Construction of Interlayered Single-Atom Active Sites on Bipyridine-Based 2D Conjugated Covalent-Organic Frameworks for Boosting the C2 Products of Electrochemical CO2 Reduction

Lu Dai; Jianning Lv; Shuo Xu; Jiawen Zong; Lisha Liang; Bo Wang; Pengfei Li

doi:10.1021/acsami.4c16371

Construction of Interlayered Single-Atom Active Sites on Bipyridine-Based 2D Conjugated Covalent-Organic Frameworks for Boosting the C₂ Products of Electrochemical CO₂ Reduction

ACS Appl Mater Interfaces. 2024 Nov 26. doi: 10.1021/acsami.4c16371. Online ahead of print.

Authors

Lu Dai¹, Jianning Lv¹, Shuo Xu¹, Jiawen Zong¹, Lisha Liang¹, Bo Wang^{1

2}, Pengfei Li^{1

3}

Affiliations

¹ Frontiers Science Center for High Energy Material, Key Laboratory of Cluster Science, Ministry of Education, Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, No. 5, Zhongguancun South Street, Haidian District, Beijing 100081, P. R. China.
² Advanced Technology Research Institute (Ji'nan), Beijing Institute of Technology, No. 8366, Haitang Road, Changqing District, Ji'nan 250300, P. R. China.
³ Advanced Research Institute of Multidisciplinary Science, Beijing Institute of Technology (Zhuhai), No. 6, Jinfeng Road, Tangjiawan, Zhuhai 519088, P. R. China.

PMID: 39589861
DOI: 10.1021/acsami.4c16371

Abstract

The electrochemical carbon dioxide reduction (eCO₂RR) shows great potential in the realization of carbon neutrality, which requires a dedicated catalyst design. To develop electrocatalysts that favor C₂ products, herein, the synthetic protocol for engineering interlayered single-atom metal active sites on the bipyridine-linked 2D conjugated covalent-organic framework (2D c-COF) has been developed by utilizing the interlayer π-π stacking. The resultant M@BTT-BPy-COF (where M = Cu, Ni, and Fe) provides fully exposed single-atom active sites with a suitable interdistance for catalyzing the key C-C coupling in the eCO₂RR process. The Faradaic efficiency of ethanol (FE_ethanol) exceeds 40% with M@BTT-BPy-COF at -0.8 V vs RHE, outperforming most reported COF-based electrocatalysts. Density functional calculations suggest that the proximal active sites in the pore channel of COFs are the key active sites for promoting the C-C coupling to generate ethanol product. This investigation presents a novel way to engineer single-atom catalytic centers on 2D c-COFs, displaying the great potential of 2D c-COFs in electrocatalysis.

Keywords: CO2 reduction; covalent-organic frameworks; electrocatalysis; interlayered active sites; single-atom catalysts.