engleski

Mechanochemical synthesis of highly-ordered microporous zirconium-based metal-organic frameworks

Metal-organic frameworks (MOF) based on dicarboxylate linkers and [Zr6(OH)4O4]12+ complex cationic nodes are nowadays extensively studied due to their potential in catalysis, unprecedented stability in water over a wide range of pH values, modularity and high surface areas.[1, 2] Their potential commercialization, however, is still hindered by the adverse synthetic procedures employing high temperatures, large amounts of organic-solvent waste and the need for aggressive reagents to achieve reproducibility.[3] Here we report mechanochemical milling and accelerated aging as mild, clean and highly- efficient procedures for the synthesis of various families of zirconium MOFs on multigram scale, from widely studied UiO-66 derivatives[4] to more complex Zr-MOF families which are hard to prepare from solution. Both solvent-free procedures employed non-aggressive reactants and proved as surprisingly simple ways to achieve materials with porosity comparable to- or even exceeding their solvothermally prepared analogues. Analyses indicated highest level of internal ordering in mechanochemically prepared Zr-MOFs, despite the fact that milling shortened the synthesis from conventional 12-48 hours to 45 minutes. The catalytic properties of these compounds, tested on warfare nerve agent simulant DMNP, showed hydrolytic activity almost identical to materials prepared by conventional procedures. These results highlight the mechanochemistry and aging procedures as viable alternatives for the synthesis of these important microporous materials.

Metal-organic frameworks ; catalytic destruction of warfare agents, mechanochemical synthesis of microporous materials ; accelerated aging

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