First-principles calculations of 0D/2D GQDs-MoS2 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)-MoS2) for generating hydrogen from water splitting are investigated based on density functional theory (DFT). The electronic and photocatalytic properties of three heterostructures, namely, C6H6-MoS2, C24H12-MoS2 and C32H14-MoS2 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 MoS2 boost charge separation. Meanwhile, all the GQDs-MoS2 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, C32H14-MoS2 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.

Theoretical insights on type I/II photoreactions of potential Zn(II) polypyridyl photosensitizers for two-photon photodynamic therapy.

Large two-photon absorption cross-sections are vital to photosensitizers (PSs) in TP-PDT, which can be used to develop in-depth treatment for diseased cells and minimize the harm to surrounding cells. Here, we conduct a study about photophysical properties of one Ru(II) polypyridyl complex and two designed Zn(II) polypyridyl complexes by means of DFT and TD-DFT methods. The main results are as follows: firstly, the two-photon absorption spectrum of two designed complexes Zn-OMe and Zn-OCOOCH3 are all within the phototherapeutic window (550-900 nm). Secondly, large SOC values and small energy gaps ΔES-T of these complexes guarantee the efficiency of ISC process. Thirdly, their T1 energy is greater than that required for generating 1O2 (0.98 eV) via Type II photoreaction. In addition, the calculated results of vertical electron affinities (VEA) and vertical ionization potentials (VIP) show that these complexes are able to form superoxide ions O2(-) via Type I photoreaction. Specifically, both of two designed Zn-centric complexes have larger TPA cross-sections than that of Ru-centric complex. In a word, we are pleased to report two potential photosensitizers with excellent performance and reasonable price for Type I/II photoreactions. We expect our study will offer some theoretical guidance and help in TP-PDT.