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Tuning Redox Transitions via Inductive Effect in Metal Oxides and Complexes, and Implications in Oxygen Electrocatalysis
Joule ( IF 38.6 ) Pub Date : 2017-12-21 , DOI: 10.1016/j.joule.2017.11.014
Denis A. Kuznetsov , Binghong Han , Yang Yu , Reshma R. Rao , Jonathan Hwang , Yuriy Román-Leshkov , Yang Shao-Horn

The reduction and oxidation (redox) of transition metals allow storing charge/energy in Li-ion batteries and electrochemical capacitors and play an important role in catalysis of electrochemical reactions, such as oxygen reduction reaction (ORR) in fuel cells and metal-air batteries and oxygen evolution reaction (OER) in electrolytic cells. In this review, we present and discuss a universal origin of inductive effect associated with metal substitution in Ni, Co, Fe, Mn-based complexes, (hydr-)oxides, and lithium intercalation compounds by alignment of the electron levels of metal complex redox with partially filled metal d-state and oxygen p-state of oxides on the absolute energy scale. Increased redox potentials of metal complexes and oxides are shown to correlate with the increased electronegativity of the substituting metal, which results in the enhancement of the ORR/OER activity. Such observations provide new insights into potential strategies to optimize ORR/OER catalytic activity by tuning the redox properties of metal sites.



中文翻译:

通过金属氧化物和络合物中的感应效应调节氧化还原转变及其在氧电催化中的意义

过渡金属的还原和氧化(redox)允许在锂离子电池和电化学电容器中存储电荷/能量,并在催化电化学反应(例如燃料电池和金属空气电池中的氧还原反应(ORR))中起重要作用和电解池中的氧气释放反应(OER)。在这篇综述中,我们通过排列金属配合物氧化还原的电子水平来介绍和讨论与镍,钴,铁,锰基配合物,(氢)氧化物和锂嵌入化合物中的金属取代相关的感应效应的普遍起源。在绝对能级上具有部分填充的金属d态和氧p态的氧化物。金属配合物和氧化物的氧化还原电势增加与取代金属的电负性增加相关,这导致ORR / OER活性增强。这些观察结果为通过调整金属位点的氧化还原特性优化ORR / OER催化活性的潜在策略提供了新见解。

更新日期:2017-12-21
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