Modulating the Density of Catalytic Sites in Multiple-Component Covalent Organic Frameworks for Electrocatalytic Carbon Dioxide Reduction

Liu, Minghao; Zhao, Xingyue; Yang, Shuai; Yang, Xiubei; Li, Xuewen; He, Jun; Chen, George Zheng; Xu, Qing; Zeng, Gaofeng

Abstract

It is generally assumed that the more metal atoms in covalent organic frameworks (COFs) contribute to higher activity toward electrocatalytic carbon dioxide reduction (CO2RR) and hindered us in exploring the correlation between the density of catalytic sites and catalytic performances. Herein, we have constructed quantitative density of catalytic sites in multiple COFs for CO2RR, in which the contents of phthalocyanine (H2Pc) and nickel phthalocyanine (NiPc) units were preciously controlled. With a molar ratio of 1/1 for the H2Pc and NiPc units in COFs, the catalyst achieved the highest selectivity with a carbon monoxide Faradaic efficiency (FECO) of 95.37% and activity with a turnover frequency (TOF) of 4713.53 h–1. In the multiple H2Pc/NiPc-COFs, the electron-donating features of the H2Pc units provide electron transport to the NiPc centers and thus improved the binding ability of CO2 and intermediates on the NiPc units. The theoretical calculation further confirmed that the H2Pc units donated their electrons to the NiPc units in the frameworks, enhanced the electron density of the Ni sites, and improved the binding ability with Lewis acidic CO2 molecules, thereby boosting the CO2RR performance. This study provides us with new insight into the design of highly active catalysts in electrocatalytic systems.

Citation

Liu, M., Zhao, X., Yang, S., Yang, X., Li, X., He, J., …Zeng, G. (2023). Modulating the Density of Catalytic Sites in Multiple-Component Covalent Organic Frameworks for Electrocatalytic Carbon Dioxide Reduction. ACS Applied Materials and Interfaces, 15(37), 44384-44393. https://doi.org/10.1021/acsami.3c10802

• Journal Article Type: Article
• Acceptance Date: Aug 28, 2023
• Online Publication Date: Sep 6, 2023
• Publication Date: Sep 20, 2023
• Deposit Date: Sep 18, 2023
• Publicly Available Date: Sep 7, 2024
• Journal: ACS Applied Materials & Interfaces
• Print ISSN: 1944-8244
• Electronic ISSN: 1944-8252
• Publisher: American Chemical Society (ACS)
• Peer Reviewed: Peer Reviewed
• Volume: 15
• Issue: 37
• Pages: 44384-44393
• DOI: https://doi.org/10.1021/acsami.3c10802
• Keywords: Covalent organic frameworks, carbon dioxide reduction reaction, structure−property correlation, phthalocyanine, alternate structure
• Public URL: https://nottingham-repository.worktribe.com/output/25081788
• Publisher URL: https://pubs.acs.org/doi/10.1021/acsami.3c10802
• Additional Information: This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Applied Materials and Interfaces. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/acsami.3c10802