Electrocatalytic CO₂ reduction to alcohols by modulating the molecular geometry and Cu coordination in bicentric copper complexes
Files
(Published version)
Date
2022
Authors
Yang, B.
Chen, L.
Xue, S.
Sun, H.
Feng, K.
Chen, Y.
Zhang, X.
Xiao, L.
Qin, Y.
Zhong, J.
Editors
Advisors
Journal Title
Journal ISSN
Volume Title
Type:
Journal article
Citation
Nature Communications, 2022; 13(1):5122-1-5122-13
Statement of Responsibility
Baiyu Yang, Ling Chen, Songlin Xue, Hao Sun, Kun Feng, Yufeng Chen, Xiang Zhang, Long Xiao, Yongze Qin, Jun Zhong, Zhao Deng, Yan Jiao, Yang Peng
Conference Name
Abstract
Electrocatalytic reduction of CO2 into alcohols of high economic value offers a promising route to realize resourceful CO2 utilization. In this study, we choose three model bicentric copper complexes based on the expanded and fluorinated porphyrin structure, but different spatial and coordination geometry, to unravel their structure-property-performance correlation in catalyzing electrochemical CO2 reduction reactions.We show that the complexes with higher intramolecular tension and coordination asymmetry manifests a lower electrochemical stability and thus more active Cu centers, which can be reduced during electrolysis to form Cu clusters accompanied by partially-reduced or fragmented ligands. We demonstrate the hybrid structure of Cu cluster and partially reduced O-containing hexaphyrin ligand is highly potent in converting CO2 into alcohols, up to 32.5% ethanol and 18.3% n-propanol in Faradaic efficiencies that have been rarely reported. More importantly, we uncover an interplay between the inorganic and organic phases to synergistically produce alcohols, of which the intermediates are stabilized by a confined space to afford extra O-Cu bonding. This study underlines the exploitation of structure-dependent electrochemical property to steer the CO2 reduction pathway, as well as a potential generic tactic to target alcohol synthesis by constructing organic/inorganic Cu hybrids.
School/Discipline
Dissertation Note
Provenance
Description
Published online: 31 August 2022
Access Status
Rights
© The Author(s) 2022. Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/ licenses/by/4.0/.