zhao Z, et al. Inhibition of brass corrosion in sodium chloride solutions by self-assembled silane films[J]. Corrosion Science, 2011, 53: 4273-4281.
2 Lyon S B, Bingham R, Mills Douglas J. Advances in corrosion protection by organic coatings: what we know and what we would like to know[J]. Progress in Organic Coatings, 2017, 102: 2-7.
3 Kokalj A, Peljhan S. Density functional theory study of ATA, BTAH, and BTAOH as copper corrosion inhibitors: adsorption onto Cu(111) from gas phase[J]. Langmuir, 2010, 26: 14582-14593.
4 Finsgar M. 2-Mercaptobenzimidazole as a copper corrosion inhibitor: Part I. Long-term immersion, 3D-profilometry, and electrochemistry[J]. Corrosion Science, 2013, 72: 82-89.
5 Finsgar M. EQCM and XPS analysis of 1,2,4-triazole and 3-amino-1,2,4-triazole as copper corrosion inhibitors in chloride solution[J]. Corrosion Science, 2013, 77: 350-359.
6 Wang Z, Gong Y, Jing C, et al. Synthesis of dibenzotriazole derivatives bearing alkylene linkers as corrosion inhibitors for copper in sodium chloride solution: a new thought for the design of organic inhibitors[J]. Corrosion Science, 2016, 113: 64-77.
7 Sherif M E S. Effects of 2-amino-5-(ethylthio)-1,3,4-thiadiazole on copper corrosion as a corrosion inhibitor in 3% NaCl solutions[J]. Applied Surface Science, 2006, 252: 8615-8623.
8 Hong S, Chen W, Zhang Y, et al. Investigation of the inhibition effect of trithiocyanuric acid on corrosion of copper in 3.0wt.% NaCl[J]. Corrosion Science, 2013, 66: 308-314.
9 Izquierdo J, Santana J J, González S, et al. Uses of scanning electrochemical microscopy for the characterization of thin inhibitor films on reactive metals: The protection of copper surfaces by benzotriazole[J]. Electrochimica Acta, 2010, 55: 8791-8800.
10 Jafari A H, Hosseini S M A, Jamalizadeh E. Investigation of smart nanocapsules containing inhibitors for corrosion protection of copper[J]. Electrochimica Acta, 2010, 55: 9004-9009.
11 Khaled K F. Studies of the corrosion inhibition of copper in sodium chloride solutions using chemical and electrochemical measurements[J]. Materials Chemistry and Physics, 2011, 125: 427-433.
12 Li C C, Guo X. Y, Shen S,et al. Adsorption and corrosion inhibition of phytic acid calcium on the copper surface in 3wt% NaCl solution[J]. Corrosion Science, 2014, 83: 147-154.
13 Liu Y, Li S, Zhang J, et al. Corrosion inhibition of biomimetic super-hydrophobic electrodeposition coatings on copper substrate[J]. Corrosion Science, 2015, 94: 190-196.
14 Khiati Z, Othman A A, Sanchez-Moreno M, et al. Corrosion inhibition of copper in neutral chloride media by a novel derivative of 1,2,4-triazole[J]. Corrosion Science, 2011, 53: 3092-3099.
15 Wang B, Gao F, Ma H. Preparation and XPS studies of macromolecule mixed-valent Cu(I, II) and Fe(II, III) complexes[J]. Journal of Hazardous Materials, 2007, 144: 363-368.
16 Doong R A, Liao C Y. Enhanced visible-light-responsive photodegradation of bisphenol A by Cu, N-codoped titanate nanotubes prepared by microwave-assisted hydrothermal method[J]. Journal of Hazardous Materials, 2017, 322: 254-262.
17 Huang H, Fu Y, Wang X, et al. Nano- to micro-self-aggregates of new bisimidazole-based copoly(ionic liquid)s for protecting copper in aqueous sulfuric acid solution[J]. ACS Applied Materials & Interfaces, 2019, 11: 10135-10145.
18 Zhang D Q, Joo H G, Lee K Y. Investigation of molybdate-benzotriazole surface treatment against copper tarnishing[J]. Surface and Interface Analysis, 2009, 41: 164-169.
19 Lou W, Cai W, Li J P, et al. Additives-assisted electrodeposition of fine spherical copper powder from sulfuric acid solution[J]. Powder Technology, 2018, 326: 84-88.
20 Sherif E S M, Erasmus R M, Comins J D. In situ Raman spectroscopy and electrochemical techniques for studying corrosion and corrosion inhibition of iron in sodium chloride solutions[J]. Electrochimica Acta, 2010, 55: 3657-3663.
21 Sudheer M A Q. Electrochemical and theoretical investigation of triazole derivatives on corrosion inhibition behavior of copper in hydrochloric acid medium[J]. Corrosion Science, 2013, 70: 161-169.
22 Mihajlovic M B P, Radovanovic M B, Tasic Z Z, et al. Imidazole based compounds as copper corrosion inhibitors in seawater[J]. Journal of Molecular Liquids, 2017, 225: 127-136.
23 Qafsaoui W, Kendig M W, Perrot H, et al. Coupling of electrochemical techniques to study copper corrosion inhibition in 0.5 mol·L-1 NaCl by 1-pyrrolidine dithiocarbamate[J]. Electrochimica Acta, 2013, 87: 348-360.
24 张景玲. 苯并三氮唑复配体系对铜的协同缓蚀性能的研究[D]. 长沙:湖南大学, 2008.
Zhang J L. Investigation of the synergistic effect between BTA and its composite corrosion inhibitiors on copper[D]. Changsha:Hunan University, 2008.
