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Electrocatalytic Water Oxidation by a Monomeric Amidate-Ligated Fe(III)–Aqua Complex

投稿者: Yuma Morimoto

Communication（桐山、論文の構成について要チェック）

同志社の人見先生が設計した配位子を使って、Tom Meyerのところが水の酸化をしています。（一応、ちゃんと引用もしているようです。）
1.58 V vs NHE、15 h で約30回転。（過電圧でかい？） 
溶媒に、propylene carbonateをつかってますが、これをつかうとなぜか効率がよくなるみたいです。
ちなみに、筆頭著者をしているのは、Julia Kovacsの元でバンバンJACSを出して学位を取った人です。PDとしてNorth Carolineに移って、うまいこと錯体を探してきて、それでJACSを出すというのは要領ええなぁ。。

Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599,United States
J. Am. Chem. Soc., Article ASAP
DOI: 10.1021/ja412822u
Publication Date (Web): March 26, 2014
Copyright © 2014 American Chemical Society
Electrochemistry

Abstract

Abstract Image
The six-coordinate FeIII-aqua complex [FeIII(dpaq)(H2O)]2+ (1, dpaq is 2-[bis(pyridine-2-ylmethyl)]amino-N-quinolin-8-yl-acetamido) is an electrocatalyst for water oxidation in propylene carbonate–water mixtures. An electrochemical kinetics study has revealed that water oxidation occurs by oxidation to FeV(O)2+ followed by a reaction first order in catalyst and added water, respectively, with ko = 0.035(4) M–1 s–1 by the single-site mechanism found previously for Ru and Ir water oxidation catalysts. Sustained water oxidation catalysis occurs at a high surface area electrode to give O2 through at least 29 turnovers over an 15 h electrolysis period with a 45% Faradaic yield and no observable decomposition of the catalyst.
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