Efficient electron transmission in covalent organic framework nanosheets for highly active electrocatalytic carbon dioxide reduction
Hong‐Jing Zhu, Meng Lu, Yirong Wang, Su‐Juan Yao, Mi Zhang, Yu‐He Kan, Jiang Liu, Yifa Chen, Shun‐Li Li, Ya‐Qian Lan
Abstract
Abstract Efficient conversion of carbon dioxide (CO 2 ) into value-added products is essential for clean energy research. Design of stable, selective, and powerful electrocatalysts for CO 2 reduction reaction (CO 2 RR) 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 CO 2 RR mechanisms are discussed and revealed by density functional theory calculations. This work paves a new way in exploring porous crystalline materials in electrocatalytic CO 2 RR.