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
a Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science and Technology (BIST), Avinguda dels Països Catalans, 16, Tarragona, Spain
b Department of Chemistry, National University of Singapore (NUS)
c Solar Energy Research Institute of Singapore (SERIS), National University of Singapore
d Swiss 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

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) 

© Fundació Scito
We use our own and third party cookies for analysing and measuring usage of our website to improve our services. If you continue browsing, we consider accepting its use. You can check our Cookies Policy in which you will also find how to configure your web browser for the use of cookies. More info