In Situ Assembly of Hydrogen‐Bonded Organic Framework on Metal–Organic Framework: An Effective Strategy for Constructing Core–Shell Hybrid Photocatalyst

The hydrogen-bonded organic frameworks (HOFs) have rarely been considered for photocatalytic application, given their weak stability and low activity. One presumably effective strategy to improve the photocatalytic performance of the HOFs is to produce a core-shell composite by fabricating a particular nanostructure using stable HOFs. To this end, the surface-functionalized metal-organic frameworks (MOFs) are used as the host matrix to support the in situ assembly and subsequent multisite growth of the stable HOFs. MOF@HOF eventually obtains core-shell hybrids, i.e., NH2-UiO-66@DAT-HOF. This newly synthesized core-shell nanostructure exhibits excellent stability and superb photocatalytic performance. For example, in terms of tetracycline degradation, the optimal composite presents an apparent reaction rate constant of 60.7 and 7.6 times higher than its parent materials NH2-UiO-66 and DAT-HOF. Such a pronounced enhancement in photocatalytic efficiency of the hybrid material is attributed to the broader visible-light utilization range compared to its individual parent material as well as the efficient separation of charge carriers supported by the S-scheme heterojunction. In addition, it is particularly notable that the photocatalytic efficiency of the yielded core-shell nanostructure can remain high after several-cycle applications. This work provides a universal scheme for synthesizing the MOF@HOF core-shell hybrids.