Please use this identifier to cite or link to this item: https://libjncir.jncasr.ac.in/xmlui/handle/10572/2420
Title: Stoichiometry-Controlled Two Flexible Interpenetrated Frameworks: Higher CO2 Uptake in a Nanoscale Counterpart Supported by Accelerated Adsorption Kinetics
Authors: Sikdar, Nivedita
Hazra, Arpan
Maji, Tapas Kumar
Keywords: Inorganic & Nuclear Chemistry
Metal-Organic Frameworks
Porous Coordination Polymer
Crystal-Structure
Air Separation
Building Units
Drug-Delivery
Selectivity
Sorption
Temperature
Gases
Issue Date: 2014
Publisher: American Chemical Society
Citation: Sikdar, N; Hazra, A; Maji, TK, Stoichiometry-Controlled Two Flexible Interpenetrated Frameworks: Higher CO2 Uptake in a Nanoscale Counterpart Supported by Accelerated Adsorption Kinetics. Inorganic Chemistry 2014, 53 (12) 5993-6002, http://dx.doi.org/10.1021/ic500234r
Inorganic Chemistry
53
12
Abstract: Here, we report the synthesis, structural characterizations, and gas storage properties of two new 2-fold interpenetrated 3D frameworks, {[Zn-2(bpdc)(2)(azpy)]center dot 2H(2)O center dot 2DMF}(n) (1) and {[Zn-3(bpdc)(3)(azpy)]center dot 4H2O center dot 2DEF}(n), (2) [bpdc = 4,4'-biphenyldicarboxylate; azpy = 4,4'-azobipyridine], obtained from the same set of organic linkers. Furthermore, 1 has been successfully miniaturized to nanoscale (MOF1N) of spherical morphology to study size dependent adsorption properties through a coordination modulation method. The two different SBUs, dinuclear paddle-wheel {Zn-2(COO)(4)} for 1 and trinuclear {Zn-3(mu(2)-OCO)(2)(COO)(4)}for 2, direct the different network topologies of the frameworks that render different adsorption characteristics into the systems. Both of the frameworks show guest induced structural transformations as supported by PXRD studies. Adsorption studies of 1 and 2 show CO2 selectivity over several other gases (such as ND HD OD and Ar) under identical experimental conditions. Interestingly, MOF1N exhibits significantly higher CO2 storage capacity compared to bulk crystals of 1 and that can be attributed to the smaller diffusion barrier at the nanoscale that is supported by studies of adsorption kinetics in both states. Kinetic measurement based on water vapor adsorption clearly distinguishes between the rate of diffusion of bulk (1) and nanospheres (MOF1N). The respective kinetic rate constant (k, s(-1)) for MOF1N (k = 1.29 X 10(-2) s(-1)) is found to be considerably higher than 1 (k = 7.1 X 10(-3) s(-1)) as obtained from the linear driving force (LDF) model. This is the first account where a new interpenetrated MOF has been scaled down to nanoscale through a coordination modulation method, and their difference in gas uptake properties has been correlated through a higher rate of mass diffusion as obtained from kinetics of adsorption.
Description: Restricted Access
URI: https://libjncir.jncasr.ac.in/xmlui/10572/2420
ISSN: 0020-1669
Appears in Collections:Research Articles (Tapas Kumar Maji)

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