Modulating Electrochemical CO2 Reduction Performance via Sulfur-Containing Linkages Engineering in Metallophthalocyanine Based Covalent Organic Frameworks AITranslate

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DOI：https://doi.org/10.1021/acsmaterialslett.3c00168

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Covalent organic frameworks (COFs) with metallophthalocyanine (MPc) units provide new opportunities for the design of advanced materials with attractive electrical properties. However, the limited synthetic linkage chemistry hinders their further exploration. Herein, we demonstrated heterocycles strategy-based linkage engineering to fabricate two novel MPc-based COFs with thiomorpholine and dithiine linkages. More S atoms in dithiine-linked CoPc-DSDS-COF contributed to the higher conductivity (0.78 mS cm–1) and higher reductive ability than those of thiomorpholine-linked CoPc-DNDS-COF (0.62 mS cm–1) and, thus, result in higher activity with a partial current density for CO of 30.42 mA cm–2 at −1.0 V vs RHE and in selectivity toward CO2 reduction with the Faradaic efficiency of 96.5% at −0.9 V. Additionally, the theoretical calculation revealed the dithiine linkages showed better suppressing ability of the competing hydrogen evolution reaction than the thiomorpholine linkages. This work gives us a new insight into catalytic COFs via strategic linkage engineering at the atomic level.