Carbon nanodot decorated graphitic carbon nitride: new insights into the enhanced photocatalytic water splitting from ab initio studies

Abstract

Interfacing carbon nanodots (C-dots) with graphitic carbon nitride (g-C₃N₄) produces a metal-free system that has recently demonstrated significant enhancement of photo-catalytic performance for water splitting into hydrogen [Science, 2015, 347, 970–974]. However, the underlying photo-catalytic mechanism is not fully established. Herein, we have carried out density functional theory (DFT) calculations to study the interactions between g-C₃N₄ and trigonal/hexagonal shaped C-dots. We find that hybrid C-dots/g-C₃N₄ can form a type-II van der Waals heterojunction, leading to significant reduction of band gap. The C-dot decorated g-C₃N₄ enhances the separation of photogenerated electron and hole pairs and the composite's visible light response. Interestingly, the band alignment of C-dots and g-C₃N₄ calculated by the hybrid functional method indicates that C-dots act as a spectral sensitizer in hybrid C-dots/g-C₃N₄ for water splitting. Our results offer new theoretical insights into this metal-free photocatalyst for water splitting.