Charge Distribution Controls On‐Target Separation of Low Nucleophilicity Anions in Layered Double Hydroxides
Charge Distribution Controls On‐Target Separation of Low Nucleophilicity Anions in Layered Double Hydroxides
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DOI：
10.1002/admi.202201484
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发表时间：
2022-09
影响因子：
5.4
通讯作者：
Tomohito Sudare;Shuhei Tamura;Maru Kashiwazaki;Yuki Nakamura;Kenta Kawaguchi;Hiromasa Shiiba;K. Fujisawa;Mongkol Tipplook;Hideki Tanaka;Fumitaka Hayashi;Katsuya Teshima
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文献类型：
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作者：
Tomohito Sudare;Shuhei Tamura;Maru Kashiwazaki;Yuki Nakamura;Kenta Kawaguchi;Hiromasa Shiiba;K. Fujisawa;Mongkol Tipplook;Hideki Tanaka;Fumitaka Hayashi;Katsuya Teshima
主-客体化学原理和机制已被用于分离有害和有价值的离子物种。然而，由于弱的主客体相互作用，使用这些方案分离低亲核性阴离子是困难的。在此，使用层状双氢氧化物（LDHs），它表明，客体-客体相互作用显着影响低亲核性硝酸盐的分离。由于共沉淀合成方法，LDH表现出相当低的硝酸根离子储存容量。因此，应用拓扑化学反应来控制LDH中的阳离子排列。结构分析确定，六方阳离子排列是便利的。等温线分析表明，所获得的LDHs的容量提高到典型的较低有序LDHs的容量的250%。最后，结合理论计算，进一步的等温线分析表明，六方排列有效地促进了层间硝酸根离子和水分子之间稳定的主客体相互作用-氢键，这有助于高离子存储。
Host–guest chemistry principles and mechanisms have been exploited to separate harmful and valuable ionic species. However, separating low nucleophilicity anions using these protocols is difficult due to weak host–guest interactions. Herein, using layered double hydroxides (LDHs), it is demonstrated that guest–guest interactions considerably influence the separation of a low nucleophilicity nitrate. LDHs exhibit considerably low nitrate ion storage capacities due to the co‐precipitation synthesis method. Hence, a topochemical reaction is applied to control the cation arrangement in the LDHs. Structural analyses determine that a hexagonal cation arrangement is facilitated. Isotherm analysis reveals that the obtained LDHs improve the capacity up to 250% of that of typical less‐ordered LDHs. Finally, further isotherm analysis in combination with theoretical calculations, it is revealed that the hexagonal arrangement effectively facilitates a stable guest–guest interactions—hydrogen‐bond between the interlayer nitrate ions and water molecules, which contributes to high ion‐storage.