A combined "electrochemical-frustrated Lewis pair" approach to hydrogen activation: surface catalytic effects at platinum electrodes

Elliot J. Lawrence, Robin J. Blagg, David L. Hughes, Andrew E. Ashley, Gregory G. Wildgoose

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Abstract

Herein, we extend our “combined electrochemical–frustrated Lewis pair” approach to include Pt electrode surfaces for the first time. We found that the voltammetric response of an electrochemical–frustrated Lewis pair (FLP) system involving the B(C6F5)3/[HB(C6F5)3]− redox couple exhibits a strong surface electrocatalytic effect at Pt electrodes. Using a combination of kinetic competition studies in the presence of a H atom scavenger, 6-bromohexene, and by changing the steric bulk of the Lewis acid borane catalyst from B(C6F5)3 to B(C6Cl5)3, the mechanism of electrochemical–FLP reactions on Pt surfaces was shown to be dominated by hydrogen-atom transfer (HAT) between Pt, [Pt[BOND]H] adatoms and transient [HB(C6F5)3]⋅ electrooxidation intermediates. These findings provide further insight into this new area of combining electrochemical and FLP reactions, and proffers additional avenues for exploration beyond energy generation, such as in electrosynthesis.
Original languageEnglish
Pages (from-to)900-906
Number of pages7
JournalChemistry - A European Journal
Volume21
Issue number2
Early online date6 Nov 2014
DOIs
Publication statusPublished - 7 Jan 2015

Keywords

  • cyclic voltammetry
  • electrochemistry
  • frustrated Lewis pairs
  • fuel cells
  • hydrogen transfer

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