Exploiting parameter space in MOFs: a 20-fold enhancement of phosphate-ester hydrolysis with UiO-66-NH2†,Chemical Science

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Exploiting parameter space in MOFs: a 20-fold enhancement of phosphate-ester hydrolysis with UiO-66-NH2†
Chemical Science ( IF 7.6 ) Pub Date : 2015-02-24 00:00:00 , DOI: 10.1039/c4sc03613a
Michael J Katz ₁ , Su-Young Moon ₁ , Joseph E Mondloch ₁ , M Hassan Beyzavi ₁ , Casey J Stephenson ₁ , Joseph T Hupp _{1,

2} , Omar K Farha _{1,

3}

Affiliation

The hydrolysis of nerve agents is of primary concern due to the severe toxicity of these agents. Using a MOF-based catalyst (UiO-66), we have previously demonstrated that the hydrolysis can occur with relatively fast half-lives of 50 minutes. However, these rates are still prohibitively slow to be efficiently utilized for some practical applications (e.g., decontamination wipes used to clean exposed clothing/skin/vehicles). We thus turned our attention to derivatives of UiO-66 in order to probe the importance of functional groups on the hydrolysis rate. Three UiO-66 derivatives were explored; UiO-66-NO₂ and UiO-66-(OH)₂ showed little to no change in hydrolysis rate. However, UiO-66-NH₂ showed a 20 fold increase in hydrolysis rate over the parent UiO-66 MOF. Half-lives of 1 minute were observed with this MOF. In order to probe the role of the amino moiety, we turned our attention to UiO-67, UiO-67-NMe₂ and UiO-67-NH₂. In these MOFs, the amino moiety is in close proximity to the zirconium node. We observed that UiO-67-NH₂ is a faster catalyst than UiO-67 and UiO-67-NMe₂. We conclude that the role of the amino moiety is to act as a proton-transfer agent during the catalytic cycle and not to hydrogen bond or to form a phosphorane intermediate.

中文翻译：

利用 MOF 中的参数空间：UiO-66-NH2 将磷酸酯水解增强 20 倍†

由于神经毒剂的严重毒性，它们的水解是首要关注的问题。使用基于 MOF 的催化剂 (UiO-66)，我们之前已经证明水解可以以 50 分钟相对较快的半衰期发生。然而，这些速率对于有效地用于某些实际应用（例如，用于清洁暴露的衣服/皮肤/车辆的去污擦拭布）来说仍然非常慢。因此，我们将注意力转向 UiO-66 的衍生物，以探讨官能团对水解速率的重要性。探索了三种 UiO-66 衍生物；UiO-66-NO ₂和UiO-66-(OH) _{2 的}水解速率几乎没有变化。然而，UiO-66-NH _{2 的}水解速率比母体UiO-66 MOF提高了20倍。使用该 MOF 观察到的半衰期为 1 分钟。为了探讨氨基部分的作用，我们将注意力转向UiO-67、UiO-67-NMe ₂和UiO-67-NH ₂。在这些 MOF 中，氨基部分非常靠近锆节点。我们观察到UiO-67-NH _{2是比UiO-67 和UiO-67-NMe}₂更快的催化剂。我们得出结论，氨基部分的作用是在催化循环过程中充当质子转移剂，而不是形成氢键或形成正膦中间体。

更新日期：2015-02-24

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