Mechanistic routes toward C3 products in copper-catalysed CO2 electroreduction. Issue 2 (7th January 2022)

• Record Type: Journal Article
• Authors: Pablo-García, Sergio; Veenstra, Florentine L. P.; Ting, Louisa Rui Lin; García-Muelas, Rodrigo; Dattila, Federico; Martín, Antonio J.; Yeo, Boon Siang; Pérez-Ramírez, Javier; López, Núria
• Is Part Of: Catalysis science & technology. Volume 12:Issue 2(2022)
• Page Start: 409
• Page End: 417
• Publication Date: 2022-01-07
• Subjects: Catalysis -- Periodicals; 541.395
• DOI: 10.1039/d1cy01423d
• Languages: English
• ISSNs: 2044-4753

Abstract

Abstract : The mechanistic insights of CO2 electrochemical reduction on Cu materials up to C3 fragments are investigated by combining experiments and theory. Abstract : The electrocatalytic CO2 reduction (eCO2 R) reaction powered by renewable electricity holds promise for the sustainable production of multi-carbon chemicals and fuels. On Cu-based catalysts, ethylene and ethanol (C2 ) have been produced in appreciable amounts. C3 products (mostly terminal oxygenates) have limited yields, whereas propylene is puzzlingly absent. Herein, we devise a divide-and-conquer strategy to explain the formation of the C3 -backbone and elucidate the mechanism responsible for the observed selectivity by combining network graphs, density functional theory, and experiments to prune the network and benchmark the identified path. Our approach concludes that the most frequently reported products, propionaldehyde and 1-propanol, originate from the coupling of CH2 CH with C(H)O. While propylene and 1-propanol share common intermediates, the former is barely produced due to the unfavourable formation of allyl alkoxy (CH2 CHCH2 O), whose crucial nature was confirmed experimentally. This work paves the way for tailoring selective routes towards C3 products via eCO2 R.