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Synthesis of cyclic carbonate by CO2 fixation to epoxides using interpenetrated MOF-5/n-Bu4NBr

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Abstract

Phase-pure interpenetrated MOF-5 ([Zn4(O)(BDC)3]) was synthesized by pH* control in a reaction medium, and its stability in the presence of epoxides was confirmed by powder X-ray diffraction analysis. Interpenetrated MOF-5/tetra-n-butylammonium bromide (int-MOF-5/n-Bu4NBr) showed a high catalytic activity toward CO2 fixation to epoxide to synthesize cyclic carbonates. The conversions of propylene oxide (PO) and styrene oxide (SO) by int-MOF-5/n-Bu4NBr were almost two times higher than those by MOF-5/n-Bu4NBr under the same conditions. From a kinetics point of view, the coupling reaction rate of PO and CO2 was much higher than that of SO and CO2, which may be due to steric effects. The optimized geometries by the density functional theory calculation revealed that Lewis acidic Zn(II) sites of tetranuclear {Zn4O} clusters can work as the catalytic center to bind epoxides to open the rings by a nucleophilic attack. This co-catalyst system may be useful for the synthesis of cyclic carbonate by CO2 fixation.

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References

  1. Martin C, Fiorani G, Kleij AW (2015) Recent advances in the catalytic preparation of cyclic organic carbonates. ACS Catal 5:1353–1370

    Article  CAS  Google Scholar 

  2. Shaikh RR, Pornpraprom S, D’Elia V (2018) Catalytic strategies for the cycloaddition of pure, diluted, and waste CO2 to epoxides under ambient conditions. ACS Catal 8:419–450

    Article  CAS  Google Scholar 

  3. Alves M, Grignard B, Mereau R, Jerome C, Tassaing T, Detrembleur C (2017) Organocatalyzed coupling of carbon dioxide with epoxides for the synthesis of cyclic carbonates: catalyst design and mechanistic studies. Catal Sci Technol 7:2651–2684

    Article  CAS  Google Scholar 

  4. Minakata S, Sasaki I, Ide T (2010) Atmospheric CO2 fixation by unsaturated alcohols using tBuOI under neutral conditions. Angew Chem Int Ed 49:1309–1311

    Article  CAS  Google Scholar 

  5. Lee EH, Ahn JY, Dharman MM, Park DW, Park SW, Kim I (2008) Synthesis of cyclic carbonate from vinyl cyclohexene oxide and CO2 using ionic liquids as catalysts. Catal Today 131:130–134

    Article  CAS  Google Scholar 

  6. Sun J, Zhang S, Cheng W, Ren J (2008) Hydroxyl-functionalized ionic liquid: a novel efficient catalyst for chemical fixation of CO2 to cyclic carbonate. Tetrahedron Lett 49:3588–3591

    Article  CAS  Google Scholar 

  7. Xie Y, Wang TT, Liu XH, Zou K, Deng WQ (2013) Capture and conversion of CO2 at ambient conditions by a conjugated microporous polymer. Nat Commun 4:1960

    Article  Google Scholar 

  8. Taherimehr M, Decortes A, Al-Amsyar SM, Lueangchaichaweng W, Whiteoak CJ, Escudero-Adán EC, Kleij AW, Pescarmona PP (2012) A highly active Zn(salphen) catalyst for production of organic carbonates in a green CO2 medium. Catal Sci Technol 2:2231–2237

    Article  CAS  Google Scholar 

  9. Maeda C, Shimonishi J, Miyazaki R, Hasegawa JY, Ema T (2016) Highly active and robust metalloporphyrin catalysts for the synthesis of cyclic carbonates from a broad range of epoxides and carbon dioxide. Chem Eur J 22:6556–6563

    Article  CAS  Google Scholar 

  10. Feng D, Chung WC, Wei Z, Gu ZY, Jiang HL, Chen YP, Darensbourg DJ, Zhou HC (2013) Construction of ultrastable porphyrin Zr metal–organic frameworks through linker elimination. J Am Chem Soc 135:17105–17110

    Article  CAS  Google Scholar 

  11. Kathalikkattil AC, Kim DW, Tharun J, Soek HG, Roshan R, Park DW (2014) Aqueous-microwave synthesized carboxyl functional molecular ribbon coordination framework catalyst for the synthesis of cyclic carbonates from epoxides and CO2. Green Chem 16:1607–1616

