Abstract Goethite widely exists among ocean sediments; it plays an important role in fixing heavy metals and adsorbing organic contaminants. So the understanding of the adsorbing process of water molecule on its surfa...Abstract Goethite widely exists among ocean sediments; it plays an important role in fixing heavy metals and adsorbing organic contaminants. So the understanding of the adsorbing process of water molecule on its surface will be very helpful to further reveal such environmental friendly processes. The configuration, electronic properties and interaction energy of water molecules adsorbed on pnma goethite （010） surface were investigated in detail by using density functional theory on 6-31G （d,p） basis set and projec- tor-augment wave （PAW） method. The mechanism of the interaction between goethite surface and H20 was proposed. Despite the differences in total energy, there are four possible types of water molecule adsorption configurations on goethite （010） surface （Aa, Ab, Ba, Bb）, forming coordination bond with surface Fe atom. Results of theoretical modeling indicate that the dissociation process of adsorbed water is an endothermic reaction with high activation energy. The dissociation of adsorbed water molecule is a proton transportation process between water＇s O atoms and surface. PDOS results indicate that the bonding between 1-120 and （010） surface is due to the overlapping of water＇s 2p orbitals and Fe＇s 3d orbitals. These results clarify the mechanism on how adsorbed water is dissociated on the surface of goethite and potentially provide useful information of the surface chemistry of goethite.展开更多
Density functional theory （DFT） plays a significant role in the development of visible light responsive photocatalysts. Based on the first-principles plane-wave ultrasoft pseudopotential （USPP） method, the crystal...Density functional theory （DFT） plays a significant role in the development of visible light responsive photocatalysts. Based on the first-principles plane-wave ultrasoft pseudopotential （USPP） method, the crystal structures of α,β,γ, and 5-Bi2O3 were optimally calculated for the total density of states （TDOS） and the partial density of states （PDOS） of Bi, O atoms. The calculation for Ti（IV） doped Bi2O3 supercell was carried out. The effects of Ti（IV）-doping on the electron structures and light absorption properties of various Bi2O3 were analyzed. The results showed that Ti 3d orbital appeared in the forbidden band of Bi2O3 and hybridized with O 2p, Bi 6p orbitals. The narrowed band gap （Eg） and red-shift of light absorption edge are responsible for the enhanced photoeatalytic activity of Bi2O3. The Ⅱ-Bi2O3 and Ti-doped β-Bi2O3 were prepared by a hydrotherrnal synthesis method. The improvement of the photoeatalytic activity of Bi2O3 has also been verified by the characteristics of the UV-vis diffuse reflection spectrum and the experimental evaluation of the photocatalytic degradation of crystal violet in aqueous solution.展开更多
Pure CaB6single crystals are synthesized under high pressure (1 GPa) and temperature (1050°C). The temperature-dependenceof electric resistivity and Hall coefficient from 2 to 300 K shows that the CaB6single crys...Pure CaB6single crystals are synthesized under high pressure (1 GPa) and temperature (1050°C). The temperature-dependenceof electric resistivity and Hall coefficient from 2 to 300 K shows that the CaB6single crystals are conductors withsemi-metallic behavior and electron carriers. Band structure calculations indicate that the conduction and valence bands meetat the X point at the Fermi level, which is consistent with the experimentally determined conducting behavior of CaB6singlecrystals. Calculations of state density suggest that the states at the Fermi level originate from the 2p orbital of the B atoms andthe 3d orbital of the Ca atom. Magnetization measurements show the paramagnetic nature of the CaB6. The micro-hardness ofCaB6is 24.39 GPa, and the Raman spectra of CaB6yield three sharp peaks at around 780.9, 1138.9, and 1282.1 cm 1for T2g,Eg, and A1g, respectively. The specific heat of the crystal is measured and found to be well described by the Debye and Einsteincombined model. The fitting results show Debye and Einstein temperatures are 1119 and 199 K, respectively.展开更多
By using the first-principles calculations,we have systematically investigated the adsorption of atomic oxygen on Cu(111) surface for a wide range of coverages Θ(from 0.11 to 1.00 ML) and adsorption sites.We found th...By using the first-principles calculations,we have systematically investigated the adsorption of atomic oxygen on Cu(111) surface for a wide range of coverages Θ(from 0.11 to 1.00 ML) and adsorption sites.We found that the fcc-hollow site is the most stable site for oxygen adsorption.The adsorption energy decreases with increasing oxygen coverage due to the increasing repulsive interaction in the overlayer O adatoms.Except for coverage of 1.00 ML,the oxygen-induced lateral relaxations and bucklings are found in the outermost three Cu layers,and the hillock-like as well as ridge-like bucklings are also found for Θ=0.25 ML and Θ=0.75 ML as well as Θ=0.50 ML,respectively.With an increasing oxygen coverage,the work function increases and the surface dipole moment decreases.Electron transfer from the first layer Cu atoms to O adatoms indicates the O-Cu bond having some degree of ionic character,while the hybridization between O 2p and Cu 3d orbitals implies that it also has some degree of covalence character.Moreover,with the increasing oxygen coverage,more Cu 3d and O 2p states are empty thus weakening the binding of O/Cu(111) system,but increase in the PDOS at the Fermi level.This implies an enhancement in the metallic character of the O/Cu(111) system.展开更多
基金financial supports from the National Natural Science Foundation of China (Nos.50673085,20677053)
文摘Abstract Goethite widely exists among ocean sediments; it plays an important role in fixing heavy metals and adsorbing organic contaminants. So the understanding of the adsorbing process of water molecule on its surface will be very helpful to further reveal such environmental friendly processes. The configuration, electronic properties and interaction energy of water molecules adsorbed on pnma goethite （010） surface were investigated in detail by using density functional theory on 6-31G （d,p） basis set and projec- tor-augment wave （PAW） method. The mechanism of the interaction between goethite surface and H20 was proposed. Despite the differences in total energy, there are four possible types of water molecule adsorption configurations on goethite （010） surface （Aa, Ab, Ba, Bb）, forming coordination bond with surface Fe atom. Results of theoretical modeling indicate that the dissociation process of adsorbed water is an endothermic reaction with high activation energy. The dissociation of adsorbed water molecule is a proton transportation process between water＇s O atoms and surface. PDOS results indicate that the bonding between 1-120 and （010） surface is due to the overlapping of water＇s 2p orbitals and Fe＇s 3d orbitals. These results clarify the mechanism on how adsorbed water is dissociated on the surface of goethite and potentially provide useful information of the surface chemistry of goethite.
