Identification of K+-determined reaction pathway for facilitated kinetics of CO2 electroreduction

Feng Wu, Xiaokang Liu, Shiqi Wang, Longfei Hu, Sebastian Kunze, Zhenggang Xue, Zehao Shen, Yaxiong Yang (), Xinqiang Wang, Minghui Fan, Hongge Pan, Xiaoping Gao (), Tao Yao () and Yuen Wu ()
Additional contact information
Feng Wu: University of Science and Technology of China
Xiaokang Liu: University of Science and Technology of China
Shiqi Wang: University of Science and Technology of China
Longfei Hu: University of Science and Technology of China
Sebastian Kunze: Seoul National University
Zhenggang Xue: Shanghai University
Zehao Shen: University of Science and Technology of China
Yaxiong Yang: Xi’an Technological University
Xinqiang Wang: Xi’an Technological University
Minghui Fan: University of Science and Technology of China
Hongge Pan: Xi’an Technological University
Xiaoping Gao: Deep Space Exploration Laboratory
Tao Yao: University of Science and Technology of China
Yuen Wu: University of Science and Technology of China

Nature Communications, 2024, vol. 15, issue 1, 1-11

Abstract: Abstract Cations such as K+ play a key part in the CO2 electroreduction reaction, but their role in the reaction mechanism is still in debate. Here, we use a highly symmetric Ni-N4 structure to selectively probe the mechanistic influence of K+ and identify its interaction with chemisorbed CO2−. Our electrochemical kinetics study finds a shift in the rate-determining step in the presence of K+. Spectral evidence of chemisorbed CO2− from in-situ X-ray absorption spectroscopy and in-situ Raman spectroscopy pinpoints the origin of this rate-determining step shift. Grand canonical potential kinetics simulations - consistent with experimental results - further complement these findings. We thereby identify a long proposed non-covalent interaction between K+ and chemisorbed CO2−. This interaction stabilizes chemisorbed CO2− and thus switches the rate-determining step from concerted proton electron transfer to independent proton transfer. Consequently, this rate-determining step shift lowers the reaction barrier by eliminating the contribution of the electron transfer step. This K+-determined reaction pathway enables a lower energy barrier for CO2 electroreduction reaction than the competing hydrogen evolution reaction, leading to an exclusive selectivity for CO2 electroreduction reaction.

Date: 2024
References: View references in EconPapers View complete reference list from CitEc
Citations:

Downloads: (external link)
https://www.nature.com/articles/s41467-024-50927-4 Abstract (text/html)

Related works:
This item may be available elsewhere in EconPapers: Search for items with the same title.

Export reference: BibTeX RIS (EndNote, ProCite, RefMan) HTML/Text

Persistent link: https://EconPapers.repec.org/RePEc:nat:natcom:v:15:y:2024:i:1:d:10.1038_s41467-024-50927-4

Ordering information: This journal article can be ordered from
https://www.nature.com/ncomms/

DOI: 10.1038/s41467-024-50927-4

Access Statistics for this article

Nature Communications is currently edited by Nathalie Le Bot, Enda Bergin and Fiona Gillespie

More articles in Nature Communications from Nature
Bibliographic data for series maintained by Sonal Shukla () and Springer Nature Abstracting and Indexing ().