Rational Design of MOF/COF Hybrid Materials for Photocatalytic H₂ Evolution in the Presence of Sacrificial Electron Donors

Crystalline and porous covalent organic frameworks (COFs) and metal-organic frameworks (MOFs) materials have attracted enormous attention in the field of photocatalytic H₂ evolution due to their long-range order structures, large surface areas, outstanding visible light absorbance, and tunable band gaps. In this work, we successfully integrated two-dimensional (2D) COF with stable MOF. By covalently anchoring NH₂ -UiO-66 onto the surface of TpPa-1-COF, a new type of MOF/COF hybrid materials with high surface area, porous framework, and high crystallinity was synthesized. The resulting hierarchical porous hybrid materials show efficient photocatalytic H₂ evolution under visible light irradiation. Especially, NH₂ -UiO-66/TpPa-1-COF (4:6) exhibits the maximum photocatalytic H₂ evolution rate of 23.41 mmol g^-1 h^-1 (with the TOF of 402.36 h^-1 ), which is approximately 20 times higher than that of the parent TpPa-1-COF and the best performance photocatalyst for H₂ evolution among various MOF- and COF-based photocatalysts.