Abstract
Electrochemical reduction of carbon dioxide (CO2) is promising to alleviate carbon emissions and produce fuels and materials in a circular way, yet effective tuning strategies and fundamental understanding are lacking. In particular, cell design is actually done by simplistic one- or two-dimensional models, which incorporate numerous assumptions, leading to potential errors and discrepancies. Here, we establish new two-dimensional multiphysics models that incorporate cell-specific geometry, gas–liquid two-phase flow, and electrochemical kinetics. We calculate the temporary and spatial variations of the local CO2 concentration, electrochemical parameters, and products selectivity on the cathode surface, under different cell configurations and operating parameters. Products include dihydrogen (H2), carbon monoxide (CO), formic acid (HCOOH), ethylene (C2H4), ethanol (C2H5OH), and propanol (C3H7OH). We further investigated the effect of local CO2 concentration on CO2 reduction performance. We find that high local CO2 concentration, above 8.7 mM, enhances the selectivity for C1 products and the cathode polarization, whereas extremely low local CO2 concentration, of 0.75–5.5 mM, favors the selectivity for C2+ products, especially alcohols. C2+ selectivity ranges from 81.3 to 88.6% at 4.8–5.5 mM local CO2 concentration, while alcohol products selectivity ranges between 54.9 and 65.4% at 0.75–1.9 mM CO2 concentration. These findings are attributed to the reduced CO2 diffusion layer thickness to less than 10 μm at the cathode. This enhances the CO2 mass transfer efficiency to the cathode, and eliminates temporal and spatial variations of the local CO2 distribution along the cathode surface.
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Acknowledgements
This work is supported by the National Natural Science Foundation of China (51888103, 51906199) and the Fundamental Research Funds for the Central Universities.
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This study was funded by the National Natural Science Foundation of China (51888103, 51906199).
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Qiu, H., Wang, F., Liu, Y. et al. Improved product selectivity of electrochemical reduction of carbon dioxide by tuning local carbon dioxide concentration with multiphysics models. Environ Chem Lett 21, 3045–3054 (2023). https://doi.org/10.1007/s10311-023-01635-w
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DOI: https://doi.org/10.1007/s10311-023-01635-w