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Rational Design of a Zn II MOF with Multiple Functional Sites for Highly Efficient Fixation of CO 2 under Mild Conditions: Combined Experimental and Theoretical Investigation
Author(s) -
Das Rajesh,
Muthukumar D.,
Pillai Renjith S.,
Nagaraja C. Mallaiah
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202002688
Subject(s) - catalysis , density functional theory , chemistry , adsorption , ligand (biochemistry) , rational design , lewis acids and bases , benzoic acid , melamine , combinatorial chemistry , materials science , computational chemistry , organic chemistry , nanotechnology , biochemistry , receptor
Abstract The development of efficient heterogeneous catalysts suitable for carbon capture and utilization (CCU) under mild conditions is a promising step towards mitigating the growing concentration of CO 2 in the atmosphere. Herein, we report the construction of a hydrogen‐bonded 3D framework, {[Zn(hfipbba)(MA)]⋅3 DMF} n (hfipbba=4,4′‐(hexaflouroisopropylene)bis(benzoic acid)) (HbMOF 1 ) utilizing Zn II center, a partially fluorinated, long‐chain dicarboxylate ligand (hfipbba), and an amine‐rich melamine (MA) co‐ligand. Interestingly, the framework possesses two types of 1D channels decorated with CO 2 ‐philic (−NH 2 and −CF 3 ) groups that promote the highly selective CO 2 adsorption by the framework, which was supported by computational simulations. Further, the synergistic involvement of both Lewis acidic and basic sites exposed in the confined 1D channels along with high thermal and chemical stability rendered HbMOF 1 a good heterogeneous catalyst for the highly efficient fixation of CO 2 in a reaction with terminal/internal epoxides at mild conditions (RT and 1 bar CO 2 ). Moreover, in‐depth theoretical studies were carried out using periodic DFT to obtain the relative energies for each stage involved in the catalytic reaction and an insight mechanistic details of the reaction is presented. Overall, this work represents a rare demonstration of rational design of a porous Zn II MOF incorporating multiple functional sites suitable for highly efficient fixation of CO 2 with terminal/internal epoxides at mild conditions supported by comprehensive theoretical studies.