化学
氧化还原
质谱法
电喷雾电离
亚胺离子
电化学
光化学
无机化学
离子
有机化学
色谱法
电极
物理化学
作者
Jiahui Bai,Mingmai Bao,Shanshan Wang,Tianlun Wen,Yuling Li,Jing Zhang,Tian‐Sheng Mei,Yinlong Guo
标识
DOI:10.1016/j.aca.2023.341794
摘要
The combination of electrochemistry and mass spectrometry is a powerful analytical tool for studying redox reaction mechanisms and identifying products or intermediates. However, the previously reported devices all require bespoke fabrication and are too complicated to be assembled and used by others. Crucially, the long ion transport distance and small spray volumes make it difficult to capture the short-lived intermediates. We present a practical mass spectrometric method in which surface-modified carbon fiber paper is innovatively applied to detect electrogenerated intermediates. Treating carbon fiber paper with dilute nitric acid removes its surface impurities, enhancing the capability of electro-redox. Electrospray ionization and redox reaction occur simultaneously on the tip of the paper. Transient electro-redox species generate and transfer into gas phase as soon as the appearance of spray. Rapid transport of quantities of electrogenerated ions to the mass spectrometer inlet makes it possible for mass spectrometric identification on the millisecond scale. The short-lived radical cations and iminium ions were successfully captured, reflecting the starting step of the cross-dehydrogenation coupling reaction. The real-time oxidation and online functionalization reactions of tertiary amines were achieved using this device without additional oxidants and electrolytes. In this way we could achieve in-depth mechanistic understanding and rapid screening of serial reactions.
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