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

IF 4.6 Q1 CHEMISTRY, ANALYTICAL
Christoph J. Bondue, Marc T. M. Koper and Kristina Tschulik*, 
{"title":"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","authors":"Christoph J. Bondue,&nbsp;Marc T. M. Koper and Kristina Tschulik*,&nbsp;","doi":"10.1021/acsmeasuresciau.3c00009","DOIUrl":null,"url":null,"abstract":"<p >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 H<sub>2</sub> and O<sub>2</sub> 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 H<sub>2</sub> and O<sub>2</sub> are readily accessible for a large range of electrode–electrolyte combinations.</p>","PeriodicalId":29800,"journal":{"name":"ACS Measurement Science Au","volume":null,"pages":null},"PeriodicalIF":4.6000,"publicationDate":"2023-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://ftp.ncbi.nlm.nih.gov/pub/pmc/oa_pdf/fc/50/tg3c00009.PMC10436368.pdf","citationCount":"1","resultStr":"{\"title\":\"A Versatile and Easy Method to Calibrate a Two-Compartment Flow Cell for Differential Electrochemical Mass Spectrometry Measurements\",\"authors\":\"Christoph J. Bondue,&nbsp;Marc T. M. Koper and Kristina Tschulik*,&nbsp;\",\"doi\":\"10.1021/acsmeasuresciau.3c00009\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >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 H<sub>2</sub> and O<sub>2</sub> 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 H<sub>2</sub> and O<sub>2</sub> are readily accessible for a large range of electrode–electrolyte combinations.</p>\",\"PeriodicalId\":29800,\"journal\":{\"name\":\"ACS Measurement Science Au\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":4.6000,\"publicationDate\":\"2023-05-19\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://ftp.ncbi.nlm.nih.gov/pub/pmc/oa_pdf/fc/50/tg3c00009.PMC10436368.pdf\",\"citationCount\":\"1\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"ACS Measurement Science Au\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acsmeasuresciau.3c00009\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, ANALYTICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Measurement Science Au","FirstCategoryId":"1085","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acsmeasuresciau.3c00009","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, ANALYTICAL","Score":null,"Total":0}
引用次数: 1

摘要

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。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

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

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

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.

求助全文
通过发布文献求助,成功后即可免费获取论文全文。 去求助
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.
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
确定
请完成安全验证×
copy
已复制链接
快去分享给好友吧!
我知道了
右上角分享
点击右上角分享
0
联系我们:info@booksci.cn Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。 Copyright © 2023 布克学术 All rights reserved.
京ICP备2023020795号-1
ghs 京公网安备 11010802042870号
Book学术文献互助
Book学术文献互助群
群 号:481959085
Book学术官方微信