Altin Abdulrahman, Krzywiecki Maciej, Sarfraz Adnan, Toparli Cigdem, Laska Claudius, Kerger Philipp, Zeradjanin Aleksandar, Mayrhofer Karl J J, Rohwerder Michael, Erbe Andreas
Max-Planck-Institut für Eisenforschung GmbH, Max-Planck-Str. 1, 40237 Düsseldorf, Germany.
Institute of Physics-CSE, Silesian University of Technology, Konarskiego 22B, 44-100 Gliwice, Poland.
Beilstein J Nanotechnol. 2018 Mar 20;9:936-944. doi: 10.3762/bjnano.9.86. eCollection 2018.
Corrosion inhibitors are added in low concentrations to corrosive solutions for reducing the corrosion rate of a metallic material. Their mechanism of action is typically the blocking of free metal surface by adsorption, thus slowing down dissolution. This work uses electrochemical impedance spectroscopy to show the cyclic oligosaccharide β-cyclodextrin (β-CD) to inhibit corrosion of zinc in 0.1M chloride with an inhibition efficiency of up to 85%. Only a monomolecular adsorption layer of β-CD is present on the surface of the oxide covered metal, with Raman spectra of the interface proving the adsorption of the intact β-CD. Angular dependent X-ray photoelectron spectroscopy (ADXPS) and ultraviolet photoelectron spectroscopy (UPS) were used to extract a band-like diagram of the β-CD/ZnO interface, showing a large energy level shift at the interface, closely resembling the energy level alignment in an n-p junction. The energy level shift is too large to permit further electron transfer through the layer, inhibiting corrosion. Adsorption hence changes the defect density in the protecting ZnO layer. This mechanism of corrosion inhibition shows that affecting the defect chemistry of passivating films by molecular inhibitors maybe a viable strategy to control corrosion of metals.
缓蚀剂以低浓度添加到腐蚀性溶液中,以降低金属材料的腐蚀速率。其作用机制通常是通过吸附来阻断金属自由表面,从而减缓溶解。本研究利用电化学阻抗谱表明,环状寡糖β-环糊精(β-CD)在0.1M氯化物溶液中对锌具有缓蚀作用,缓蚀效率高达85%。在覆盖有氧化物的金属表面仅存在单分子吸附层的β-CD,界面的拉曼光谱证明了完整β-CD的吸附。利用角分辨X射线光电子能谱(ADXPS)和紫外光电子能谱(UPS)提取了β-CD/ZnO界面的带状图,显示界面处有较大的能级移动,与n-p结中的能级排列非常相似。能级移动太大,无法允许电子进一步穿过该层,从而抑制了腐蚀。因此,吸附改变了保护性ZnO层中的缺陷密度。这种缓蚀机制表明,通过分子抑制剂影响钝化膜的缺陷化学可能是控制金属腐蚀的一种可行策略。