Kinetic and Mechanistic Studies of the Electrocatalytic Reduction of O2 to H2O with Mononuclear Cu Complexes of Substituted MO-Phenanthrolines

Charles C.L.McCrory; Xavier Ottenwaelder; T.Daniel P.Stack

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Kinetic and Mechanistic Studies of the Electrocatalytic Reduction of O2 to H2O with Mononuclear Cu Complexes of Substituted MO-Phenanthrolines

机译：取代MO-邻菲咯啉单核铜配合物电催化将O2还原为H2O的动力学和机理研究

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Mononuclear Cu complexes with a 1,10-phenanthroline-based ligand adsorbed onto an edge-plane graphite electrode act as electrocatalysts for the 4-electron reduction of O2 to H2O.A mechanism is proposed for the electrocatalytic O2 reduction that accounts for the observed redox and kinetic dependences on coordinating anions and proton donors in the buffer.Systematic increases of ligand electron-withdrawing properties and/or the steric demands near the Cu center increase the E~0 of the Cu catalysts but decrease the rate of O2 reduction.The kinetic rate of O2 reduction at E~0,reported as kinetic current divided by catalyst redox charge,decreases as E~0 increases:from 16 s~(-1)measured at E~0 in air-saturated solutions for adsorbed Cu(phen)to 0.4 s~(-1)for Cu(2,9-Et2-phen).The maximum value of E for which catalytic activity can be attained is estimated to be+350 mV vs NHE.Near E~0,the kinetic current deviates from that expected if O2 binding were the sole rate-limiting step.This indicates that one or more of the electrochemical reduction steps are rate limiting at potentials near E~0.

机译：边缘平面石墨电极上吸附有1,10-菲咯啉基配体的单核Cu络合物用作将O2还原为H2O的4电子还原的电催化剂。动力学和动力学对缓冲液中配位阴离子和质子给体的依赖性。系统地增加配体吸电子性能和/或在Cu中心附近的空间需求增加了Cu催化剂的E〜0，但降低了O2的还原速率。在E〜0时O2还原速率，以动电流除以催化剂氧化还原电荷表示，随着E〜0的增加而降低：从在E〜0的空气饱和溶液中吸附的Cu（phen）的16 s〜（-1）开始对于Cu（2,9-Et2-phen）为0.4 s〜（-1）。可达到催化活性的E的最大值估计为+350 mV vs NHE.E〜0附近，动电流如果O2结合是唯一的限速步骤，则偏离预期值。电化学还原步骤中的一个或多个是在接近E〜0的电势下进行速率限制。

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《The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory》 |2007年第49期|共10页
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Charles C.L.McCrory; Xavier Ottenwaelder; T.Daniel P.Stack;
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1. Kinetic and Mechanistic Studies of the Electrocatalytic Reduction of O2 to H2O with Mononuclear Cu Complexes of Substituted MO-Phenanthrolines [J] . Charles C.L.McCrory, Xavier Ottenwaelder, T.Daniel P.Stack The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory . 2007,第49期

机译：取代MO-邻菲咯啉单核铜配合物电催化将O2还原为H2O的动力学和机理研究
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4. Syntheses and Crystal Structure of Nine-Coordinate Mononuclear Na EuⅢ (edta)(H2O)3 · 4H2O and Binuclear Na4Eu2Ⅲ(Httha)2·10H2O Complexes [C] . International Conference on Rare Earth Research and Application; 2004; . 2004

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机译：1,2-二氧戊环的形成：I. H2O2酸催化加成至ss，γ-环氧酮II。通过使用O2 III对三萜进行铬催化的烯丙基过氧化。通过α-酰基自由基通过金属催化将O2取代为取代的ss-Keto酯。
6. Electrocatalytic O2 Reduction by Covalently Immobilized Mononuclear Copper(I) Complexes: Evidence for a Binuclear Cu2O2 Intermediate [O] . Charles C. L. McCrory, Anando Devadoss, Xavier Ottenwaelder, -1

机译：电O2还原价固定单核铜（I）配合物：证据的双核Cu2O2中级
7. Kinetic and Mechanistic Studies of the Electrocatalytic Reduction of O2 to H2O with Mononuclear Cu Complexes of Substituted 1,10-Phenanthrolines [O] . -1

机译：用1,10菲络合物单核Cu络合物对O2至H2O电催化还原的动力学和机械研究

Kinetic and Mechanistic Studies of the Electrocatalytic Reduction of O2 to H2O with Mononuclear Cu Complexes of Substituted MO-Phenanthrolines

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