Introduction Robust metal-organic frameworks (MOFs), which are resistant to reactive species, are of critical importance to a variety of applications. In particular, MOFs that are easy to scale up and moisture-resistant with high gas storage capacity are desired for automotive applications. [1-3] However, making robust MOFs with controlled internal surface property has always been a challenge. Almost all MOFs, in particular moisture-resistant MOFs constructed with high-valence metal ions, were made from the “one-pot” synthetic route, making it difficult to control the metal-containing nodes and therefore the topology of the MOF. [4] Results and Discussion Based on a kinetic model of ligand-substitution reactions, utilizing pre-formed [Fe2M(μ3-O)(COOCH3)6] clusters (M represents Fe(II,III), Mn(II), Co(II), Ni(II), or Zn(II)), we have developed a kinetically tuned dimensional augmentation (KTDA) synthetic route for the preparation of highly crystalline and extremely robust metal-organic frameworks (MOFs) with the preserved metal cluster core. Through this versatile synthetic route, we have obtained large single crystals of thirty-four different Fe-MOFs. Among them, PCN-250(Fe2Co) exhibits a record-high gravimetric and volumetric H2 uptake at 77 K/1.2 bar as well as an exceptionally high volumetric uptake at high pressure. The total CH4 uptake (210 V(STP)/V) of PCN-250(Fe2Co) at 298 K and 35 bar is also among the highest reported. Remarkably, PCN-250(Fe2Co) exhibits extraordinary stability in water and aqueous solutions with a wide range of pH values.[5] References 1. H.-C. Zhou, S. Kitagawa, Chem. Soc. Rev. 43, 5415(2014) 2. H.-C. Zhou, O. M. Yaghi, J. Long, Chem.Rev. 112, 673(2012) 3. J. R. Long, O. M. Yaghi, Chem. Soc. Rev. 38, 1213(2009) 4. D. J. Tranchemontagne, J. L. Mendoza-Corte´s, M. O’Keeﬀe, O. M. Yaghi, Chem. Soc. Rev. 38, 1257( 2009). 5. D. Feng, K. Wang, H.-C. Zhou, et al. Nature Comm. Accepted.

Robust metal-organic frameworks: rational design and gas storage

249th National Meeting (2015)

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