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Redox-neutral electrochemical conversion of CO2 to dimethyl carbonate

Abstract

The electrochemical reduction of CO2 to value-added products is a promising approach for using CO2. However, the products are limited to reduced forms, such as CO, HCOOH and C2H4. Decreasing the anodic overpotential and designing membrane-separated systems are important determinants of the overall efficiency of the process. In this study we explored the use of redox-neutral reactions in electrochemical CO2 reduction to expand the product scope and achieve higher efficiency. We combined the CO2 reduction reaction with two redox cycles in an undivided cell so that the input electrons are carried through the electrolyte rather than settling in CO2. As a result, dimethyl carbonate—a useful fuel additive—has been synthesized directly from CO2 in methanol solvent with a Faradaic efficiency of 60% at room temperature. Our study shows that the formation of methoxide intermediates and the cyclic regeneration of the uniformly dispersed palladium catalyst by in situ-generated oxidants are important for dimethyl carbonate synthesis at room temperature. Furthermore, we successfully synthesized diethyl carbonate from CO2 and ethanol, demonstrating the generality and expandability of our system.

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Fig. 1: Redox-neutral electrochemical system for DMC synthesis from CO2.
Fig. 2: Electrochemical investigation of the electrodes for efficient coupling of the CO2RR and the two redox cycles.
Fig. 3: Selection of metal catalysts dispersed in solution for efficient DMC synthesis.
Fig. 4: Characterization of the optimized conditions for the redox-neutral conversion of CO2 to DMC.
Fig. 5: Mechanistic study of redox-neutral DMC synthesis.
Fig. 6: Role of CO2 in suppressing the loss of Br2.
Fig. 7: Performance comparison of DMC synthesis and expandability to diverse dialkyl carbonates.

Data availability

The authors declare that all data supporting the findings of this study are available within the paper and Supplementary Information files.

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Acknowledgements

This work was supported by National Research Foundation of Korea (NRF) grants funded by the Korean government (MSIT; NRF-2017R1A2B3012003 and NRF-2018M3C1B7021994), the KIST Institutional Program (NRF-2020M3H4A1A02084594), the Creative Materials Discovery Program through the NRF, funded by the Ministry of Science and ICT (NRF-2017M3D1A1039377) and the Korea Environment Industry & Technology Institute (KEITI) through the Ecological Imitation-based Environmental Pollution Management Technology Development Project, funded by the Korea Ministry of Environment (MOE; 2021002800009). K.T.N. appreciates support from the Institute of Engineering Research, the Research Institute of Advanced Materials (RIAM) and the Soft Foundry at Seoul National University.

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Contributions

K.M.L., J.H.J. and K.T.N. designed the research and wrote the manuscript. K.M.L., J.H.J. and M.B. conducted the electrochemical experiments and optimized the DMC synthesis conditions. K.M.L., J.H.J. and J.E.K. performed the mechanistic investigation and analysed the data. K.M.L., J.H.J. and Y.I.J. investigated the Br2 loss mechanism. All authors discussed the experiments and contributed to the writing of this manuscript. K.T.N. guided all aspects of the work.

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Correspondence to Ki Tae Nam.

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Peer review information Nature Energy thanks Markus Kärkäs, Marc Robert and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

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Supplementary Figs. 1–15 and Table1.

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Lee, K.M., Jang, J.H., Balamurugan, M. et al. Redox-neutral electrochemical conversion of CO2 to dimethyl carbonate. Nat Energy 6, 733–741 (2021). https://doi.org/10.1038/s41560-021-00862-1

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