Kinetics of heterogeneous electron transfer at liquid/liquid interfaces as studied by SECM

被引：101

作者：

Ding, ZF ^{[1
]}

Quinn, BM ^{[1
]}

Bard, AJ ^{[1
]}

机构：

[1] Univ Texas, Dept Chem & Biochem, Austin, TX 78712 USA

来源：

JOURNAL OF PHYSICAL CHEMISTRY B | 2001年 / 105卷 / 27期

关键词：

D O I：

10.1021/jp0100598

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Scanning electrochemical microscopy (SECM) was used to investigate the kinetics of heterogeneous electron transfer (ET) as a function of driving force at the interface between two immiscible electrolyte solutions. At high driving force, experimental rate constants decreased with increasing overpotential, deviating from predictions based on Butler-Volmer kinetics. This decrease in ET rate with increasing driving force is consistent with Marcus theory inverted region behavior. Ar low driving force, the potential dependence of the forward and reverse ET rate constants followed Butler-Volmer theory. SECM is also demonstrated to be a useful means of studying the effect of high ionic strength on the kinetics of heterogeneous ET.

引用

页码：6367 / 6374

页数：8

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