Efficient electron transmission in covalent organic framework nanosheets for highly active electrocatalytic carbon dioxide reduction

Hong-Jing Zhu; Meng Lu; Yi-Rong Wang; Su-Juan Yao; Mi Zhang; Yu-He Kan; Jiang Liu; Yifa Chen; Shun-Li Li; Ya-Qian Lan

doi:10.1038/s41467-019-14237-4

Efficient electron transmission in covalent organic framework nanosheets for highly active electrocatalytic carbon dioxide reduction

Nat Commun. 2020 Jan 24;11(1):497. doi: 10.1038/s41467-019-14237-4.

Authors

Hong-Jing Zhu^#¹, Meng Lu^#¹, Yi-Rong Wang¹, Su-Juan Yao¹, Mi Zhang¹, Yu-He Kan², Jiang Liu¹, Yifa Chen¹, Shun-Li Li¹, Ya-Qian Lan³

Affiliations

¹ 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.
² Jiangsu Province Key Laboratory for Chemistry of Low-Dimensional Materials, School of Chemistry and Chemical Engineering, Huaiyin Normal University, Huai'an, 223300, China.
³ 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. yqlan@njnu.edu.cn.

^# Contributed equally.

Abstract

Efficient conversion of carbon dioxide (CO₂) into value-added products is essential for clean energy research. Design of stable, selective, and powerful electrocatalysts for CO₂ reduction reaction (CO₂RR) is highly desirable yet largely unmet. In this work, a series of metalloporphyrin-tetrathiafulvalene based covalent organic frameworks (M-TTCOFs) are designed. Tetrathiafulvalene, serving as electron donator or carrier, can construct an oriented electron transmission pathway with metalloporphyrin. Thus-obtained M-TTCOFs can serve as electrocatalysts with high FE_CO (91.3%, -0.7 V) and possess high cycling stability (>40 h). In addition, after exfoliation, the FE_CO value of Co-TTCOF nanosheets (~5 nm) is higher than 90% in a wide potential range from -0.6 to -0.9 V and the maximum FE_CO can reach up to almost 100% (99.7%, -0.8 V). The electrocatalytic CO₂RR mechanisms are discussed and revealed by density functional theory calculations. This work paves a new way in exploring porous crystalline materials in electrocatalytic CO₂RR.