Photocatalytic Hydrogen Production on a sp2‐Carbon‐Linked Covalent Organic Framework

Abstract Two‐dimensional covalent organic frameworks (2D‐COFs) have emerged as attractive platforms for solar‐to‐chemical energy conversion. In this study, we have implemented a gradient heating strategy to synthesize a sp2‐carbon‐linked triazine‐based COF, COF‐JLU100, exhibiting high crystallinity, large surface area, good durability and carrier mobility for solar‐driven photocatalytic hydrogen evolution. The Pt‐doped COF‐JLU100 demonstrated a high hydrogen evolution rate of over 100 000 μmol g−1 h−1 for water splitting under visible‐light illumination (λ>420 nm). Experimental and theoretical studies corroborate that the cyano‐vinylene segments in COF‐JLU100 extend the π‐delocalization and enable fast charge transfer and separation rates as well as good dispersion in water. Moreover, COF‐JLU100 can be prepared by low‐cost and easily available monomers and has excellent stability, which is desirable for practical solar‐driven hydrogen production.