Electrocatalytic Water Oxidation by a Monomeric Amidate-Ligated Fe(III)鈥揂qua Complex

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• 作者：Michael K. Coggins ; Ming-Tian Zhang ; Aaron K. Vannucci ; Christopher J. Dares ; Thomas J. Meyer
• 刊名：Journal of the American Chemical Society
• 出版年：2014
• 出版时间：April 16, 2014
• 年：2014
• 卷：136
• 期：15
• 页码：5531-5534
• 全文大小：279K
• 年卷期：v.136,no.15(April 16, 2014)
• ISSN：1520-5126

文摘

The six-coordinate Fe^III-aqua complex [Fe^III(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鈥搘ater mixtures. An electrochemical kinetics study has revealed that water oxidation occurs by oxidation to Fe^V(O)²⁺ followed by a reaction first order in catalyst and added water, respectively, with k_o = 0.035(4) M^鈥? s^鈥? 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.