Facile Green Synthesis of New Copper-Based Metal–Organic Frameworks: Experimental and Theoretical Study of the CO2 Fixation Reaction

Jintu Francis Kurisingal, Yadagiri Rachuri, Yunjang Gu, Ramesh Kumar Chitumalla, Srimai Vuppala, Joonkyung Jang, Kamal Kumar Bisht, Eringathodi Suresh, Dae-Won Park

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Two new entangled Cu(II)-based metal–organic frameworks (MOFs) have been synthesized, namely [Cu(BDC)(BPDB)0.5]n (PNU-25) and [Cu(NH2-BDC)(BPDB)0.5]n (PNU-25-NH2), using a H2O-MeOH solvent mixture. Both the PNU-25 and PNU-25-NH2 MOF materials were characterized by various analytical techniques and their catalytic potential of CO2 fixation into cyclic carbonates at an atmospheric pressure, a low reaction temperature, and in the neat conditions were demonstrated. The amine-functionalized PNU-25-NH2 exhibited a significant high conversion of epichlorohydrin (ECH) at the 1 bar of CO2 pressure, at 55 °C, and a moderate catalyst amount (1 mol%), with over 99% selectivity toward the corresponding cyclic carbonate of ECH. The superior catalytic activity of PNU-25-NH2 may be attributed to its high amount of acidic-basic sites and large BET surface area in comparison with the PNU-25. The PNU-25-NH2 catalyst could be reused up to four cycles without compromising its structural integrity and the ECH conversion. The reaction mechanism of CO2 and ECH cycloaddition reaction mediated by the PNU-25-NH2 was investigated in detail based on the experimental inferences and periodic calculations of density functional theory (DFT). The energy barrier of the rate-determining step of the PNU-25-NH2/TBAB-catalyzed reaction was significantly lower than those of the rate-determining steps of un-catalyzed and TBAB-catalyzed reactions.
Original languageEnglish (US)
JournalACS Sustainable Chemistry & Engineering
StatePublished - Jun 29 2020

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: This study was supported by the National Research Foundation of Korea through Basic Research Program (2019–057644), Brain Korea 21 Plus Program, and also the Korea Research Fellowship Program through the National Research Foundation of Korea (NRF), funded by the Ministry of Science and ICT (2018R1A2A2A05019776).


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