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 FECO (91.3%, −0.7 V) and possess high cycling stability (>40 h). In addition, after exfoliation, the FECO 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 FECO 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.
Highlights
Efficient conversion of carbon dioxide (CO2) into value-added products is essential for clean energy research
The electrocatalytic CO2 reduction reaction (CO2RR) mechanisms of M-TTCOFs with diverse metal centers imply that CoTTCOF exhibits the lowest activation energy for the determine step in electrocatalytic CO2RR compared with other M-TTCOFs as revealed by density functional theory (DFT) calculations, which can fully support the performances
The crystal structures of M-TTCOFs are resolved by using powder X-ray diffraction (PXRD) measurements in conjunction with Pawley refinements and the structural simulations are performed in Materials Studio 7.0
Summary
Efficient conversion of carbon dioxide (CO2) into value-added products is essential for clean energy research. Owing to the inherent thermodynamic stability of CO2 and competitive kinetically favored H2 generation reaction, electrocatalytic CO2RR generally faces drawbacks such as low reaction activity, selectivity, or electrical conductivity, which is far from meeting the demand of practical applications[8,9,10]. To conquer these problems, diverse electrocatalysts such as metals (e.g., Cu or Fe, etc.)[11,12], metal dichalcogenide (e.g., WSe2, Ag2S or CuS, etc.)[13], and metal oxide (e.g., Co3O4, Cu2O, or SnO2, etc.)[14,15,16] have been explored for electrocatalytic CO2RR. The combination of them in a COF structure might be of high significance in electron transfer efficiency to enhance the electrocatalytic CO2RR activity
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