Issue 35, 2023

Theoretical understanding of the effect of specifically adsorbed halide anions on Cu-catalyzed CO2 electroreduction activity and product selectivity

Abstract

Initial CO2 electroreduction into CO and its subsequent electroreduction pathways were selected to study the effect of specifically adsorbed halide anions X (X = F, Cl, Br, I) on CO2 electroreduction activity and product selectivity at Cu(111)/H2O interfaces via DFT calculations. The calculated results show that the presence of halide anions can exert a notable effect on the CO2 adsorption characteristics and that chemically adsorbed CO2 molecules can be formed. Furthermore, the halide-anion-modified Cu(111)/H2O interfaces could significantly enhance the initial CO2 electroreduction into CO activity, which is regarded as the rate-determining step during CO2 electroreduction at clean Cu(111)/H2O interfaces. Analysis of the initial CO2 electroreduction and Volmer reaction pathways showed that the halide-anion-modified Cu(111)/H2O interfaces could suppress the HER and thus improve the CO2 electroreduction activity and product selectivity. It is speculated that the enhanced initial CO2 electroreduction activity at the F-, Cl-, Br-, and I-modified Cu(111)/H2O interfaces may originate from the decreased work functions and anion radical ·CO2 formations. Simultaneously, we concluded that dimer OCCO formations in the presence of halide anions were more favorable than CHO during CO electroreduction according to the order of I > Br > Cl > F and could result in the production of C2 product, suggesting an improved CO2 electroreduction product selectivity. The present analyses of electronic structure may explain the more favorable OCCO formations in the order of I > Br > Cl > F. The present understanding of this effect will provide an improved scientific guideline for the control of CO2 electroreduction pathways and design of more efficient electrocatalysts.

Graphical abstract: Theoretical understanding of the effect of specifically adsorbed halide anions on Cu-catalyzed CO2 electroreduction activity and product selectivity

Supplementary files

Article information

Article type
Paper
Submitted
26 Apr 2023
Accepted
14 Aug 2023
First published
15 Aug 2023

Phys. Chem. Chem. Phys., 2023,25, 23977-23987

Theoretical understanding of the effect of specifically adsorbed halide anions on Cu-catalyzed CO2 electroreduction activity and product selectivity

L. Ou, W. You, J. Jin and Y. Chen, Phys. Chem. Chem. Phys., 2023, 25, 23977 DOI: 10.1039/D3CP01900D

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