Electrocatalytic O2 reduction by covalently immobilized mononuclear copper(I) complexes: evidence for a binuclear Cu2O2 intermediate.

Electrocatalytic O2 reduction by covalently immobilized mononuclear copper(I) complexes: evidence for a binuclear Cu2O2 intermediate.
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DOI:
10.1021/ja106338h
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发表时间:
2011-03-23
影响因子:
15
通讯作者:
Chidsey CE
Chidsey CE
中科院分区:
化学1区
文献类型:
--
作者:
McCrory CC;Devadoss A;Ottenwaelder X;Lowe RD;Stack TD;Chidsey CE

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共价固定在叠氮化物修饰的玻碳表面的3-乙炔基-菲咯啉的CuI络合物是用于O2到H2O的4-电子还原的活性电催化剂。O2的还原率是第二阶Cu覆盖在中等过电位,这表明两个CuI物种是必要的有效的4-电子还原O2。O2还原的机制,提出了与此共价固定化系统的观察和以前报道的结果为类似的物理吸附CuI系统是一致的。
A CuI complex of 3-ethynyl-phenanthroline covalently immobilized to an azide-modified glassy carbon surface is an active electrocatalyst for the 4-electron reduction of O2 to H2O. The rate of O2 reduction is 2nd order in Cu coverage at moderate overpotential, suggesting that two CuI species are necessary for efficient 4-electron reduction of O2. Mechanisms for O2 reduction are proposed that are consistent with the observations for this covalently immobilized system and previously reported results for a similar physisorbed CuI system.
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