title: Switching Transient Generation in Surface Interrogation Scanning Electrochemical Microscopy and Time-of-Flight Techniques.
abstract: In surface interrogation scanning electrochemical microscopy (SI-SECM), fine and accurate control of the delay time between substrate generation and tip interrogation (tdelay) is crucial because tdelay defines the decay time of the reactive intermediate. In previous applications of the SI-SECM, the resolution in the control of tdelay has been limited to several hundreds of milliseconds due to the slow switching of the bipotentiostat. In this work, we have improved the time resolution of tdelay control up to ca. 1 μs, enhancing the SI-SECM to be competitive in the time domain with the decay of many reactive intermediates. The rapid switching SI-SECM has been implemented in a substrate generation-tip collection time-of-flight (SG-TC TOF) experiment of a solution redox mediator, and the results obtained from the experiment exhibited good agreement with that obtained from digital simulation. The reaction rate constant of surface Co(IV) on oxygen-evolving catalyst film, which was inaccessible thus far due to the lack of tdelay control, has been measured by the rapid switching SI-SECM.
authors.affiliation: Center for Electrochemistry, Department of Chemistry, The University of Texas at Austin , 105 East 24th Street, STOP A5300, Austin, Texas 78712-1224, United States.
authors.forename: Hyun S
authors.initials: HS
authors.lastname: Ahn
authors.affiliation: Center for Electrochemistry, Department of Chemistry, The University of Texas at Austin , 105 East 24th Street, STOP A5300, Austin, Texas 78712-1224, United States.
authors.forename: Allen J
authors.initials: AJ
authors.lastname: Bard