Quantitative Measurement Technique for Anodic Corrosion of BDD Advanced Oxidation Electrodes

IF 4.6 Q1 CHEMISTRY, ANALYTICAL
Joshua J. Tully*, Daniel Houghton, Ben G. Breeze, Timothy P. Mollart and Julie V. Macpherson*, 
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Abstract

Electrochemical advanced oxidation (EAO) systems are of significant interest due to their ability to treat a wide range of organic contaminants in water. Boron doped diamond (BDD) electrodes have found considerable use in EAO. Despite their popularity, no laboratory scale method exists to quantify anodic corrosion of BDD electrodes under EAO conditions; all are qualitative using techniques such as scanning electron microscopy, electrochemistry, and spectroscopy. In this work, we present a new method which can be used to quantify average corrosion rates as a function of solution composition, current density, and BDD material properties over relatively short time periods. The method uses white light interferometry (WLI), in conjunction with BDD electrodes integrated into a 3D-printed flow cell, to measure three-dimensional changes in the surface structure due to corrosion over a 72 h period. It is equally applicable to both thin film and thicker, freestanding BDD. A further advantage of WLI is that it lends itself to large area measurements; data are collected herein for 1 cm diameter disk electrodes. Using WLI, corrosion rates as low as 1 nm h–1 can be measured. This enables unequivocal demonstration that organics in the EAO solution are not a prerequisite for BDD anodic corrosion. However, they do increase the corrosion rates. In particular, we quantify that addition of 1 M acetic acid to 0.5 M potassium sulfate results in the average corrosion rate increasing ∼60 times. In the same solution, microcrystalline thin film BDD is also found to corrode ∼twice as fast compared to freestanding polished BDD, attributed to the presence of increased sp2 carbon content. This methodology also represents an important step forward in the prediction of BDD electrode lifetimes for a wide range of EAO applications.

Abstract Image

Abstract Image

BDD 高级氧化电极阳极腐蚀定量测量技术
电化学高级氧化(EAO)系统能够处理水中的各种有机污染物,因此备受关注。掺硼金刚石(BDD)电极在 EAO 中得到了广泛应用。尽管它们很受欢迎,但目前还没有实验室规模的方法来量化 BDD 电极在 EAO 条件下的阳极腐蚀;所有方法都是使用扫描电子显微镜、电化学和光谱学等技术进行定性分析。在这项工作中,我们提出了一种新方法,可用于量化相对较短时间内作为溶液成分、电流密度和 BDD 材料特性函数的平均腐蚀率。该方法使用白光干涉仪(WLI),结合集成到三维打印流动池中的 BDD 电极,测量 72 小时内因腐蚀引起的表面结构的三维变化。它同样适用于薄膜和较厚的独立 BDD。WLI 的另一个优点是适合大面积测量;本文收集的数据是直径为 1 厘米的圆盘电极。使用 WLI 可以测量低至 1 nm h-1 的腐蚀速率。这就明确证明了 EAO 溶液中的有机物并不是 BDD 阳极腐蚀的先决条件。但是,有机物确实会增加腐蚀速率。特别是,我们发现在 0.5 M 硫酸钾中加入 1 M 乙酸会使平均腐蚀速率增加 60 倍。在同一溶液中,微晶薄膜 BDD 的腐蚀速度也是独立抛光 BDD 的两倍,这归因于 Sp2 碳含量的增加。这种方法也代表了在预测 BDD 电极寿命方面向前迈出的重要一步,它适用于广泛的 EAO 应用。
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来源期刊
ACS Measurement Science Au
ACS Measurement Science Au 化学计量学-
CiteScore
5.20
自引率
0.00%
发文量
0
期刊介绍: ACS Measurement Science Au is an open access journal that publishes experimental computational or theoretical research in all areas of chemical measurement science. Short letters comprehensive articles reviews and perspectives are welcome on topics that report on any phase of analytical operations including sampling measurement and data analysis. This includes:Chemical Reactions and SelectivityChemometrics and Data ProcessingElectrochemistryElemental and Molecular CharacterizationImagingInstrumentationMass SpectrometryMicroscale and Nanoscale systemsOmics (Genomics Proteomics Metabonomics Metabolomics and Bioinformatics)Sensors and Sensing (Biosensors Chemical Sensors Gas Sensors Intracellular Sensors Single-Molecule Sensors Cell Chips Arrays Microfluidic Devices)SeparationsSpectroscopySurface analysisPapers dealing with established methods need to offer a significantly improved original application of the method.
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