Crystal facet-dependent CO₂ cycloaddition to epoxides over ZnO catalysts

Abstract

With regard to green chemistry and sustainable development, the fixation of CO₂ into epoxides to form cyclic carbonates is an attractive and promising pathway for CO₂ utilization. Metal oxides, renowned as promising eco-friendly catalysts for industrial production, are often undervalued in terms of their impact on the CO₂ addition reaction. In this work, we successfully developed ZnO nanoplates with (002) surfaces and ZnO nanorods with (100) surfaces via morphology-oriented regulation to explore the effect of crystal faces on CO₂ cycloaddition. The quantitative data obtained from electron paramagnetic resonance spectroscopy indicated that the concentration of oxygen vacancies on the ZnO nanoplate surfaces was more than twice that on the ZnO nanorod surfaces. Density functional theory calculations suggested that the (002) surfaces have lower adsorption energies for CO₂ and epichlorohydrin than the (100) surfaces. As a result, the yield of cyclochloropropene carbonate on the ZnO nanoplates (64.7%) was much greater than that on the ZnO nanorods (42.3%). Further evaluation of the reused catalysts revealed that the decrease in the oxygen vacancy concentration was the primary factor contributing to the decrease in catalytic performance. Based on these findings, a possible catalytic mechanism for CO₂ cycloaddition with epichlorohydrin was proposed. This work provides a new idea for the controllable preparation of high-performance ZnO catalysts for the synthesis of cyclic carbonates from CO₂ and epoxides.

Key words： carbon dioxide; cycloaddition; zinc oxide; crystal face; oxygen vacancy

Competing interests

The authors declare that they have no competing interests.

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Grant No. 22008177), the Natural Science Foundation of Inner Mongolia (Grant Nos. 2023MS02004 and 2023MS02011), the Foundation of Inner Mongolia Education Department (Grant No. JY20220266), and the Program for Young Talents of Science and Technology of Inner Mongolia (Grant No. NJYT23040).

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11705-024-2412-6 and is accessible for authorized users.

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