Photoelectron Migration Boosted by Hollow Double‐Shell Dyads Based on Covalent Organic Frameworks for Highly Efficient Photocatalytic Hydrogen Generation

Abstract Photocatalytic hydrogen production based on noble metal‐free systems is a promising technology for the conversion of solar energy into green hydrogen, it is pivotal and challenging to tailor‐make photocatalysts for achieving high photocatalytic efficiency. Herein, we reported a hollow double‐shell dyad through uniformly coating covalent organic frameworks (COFs) on the surface of hollow Co 9 S 8 . The double shell architecture enhances the scattering and refraction efficiency of incident light, shortens the transmission distance of the photogenerated charge carriers, and exposes more active sites for photocatalytic conversion. The hydrogen evolution rate is as high as 23.15 mmol g −1 h −1 , which is significantly enhanced when compared with that of their physical mixture (0.30 mmol g −1 h −1 ) and Pt‐based counterpart (11.84 mmol g −1 h −1 ). This work provides a rational approach to the construction of noble‐metal‐free photocatalytic systems based on COFs to enhance hydrogen evolution performance.