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Hybrid Nanosheets of an Inorganic–Organic Framework Material: Facile Synthesis, Structure, and Elastic Properties

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Department of Materials Science and Metallurgy, University of Cambridge, Pembroke Street, Cambridge CB2 3QZ, U.K.
*Address correspondence to [email protected]
Cite this: ACS Nano 2012, 6, 1, 615–621
Publication Date (Web):November 27, 2011
https://doi.org/10.1021/nn204054k
Copyright © 2011 American Chemical Society
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Abstract

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We report a new 2-D inorganic–organic framework material, MnDMS [Mn 2,2-dimethylsuccinate], featuring weakly bound hybrid layers in its bulk crystals that can be readily exfoliated into nanosheets via ultrasonication. The fully exfoliated hybrid nanosheets correspond to a unilamellar thickness of about 1 nm, while the partially exfoliated nanosheets (multilayer films) exhibit a typical thickness on the order of 10 nm. We used atomic force microscopy to characterize their surface topography and to map the variation of nanomechanical properties across the surface of the delaminated nanosheets. The morphology and crystallographic orientation of the exfoliated layers were further studied by transmission electron microscopy. Additionally, we investigated the elastic anisotropy underlying the bulk host material by means of single-crystal nanoindentation, from which the critical resolved shear stress (τcrit) needed for the micromechanical delamination of individual layers was determined to be relatively small (≲0.4 GPa).

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Table S1 lists the crystallographic data of bulk MnDMS. Table S2 lists the data used for the critical shear stress analysis. Figures S1 and S2 show the Le Bail fit to the X-ray diffraction pattern of bulk MnDMS and the reconstituted nanosheets after ultrasonication, respectively. Figure S3 depicts the coordination environment around the Mn center. Figure S4 shows the TGA profile of bulk MnDMS. Figure S5 shows the TEM micrograph of the hexane-exfoliated nanosheets. Figure S6 depicts micromechanical delamination of hybrid layers via a spherical nanoindenter tip. X-ray crystallographic file (CIF) of the MnDMS structure. This material is available free of charge via the Internet at http://pubs.acs.org.

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