Self-assembly of single metal sites embedded covalent organic frameworks into multi-dimensional nanostructures for efficient CO2 electroreduction

• Published in: Chinese chemical letters Vol. 33; no. 3; pp. 1439 - 1444
• Main Authors: Yang, Yi-Lu, Wang, Yi-Rong, Gao, Guang-Kuo, Liu, Ming, Miao, Chang, Li, Le-Yan, Cheng, Wei, Zhao, Zi-Yue, Chen, Yifa, Xin, Zhifeng, Li, Shun-Li, Li, Dong-Sheng, Lan, Ya-Qian
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 01.03.2022; School of Chemistry,South China Normal University,Guangzhou 510006,China%Institute of Molecular Engineering and Applied Chemistry,Anhui University of Technology,Ma'anshan 243002,China%College of Materials and Chemical Engineering,Hubei Provincial Collaborative Innovation Center for New Energy Microgrid,Key Laboratory of Inorganic Nonmetallic Crystalline and Energy Conversion Materials,China Three Gorges University,Yichang 443002,China; Jiangsu Collaborative Innovation Centre of Biomedical Functional Materials,Jiangsu Key Laboratory of New Power Batteries,School of Chemistry and Materials Science,Nanjing Normal University,Nanjing 210023,China%Jiangsu Collaborative Innovation Centre of Biomedical Functional Materials,Jiangsu Key Laboratory of New Power Batteries,School of Chemistry and Materials Science,Nanjing Normal University,Nanjing 210023,China
• Subjects: CO2 electroreduction; Covalent organic frameworks; Hollow sphere; Nanofiber; Nanosheet; Covalent organic frameworks; CO2 electroreduction; Hollow sphere; Nanofiber; Nanosheet
• ISSN: 1001-8417; 1878-5964
• DOI: 10.1016/j.cclet.2021.08.063

Morphology-controlled electrocatalysts with the ability of CO2 adsorption/activation, mass transfer, high stability and porosity are much desired in electrochemical CO2 reduction reaction (CO2RR). Here, three kinds of multi-dimensional nanostructures (i.e., hollow sphere, nanosheets and nanofibers) have been successfully produced through the modulation of porphyrin-based covalent organic frameworks (COFs) with various modulators. The obtained nanostructures with high-stability, large surface-area, and single metal sites enable efficient CO2RR into CH4. Notably, they all exhibit higher FECH4 (hollow sphere, 68.2%; nanosheet, 64.2% and nanofiber, 71.0%, −0.9 V) than COF-366-Cu (43.0%, −0.9 V) after morphology control. Noteworthy, the FECH4 of COF-366-Cu (HS) keeps higher than 52.4% over a wide potential range from −0.9 V to −1.1 V and the achieved FECH4+C2H4 (82.8%, −0.9 V) is superior to most of reported COFs and copper-based electrocatalysts. This work paves a new way in the exploration of COF-based multi-dimensional nanostructures applicable in efficient CO2RR to CH4. [Display omitted] Three kinds of multi-dimensional superstructures (e.g., hollow sphere, nanosheets and nanofibers) based on Cu-porphyrin COFs have been synthesized and successfully applied in efficient CO2 electroreduction to CH4.