Stabilizing copper sites in coordination polymers toward efficient electrochemical C-C coupling

Yongxiang Liang, Jiankang Zhao, Yu Yang, Sung-Fu Hung, Jun Li, Shuzhen Zhang, Yong Zhao, An Zhang, Cheng Wang, Dominique Appadoo, Lei Zhang, Zhigang Geng (), Fengwang Li () and Jie Zeng ()
Additional contact information
Yongxiang Liang: University of Science and Technology of China
Jiankang Zhao: University of Science and Technology of China
Yu Yang: School of Chemical and Biomolecular Engineering and The University of Sydney Nano Institute, The University of Sydney
Sung-Fu Hung: National Yang Ming Chiao Tung University
Jun Li: Shanghai Jiao Tong University
Shuzhen Zhang: School of Chemical and Biomolecular Engineering and The University of Sydney Nano Institute, The University of Sydney
Yong Zhao: School of Chemical and Biomolecular Engineering and The University of Sydney Nano Institute, The University of Sydney
An Zhang: University of Science and Technology of China
Cheng Wang: University of Science and Technology of China
Dominique Appadoo: Australian Synchrotron
Lei Zhang: University of Science and Technology of China
Zhigang Geng: University of Science and Technology of China
Fengwang Li: School of Chemical and Biomolecular Engineering and The University of Sydney Nano Institute, The University of Sydney
Jie Zeng: University of Science and Technology of China

Nature Communications, 2023, vol. 14, issue 1, 1-10

Abstract: Abstract Electroreduction of carbon dioxide with renewable electricity holds promise for achieving net-zero carbon emissions. Single-site catalysts have been reported to catalyze carbon-carbon (C-C) coupling—the indispensable step for more valuable multi-carbon (C2+) products—but were proven to be transformed in situ to metallic agglomerations under working conditions. Here, we report a stable single-site copper coordination polymer (Cu(OH)BTA) with periodic neighboring coppers and it exhibits 1.5 times increase of C2H4 selectivity compared to its metallic counterpart at 500 mA cm−2. In-situ/operando X-ray absorption, Raman, and infrared spectroscopies reveal that the catalyst remains structurally stable and does not undergo a dynamic transformation during reaction. Electrochemical and kinetic isotope effect analyses together with computational calculations show that neighboring Cu in the polymer provides suitably-distanced dual sites that enable the energetically favorable formation of an *OCCHO intermediate post a rate-determining step of CO hydrogenation. Accommodation of this intermediate imposes little changes of conformational energy to the catalyst structure during the C-C coupling. We stably operate full-device CO2 electrolysis at an industry-relevant current of one ampere for 67 h in a membrane electrode assembly. The coordination polymers provide a perspective on designing molecularly stable, single-site catalysts for electrochemical CO2 conversion.

Date: 2023
References: View references in EconPapers View complete reference list from CitEc
Citations: View citations in EconPapers (5)

Downloads: (external link)
https://www.nature.com/articles/s41467-023-35993-4 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:14:y:2023:i:1:d:10.1038_s41467-023-35993-4

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

DOI: 10.1038/s41467-023-35993-4

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 ().