Covalent Pyrimidine Frameworks via a Tandem Polycondensation Method for Photocatalytic Hydrogen Production and Proton Conduction

The development of heteroaromatic conjugated porous polymers (H-CPPs) have received enormous research interests, because of the important functional roles of the heteroatoms in photocatalysis and proton conduction. However, due to the synthetic challenges deriving from the stable structures, the structural diversity and synthetic methods of them are still limited. Herein, a new type of H-CPPs, covalent pyrimidine frameworks (CPFs), via an efficient tandem polycondensation reaction between aldehyde, acetyl, and amidine monomers is reported. The resulting CPFs are bridged by pyrimidine units, rich of nitrogen atoms and can be structurally regulated on demand. The CPFs are shown to be active photocatalysts for hydrogen evolution from methanol via a photo-thermo-catalysis process, achieving an excellent hydrogen evolution rate of 5282.8 µmol h⁻¹ g⁻¹. The CPFs can be further processed into a mixed matrix membrane, displaying an excellent proton conductivity of 1.30 × 10⁻² S cm⁻¹ at 413 K under anhydrous condition.