Cation-induced changes in the inner- and outer-sphere mechanisms of electrocatalytic CO2 reduction
Qin, X., Hansen, H. A., Honkala, K., & Melander, M. M. (2023). Cation-induced changes in the inner- and outer-sphere mechanisms of electrocatalytic CO2 reduction. Nature Communications, 14, Article 7607. https://doi.org/10.1038/s41467-023-43300-4
Julkaistu sarjassa
Nature CommunicationsPäivämäärä
2023Oppiaine
Fysikaalinen kemiaKemiaResurssiviisausyhteisöNanoscience CenterPhysical ChemistryChemistrySchool of Resource WisdomNanoscience CenterTekijänoikeudet
© 2023 the Authors
The underlying mechanism of cation effects on CO2RR remains debated. Herein, we study cation effects by simulating both outer-sphere electron transfer (OS-ET) and inner-sphere electron transfer (IS-ET) pathways during CO2RR via constrained density functional theory molecular dynamics (cDFT-MD) and slow-growth DFT-MD (SG-DFT-MD), respectively. Our results show without any cations, only OS-ET is feasible with a barrier of 1.21 eV. In the presence of K+ (Li+), OS-ET shows a very high barrier of 2.93 eV (4.15 eV) thus being prohibited. However, cations promote CO2 activation through IS-ET with the barrier of only 0.61 eV (K+) and 0.91 eV (Li+), generating the key intermediate (adsorbed CO). Without cations, CO2-to-CO (ads) conversion cannot proceed. Our findings reveal cation effects arise from short-range Coulomb interactions with reaction intermediates. These results disclose that cations modulate the inner- and outer-sphere pathways of CO2RR, offering substantial insights on the cation specificity in the initial CO2RR steps.
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Nature Publishing GroupISSN Hae Julkaisufoorumista
2041-1723Julkaisu tutkimustietojärjestelmässä
https://converis.jyu.fi/converis/portal/detail/Publication/194574383
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M.M.M. acknowledges the financial support by the Academy of Finland (CompEL project, #338228). The authors acknowledge the computer resources provided by CSC - IT CENTER FOR SCIENCE LTD. H.A.H acknowledges support from the Carlsberg Foundation Young Researcher Fellowship (Grant No. CF19-0304) and Villum Fonden through the project V-sustain (No. 9455).Lisenssi
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