25 Zhang D Q, Gao L X, Zhou G D. Inhibition of copper corrosion by bis-(1-benzotriazolymethylene)-(2,5-thiadiazoly)-disulfide in chloride media[J]. Applied Surface Science, 2004, 225: 287-293.
26 Singh M M, Rastogi R B, Upadhyay B N, et al. Thiosemicarbazide, phenyl isothiocyanate and their condensation product as corrosion inhibitors of copper in aqueous chloride solutions[J]. Materials Chemistry and Physics, 2003, 80: 283-293.
27 Hu L, Zhang S, Li W, et al. Electrochemical and thermodynamic investigation of diniconazole and triadimefon as corrosion inhibitors for copper in synthetic seawater[J]. Corrosion Science, 2010, 52: 2891-2896.
28 Qiang Y, Zhang S, Yan S, et al. Three indazole derivatives as corrosion inhibitors of copper in a neutral chloride solution[J]. Corrosion Science, 2017, 126: 295-304.
29 Solomon M M, Umoren S A. In-situ preparation, characterization and anticorrosion property of polypropylene glycol/silver nanoparticles composite for mild steel corrosion in acid solution[J]. Journal of Colloid and Interface Science, 2016, 462: 29-41.
30 Scendo M. Inhibition of copper corrosion in sodium nitrate solutions with nontoxic inhibitors[J]. Corrosion Science, 2008, 50: 1584-1592.
31 Scendo M. The effect of purine on the corrosion of copper in chloride solutions[J]. Corrosion Science, 2007, 49: 373-390.
32 Mendonça G L F, Costa S N, Freire V N, et al. Understanding the corrosion inhibition of carbon steel and copper in sulphuric acid medium by amino acids using electrochemical techniques allied to molecular modelling methods[J]. Corrosion Science, 2017, 115: 41-55.
33 Zhang J, Liu Z, Han G C, et al. Inhibition of copper corrosion by the formation of Schiff base self-assembled monolayers[J]. Applied Surface Science, 2016, 389: 601-608.
[1] Chen WANG, Xiaohui SHE, Xiaosong ZHANG. Thermodynamic study of liquid air energy storage with air purification unit [J]. CIESC Journal, 2020, 71(S1): 23-30.
[2] Huizhong ZHAO, Min LEI, Tianhou HUANG, Tao LIU, Min ZHANG. Water vapor adsorption performance of composite adsorbent MWCNT/MgCl2 [J]. CIESC Journal, 2020, 71(S1): 272-281.
[3] Wenxiang WU, Xiaoqu HAN, Zhijie ZHOU, Yu WANG, Daotong CHONG. Dehumidification characteristics of recirculated desiccant wheel dehumidification system under variable working conditions [J]. CIESC Journal, 2020, 71(S1): 355-360.
[4] Bowen LIU, Shuai DENG, Shuangjun LI, Li ZHAO, Zhenyu DU, Lijin CHEN. Experimental investigation on energy-efficiency performance of temperature swing adsorption system for CO2 capture [J]. CIESC Journal, 2020, 71(S1): 382-390.
[5] Junyuan WU, Weizhi HUO, Zhiqiang LI, Jiaheng ZENG, Yanbin JIANG. Preparation of coaxial electrospun zein nanofiber film embedding sodium lignosulfonate for enhanced adsorption of heavy metal ions [J]. CIESC Journal, 2020, 71(S1): 252-260.
[6] Zhongyi HE, Guangyue JIA, Mengmeng ZHANG, Jincan YAN, Liping XIONG, Hongbing JI. Tribological performance of hexagonal boron nitride supported ionic liquid lubricant additives [J]. CIESC Journal, 2020, 71(9): 4303-4313.
[7] Xin LIU, Pingli FENG, Wenshuo HOU, Zhenhua WANG, Kening SUN. Research progress of interlayers for lithium-sulfur batteries [J]. CIESC Journal, 2020, 71(9): 4031-4045.
[8] Zhe BAI, Ruijian LI, Wenshuo HOU, Haijun LI, Zhenhua WANG. Synthesis of bimetallic sulfide CuCo2S4 and its application in lithium-sulfur batteries [J]. CIESC Journal, 2020, 71(9): 4282-4291.
[9] Puxu LIU, Chaohui HE, Libo LI, Jinping LI. Stable mixed metal-organic framework for efficient C2H6/C2H4 separation [J]. CIESC Journal, 2020, 71(9): 4211-4218.
[10] Zhipeng LI, Shengli NIU, Kuihua HAN, Chunmei LU. Molecular simulation of the effect of doping modification on the adsorption properties of calcium-aluminum-based composites ester exchange catalysts [J]. CIESC Journal, 2020, 71(8): 3625-3632.
[11] Jian LI, Ge PU, Jiashan CHEN, Qiwen LIU. High-temperature volatility characteristics and pyrolysis mechanism of common sodium salts [J]. CIESC Journal, 2020, 71(8): 3452-3459.
[12] Jingyu HU, Rong YAO, Yuhang PAN, Chao ZHU, Shuang SONG, Yi SHEN. Photo-assisted regeneration of titanium dioxide/layered double hydroxide for removal of organic dyes in water [J]. CIESC Journal, 2020, 71(7): 3296-3303.
[13] Hua LIU, Jiajie PENG, Kai YU, Yi NI, Fang WANG, Quanwen PAN, Tianshu GE, Ruzhu WANG. Preparation and thermal storage performance of novel composite sorbent with activated alumina matrix [J]. CIESC Journal, 2020, 71(7): 3354-3361.
[14] Changhui LIU,Wenbo HUANG,Yanlong GU,Zhonghao RAO. Recent advances in high value added reuse of waste polystyrene in environment and energy [J]. CIESC Journal, 2020, 71(7): 2956-2972.
[15] Tao LIU, Shuting ZHANG. Study on low temperature selective catalytic reduction of NO by Ba and Co co-doped MnOx [J]. CIESC Journal, 2020, 71(7): 3106-3113.
Full text



