Single-layer ZnMN2 (M = Si, Ge, Sn) zinc nitrides as promising photocatalysts.

Searching for two-dimensional semiconductor materials that are suitable for visible-light photocatalytic water splitting provides a sustainable solution to deal with the future energy crisis and environmental problems. Herein, based on first-principles calculations, single-layer ZnMN2 (M = Si, Ge, Sn) zinc nitrides are proposed as efficient photocatalysts for water splitting. Stability analyses show that the single-layer ZnMN2 zinc nitrides exhibit energetic and dynamical stability. The electronic properties reveal that all of the single-layer ZnMN2 zinc nitrides are semiconductors. Interestingly, single-layer ZnSnN2 is a direct band gap semiconductor with a desirable band gap (1.74 eV), and the optical adsorption spectrum confirms its optical absorption in the visible light region. The hydrogen evolution reaction (HER) calculations show that the catalytic activity for single-layer ZnMN2 (M = Ge, Sn) is better than that of single-layer ZnSiN2. Furthermore, the band gaps and band edge positions for the single-layer ZnMN2 zinc nitrides can be effectively tuned by biaxial strain. Especially, single-layer ZnGeN2 can be effectively tuned to match better with the redox potentials of water and enhance the light absorption in the visible light region at a tensile strain of 5%, which is confirmed by the corresponding optical absorption spectrum. Our results provide guidance for experimental synthesis efforts and future searches for single-layer materials suitable for photocatalytic water splitting.

GaS0.5Te0.5 monolayer as an efficient water splitting photocatalyst.

Herein, two-dimensional materials for photocatalytic water splitting are drawing more attention due to the larger surface areas for photocatalytic reactions and shorter migration distances for photogenerated carriers. In this present study, we systematically investigated the fundamental electronic properties of GaS1-xTex monolayers (x = 0, 0.125, 0.25, 0.5, 0.75, 0.875, and 1) for water splitting based on density functional theory (DFT) using the HSE06 functional. The simulation of the defect formation energy under each experimental synthetic condition shows that the Te substitutional impurity in GaS can be relatively easily realized under Ga-rich conditions. Our results show that the GaS0.5Te0.5 monolayer is a direct band gap (2.09 eV) semiconductor, which is attributed to the elevation of Te px/py states at the Γ point by the strain effect. Moreover, the GaS0.5Te0.5 monolayer has appropriate band edge alignment with respect to the water redox potentials in both acidic and neutral environments. Additionally, the carrier effective mass of the GaS0.5Te0.5 monolayer along the direction of Γ â†’ K is smaller than those of pristine GaS and GaTe monolayers, which can cause the carriers to quickly transfer from the photogenerated center to the surface of the photocatalyst. These results imply that the GaS0.5Te0.5 monolayer is a promising candidate as a visible-light water splitting photocatalyst, which should be properly synthesized and tested in further experimental investigations.

Hole defects and nitrogen doping in graphene: implication for supercapacitor applications.

One great challenge for supercapacitor is to achieve high energy capacity and fast charge/discharge rates simultaneously. Porous graphene with large surface area is a promising candidate for electrode materials of supercapacitor. Using first-principles calculations and non-equilibrium Green's function technique, we have explored the formation energies, mechanical properties, diffusion behaviors and electrical conductance of graphene sheets with various hole defects and/or nitrogen doping. Interestingly, graphene sheets with pyridinic-like holes (especially hexagonal holes) can be more easily doped with nitrogen and still retain the excellent mechanical properties of pristine graphene that is beneficial for the long cycle life. Porous graphene electrode with moderate hole diameter of 4.2-10 Å facilitates efficient access of electrolyte and exhibit excellent rate capability. In addition, doping with nitrogen as electron donors or proton attractors leads to charge accumulation and generates higher pseudocapacitance. Transmission coefficients of N-doped graphene sheets with pyridinic-like holes are only moderately reduced with regard to that of pristine graphene and are insensitive to the detailed geometry parameters. Overall, N-doped graphene with pyridinic-like holes exhibits exciting potentials for high performance energy storage in supercapacitor devices.

Oxygen vacancy formation energy in Pd-doped ceria: a DFT+U study.

Using the DFT+U method, i.e., first principles density functional theory calculations with the inclusion of on-site Coulomb interaction, the effects of Pd doping on the O vacancy formation energy (E(vac)) in CeO(2) has been studied. We find that E(vac) is lowered from 3.0 eV in undoped ceria to 0.6 eV in the Pd-doped compound. Much of this decrease can be attributed to emerging Pd-induced gap states above the valence band and below the empty Ce 4f states. These localized defect states involve the Pd ion and its nearest neighbors, which are also the main acceptors of the extra electrons left on reduction. The effect of the Pd dopant on the geometric structure is very modest for CeO(2) but considerable for CeO(2-x).