Amine-functionalized metal-organic frameworks loaded with Ag nanoparticles for cycloaddition of CO₂ to epoxides

Abstract

With the advantages of low raw material cost and 100% atom utilization, the synthesis of high value-added chemical product cyclic carbonates by the cycloaddition of CO₂ to epoxides has become one of the most prospective approaches to achieve the industrial utilization of CO₂. In the reported catalytic systems, the complexity of the catalyst synthesis process, high cost, separation difficulties, and low CO₂ capture limit the catalytic efficiency and its large-scale application. In this paper, Ag nanoparticles loaded on polyethyleneimine (PEI)-modified UiO-66-NH₂ (Ag/PEI@UiO-66-NH₂) are successfully synthesized by in situ immersion reduction. The Ag nanoparticles and the amino groups on the surfaces of PEI@UiO-66-NH₂ contribute to the adsorption of CO₂ and polarization of C–O bonds in epoxides, thereby boosting the conversion capability for the CO₂ cycloaddition reaction. At the amount of propylene oxide of 0.25 mol and the catalyst dosage of 1% of the substrate, the yield and selectivity of propylene carbonate are up to 99%. In addition, the stability and recyclability of Ag/PEI@UiO-66-NH₂ catalyst are attained. The Ag/PEI@UiO-66-NH₂ catalyst also demonstrates a wide range of activity and distinctive selectivity toward cyclo-carbonates in the cycloaddition of CO₂ to epoxides. This work provides a guide to designing a highly efficient catalyst for in situ capture and high-value utilization of CO₂ in industrial applications.

Key words： cycloaddition; CO₂ capture; cyclic carbonates; amine-functionalized UiO-66-NH₂; Ag NPs

Competing interests

The authors declare that they have no competing interests.

Acknowledgements

We acknowledge with pleasure the support of this work by the National Key R&D Program of China (Grant No. 2023YFB4103404), the National Natural Science Foundation of China (Grant Nos. 22272014 and 22161132005), the Science and Technology Plan Project of Liaoning Province (Grant No. 2023JH1/10400040), the Fundamental Research Funds for the Central Universities (Grant No. DUT2021TD103). We thank Dr. Alex C. W. Tsang from the Technological and Higher Education Institute of Hong Kong for improving the English of the manuscript.

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11705-024-2477-2 and is accessible for authorized users.

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