Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, IL, 60208-3113, USA.
Department of Chemistry, Supercomputing Institute, and Chemical Theory Center, University of Minnesota, Minneapolis, MN, 55455, USA.
Angew Chem Int Ed Engl. 2018 Feb 12;57(7):1949-1953. doi: 10.1002/anie.201712645. Epub 2018 Jan 18.
Amino-functionalized zirconium-based metal-organic frameworks (MOFs) have shown unprecedented catalytic activity compared to non-functionalized analogues for hydrolysis of organophosphonate-based toxic chemicals. Importantly, the effect of the amino group on the catalytic activity is significantly higher in the case of UiO-66-NH , where the amino groups reside near the node, compared to UiO-67-m-NH , where they are directed away from the node. Herein, we show that the proximity of the amino group is crucial for fast catalytic activity towards hydrolysis of organophosphonate-based nerve agents. The generality of the observed amine-proximity-dictated catalytic activity has been tested on two different MOF systems which have different topology. DFT calculations reveal that amino groups on all the MOFs studied are not acting as Brønsted bases; instead they control the microsolvation environment at the Zr -node active site and therefore increase the overall catalytic rates.
氨基功能化的锆基金属有机骨架（MOFs）在水解有机膦酸盐类有毒化学品方面表现出比非功能化类似物前所未有的催化活性。重要的是，与氨基远离节点的 UiO-67-m-NH 相比，氨基位于节点附近的 UiO-66-NH 对催化活性的影响要高得多。在这里，我们表明，氨基的接近程度对于水解有机膦酸盐类神经毒剂的快速催化活性至关重要。所观察到的胺接近控制催化活性的普遍性已经在两种具有不同拓扑结构的不同 MOF 体系上进行了测试。DFT 计算表明，研究中所有 MOF 上的氨基都不作为布朗斯台德碱；相反，它们控制着 Zr-节点活性位点的微溶剂化环境，从而提高了整体催化速率。
