Crystal Growth & Design - ACS Publications - American Chemical

Crystal Growth & Design - ACS Publications - American Chemical...

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Polar pore surface guided selective CO2 adsorption in a pre-functionalized metal-organic framework Soumya Mukherjee, Ravichandar Babarao, Aamod V. Desai, Biplab Manna, and Sujit K. Ghosh Cryst. Growth Des., Just Accepted Manuscript • Publication Date (Web): 15 Jun 2017 Downloaded from on June 15, 2017

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Crystal Growth & Design

Polar pore surface guided selective CO2 adsorption in a prefunctionalized metal-organic framework Soumya Mukherjee,a,b Ravichandar Babarao,c,d Aamod V. Desai,a Biplab Manna,a and Sujit K. Ghosh*a,e a

Indian Institute of Science Education and Research (IISER), Dr. Homi Bhabha Road, Pashan, Pune-411008, India. Phone: +91 20 2590 8076; Fax: +91 20 2590 8186; E-mail: [email protected] b Bernal Institute, Department of Chemical Sciences, University of Limerick, Ireland. c School of Science, RMIT University, Melbourne, 3001, Australia. d Commonwealth Scientific and Industrial Research Organisation (CSIRO) Manufacturing, Clayton, Victoria 3169, Australia. e Centre for Research in Energy & Sustainable Materials, IISER Pune, India.

ABSTRACT: Selective CO2 adsorption over other small gases has been realized in an ultramicroporous metal-organic framework (MOF). In the quest of manifesting such selective carbon capture performance, the pre-functionalized linker strategy has been espoused. A new Zn(II)-based three-dimensional, three-fold interpenetrated MOF material [Zn(PBDA)(DPNI)]n.xG (PBDA: 4,4'-((2-(tert-butyl)-1,4-phenylene)bis(oxy))dibenzoic acid; DPNI: N,N'-di-(4-pyridyl)1,4,5,8-naphthalenetetracarboxydiimide; xG: x number of guest species) with unusual rob topology is synthesized following a typical solvothermal synthesis protocol, which gleans a modest CO2-selective adsorption trend over its congener gases (saturation CO2 uptake capacity: 2.39 and 3.44 mmolg-1, at 298K and 273K; volumetric single component isotherm based separation ratios at 0.2 bar: 189.4 (CO2/N2, 256.5 (CO2/H2), 12.3 (CO2/CH4); at 1 bar: 6.8 (CO2/N2, 17.1 (CO2/H2), 7.1 (CO2/CH4)). The compound also exhibits selective benzene sorption over its aliphatic C6-analogue cyclohexane. The structure-property correlation guided results supported by theoretical introspection further emphasize the omnipresent role of crystal engineering principles behind culmination of such targeted properties in the nanoporous MOF domain, to realize selective sorption facets.

Operational capturing and effective separation of the anthropogenic greenhouse gas CO2 poses an imperative challenge under various energy and environment-related contexts.1-3 A plethora of such relevant backdrops particularly focus upon drastically lessening the CO2 emission concomitant with pre-combustion technology based purification of natural gas, biogas and landfill gas along with combustion of flue gas.4-6 Stupendous research efforts have been lately instigated toward the strategic development of chemically customized and permanently porous organic-inorganic hybrid network materials namely, metal-organic frameworks (MOFs),7 aimed at selective CO2 removal from mixed gases.8-10 MOFs are arguably one of the most exciting functional materials in this milieu, owing to the sheer diversity and vast modular facet revolving around their designed syntheses.11, 12 Recent developments in the crystal engineered MOF adsorbents’ regime has witnessed coherent pore surface engineering principles climb up the ladder to craft multifarious opportunities to systematically fine-tune and control performance.13, 14 Apart from the seemingly interminable MOF research domain entailing massively high surface areas, benign crystal engineering approaches have steadily transpired as vital footprints to draw more and more impetus on rationally functionalized ultrami-

cropores.15-17 Based upon suitable incorporation of linker or metal node-based functionalization principles, astute design and synthesis of such rationally integrated ultramicroporous (