Proton uptake vs. redox driven release from metal-organic-frameworks: Alizarin red S reactivity in UMCM-1
Proton uptake vs. redox driven release from metal-organic-frameworks: Alizarin red S reactivity in UMCM-1
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DOI：
10.1016/j.jelechem.2012.11.016
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发表时间：
2013-01-15
影响因子：
4.5
通讯作者：
Marken, Frank
中科院分区：
文献类型：
--
作者：
Halls, Jonathan E.;Ahn, Sunyhik D.;Marken, Frank
小的氧化还原活性分子，如茜素红S，很容易被吸附和结合到氧化还原非活性的金属有机骨架主体，如UMCM-1。结合的客体分子的氧化还原活性对于孔内的电化学转化和电催化是感兴趣的。对于茜素红S的还原，预期质子吸收进入孔的电荷补偿。然而，它在这里示出，茜素红S的氧化还原过程中UMCM-1浸泡在电解质水溶液中，乙醇电解质，和乙腈电解质介质中占主导地位，而不是由表面过程和潜在的驱动还原释放到周围的溶液中的无色茜素红S。通过释放茜素红S的自我调解发生，而在乙腈中的二茂钴氧化还原介体用于从UMCM-1主机晶格的茜素红S的电位驱动的氧化还原释放。(C)2012爱思唯尔有限公司版权所有。
Small redox active molecules such as alizarin red S are readily adsorbed and bound into redox-inactive metal-organic framework hosts such as UMCM-1. Redox activity of the bound guest molecule is of interest for electrochemical conversions and electrocatalysis within pores. For the reduction of alizarin red S charge compensating proton uptake into pores is expected. However, it is shown here that alizarin red S redox processes in UMCM-1 immersed in aqueous electrolyte, ethanolic electrolyte, and in acetonitrile electrolyte media are dominated instead by surface processes and the potential driven reductive release of leuco-alizarin red S into the surrounding solution. Self-mediation via released alizarin red S occurs, whereas in acetonitrile a cobaltocene redox mediator is employed for the potential driven redox release of alizarin red S from the UMCM-1 host lattice. (C) 2012 Elsevier B.V. All rights reserved.