A Highly Crystalline Perylene Imide Polymer with the Robust Built‐In Electric Field for Efficient Photocatalytic Water Oxidation

A highly crystalline perylene imide polymer (Urea-PDI) photocatalyst is successfully constructed. The Urea-PDI presents a wide spectrum response owing to its large conjugated system. The Urea-PDI performs so far highest oxygen evolution rate (3223.9 µmol g^-1 h^-1 ) without cocatalysts under visible light. The performance is over 107.5 times higher than that of the conventional PDI supramolecular photocatalysts. The strong oxidizing ability comes from the deep valence band (+1.52 eV) which is contributed by the covalent-bonded conjugated molecules. Besides, the high crystallinity and the large molecular dipoles of the Urea-PDI contribute to a robust built-in electric field promoting the separation and transportation of photogenerated carriers. Moreover, the Urea-PDI is very stable and has no performance attenuation after 100 h continuous irradiation. The Urea-PDI polymer photocatalyst provides with a new platform for the use of photocatalytic water oxidation, which is expected to contribute to clean energy production.