A Versatile and Easy Method to Calibrate a Two-Compartment Flow Cell for Differential Electrochemical Mass Spectrometry Measurements

IF 4.6 Q1 CHEMISTRY, ANALYTICAL ACS Measurement Science Au Pub Date : 2023-05-19 DOI:10.1021/acsmeasuresciau.3c00009
Christoph J. Bondue, Marc T. M. Koper and Kristina Tschulik*, 
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引用次数: 1

Abstract

Online techniques for the quantitative analysis of reaction products have many advantages over offline methods. However, owing to the low product formation rates in electrochemical reactions, few of these techniques can be coupled to electrochemistry. An exception is differential electrochemical mass spectrometry (DEMS), which gains increasing popularity not least because of its high time resolution in the sub-second regime. DEMS is often combined with a dual thin-layer cell (a two-compartment flow cell), which helps to mitigate a number of problems that arise due to the existence of a vacuum|electrolyte interface. However, the efficiency with which this cell transfers volatile reaction products into the vacuum of the mass spectrometer is far below 100%. Therefore, a calibration constant that considers not only the sensitivity of the DEMS setup but also the transfer efficiency of the dual thin-layer cell is needed to translate the signals observed in the mass spectrometer into electrochemical product formation rates. However, it can be challenging or impossible to design an experiment that yields such a calibration constant. Here, we show that the transfer efficiency of the dual thin-layer cell depends on the diffusion coefficient of the analyte. Based on this observation, we suggest a two-point calibration method. That is, a plot of the logarithm of the transfer efficiencies determined for H2 and O2 versus the logarithm of their diffusion coefficients defines a straight line. Extrapolation of this line to the diffusion coefficient of another analyte yields a good estimate of its transfer efficiency. This is a versatile and easy calibration method, because the transfer efficiencies of H2 and O2 are readily accessible for a large range of electrode–electrolyte combinations.

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一个通用的和简单的方法来校准一个双室流动电池的微分电化学质谱测量
用于反应产物定量分析的在线技术比离线方法具有许多优点。然而,由于电化学反应中产物形成率低,这些技术很少能与电化学结合。微分电化学质谱法(DEMS)是一个例外,它越来越受欢迎,尤其是因为它在亚秒范围内的高时间分辨率。DEMS通常与双薄层电池(双室流动电池)相结合,这有助于缓解由于真空电解质界面的存在而出现的许多问题。然而,该池将挥发性反应产物转移到质谱仪的真空中的效率远低于100%。因此,需要一个不仅考虑DEMS设置的灵敏度,还考虑双薄层电池的转移效率的校准常数,以将质谱仪中观察到的信号转化为电化学产物形成速率。然而,设计一个产生这样一个校准常数的实验可能具有挑战性或不可能。在这里,我们证明了双薄层细胞的转移效率取决于分析物的扩散系数。基于这一观察结果,我们提出了一种两点校准方法。也就是说,为H2和O2确定的转移效率的对数与它们的扩散系数的对数的关系图定义了一条直线。将这条线外推到另一种分析物的扩散系数可以很好地估计其转移效率。这是一种通用且简单的校准方法,因为H2和O2的转移效率对于大范围的电极-电解质组合来说很容易获得。
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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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