Engineering Hierarchical Architecture of Metal‐Organic Frameworks for Highly Efficient Overall CO 2 Photoreduction

Abstract Previous studies on syntheses of metal‐organic frameworks (MOFs) for photocatalytic CO 2 reduction are mainly focused on the exquisite control over the net topology and the functionality of metal clusters/organic building blocks. This contribution demonstrates that the rational design of MOF‐based photocatalyst can be further extended to the hierarchical structure at micrometer scales well beyond the conventional MOF design at the molecular level. By taking advantage of the disparity of two selective MOFs in nucleation kinetics, a hierarchical core–shell MOF@MOF structure is successfully constructed through a simple one‐pot synthesis. Besides inheriting the high porosity, crystallinity, and robustness of parent MOFs, the obtained heterojunction exhibits extended photoresponse, optimized band alignment with large overpotential, and greatly enhanced photogenerated charge separation, which would be hardly realized by the merely molecular‐level assembly. As a result, the challenging overall CO 2 photoreduction is achieved, which generates a record high HCOOH production (146.0 µmol/g/h) without using any sacrificial reagents. Moreover, the core–shell structure exhibits a more effective use of photogenerated electrons than the individual MOFs. This work shows that harnessing the hierarchical architecture of MOFs present a new and effective alternative to tuning the photocatalytic performance at a mesoscopic level.