A spray-drying strategy for synthesis of nanoscale metal–organic frameworks and their assembly into hollow superstructures

Abstract

Metal–organic frameworks (MOFs) are among the most attractive porous materials known today. Their miniaturization to the nanoscale—into nanoMOFs—is expected to serve myriad applications from drug delivery to membranes, to open up novel avenues to more traditional storage and catalysis applications, and to enable the creation of sophisticated superstructures. Here, we report the use of spray-drying as a versatile methodology to assemble nanoMOFs, yielding spherical hollow superstructures with diameters smaller than 5 µm. This strategy conceptually mimics the emulsions used by chemists to confine the synthesis of materials, but does not require secondary immiscible solvents or surfactants. We demonstrate that the resulting spherical, hollow superstructures can be processed into stable colloids, whose disassembly by sonication affords discrete, homogeneous nanoMOFs. This spray-drying strategy enables the construction of multicomponent MOF superstructures, and the encapsulation of guest species within these superstructures. We anticipate that this will provide new routes to capsules, reactors and composite materials.

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Figure 1: Spray-drying synthesis of spherical hollow HKUST-1 superstructures.
Figure 2: Size control in spray-drying synthesis of nanoHKUST-1 crystals.
Figure 3: Series of MOF superstructures and discrete nanoMOF crystals synthesized by spray-drying.
Figure 4: Synthetic versatility in preparing MOF superstructures and nanoMOFs by spray-drying.
Figure 5: Introduction of guest species into MOF superstructures by spray-drying.

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Acknowledgements

The authors acknowledge the Servei de Microscopia of the UAB, and Carlos Carbonell for helping with the illustrations. I.I. and M.C.S. thank MICINN and ICN for a Ramón y Cajal grant and a research contract, respectively. A.C. thanks the Generalitat de Catalunya for a FI fellowship.

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A.C., I.I. and M.C.S. designed the experiments, performed the syntheses and carried out the characterization, encapsulation and property studies. D.M. conceived the project and drafted the manuscript. All authors discussed the results and commented on the manuscript.

Corresponding author

Correspondence to Daniel Maspoch.

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The authors have a patent pending on the methods described in this manuscript, filed on 4 October 2011 (European Union application number EP 11183773.8).

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Carné-Sánchez, A., Imaz, I., Cano-Sarabia, M. et al. A spray-drying strategy for synthesis of nanoscale metal–organic frameworks and their assembly into hollow superstructures. Nature Chem 5, 203–211 (2013). https://doi.org/10.1038/nchem.1569

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