Abstract

AbstractHyphenation of electrochemistry and mass spectrometry is an attractive method to investigate oxidation and reduction processes. By using mass spectrometry, electrochemically generated products can be identified. In this Review, different approaches to electrochemistry–mass spectrometry will be summarized, including hyphenation of electrochemical flow cells to mass spectrometry as well as integration of separation steps between electrochemical reactions and detection of products. Fields of application range from bioanalytical studies to studies regarding corrosion, electrosynthesis and energy carriers. Important historical developments will be highlighted, followed by an overview of terminology and instrumental setups and discussion of developments within recent years (2017–2020).

Highlights

  • EC-Mass spectrometry (MS) approach and named it differential electrochemistry mass spectrometry (DEMS) to distinguish from offline sampling methods

  • Mass spectrometry (MS) is ideally suited for this purpose as it can be used in combination with electrochemical flow cells as well as separation methods like high-performance liquid chromatography (HPLC) and capillary electrophoresis (CE)

  • The electrochemical cell has to be decoupled from the ionization voltage of several kV, and the inherent electrochemistry of the Electrospray ionization (ESI) source has to be kept in www.chemelectrochem.org mind.[6]

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Summary

Historical Developments

One of the main challenges of the investigation of electrochemical reactions is the rather small amount of products generated by electrochemistry compared to solution chemistry,[14] so that the transfer of analytes from electrode to detection system plays an important role. Esaka et al focused on the characterization of electrochemically generated anion radicals of phenanthrenequinone and anthraquinone while Matysik proposed so-called electrochemically assisted injection as an online sample preparation method for enhanced separation performance in CE and detectability of non-polar analytes in ESI-MS. The latter was Thomas Herl studied chemistry at the University of Regensburg (Germany) from 2011 to. Chemo- and Biosensors of the University of Regensburg (Germany) His PhD research is focused on the hyphenation of instrumental analytical systems including electrochemistry, capillary electrophoresis, and mass spectrometry. The different methodologies of online EC-MS, EC-HPLC-MS, HPLC-EC-MS and EC-CEMS have been widely applied, as several reviews show.[1,2,11,37,38,39,3,4,5,6,7,8,9,10]

Terminology
Instrumental Setups
Latest Developments and Applications
Energy Carriers and Corrosion
Electrosynthesis and Metabolism Studies
Real-Time EC-MS
EC-HPLC-MS
EC-CE-MS
Summary and Outlook
Method
Conflict of Interest
Full Text
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