Local Activities of Hydroxide and Water Determine the Operation of Silver-Based Oxygen Depolarized Cathodes

Angew Chem Int Ed Engl. 2018 Sep 17;57(38):12285-12289. doi: 10.1002/anie.201807798. Epub 2018 Aug 28.

Abstract

Local ion activity changes in close proximity to the surface of an oxygen depolarized cathode (ODC) were measured by scanning electrochemical microscopy (SECM). While the operating ODC produces OH- ions and consumes O2 and H2 O through the electrocatalytic oxygen reduction reaction (ORR), local changes in the activity of OH- ions and H2 O are detected by means of a positioned Pt microelectrode serving as an SECM tip. Sensing at the Pt tip is based on the pH-dependent reduction of PtO and obviates the need for prior electrode modification steps. It can be used to evaluate the coordination numbers of OH- ions and H2 O, and the method was exploited as a novel approach of catalyst activity assessment. We show that the electrochemical reaction on highly active catalysts can have a drastic influence on the reaction environment.

Keywords: electrochemistry; gas diffusion electrodes; local ion activities; nanostructures; scanning probe microscopy.