Issue 11, 2019

Environment-friendly, co-catalyst- and solvent-free fixation of CO2 using an ionic zinc(ii)–porphyrin complex immobilized in porous metal–organic frameworks

Abstract

Herein an ionic Zn(II)–porphyrin complex, [Zn(II)NMeTPyP]4+[I]4 (Zn(II)NMeTPyP = 5,10,15,20-tetrakis(1-methylpyridinium-4′-yl) zinc(II) porphyrin), was immobilized in a porous metal–organic framework, PCN-224. The resulting [Zn(II)NMeTPyP]4+[I]4@PCN-224 hybrid was thoroughly characterized by PXRD, UV-vis, FTIR, MP-AES, SEM-EDS and BET analysis. Further, DFT calculations confirmed the incorporation of the [Zn(II)NMeTPyP]4+[I]4 complex in the 1D channels of PCN-224 owing to appropriate matching of the pore size with the size of the complex and stabilization via π–π interactions. Interestingly, the [Zn(II)NMeTPyP]4+[I]4@PCN-224 hybrid showed high affinity for CO2 with a high heat of adsorption (Qst) value of 40.5 kJ mol−1 compared to the pristine MOF, PCN-224, with a Qst value of 36.8 kJ mol−1. Remarkably, the hybrid material acts as an efficient environment-friendly, co-catalyst- and solvent-free heterogeneous catalyst for chemical fixation of CO2 to generate cyclic carbonates with high yield and selectivity due to synergistic cooperation between the complex and the framework.

Graphical abstract: Environment-friendly, co-catalyst- and solvent-free fixation of CO2 using an ionic zinc(ii)–porphyrin complex immobilized in porous metal–organic frameworks

Supplementary files

Article information

Article type
Communication
Submitted
05 maj 2019
Accepted
17 jul 2019
First published
18 jul 2019

Sustainable Energy Fuels, 2019,3, 2977-2982

Environment-friendly, co-catalyst- and solvent-free fixation of CO2 using an ionic zinc(II)–porphyrin complex immobilized in porous metal–organic frameworks

N. Sharma, S. S. Dhankhar and C. M. Nagaraja, Sustainable Energy Fuels, 2019, 3, 2977 DOI: 10.1039/C9SE00282K

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