Angewandte Chemie, Accepted Article.

We report a new mass spectrometric method for detecting electrogenerated intermediates. This approach is based on simultaneous activation of electrospray ionization and redox reaction on a wireless bipolar ultramicroelectrode, which is fabricated in the tip of a quartz nanopipette. The hollow structure of the ultramicroelectrode permits rapid transferring the transient species from electrode‐electrolyte interfaces into gas phase for mass spectrometric identification on the time scale of microseconds. The long‐sought fleeting intermediates including TPrA●+, whose lifetime in solution is only 200 μs, and catecholamine o‐semiquinone radicals, whose second‐order rate constant is typically ~109 M‐1s‐1, were successfully identified, helping clarify the previously hidden reaction pathways. Accordingly, our method may have wide applicability in exploring the dynamics of many electrochemical reactions, especially their ultrafast initial steps.