Mixed-metal or heterometallic metal-organic frameworks (MOFs) are gaining importance as a route to produce materials with increasing chemical and functional complexities. We report a family of heterometallic titanium frameworks, MUV-101(M), and use them to exemplify the advantages of controlling metal distribution across the framework in heterogeneous catalysis by exploring their activity toward the degradation of a nerve agent simulant of Sarin gas. MUV-101(Fe) is the only pristine MOF capable of catalytic degradation of diisopropyl-fluorophosphate (DIFP) in non-buffered aqueous media. This activity cannot be explained only by the association of two metals, but to their synergistic cooperation, to create a whole that is more efficient than the simple sum of its parts. Our simulations suggest a dual-metal mechanism reminiscent of bimetallic enzymes, where the combination of Ti(IV) Lewis acid and Fe(III)–OH Brönsted base sites leads to a lower energy barrier for more efficient degradation of DIFP in absence of a base.

混合金属或异金属金属有机骨架（MOF）作为生产化学和功能复杂性日益提高的材料的途径正变得越来越重要。我们报告了一系列的杂金属钛骨架MUV-101（M），并通过探索它们对Sarin气体神经毒剂模拟物降解的活性，使用它们来举例说明控制金属在整个框架中在非均相催化中的优势。MUV-101（Fe）是唯一能够在非缓冲水性介质中催化降解二异丙基氟磷酸盐（DIFP）的原始MOF。不能仅通过两种金属的结合来解释这种活动，而是要通过它们的协同合作来解释，以创建一个比其各个部分的简单总和更有效的整体。