Chlorine-Promoted Copper Catalysts for CO2 Electroreduction into Highly Reduced Products
Enric Ibáñez-Alé a, Rodrigo García-Muelas a, Florentine L. P. Veenstra b, Tangsheng Zou b, Antonio J. Martín b, Núria López a, Javier Pérez-Ramírez b
a Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science and Technology (BIST), ES
b Institute for Chemical and Bioengineering, Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog-Weg 1, 8093 Zürich
Proceedings of International Conference on Frontiers in Electrocatalytic Transformations (INTERECT22)
València, Spain, 2022 November 21st - 22nd
Organizers: Sara Barja, Nongnuch Artrith and Matthew Mayer
Poster, Enric Ibáñez-Alé, 022
Publication date: 11th October 2022

Copper catalysts are unique in CO2 electrochemical reduction as they allow
the formation of C2+ products [1]. Thus, selective and efficient catalysts are needed to
open new routes to synthesize fuels and chemicals, as product distribution varies
significantly depending on material’s synthesis [2][3]. The search of nanostructuring and promotional effects in copper-based catalysts able to drive the selectivity of the CO2 reduction reaction is one of the most active fields in electrocatalysis. This work unveils that halogen-promoted copper systems can exhibit enhanced performance towards highly reduced products (HRP, those requiring the transfer of more than 2e−) for certain copper matrices and halogenation degrees. The controlled chlorination of metallic Cu, CuO, and Cu2O foils resulted on surfaces with starkly different chemical natures, among which Cu2O-based systems yielded an increasingly high Faradaic efficiency towards HRP as the surface concentration of chlorine after reaction rose. The latter was maximized for mild chlorination treatments leading to chloride and oxide phases coexisting in comparable amounts in the fresh materials. Those results suggest that the presence of residual oxygen is required for  generating Cl-Cu sites stable under operation conditions, which are responsible of promoting HRP generation. Here we present how our computational simulations bring a better understanding of how chlorine enhances the catalytic performance of copper catalysts. DFT-based methods are used to characterize how Cl incorporates, which effect it has on material’s physical properties, and also how it
lowers the energy barriers of some key steps of the reaction mechanisms towards those HRP. 

This work was financed by the Spanish Ministry of Science and Innovation
(RTI2018-101394-B-I00, Severo Ochoa Centre of Excellence CEX2019-000925-S
10.13039/501100011033. The Barcelona Supercomputing Centre – MareNostrum
(BSC-RES) is acknowledged for providing generous computational resources.

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