Constructing an Asymmetric Covalent Triazine Framework to Boost the Efficiency and Selectivity of Visible‐Light‐Driven CO2 Photoreduction

The photocatalytic reduction of CO2 represents an environmentally friendly and sustainable approach for generating valuable chemicals. In this study, a thiophene‐modified highly conjugated asymmetric covalent triazine framework (As‐CTF‐S) is developed for this purpose. Significantly, single‐component intramolecular energy transfer can enhance the photogenerated charge separation, leading to the efficient conversion of CO2 to CO during photocatalysis. As a result, without the need for additional photosensitizers or organic sacrificial agents, As‐CTF‐S demonstrates the highest photocatalytic ability of 353.2 µmol g−1 and achieves a selectivity of ≈99.95% within a 4 h period under visible light irradiation. This study provides molecular insights into the rational control of charge transfer pathways for high‐efficiency CO2 photoreduction using single‐component organic semiconductor catalysts. A thiophene‐modified highly conjugated asymmetric covalent triazine framework (As‐CTF‐S) has been constructed. As‐CTF‐S exhibits excellent the photogenerated charge separation, leading to the efficient conversion of CO2 to CO during photocatalysis. This study provides a promising path for D–A type CTFs as highly effective heterogeneous catalysts for the selective photoreduction of CO2 under gaseous phase with no toxic sacrificial agent.