基金supported by the National High Technology Research and Development Program (863 program, 2006AA06Z323)National Key Technology R&D Program (2008BAC32B06-3) of Chinaspecial fund of State Key Laboratory of Water Environment Simulation (08ESPCT-Z)
文摘Density functional theory （DFT） plays a significant role in the development of visible light responsive photocatalysts. Based on the first-principles plane-wave ultrasoft pseudopotential （USPP） method, the crystal structures of α,β,γ, and 5-Bi2O3 were optimally calculated for the total density of states （TDOS） and the partial density of states （PDOS） of Bi, O atoms. The calculation for Ti（IV） doped Bi2O3 supercell was carried out. The effects of Ti（IV）-doping on the electron structures and light absorption properties of various Bi2O3 were analyzed. The results showed that Ti 3d orbital appeared in the forbidden band of Bi2O3 and hybridized with O 2p, Bi 6p orbitals. The narrowed band gap （Eg） and red-shift of light absorption edge are responsible for the enhanced photoeatalytic activity of Bi2O3. The Ⅱ-Bi2O3 and Ti-doped β-Bi2O3 were prepared by a hydrotherrnal synthesis method. The improvement of the photoeatalytic activity of Bi2O3 has also been verified by the characteristics of the UV-vis diffuse reflection spectrum and the experimental evaluation of the photocatalytic degradation of crystal violet in aqueous solution.
基金supported by the National Natural Science Foundation of China (Grant Nos. 51072174, 50772094 and 50821001)the NBRPC(Grant No. 2011CB808205)
文摘Pure CaB6single crystals are synthesized under high pressure (1 GPa) and temperature (1050°C). The temperature-dependenceof electric resistivity and Hall coefficient from 2 to 300 K shows that the CaB6single crystals are conductors withsemi-metallic behavior and electron carriers. Band structure calculations indicate that the conduction and valence bands meetat the X point at the Fermi level, which is consistent with the experimentally determined conducting behavior of CaB6singlecrystals. Calculations of state density suggest that the states at the Fermi level originate from the 2p orbital of the B atoms andthe 3d orbital of the Ca atom. Magnetization measurements show the paramagnetic nature of the CaB6. The micro-hardness ofCaB6is 24.39 GPa, and the Raman spectra of CaB6yield three sharp peaks at around 780.9, 1138.9, and 1282.1 cm 1for T2g,Eg, and A1g, respectively. The specific heat of the crystal is measured and found to be well described by the Debye and Einsteincombined model. The fitting results show Debye and Einstein temperatures are 1119 and 199 K, respectively.
基金supported by the National Natural Science Foundation of China (Grant No. 51071098)the State Key Development for Basic Research of China (Grant No. 2010CB631002)
文摘By using the first-principles calculations,we have systematically investigated the adsorption of atomic oxygen on Cu(111) surface for a wide range of coverages Θ(from 0.11 to 1.00 ML) and adsorption sites.We found that the fcc-hollow site is the most stable site for oxygen adsorption.The adsorption energy decreases with increasing oxygen coverage due to the increasing repulsive interaction in the overlayer O adatoms.Except for coverage of 1.00 ML,the oxygen-induced lateral relaxations and bucklings are found in the outermost three Cu layers,and the hillock-like as well as ridge-like bucklings are also found for Θ=0.25 ML and Θ=0.75 ML as well as Θ=0.50 ML,respectively.With an increasing oxygen coverage,the work function increases and the surface dipole moment decreases.Electron transfer from the first layer Cu atoms to O adatoms indicates the O-Cu bond having some degree of ionic character,while the hybridization between O 2p and Cu 3d orbitals implies that it also has some degree of covalence character.Moreover,with the increasing oxygen coverage,more Cu 3d and O 2p states are empty thus weakening the binding of O/Cu(111) system,but increase in the PDOS at the Fermi level.This implies an enhancement in the metallic character of the O/Cu(111) system.