[1] WEI Feng, SHEN Bo, CHEN Mingjie, ZHAO Yingxian, SHAO Liping. Modeling on a Modified Feeding Mode of Simulated Moving Bed for Improving Productivity[J]. , 2010, 18(2): 239 -243 .
[2] CHEN CHIA-YUNG AND HSIA KWANG-HSIANG (Institute of Chemical Metallurgy,Academia Sinica). THE KINETICS OF CuO REACTING WITH GASEOUS SO_2 AND O_2[J]. , 1965, 16(1): 1 -12 .
[3] Chen Yuchen, Ding Jie and Shen Ziqiu Dalian Institute of Technology. Interphase Mass Transfer (Ⅲ) Determination ofInterfacial Area in a Packed Column andInvestigation of Mass Transfer Model[J]. , 1984, 35(4): 294 -302 .
[4] Gu Zhongmao Zhang Hefei (Institute of Atomic Energy) (Northwestern Polytechnical University) D. T. Wasan and N. N. Li (Illinois Institute of Technology) (UOP Inc. ). Mass Transfer Modeling for Liquid Surfactant Membranes[J]. , 1986, 37(1): 1 -9 .

QIU Kunyu;LV Hexiang;CHEN Jianfeng

. Mathematical model for calculating micro-mixingchemical reaction in rotating packed bed[J]. , 2005, 56(7): 1218 -1224 .
[6] MA Xuehu;SONG Tianyi;LAN Zhong;ZHOU Xingdong;YANG Jinzong. Advances in liquid-solid-interfacial-energy-difference effect and condensation heat transfer enhancement[J]. , 2006, 57(8): 1763 -1775 .
[7] LIU Qibin;HE Yaling;ZHANG Dingcai;TAO Wenquan.

Boiling heat transfer of R123 outside single horizontal doubly-enhanced tubes

[J]. , 2006, 57(2): 251 -257 .
[8] WU Hailing, CHEN Tingkuan, LUO Yushan, GONG Wuqi. DPIV EXPERIMENTAL STUDY OF SQUARE JET INTO CROSSFLOW[J]. CIESC Journal, 2003, 54(2): 250 -254 .
[9] LEI Wu;WANG Fenghe;XIA Mingzhu;LU Lude;WANG Fengyun.

Properties of fluorescent polymer F-PAM prepared by reverse microemulsion polymerization

[J]. , 2006, 57(10): 2464 -2468 .
[10] . The Editorial Board of Journal of Chemical Industry and Engineering (China)[J]. , 1997, 48(1): 127 .