Ordered Bicontinuous Mesoporous Polymeric Semiconductor Photocatalyst

Owning triply periodic minimal surfaces and three-dimensional (3D) interconnected pores, bicontinuous porous materials have drawn enormous attention due to their great academic interest and potential applications in many fields including energy and catalysis. However, their synthesis has remained a great challenge. Here, we demonstrate the synthesis of a bicontinuous porous organic semiconductor photocatalyst, which involves the preparation of SiO₂ with a shifted double diamond (DD) structure through solvent evaporation-induced self-assembly of a polystyrene-block-poly(ethylene oxide) diblock copolymer and tetraethyl orthosilicate, followed by SiO₂-templated self-condensation of melamine monomers in a vacuum. Strikingly, the resultant DD-structured graphitic carbon nitride (g-CN) possesses two sets of 3D continuous mesopores with a mean diameter of 14 nm, which afford a high specific surface area of 131 m² g^-1 and an optical band gap of 2.8 eV. Being a visible-light-driven photocatalyst, the bicontinuous mesoporous g-CN exhibits high catalytic activity for water splitting to generate H₂ (6831 μmol g^-1 h^-1) with excellent cycling stability. This study provides a protocol for the construction of ordered mesoporous materials containing 3D continuous channels, which holds promise for catalysis applications.