Reversible adsorption of outer-sphere redox molecules at Pt electrodes

Dileep Mampallil, Klaus Mathwig, Shuo Kang, Serge G. Lemay*

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

34 Citations (Scopus)
7 Downloads (Pure)


Adsorption often dominates the response of nanofluidic systems due to their high surface-to-volume ratios. Here we harness this sensitivity to investigate the reversible adsorption of outer-sphere redox species at electrodes, a phenomenon that is easily overlooked in bulk measurements. We find that even though adsorption does not necessarily play a role in the electron-transfer process, such adsorption is nevertheless ubiquitous for the widely used outer-sphere species. We investigate the physical factors driving adsorption and find that this counterintuitive behavior is mediated by the anionic species in the supporting electrolyte, closely following the well-known Hofmeister series. Our results provide foundations both for theoretical studies of the underlying mechanisms and for contriving strategies to control adsorption in micro/nanoscale electrochemical transducers where surface effects are dominant.

Original languageEnglish
Pages (from-to)636-640
Number of pages5
JournalThe journal of physical chemistry letters
Issue number3
Publication statusPublished - 6 Feb 2014


  • adsorption
  • Hofmeister series
  • nanofluidics
  • outer-sphere species
  • redox cycling


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