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Oriented Attachment Growth of Anisotropic Meso/Nanoscale MOFs: Tunable Surface Area and CO2 separation

Abstract

Scaling down bulk MOFs (metal-organic frameworks) to nano/mesoscale is of paramount importance due to improved diffusion kinetics and surface area. To achieve this, crystal growth mechanism and evolution of different multidimensional morphologies of MOFs in nano/meso regime need to be fully understood. Here, we report downsizing of a mixed-linkers based 3D MOF to nano/mesoscale by coordination modulation method using n-dodecanoic acid as modulator. We demonstrate changes in morphology and dimensionality (hexagonal nanoparticlenanorodmesosheet) by varying modulator concentration. The time-dependent FESEM (field emission scanning electron microscopy) studies of the products obtained at different stages of synthesis suggest that the morphological transformation is driven by the kinetically controlled oriented attachment (OA) growth mechanism. Among various morphologies, hexagonal nanoparticles show strikingly improved BET (Brunauer–Emmett–Teller) surface area compared to its bulk form due to reduced diffusion barrier at nanoscale as inferred from higher mass transfer kinetics. This is also reflected in better CO2/N2 separation efficiency in breakthrough column experiment at 298 K. This unprecedented on/off porosity with respect to N2 in nano vs. bulk MOF, respectively, is theoretically explained in terms of energetics of adsorption, atomic structural changes and electrostatic interactions between the MOF and adsorbate molecules.

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Publication details

The article was received on 03 Apr 2017, accepted on 03 Sep 2017 and first published on 04 Sep 2017


Article type: Paper
DOI: 10.1039/C7TA02896B
Citation: J. Mater. Chem. A, 2017, Accepted Manuscript
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    Oriented Attachment Growth of Anisotropic Meso/Nanoscale MOFs: Tunable Surface Area and CO2 separation

    N. Sikdar, M. Bhogra, U. V. Waghmare and T. K. Maji, J. Mater. Chem. A, 2017, Accepted Manuscript , DOI: 10.1039/C7TA02896B

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