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

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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

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Publication details

The article was received on 05 May 2019, accepted on 17 Jul 2019 and first published on 18 Jul 2019


Article type: Communication
DOI: 10.1039/C9SE00282K
Sustainable Energy Fuels, 2019, Advance Article

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    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, Advance Article , DOI: 10.1039/C9SE00282K

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