Adsorption of the prototypical organic corrosion inhibitor benzotriazole on the Cu(100) surface
Adsorption of the prototypical organic corrosion inhibitor benzotriazole on the Cu(100) surface
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DOI：
10.1016/j.corsci.2022.110589
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发表时间：
2022-08
影响因子：
8.3
通讯作者：
M. Turano;M. Walker;F. Grillo;C. Gattinoni;G. Hunt;P. Kirkman;N. Richardson;C. Baddeley;G. Costantini
中科院分区：
文献类型：
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作者：
M. Turano;M. Walker;F. Grillo;C. Gattinoni;G. Hunt;P. Kirkman;N. Richardson;C. Baddeley;G. Costantini
用实验和理论相结合的方法研究了苯并三氮唑(BTAH)与铜(100)的相互作用。结合扫描隧道显微镜(STM)、X射线光电子能谱(XPS)、高分辨电子能量损失谱(HREELS)和密度泛函理论(DFT)对该体系的结构和化学性质进行了研究。研究发现，BTAH在铜表面吸附时会发生去质子化，其取向依赖于分子的覆盖度。苯并三氮唑(BTA)物种最初位于与底物平行的平面，但在较高的分子覆盖率时，发生向直立吸附几何结构的转变。随着BTAH曝光量的增加，随着分子密度的增加，观察到垂直排列的BTA的不同相，直到形成最终的自限单层。理论和实验都表明，CuBTA和Cu(BTA)_2金属有机络合物是这种单分子膜的基本构成单元。这项工作与以前关于苯并三唑与其他低米勒指数铜表面相互作用的研究结果有几个相似之处，从而理想地完成并总结了这些结果。这一总体情况构成了理解保护铜免受腐蚀的机制的重要起点。
The interaction of benzotriazole (BTAH) with Cu(100) has been studied as a function of BTAH exposure in a joint experimental and theoretical effort. Scanning tunnelling microscopy (STM), X-ray photoelectron spectroscopy (XPS), high resolution electron energy loss spectroscopy (HREELS) and density functional theory (DFT) calculations have been combined to elucidate the structural and chemical characteristics of this system. BTAH is found to deprotonate upon adsorption on the copper surface and to adopt an orientation that depends on the molecular coverage. Benzotriazolate (BTA) species initially lie with their planes parallel to the substrate but, at a higher molecular coverage, a transition occurs to an upright adsorption geometry. Upon increasing the BTAH exposure, different phases of vertically aligned BTAs are observed with increasing molecular densities until a final, self-limiting monolayer is developed. Both theory and experiment agree in identifying CuBTA and Cu(BTA)2metal-organic complexes as the fundamental building blocks of this monolayer. This work shows several similarities with the results of previous studies on the interaction of benzotriazole with other low Miller index copper surfaces, thereby ideally completing and concluding them. The overall emerging picture constitutes an important starting point for understanding the mechanism for protection of copper from corrosion.