Rational Design of Covalent Organic Framework Catalysts for Photocatalytic Carbon Dioxide Fixation

Abstract

The photo-thermal synergistic conversion of CO₂, which harnesses complementary photochemical and thermochemical processes to enhance catalytic efficiency, is gaining increasing attention. Notably, photo-mediated CO₂ cycloaddition exhibits significant promise for practical applications. Catalysts based on metallosalen structures have garnered considerable attention for their role in the formation of cyclic carbonates through CO₂ cycloaddition, owing to their favorable CO₂ and epoxide activation capabilities. In this study, we establish a computational database comprising 300 Salen(Zn)-COFs and screen for optimal photothermal catalysts for CO₂ cycloaddition. Three parameters determine catalyst selection: π-conjugation extent, CO₂ adsorption energy values, and epoxide binding energy values. This approach identifies three pyrene-functionalized COF candidates—Py-EDA-COF, Py-DAC-COF, and Py-OPD-COF—as superior catalytic materials. These three COFs demonstrate outstanding performance in photo-driven CO₂ cycloaddition with various epoxides, particularly phenyl glycidyl ether. Furthermore, we demonstrate that the substituents on the diamine backbone of the salen moiety significantly modulate catalytic activity. Among them, the Py-OPD-COF, which features a benzene unit that enhances π conjugation and exhibits strong electron-donating properties, achieves the highest conversion rate (84%) and a turnover frequency (TOF) of 115.2 h⁻¹, surpassing all previously reported catalysts. This research establishes a viable strategy for the developing of highly efficient catalysts for photo-driven CO₂ conversion.

Keywords

CO₂ fixation / computational screening / covalent organic frameworks / heterogeneous catalysis / photo-driven

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