Construction of Core-Shell MOF@COF Hybrids with Controllable Morphology Adjustment of COF Shell as a Novel Platform for Photocatalytic Cascade Reactions.

Recently, novel core-shell MOF@COF hybrids display excellent performance in various fields because of their inherited advantages from their parent MOFs and/or COFs. However, it is still a grand challenge to adjust the morphology of MOFs and/or COFs for consequent performance improvement. Herein, a Ti-MOF@TpTt hybrid coated with ultra-thin COF nanobelt, which is different from the fibrillar-like parent COF, is successfully synthesized through a sequential growth strategy. The as-obtained Pd decorated Ti-MOF@TpTt catalyst exhibits much higher photocatalytic performance than those of Ti-MOF, TpTt-COF, and Ti-MOF@TpTt hybrids with fibrillar-like COF shell for the photocatalytic cascade reactions of ammonia borane (AB) hydrolysis and nitroarenes hydrogenation. These can be attributed to its high BET surface area, core-shell structure, and type II heterojunction, which offers more accessible active sites and improves the separation efficiency of photo-generated carriers. Finally, the possible mechanisms of the cascade reaction are also proposed to well explain the improved performance of this photocatalytic system. This work presents a constructive route for designing core-shell MOF@COF hybrids with controllable morphology adjustment of COF shell, leading to the improved photocatalytic ability to broaden the applications of MOF/COF hybrid materials.