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Single-Site Copper(II) Water Oxidation Electrocatalysis: Rate Enhancements with HPO42− as a Proton Acceptor at pH 8
Ist Teil von
Angewandte Chemie (International ed.), 2014-11, Vol.53 (45), p.12226-12230
Ort / Verlag
Weinheim: WILEY-VCH Verlag
Erscheinungsjahr
2014
Link zum Volltext
Quelle
Alma/SFX Local Collection
Beschreibungen/Notizen
The complex CuII(Py3P) (1) is an electrocatalyst for water oxidation to dioxygen in H2PO4−/HPO42− buffered aqueous solutions. Controlled potential electrolysis experiments with 1 at pH 8.0 at an applied potential of 1.40 V versus the normal hydrogen electrode resulted in the formation of dioxygen (84 % Faradaic yield) through multiple catalyst turnovers with minimal catalyst deactivation. The results of an electrochemical kinetics study point to a single‐site mechanism for water oxidation catalysis with involvement of phosphate buffer anions either through atom–proton transfer in a rate‐limiting OO bond‐forming step with HPO42− as the acceptor base or by concerted electron–proton transfer with electron transfer to the electrode and proton transfer to the HPO42− base.
Metal‐catalyzed water oxidation: CuII(Py3P) (1) is a water oxidation electrocatalyst in H2PO4−/HPO42− buffered aqueous solutions (see picture). Electrolysis experiments with 1 at pH 8.0 and at a potential of 1.40 V versus the normal hydrogen electrode resulted in the formation of dioxygen (84 % Faradaic yield) through multiple catalyst turnovers with minimal catalyst deactivation.