Defect Engineering Simultaneously Regulating Exciton Dissociation in Carbon Nitride and Local Electron Density in Pt Single Atoms Toward Highly Efficient Photocatalytic Hydrogen Production.

Abstract

The high exciton binding energy (Eb) and sluggish surface reaction kinetics have severely limited the photocatalytic hydrogen production activity of carbon nitride (CN). Herein, a hybrid system consisting of nitrogen defects and Pt single atoms is constructed through a facile self-assembly and photodeposition strategy. Due to the acceleration of exciton dissociation and regulation of local electron density of Pt single atoms along with the introduction of nitrogen defects, the optimized Pt-MCT-3 exhibits a hydrogen production rate of 172.0µmolh-1 (λ ≥ 420nm), ≈41 times higher than pristine CN. The apparent quantum yield for the hydrogen production is determined to be 27.1% at 420nm. The experimental characterizations and theoretical calculations demonstrate that the nitrogen defects act as the electron traps for the exciton dissociation, resulting in a decrease of Eb from 86.92 to 43.20meV. Simultaneously, the stronger interaction between neighboring nitrogen defects and Pt single atoms directionally drives free electrons to aggregate around Pt single atoms, and tailors the d-band electrons of Pt, forming a moderate binding strength between Pt atoms and H* intermediates.