Molecular Engineering for Modulating Photocatalytic Hydrogen Evolution of Fully Conjugated 3D Covalent Organic Frameworks

Abstract Covalent organic frameworks (COFs) have recently shown great potential for photocatalytic hydrogen production. Currently almost all reports are focused on two‐dimensional (2D) COFs, while the 3D counterparts are rarely explored due to their non‐conjugated frameworks derived from the sp 3 carbon based tetrahedral building blocks. Here, we rationally designed and synthesized a series of fully conjugated 3D COFs by using the saddle‐shaped cyclooctatetrathiophene derivative as the building block. Through molecular engineering strategies, we thoroughly discussed the influences of key factors including the donor‐acceptor structure, hydrophilicity, specific surface areas, as well as the conjugated/non‐conjugated structures on their photocatalytic hydrogen evolution properties. The as‐synthesized fully conjugated 3D COFs could generate the hydrogen up to 40.36 mmol h −1 g −1 . This is the first report on intrinsic metal‐free 3D COFs in photocatalytic hydrogen evolution application. Our work provides insight on the structure design of 3D COFs for highly‐efficient photocatalysis, and also reveals that the semiconducting fully conjugated 3D COFs could be a useful platform in clear energy‐related fields.