Screening the Surface Structure-Dependent Action of a Benzotriazole Derivative on Copper Electrochemistry in a Triple-Phase Nanoscale Environment.
Screening the Surface Structure-Dependent Action of a Benzotriazole Derivative on Copper Electrochemistry in a Triple-Phase Nanoscale Environment.
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DOI：
10.1021/acs.jpcc.2c04494
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发表时间：
2022-09-08
影响因子：
3.7
通讯作者：
Unwin, Patrick R.
中科院分区：
文献类型：
--
作者：
Daviddi, Enrico;Shkirskiy, Viacheslav;Kirkman, Paul M.;Robin, Mathew P.;Bentley, Cameron L.;Unwin, Patrick R.
铜 (Cu) 腐蚀是汽车行业、炼油厂和运输业中一个引人注目的问题，主要是由分散在油相中的酸性水滴的作用引起的。腐蚀抑制剂，例如苯并三唑（BTAH）及其衍生物，被广泛用于限制此类腐蚀过程。腐蚀抑制剂的功效预计取决于暴露于腐蚀环境的金属的表面晶体学。然而，对添加剂对多晶金属表面晶体结构局部水平的影响的研究具有挑战性，特别是缺乏三相腐蚀问题（金属/水/油）。为了解决这个问题，扫描电化学细胞显微镜 (SECCM) 用于酸性纳米液滴弯月面|油层|多晶铜构型，以探索油溶性 BTAH 衍生物 (BTA-R) 在局部水性纳米探针范围内对铜电化学的颗粒依赖性影响。以伏安模式在铜表面上超过 1000 个点的阵列收集的电化学图揭示了与腐蚀相关的阴极（主要是氧还原反应）和阳极（铜电氧化）过程，作为局部晶体结构的函数，通过同位电子背散射衍射 (EBSD) 推导出来。 BTA-R 在所分析的整个晶体取向谱上都具有活性，但存在复杂的晶粒依赖性作用，对于氧还原和铜氧化而言是不同的。该方法精确定位了促进腐蚀相关过程的表面结构图案以及 BTA-R 最有效的工作位置。组合的 SECCM-EBSD 提供了一系列表面位点的详细筛选，其结果将为未来的建模研究提供信息，最终有助于更好的抑制剂设计。
Copper (Cu) corrosion is a compelling problem in the automotive sector and in oil refinery and transport, where it is mainly caused by the action of acidic aqueous droplets dispersed in an oil phase. Corrosion inhibitors, such as benzotriazole (BTAH) and its derivatives, are widely used to limit such corrosion processes. The efficacy of corrosion inhibitors is expected to be dependent on the surface crystallography of metals exposed to the corrosion environment. Yet, studies of the effect of additives at the local level of the surface crystallographic structure of polycrystalline metals are challenging, particularly lacking for the triple-phase corrosion problem (metal/aqueous/oil). To address this issue, scanning electrochemical cell microscopy (SECCM), is used in an acidic nanodroplet meniscus|oil layer|polycrystalline Cu configuration to explore the grain-dependent influence of an oil soluble BTAH derivative (BTA-R) on Cu electrochemistry within the confines of a local aqueous nanoprobe. Electrochemical maps, collected in the voltammetric mode at an array of >1000 points across the Cu surface, reveal both cathodic (mainly the oxygen reduction reaction) and anodic (Cu electrooxidation) processes, of relevance to corrosion, as a function of the local crystallographic structure, deduced with co-located electron backscatter diffraction (EBSD). BTA-R is active on the whole spectrum of crystallographic orientations analyzed, but there is a complex grain-dependent action, distinct for oxygen reduction and Cu oxidation. The methodology pinpoints the surface structural motifs that facilitate corrosion-related processes and where BTA-R works most efficiently. Combined SECCM–EBSD provides a detailed screen of a spectrum of surface sites, and the results should inform future modeling studies, ultimately contributing to a better inhibitor design.
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