Redox Reactivity of Methylene Blue Bound in Pores of UMCM-1 Metal-Organic Frameworks
Redox Reactivity of Methylene Blue Bound in Pores of UMCM-1 Metal-Organic Frameworks
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UMCM-1 金属有机框架孔中亚甲基蓝的氧化还原反应性
DOI：
10.1080/15421406.2012.632738
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发表时间：
2012
影响因子：
0.7
通讯作者：
Halls J
中科院分区：
文献类型：
--
作者：
Halls J
研究了结晶UMCM-1金属有机骨架（MOF）材料的孔中的氧化还原过程。亚甲蓝被用作吸附的氧化还原活性染料组分。从染料吸附过程中着色的变化，可以得出结论，发生了具有所得MOF结构的高孔负载的基本上不可逆的吸附过程。吸附的亚甲蓝在MOF孔中保持氧化还原活性，并且没有证据表明在延长的氧化还原循环期间有显著损失。由于孔隙的大小，孔隙结合的亚甲蓝的反应性与亚甲蓝在水溶液中的预期反应性密切相关。溶液pH对伏安响应的影响的研究揭示了孔电导率从在酸性条件下传导不良到在碱性条件下传导良好的有趣的逐渐变化。这是解释在通过单电子跳跃导电孔的电荷传输。在pH 7时，表观电荷扩散系数Dapp= 1.4 × 10− 15 m2 s −2。指出了氧化还原活性杂化MOF材料的新家族的潜在应用。
Redox processes were studied in the pores of a crystalline UMCM-1 metal organic framework (MOF) material. Methylene blue was employed as an absorbed redox active dye component. From the change in coloration during dye adsorption, it was concluded that an essentially irreversible adsorption process with high pore loading of the resulting MOF structure occurred. The adsorbed methylene blue remained redox active in the MOF pores and there was no evidence of significant losses during extended redox cycling. Due to the size of the pores, the reactivity of the pore-bound methylene blue is closely related to that expected for methylene blue in an aqueous solution. A study of the effect of solution pH on the voltammetric responses revealed an interesting gradual change in electrical pore conductivity form conducting poorly under acidic conditions to conducting very well under alkaline conditions. This is interpreted in terms of charge transport via single-electron hopping conduction in pores. An estimate of the apparent charge diffusion coefficient at pH 7, Dapp= 1.4 × 10−15m2s−2, is obtained. Potential applications of the new family of redox active hybrid MOF materials are indicated.
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