Quantification of photoelectrogenerated hydroxyl radical on TiO2 by surface interrogation scanning electrochemical microscopy

Dodzi Zigah, Joaquín Rodríguez-López, Allen J. Bard

Research output: Contribution to journalArticlepeer-review


The surface interrogation mode of scanning electrochemical microscopy (SI-SECM) was used for the detection and quantification of adsorbed hydroxyl radical OH(ads) generated photoelectrochemically at the surface of a nanostructured TiO2 substrate electrode. In this transient technique, a SECM tip is used to generate in situ a titrant from a reversible redox pair that reacts with the adsorbed species at the substrate. This reaction produces an SECM feedback response from which the amount of adsorbate and its decay kinetics can be obtained. The redox pair IrCl62-/3- offered a reactive, selective and stable surface interrogation agent under the strongly oxidizing conditions of the photoelectrochemical cell. A typical OH(ads) saturation coverage of 338 μC cm-2 was found in our nanostructured samples by its reduction with the electrogenerated IrCl 63-. The decay kinetics of OH(ads) by dimerization to produce H2O2 were studied through the time dependence of the SI-SECM signal and the surface dimerization rate constant was found to be ∼kOH = 2.2 × 103 mol-1 m2 s-1. A radical scavenger, such as methanol, competitively consumes OH(ads) and yields a shorter SI-SECM transient, where a pseudo-first order rate analysis at 2 M methanol yields a decay constant of k′MeOH ∼ 1 s-1.

Original languageEnglish (US)
Pages (from-to)12764-12772
Number of pages9
JournalPhysical Chemistry Chemical Physics
Issue number37
StatePublished - Oct 5 2012
Externally publishedYes

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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