Covalent Organic Frameworks‐Based Dyads with Highly Exposed Active Sites and Promoted Mass Transfer for Photocatalytic Hydrogen Evolution

Covalent organic frameworks (COFs)‐based dyads are emerging photocatalysts in solar‐driven hydrogen production, it is crucial to expose active sites and promote mass transfer for promoting photocatalytic efficiency. Herein, surfactant‐induced dynamic pore‐making strategy to construct noble‐metal‐free photocatalytic systems by combining the ketoenamine‐linked COFs on the surface of spinel‐structured CuCo 2 S 4 (CuCo 2 S 4 /TpPa‐Cl 2 ) is developed. The open hierarchically porous dyads supply rich active sites and enough channels for mass transfer. Hydrogen evolution rate of CuCo 2 S 4 /TpPa‐Cl 2 is as high as 25.56 mmol g −1 h −1 under visible light irradiation, which significantly surpasses those in surfactant‐free counterpart (1.63 mmol g −1 h −1 ) and Pt‐loaded TpPa‐Cl 2 (12.38 mmol g −1 h −1 ). Apparent quantum efficiency at 420 nm reaches 2.24%. This study presents new protocols for constructing noble‐metal‐free COFs‐based photocatalytic systems with efficient solar energy conversion.