Ether‐Embedded Covalent Organic Frameworks Enable Efficient Photocatalytic CO 2 Reduction

Abstract The photocatalytic conversion of carbon dioxide (CO 2 ) into valuable solar fuels is a promising strategy for addressing energy crises and mitigating the greenhouse effect. However, the challenge of efficiently regulating photogenerated electrons to CO 2 active sites remains a key hurdle for high‐performance CO 2 reduction. Herein, an embedded functional group, ether group is introduced into porphyrin‐triazine COFs to regulate the transfer behavior of photogenerated electrons. The ether‐embedded COFs (TOT‐TAPP, BOD‐TAPP and QOB‐TAPP) demonstrate significantly faster charge transport and higher photoactivity compared with the corresponding non‐ether‐embedded counterpart COFs. The theoretical calculations and in situ characterizations reveal that the ether group could not only accelerate the separation of photogenerated charge carriers, but also lead to a more substantial accumulation of electrons at the CO 2 adsorption region (C=N imine bond), thus greatly promoting the efficiency of CO 2 photoreduction.