Metal‐Modified Zr‐MOFs with AIE Ligands for Boosting CO <sub>2</sub> Adsorption and Photoreduction
Bolun Wang, Wen Li, Junmin Liu, Tao Gan, Shiqin Gao, Lin Li, Tianjun Zhang, Yida Zhou, Zhaohui Shi, Jiyang Li, Yunling Liu, Jihong Yu
Abstract
Abstract The design and synthesis of metal–organic frameworks (MOFs) with outstanding light‐harvesting and photoexcitation for artificial photocatalytic CO 2 reduction is an attractive but challenging task. In this work, a novel aggregation‐induced emission (AIE)‐active ligand, tetraphenylpyrazine (PTTBPC) is proposed and utilized for the first time to construct a Zr‐MOF photocatalyst via coordination with stable Zr‐oxo clusters. Zr‐MOF is featured by a scu topology with a two‐fold interpenetrated framework, wherein the PTTBPC ligands enable strong light‐harvesting and photoexcitation, while the Zr‐oxo clusters facilitate CO 2 adsorption and activation, as well as offer potential sites for further metal modification. Consequently, the Zr‐PTTBPC and its Co/Ni derivatives not only exhibit exceptional stability and high CO 2 adsorption capability (73 cm 3 g −1 at 273 K and 1 atm), but also demonstrate a CO production rate of up to 293.2 µmol g h −1 under 420 nm LED light that can be reused for at least three cycles. With insights from charge‐carrier dynamics and theoretical calculations, the underlying mechanism is revealed, confirming that the single‐phase multi‐component synergy is the key for the outstanding photocatalytic CO 2 reduction. This work showcases a brand‐new type of MOF photocatalyst based on AIE ligands and their promising applications in photocatalytic C1 conversion.