One-electron activation of water oxidation catalysis Article

Tamaki, Y, Vannucci, AK, Dares, CJ et al. (2014). One-electron activation of water oxidation catalysis . Journal of the American Chemical Society, 136(19), 6854-6857. 10.1021/ja502637s

cited authors

  • Tamaki, Y; Vannucci, AK; Dares, CJ; Binstead, RA; Meyer, TJ

abstract

  • Rapid water oxidation catalysis is observed following electrochemical oxidation of [RuII(tpy)(bpz)(OH)]+ to [Ru V(tpy)(bpz)(O)]3+ in basic solutions with added buffers. Under these conditions, water oxidation is dominated by base-assisted Atom Proton Transfer (APT) and direct reaction with OH-. More importantly, we report here that the RuIV=O2+ form of the catalyst, produced by 1e- oxidation of [RuII(tpy)(bpz)(OH 2)]2+ to Ru(III) followed by disproportionation to [RuIV(tpy)(bpz)(O)]2+ and [RuII(tpy)(bpz) (OH2)]2+, is also a competent water oxidation catalyst. The rate of water oxidation by [RuIV(tpy)(bpz)(O)]2+ is greatly accelerated with added PO43- with a turnover frequency of 5.4 s-1 reached at pH 11.6 with 1 M PO4 3- at an overpotential of only 180 mV. © 2014 American Chemical Society.

authors

publication date

  • May 14, 2014

published in

Digital Object Identifier (DOI)

start page

  • 6854

end page

  • 6857

volume

  • 136

issue

  • 19