碳纳米管-多酸团簇的限域组装与机理研究

碳纳米管以其优异的性质在许多领域都展现出了极大的发展潜力，管 内腔的纳米级空间为限域组装提供了合适的位点，而多金属氧酸盐明确的 刚性结构、氧化还原特性、配位接枝能力使其在组装材料中得到了广泛的 应用。二者组装而成的碳纳米管封装多酸团簇结构表现出独特的结构特点。 这种适配的主客体结构的形成机理蕴含了复杂的化学行为，并且由于其继 承碳纳米管骨架和多金属氧酸盐功能化性质，在各个领域都体现了潜在的 应用价值。 我们对团簇装填进入碳纳米管内部的机理进行了深入的研究，与多酸 在碳纳米管外壁的修饰明显不同，碳纳米管和多酸团簇间剧烈的氧化还原 反应为装填提供了由电子转移而形成库仑力作用，以库仑力为驱动力，团 簇在秒级的时间即可装填进入碳纳米管内部，金属阳离子不会进入碳纳米 管内部但氢离子可以实现装填，同时装填的效果受到溶剂效应的影响。基 于溶解平衡原理难溶团簇同样可以装填进入碳纳米管内腔。在进行选择性 装填时，装填过程由氧化还原发起，受阴阳离子的库仑力作用，因此团簇 装填受电荷密度和氧化性影响，电荷密度越小装填越容易进行，而氧化性 越强，团簇占比越大，电荷密度的优先级高于氧化性。 团簇装填进入碳纳米管后受其保护可以在易分解的碱性条件下存在， 而碳纳米管装填团簇后侧壁的石墨化程度不受内部装填的影响，在空气中 依旧保持良好的石墨化程度。在使用功能多酸分子，具有荧光性质和磁性 性质的多酸进行装填后，碳纳米管并不表现出荧光性质和磁性性质。在钙 钛矿太阳能电池的构建中，使用装填多酸的碳纳米管在空穴传输层和金属 电极间进行掺杂，电池的光电转换效率有明显提升，但难以保持稳定性。

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