Hierarchical NiO@N‐Doped Carbon Microspheres with Ultrathin Nanosheet Subunits as Excellent Photocatalysts for Hydrogen Evolution

Achieving highly efficient hierarchical photocatalysts for hydrogen evolution is always challenging. Herein, hierarchical mesoporous NiO@N‐doped carbon microspheres (HNINC) are successfully fabricated with ultrathin nanosheet subunits as high‐performance photocatalysts for hydrogen evolution. The unique architecture of N‐doped carbon layers and hierarchical mesoporous structures from HNINC could effectively facilitate the separation and transfer of photo‐induced electron–hole pairs and afford rich active sites for photocatalytic reactions, leading to a significantly higher H2 production rate than NiO deposited with platinum. Density functional theory calculations reveal that the migration path of the photo‐generated electron transfer is from Ni 3d and O 2p hybrid states of NiO to the C 2p state of graphite, while the photo‐generated holes locate at Ni 4s and Ni 4p hybrid states of NiO, which is beneficial to improve the separation of photo‐generated electron–hole pairs. Gibbs free energy of the intermediate state for hydrogen evolution reaction is calculated to provide a fundamental understanding of the high H2 production rate of HNINC. This research sheds light on developing novel photocatalysts for efficient hydrogen evolution. Hierarchical NiO@N‐doped carbon microspheres assembled by ultrathin nanosheets are developed by in situ decomposition of nickel complexes. The unique N‐doped carbon layer and hierarchical mesoporous structure effectively facilitate the separation and transfer of photo‐induced electron–hole pairs, affording rich active sites for excellent photocatalytic hydrogen production.