    Article  CAS  Google Scholar 

  12. Guillerm V, Weseliński ŁJ, Belmabkhout Y, Cairns AJ, D’Elia V, Wojtas Ł, Adil K, Eddaoudi M (2014) Discovery and introduction of a (3,18)-connected net as an ideal blueprint for the design of metal–organic frameworks. Nat Chem 6:673–680

    Article  CAS  Google Scholar 

  13. Li Z, Rayder TM, Luo L, Byers JA, Tsung CK (2018) Aperture-opening encapsulation of a transition metal catalyst in a metal–organic framework for CO2 hydrogenation. J Am Chem Soc 140:8082–8085

    Article  CAS  Google Scholar 

  14. Lee WT, van Muyden AP, Bobbink FD, Huang Z, Dyson PJ (2019) Indirect CO2 methanation: hydrogenolysis of cyclic carbonates catalyzed by Ru-modified zeolite produces methane and diols. Angew Chem Int Ed 58:557–560

    Article  CAS  Google Scholar 

  15. Zhang X, Sun J, Wei G, Liu Z, Yang H, Wang K, Fei H (2019) In situ generation of an N-heterocyclic carbene functionalized metal-organic framework by postsynthetic ligand exchange: efficient and selective hydrosilylation of CO2. Angew Chem Int Ed 58:2844–2849

    Article  CAS  Google Scholar 

  16. Beyzavi MH, Klet RC, Tussupbayev S, Borycz J, Vermeulen NA, Cramer CJ, Stoddart JF, Hupp JT, Farha OK (2014) A hafnium-based metal–organic framework as an efficient and multifunctional catalyst for facile CO2 fixation and regioselective and enantioretentive epoxide activation. J Am Chem Soc 136:15861–15864

    Article  CAS  Google Scholar 

  17. Song J, Zhang Z, Hu S, Wu T, Jiang T, Han B (2009) MOF-5/n-Bu4NBr: an efficient catalyst system for the synthesis of cyclic carbonates from epoxides and CO2 under mild conditions. Green Chem 11:1031–1036

    Article  CAS  Google Scholar 

  18. Kim H, Das S, Kim MG, Dybtsev DN, Kim Y, Kim K (2010) Synthesis of phase-pure interpenetrated MOF-5 and its gas sorption properties. Inorg Chem 50:3691–3696

    Article  Google Scholar 

  19. Yoon M, Srirambalaji R, Kim K (2012) Homochiral metal–organic frameworks for asymmetric heterogeneous catalysis. Chem Rev 112:1196–1231

    Article  CAS  Google Scholar 

  20. Kresse G, Hafner J (1993) Ab initio molecular dynamics for liquid metals. Phys Rev B 47:558–561

    Article  CAS  Google Scholar 

  21. Guo L, Deng L, Jin X, Wang Y, Wang H (2018) Catalytic conversion of CO2 into propylene carbonate in a continuous fixed bed reactor by immobilized ionic liquids. RSC Adv 8:26554–2655462

    Article  CAS  Google Scholar 

  22. Tharun J, Kim DW, Roshan R, Kathalikkattil AC, Selvaraj M, Park DW (2013) Cycloaddition of styrene oxide and CO2 mediated by pyrolysis of urea. RSC Adv 3:14290–14293

    Article  CAS  Google Scholar 

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Acknowledgements

This work was conducted under the framework of the Research and Development Program of the Korea Institute of Energy Research (KIER) (B9-2441) and was also supported by the Center for Advanced Meta-Materials (CAMM) funded by the Ministry of Science and ICT (MSIT) as a Global Frontier Program (NRF-2019M3A6B3030636).

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Authors and Affiliations

  1. Korea Institute of Energy Research (KIER), Daejeon, 34129, Republic of Korea

    Hyunuk Kim, Hyun-Sik Moon, Muhammad Sohail, Yang-No Yoon, Syed Fawad Ali Shah, Kanghoon Yim, Jong-Ho Moon & Young Cheol Park

  2. Advanced Energy and System Technology, University of Science and Technology (UST), Daejeon, 34113, Republic of Korea

    Hyunuk Kim, Muhammad Sohail & Syed Fawad Ali Shah

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  1. Hyunuk Kim
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Correspondence to Hyunuk Kim or Young Cheol Park.

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Kim, H., Moon, HS., Sohail, M. et al. Synthesis of cyclic carbonate by CO2 fixation to epoxides using interpenetrated MOF-5/n-Bu4NBr. J Mater Sci 54, 11796–11803 (2019). https://doi.org/10.1007/s10853-019-03702-6

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  • DOI: https://doi.org/10.1007/s10853-019-03702-6

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