Controllable Synthesis of COFs‐Based Multicomponent Nanocomposites from Core‐Shell to Yolk‐Shell and Hollow‐Sphere Structure for Artificial Photosynthesis

Abstract The precise tuning and multi‐dimensional processing of covalent organic frameworks (COFs)‐based materials into multicomponent superstructures with appropriate diversity are essential to maximize their advantages in catalytic reactions. However, up to now, it remains an ongoing challenge for the precise design of COFs‐based multicomponent nanocomposites with diverse architectures. Herein, a metal organic framework (MOF)‐sacrificed in situ acid‐etching (MSISAE) strategy that enables continuous synthesis of core‐shell, yolk‐shell, and hollow‐sphere COFs‐based nanocomposites through tuning of core decomposition (NH 2 ‐MIL‐125 into TiO 2 ) rate is developed. More importantly, due to the multiple active sites, fast transfer of carriers, increased light utilization ability, et al, one of the obtained samples, NH 2 ‐MIL‐125/TiO 2 @COF‐366‐Ni‐OH‐HAc (yolk‐shell) with special three components, exhibits high photocatalytic CO 2 ‐to‐CO conversion efficiency in the gas‐solid mode. The MSISAE strategy developed in this work achieves the precise morphology design and control of multicomponent hybrid composites based on COFs, which may pave a new way in devealoping porous crystalline materials with powerful superstructures for multifunctional catalytic reactions.