First-principles calculations of 0D/2D GQDs-MoS 2 mixed van der Waals heterojunctions for photocatalysis: a transition from type I to type II.

The fabrication of type II heterojunctions is an efficient strategy to facilitate charge separation in photocatalysis. Here, mixed dimensional 0D/2D van der Waals (vdW) heterostructures (graphene quantum dots (GQDs)-MoS 2 ) for generating hydrogen from water splitting are investigated based on density functional theory (DFT). The electronic and photocatalytic properties of three heterostructures, namely, C 6 H 6 -MoS 2 , C 24 H 12 -MoS 2 and C 32 H 14 -MoS 2 are estimated by analyzing the density of states, charge density difference, work function, Bader charge, absorption spectra and band alignment. The results indicated that the built-in electric fields from GQDs to MoS 2 boost charge separation. Meanwhile, all the GQDs-MoS 2 exhibit strong absorption in the visible light region. Surprisingly, the transition of heterojunctions from type I to type II is realized by tuning the size of GQDs. In particular, C 32 H 14 -MoS 2 with enhanced visible-light absorption and an appropriate band edge position, as a type II heterostructure, may be a promising photocatalyst for generating hydrogen from water splitting. Thus, in this work a novel type II 0D/2D nanocomposite as a photocatalyst is constructed that provides a strategy to regulate the type of heterostructure from the perspective of theoretical calculation.