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Electrochemical Reduction of Carbon Dioxide to 1-Butanol on Oxide-Derived Copper |
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| Authors: | Louisa Rui Lin Ting Dr Rodrigo García-Muelas Dr Antonio J Martín Florentine L P Veenstra Stuart Tze-Jin Chen Yujie Peng Edwin Yu Xuan Per Sergio Pablo-García Prof Dr Núria López Prof Dr Javier Pérez-Ramírez Prof Dr Boon Siang Yeo |
| Institution: | 1. Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore, 117543 Singapore
Solar Energy Research Institute of Singapore, National University of Singapore, 7 Engineering Drive 1, Singapore, 117574 Singapore These authors contributed equally to this work.;2. Institute of Chemical Research of Catalonia, The Barcelona Institute of Science and Technology, Av. Països Catalans 16, 43007 Tarragona, Spain These authors contributed equally to this work.;3. Institute for Chemical and Bioengineering, Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog-Weg 1, 8093 Zürich, Switzerland These authors contributed equally to this work.;4. Institute for Chemical and Bioengineering, Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog-Weg 1, 8093 Zürich, Switzerland;5. Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore, 117543 Singapore;6. Institute of Chemical Research of Catalonia, The Barcelona Institute of Science and Technology, Av. Països Catalans 16, 43007 Tarragona, Spain;7. Institute for Chemical and Bioengineering, Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog-Weg 1, 8093 Zürich, Switzerland Department of Chemical and Biomolecular Engineering, National University of Singapore, 4 Engineering Drive 4, Singapore, 117585 Singapore |
| Abstract: | The electroreduction of carbon dioxide using renewable electricity is an appealing strategy for the sustainable synthesis of chemicals and fuels. Extensive research has focused on the production of ethylene, ethanol and n-propanol, but more complex C4 molecules have been scarcely reported. Herein, we report the first direct electroreduction of CO2 to 1-butanol in alkaline electrolyte on Cu gas diffusion electrodes (Faradaic efficiency=0.056 %, j1-Butanol=−0.080 mA cm−2 at −0.48 V vs. RHE) and elucidate its formation mechanism. Electrolysis of possible molecular intermediates, coupled with density functional theory, led us to propose that CO2 first electroreduces to acetaldehyde-a key C2 intermediate to 1-butanol. Acetaldehyde then undergoes a base-catalyzed aldol condensation to give crotonaldehyde via electrochemical promotion by the catalyst surface. Crotonaldehyde is subsequently electroreduced to butanal, and then to 1-butanol. In a broad context, our results point to the relevance of coupling chemical and electrochemical processes for the synthesis of higher molecular weight products from CO2. |
| Keywords: | 1-butanol carbon dioxide reduction density functional theory electrochemistry reaction mechanisms |