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 H 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 H production rate of HNINC. This research sheds light on developing novel photocatalysts for efficient hydrogen evolution.