Issue 11, 2021

Elucidating the role of non-covalent interactions in unexpectedly high and selective CO2 uptake and catalytic conversion of porphyrin-based ionic organic polymers

Abstract

Here, we present viologen-porphyrin based ionic covalent organic polymers (H2-ICOP and Zn-ICOP) with multiple CO2-philic sites. The specific surface areas of H2-ICOP and Zn-ICOP were found to be 9 m2 g−1 and 20 m2 g−1, respectively. CO2 uptake analyses reveal that H2-ICOP exhibits very high CO2 capture uptake (62.9 mg g−1), which is one of the highest values among previously reported ICOPs. The results indicate very efficient non-covalent interactions between H2-ICOP and CO2. The possible non-covalent interactions of hydrogen (OCO2⋯H–N), tetrel (CCO2⋯N, CCO2⋯Cl), pnicogen (OCO2⋯N+), and spodium bonds (OCO2⋯Zn) between CO2 and H2-ICOP and Zn-ICOP are investigated via symmetry adapted perturbation theory (SAPT) analysis and electrostatic potential maps (MEP). The strength of non-covalent interactions in H2-ICOP and Zn-ICOP is decreasing in the following order ΔEC⋯N > ΔEC⋯Cl > ΔEO⋯N+ and ΔEZn⋯O > ΔEC⋯Cl > ΔEC⋯N > ΔEO⋯N+, respectively. The major CO2 uptake contribution comes from CCO2⋯N tetrel bonding (−22.02 kJ mol−1) interactions for H2-ICOP, whereas OCO2⋯Zn spodium bonding (−21.065 kJ mol−1) interactions for Zn-ICOP. H2-ICOP has more CO2-philic moieties with powerful non-covalent interactions compared to Zn-ICOP, which is in good agreement with the experimental results. Furthermore, the CO2 catalytic conversion performances of Zn-ICOP and H2-ICOP gave good yields of 83% and 54%, respectively. Surprisingly, Zn-ICOP, despite having significantly lower CO2 uptake capacity, displayed better catalytic activity than H2-ICOP, owing to a higher number of counter anions (Cl) on its surface, which shows the crucial role of the counter anion (Cl) in the mechanism of this catalytic reaction.

Graphical abstract: Elucidating the role of non-covalent interactions in unexpectedly high and selective CO2 uptake and catalytic conversion of porphyrin-based ionic organic polymers

Supplementary files

Article information

Article type
Paper
Submitted
11 Marts 2021
Accepted
11 Apr. 2021
First published
12 Apr. 2021
This article is Open Access
Creative Commons BY-NC license

Mater. Adv., 2021,2, 3685-3694

Elucidating the role of non-covalent interactions in unexpectedly high and selective CO2 uptake and catalytic conversion of porphyrin-based ionic organic polymers

S. T. Kostakoğlu, Y. Chumakov, Y. Zorlu, A. E. Sadak, S. Denizaltı, A. G. Gürek and M. M. Ayhan, Mater. Adv., 2021, 2, 3685 DOI: 10.1039/D1MA00217A

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