The first-principles calculations were performed to investigate the stability, band structure, density of states and redox potential of Al-, Ga-, and In-doped monoclinic BiVO4（mBiVO4）. The calculated formation energies show that Al-doped mBiVO4 inducing an O vacancy is energetically favorable with a smaller defect formation value. With the incorporation of Al, Ga, and In, the band gap of the doped systems will be narrowed in the order of Al-doped 〈 Ga-doped 〈 In-doped mBiVO4, which is beneficial for the response to the visible light. And the substitution of an Al or Ga for a V atom will significantly enhance the reducibility of mBiVO4, improving the efficiency of H2 evolution from H2 O. Our results show that the photocatalytic activity of mBiVO4 can be modulated by substitutional doping of Al, Ga, and In.
We applied periodic density-functional theory to investigate the adsorption of HCN on x Ni@Pt（111） bimetallic surfaces（x = 1~4）. The results have been compared with those obtained on pure Ni（111） and Pt（111） surfaces. For all bimetallic surfaces,HCN is preferentially tilted with the CN bond parallel to the surface,and adsorption energies increase with an increasing number of layer Ni atoms on the surface. The adsorption energies of HCN on all bimetallic surfaces are larger than that on the Pt（111） surface,whereas the adsorption energies of HCN on 3Ni@Pt（111） and 4Ni@Pt（111） are larger than that on the Ni（111） surface,indicating that the introduction of Ni to the Pt catalyst could increase the activity of bimetallic catalyst in the hydrogenation reaction for nitriles. Larger adsorption energy of HCN leads to a longer C–N bond length and a smaller CN vibrational frequency. The analysis of Bader charge and vibrational frequencies showed obvious weakening of the adsorbed C–N bond and an indication of sp2 hybridization of both carbon and nitrogen atoms.
Density functional theory calculations have been performed to study the interaction of small silver clusters, Ag2-Ag9, with HCN. The adsorption of HCN on-top site of the silver cluster, among various possible sites, is energetically preferred. The adsorption energies of HCN on the silver clusters reach a local maximum at n = 4, which is only about 0.450 eV, indicating that the adsorbed HCN molecule is weakly perturbed. The adsorbed C-N and C-H stretching frequencies are blue- and red-shifted compared with the values of free HCN, respectively.
Periodic density functional theory calculations have been performed to investigate the chemisorption behavior of COz molecule on a series of surface alloys that are built by dispersing individual middle-late transition metal （TM） atoms （TM = Fe, Co, Ni, Ru, Rh, Pd, Ag, Os, lr, Pt, Au） on the Cu（100） and Cu（lll） surfaces. The most stable configurations of CO2 chemisorbed on different TM/Cu surfaces are determined, and the results show that among the late transition metals, Co, Ru, and Os are potentially good dopants to enhance the chemisorption and activation of CO2 on copper surfaces. To obtain a deep understanding of the adsorption property, the bonding characteristics of the adsorption bonds are carefully examined by the crystal orbital Hamilton population technique, which reveals that the TM atom primarily provides d orbitals with z-component, namely dz2, dxz, and dvz orbitals to interact with the adsorbate.
