The preparation of self-assembled porphyrins with orderly stacked nanostructures for emulating natural photosynthesis has stimulated extensive efforts to optimize the energy conversion efficiency. However, the elucidation of how orderly stacked structures promote photocatalysis at the molecular level remains a great challenge. Here, unique porphyrin nanoleaves with designed and ordered structure are synthesized and show a hydrogen evolution rate higher than that of commercial powder. Photodeposition of cocatalysts and Kelvin probe force microscopy measurement suggest selective aggregation of photogenerated electrons and holes at different active sites. Combined with theoretical calculations, we find that the orderly packing changes molecular symmetry and induces a molecular dipole, which increases linearly along the π-π stacking direction and forms a strong built-in electric field. The built-in electric field drives photogenerated electrons and holes for the unique crossed transportation along different directions. These findings reveal how orderly stacked structures promote photocatalysis and provide a novel approach for highly efficient water splitting.
Keywords: built-in electric field; crossed transportation; photocatalytic hydrogen production; photogenerated carriers; porphyrin; self-assembly.