Immobilization of Molecular Catalysts for Enhanced Redox Catalysis,ChemCatChem

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Immobilization of Molecular Catalysts for Enhanced Redox Catalysis
ChemCatChem ( IF 3.8 ) Pub Date : 2018-02-14 , DOI: 10.1002/cctc.201701786
Shunichi Fukuzumi _{1,

2} , Yong‐Min Lee ₁ , Wonwoo Nam ₁

Affiliation

In the homogenous phase, redox catalysts are often deactivated by bimolecular reactions. For example, the charge‐separated state of photoredox catalysts decayed via bimolecular back electron transfer reactions between the charge‐separated molecules to decrease the lifetimes of the catalytically active species. When photoredox catalysts are immobilized on solid supports, the lifetime of the charge‐separated state was remarkably elongated to enhance the photocatalytic activity. Immobilization of photoredox catalysts on electrodes is required for photocurrent generation, leading to development of solar cells. Metal‐oxygen intermediates, which are active for oxidation of various substrates including water oxidation, are also deactivated via bimolecular reactions to produce inactive forms such as dinuclear metal bis‐μ‐oxo complexes. Immobilization of metal complex catalysts on solid supports prohibits the bimolecular deactivation, enhancing the catalytic activity and stability. This Review focuses on recent development of immobilization of both organic and inorganic molecular catalysts on various supports for enhancement of the catalytic activity, selectivity and stability in thermal and photoinduced redox reactions.

中文翻译：

固定化分子催化剂以增强氧化还原催化作用

在均相中，氧化还原催化剂通常通过双分子反应而失活。例如，光氧化还原催化剂的电荷分离状态通过电荷分离的分子之间的双分子背电子转移反应而衰减，从而降低了催化活性物质的寿命。当将光氧化还原催化剂固定在固体载体上时，电荷分离态的寿命会显着延长，从而增强了光催化活性。为了产生光电流，需要将光氧化还原催化剂固定在电极上，从而导致太阳能电池的发展。金属氧中间体对多种底物的氧化具有活性，包括水的氧化作用，也可以通过双分子反应失活，生成非活性形式，例如双核金属双-μ-氧代络合物。将金属络合物催化剂固定在固体载体上可防止双分子失活，从而增强催化活性和稳定性。这篇综述的重点是将有机和无机分子催化剂固定在各种载体上的最新进展，以增强热和光致氧化还原反应中的催化活性，选择性和稳定性。

更新日期：2018-02-14

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