Metal-organic frameworks (MOFs) are exceptional as gas adsorbents but their mechanical properties are poor. We present a successful strategy to improve the mechanical properties along with gas adsorption characteristics, wherein graphene (Gr) is covalently bonded with M/DOBDC (M=Mg(2+) , Ni(2+) , or Co(2+) , DOBDC=2,5-dioxido-1,4-benzene dicarboxylate) MOFs. The surface area of the graphene-MOF composites increases up to 200-300 m(2)  g(-1) whereas the CO2 uptake increases by ca. 3-5 wt % at 0.15 atm and by 6-10 wt % at 1 atm. What is significant is that the composites exhibit improved mechanical properties. In the case of Mg/DOBDC, a three-fold increase in both the elastic modulus and hardness with 5 wt % graphene reinforcement is observed. Improvement in both the mechanical properties and gas adsorption characteristics of porous MOFs on linking them to graphene is a novel observation and suggests a new avenue for the design and synthesis of porous materials.

A simple solution-processing and self-assembly approach that exploits the synergistic interactions between multiple hydrogen bonded networks and aromatic interactions was utilized to synthesize molecular crystals of cyclic dipeptides (CDPs), whose molecular weights (~0.2 kDa) are nearly three orders of magnitude smaller than that of natural structural proteins (50–300 kDa). Mechanical properties of these materials, measured using the nanoindentation technique, indicate that the stiffness and strength are comparable and sometimes better than those of natural fibres. The measured mechanical responses were rationalized by recourse to the crystallographic structural analysis and intermolecular interactions in the self-assembled single crystals. With this work we highlight the significance of developing small molecule based bioinspired design strategies to emulate biomechanical properties. A particular advantage of the successfully demonstrated reductionistic strategy of the present work is its amenability for realistic industrial scale manufacturing of designer biomaterials with desired mechanical properties.

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Scheme 1 Chemical structures of (a) L-alanine, (b) saccharine, (c) sulfathiazole and (d) p-nitroaniline.

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