Mechanistic Routes toward C3-C4 products in Copper-Catalysed CO2 Electroreduction

Rodrigo García-Muelas^a, Sergio Pablo-García^a, Louisa R L Ting^b^,^c, Florentine L P Veenstra^d, Antonio J Martin^d, Jason Boon Siang Yeo^b^,^c, Javier Pérez-Ramírez^d, Núria López^a

^aInstitute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science and Technology (BIST), Avinguda dels Països Catalans, 16, Tarragona, Spain

^bDepartment of Chemistry, National University of Singapore (NUS)

^cSolar Energy Research Institute of Singapore (SERIS), National University of Singapore

^dSwiss Federal Institute of Technology ETH Zurich, Switzerland

Proceedings of International Conference on Frontiers in Electrocatalytic Transformations (INTERECT)

València, Spain, 2021 November 22nd - 23rd

Organizers: Elena Mas Marzá and Ward van der Stam

Poster, Rodrigo García-Muelas, 029
Publication date: 10th November 2021

The electroreduction of carbon dioxide powered by renewable electricity is a sustainable alternative to synthesize chemicals and fuels. Extensive research has focused on the production of C₁-C₂ products, such as methanol, ethylene, and ethanol. Yet, higher molecules, such as n-propanol and more complex C₄ molecules have been scarcely reported. Here we explore the mechanisms that allow the formation of C₃ and C4 backbones. The electrolysis of possible molecular intermediates, coupled with density functional theory, allowed us to elucidate the mechanistic aspects responsible for the observed selectivity. Firstly, CO₂ is electroreduced to acetaldehyde, a common intermediate to most C₂-C₄ products. Propionaldehyde and 1 propanol come from the coupling of CH₂CH with CHO. While propylene and 1-propanol share common intermediates, the former is barely produced in eCO₂R, due to the unfavourable formation of its allyl alkoxy precursor, CH₂CHCH₂O. In turn, C₄ products come from the aldol condensation catalyzed in the basic media to give crotonaldehyde, which is then reduced to butanal and 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.

References:

[1] Ting, L. R. L.; García-Muelas, R.; Martín, A. J.; Veenstra, F. L. P.; Chen, S. T.-J.; Peng, Y.; Per, E. Y. X.; Pablo-García, S.; López, N.; Pérez-Ramírez, J.; Yeo, B. S. Electrochemical Reduction of Carbon Dioxide to 1-Butanol on Oxide-Derived Copper. Angew. Chem. Intl. Ed. 2020, 59, 21072-21079.

[2] Pablo-García, S.; Veenstra, F. L. P.; Ting, L. R. L.; García-Muelas, R.; Martín, A. J.; Yeo, B. S.; Pérez-Ramírez, J.; López, N. Mechanistic Routes toward C3 products in Copper-Catalysed CO2 Electroreduction. Submitted.

Acknowledgements:

Spanish Ministry of Science RTI2018-101394-B-I00
Severo Ochoa CEX2019-000925-S 10.13039/501100011033
FlowPhotoChem 862453
National University of Singapore Flagship Green Energy Program (R143-000-A64-114, R143-000-A55-733 and R143-000-A55-646)
Ministry of Education of Singapore (R143-000-B52-114).
ETH Research Grant ETH-47 19-1
Swiss National Science Foundation - NCCR Catalysis National Centre of Competence in Research
The Barcelona Supercomputing Centre – MareNostrum (BSC-RES)

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