苝酰胺功能化磁性纳米材料的合成及其光/电性质

为了制备磁性荧光以及光电化学性能良好的多功能纳米粒子,采用微相乳液法,用二氧化硅（SiO2）包裹Fe3O4磁性纳米粒子的同时,将苝酰胺与SiO2表面的羟基反应,生成共价键连接的Fe3O4@SiO2-（1a）和Fe3O4@SiO2-（2a）纳米粒子,用红外光谱、XRD、SEM、UV-Vis吸收光谱、荧光光谱及ECL进行表征。结果表明,与化合物1a、2a相比,复合物Fe3O4@SiO2-（1a/2a）的电子吸收和荧光光谱峰型相同,峰位置略有移动。在一定浓度范围内,Fe3O4@SiO2-（2a）纳米粒子的ECL强度随浓度增大而降低,且其在50100 s的区间内基本稳定。

Electronic and Optical Properties of O-Terminated Armchair Graphene Nanoribbons

The structure, electromagnetic and optical properties of the O-terminated graphene nanorib- bons with armchair edge are studied using first-principles theory. The results show that the O-terminated armchair edge are more stable than the H-terminated ribbons and show metal- lic character. Spin-polarized calculations reveal that the antiferromagnetic state are more stable than the ferromagnetic state. The energy band and density of states analyses show that the O-terminated armchair edge are antiferromagnetic semiconductors. Because of the terminated 0 atoms, the dielectric function has an evident red shift and the first peak is the strongest with its main contribution derived from the highest valence band. The peaks of the dielectric function, reflection, absorption, energy loss are related to the transition of electrons. Our results suggest that the O-terminated graphene nanoribbons have potential applications in nanoelectronics, opto-electric devices.

Impact of Oxygen Vacancy on Band Structure Engineering of n-p Codoped Anatase TiO2

Doping with various impurities is an effective approach to improve the photoelectrochemical properties of TiO2. Here, we explore the effect of oxygen vacancy on geometric and elec- tronic properties of compensated （i.e. V-N and Cr-C） and non-compensated （i.e. V-C and Cr-N） codoped anatase TiO2 by performing extensive density functional theory calculations. Theoretical results show that oxygen vacancy prefers to the neighboring site of metal dopant （i.e. V or Cr atom）. After introduction of oxygen vacancy, the unoccupied impurity bands located within band gap of these codoped TiO2 will be filled with electrons, and the posi- tion of conduction band offset does not change obviously, which result in the reduction of photoinduced carrier recombination and the good performance for hydrogen production via water splitting. Moreover, we find that oxygen vacancy is easily introduced in V-N codoped TiO2 under O-poor condition. These theoretical insights are helpful for designing codoped TiO2 with high photoelectrochemical performance.

Synthesis and photophysical and electrochemical properties of new cyclometalated platinum complex containing oxadiazole ligand

A new cyclometalated platinum complex containing 2, 5-bis(naphthalene-1-yl)-1,3,4-oxadiazole ligand was synthesized and characterized. The UV-Vis absorptions and photoluminescent properties of the ligand and its platinum complex were investigated. A characteristic metal-ligand charge transfer absorption peak at 439 nm in the UV spectrum and a strong emission peak at 625 nm in the photoluminescence spectrum were observed for this complex in dichloromethane. Cyclic voltammtry (CV) analysis shows that the EHOMO (energy level of the highest occupied molecular orbital) and ELUMO (energy level of the lowest unoccupied molecular orbital) of the platinum complex are about 、5.69 and 、3.25 eV, respectively, indicating that the oxadiazole-based platinum complex has a potential application in electrophosphorescent devices used as a red-emitting material.

Effects of structures of molybdenum catalysts on selectivity in gas-phase propylene oxidation

Molybdenum-based catalysts for the gas-phase oxidation of propylene with air were investigated. Various types of silica-supported molybdenum oxide and molybdenum-bismuth mixed oxide cata- lysts were prepared from inorganic and organometallic molybdenum precursors using wet impregnation and physical vapor deposition methods. The epoxidation activities of the prepared cata- lysts showed direct correlations with their nanostructures, which were identified using transmission electron microscopy. The appearance of a partly or fully crystalline molybdenum oxide phase, which interacted poorly with the silica support, decreased the selectivity for propylene oxide for- mation to below 10%; non-crystalline octahedrally coordinated molybdenum species anchored on the support gave propylene oxide formations greater than 55%, with 11% propylene conversion. Electrochemical characterization of molybdenum oxides with various morphologies showed the importance of structural defects. Direct promotion by bismuth of the epoxidation reactivities over molybdenum oxides is disputed.

High photocatalytic activities of zinc oxide nanotube arrays modified with tungsten trioxide nanoparticles

Well‐aligned zinc oxide(ZnO)nanotube arrays loaded with tungsten trioxide(WO3)nanoparticles were synthesized by a process involving chemical bath deposition in combination with pyrolysis.The prepared ZnO–WO3composites were characterized by X‐ray diffraction,energy dispersive spectrometer,field emission scanning electron microscopy,X‐ray photoelectron spectroscopy,photoluminescence spectroscopy,Fourier transform infrared spectroscopy and UV–vis diffuse reflectance spectroscopy.The photocatalytic activities of the ZnO–WO3composite photocatalysts with different WO3contents for the degradation of the herbicide chlorinated phenoxyacetic acid(MCPA‐Na)under simulated sunlight irradiation were systematically evaluated.It was found that the WO3content had a great effect on the photocatalytic activity of the ZnO–WO3composites.The composite with3%WO3showed the highest photocatalytic activity,with a degradation rate of chlorinated phenoxyacetic acid of98.5%after200min with20mg of photocatalyst.This photodegradation rate was about twice that of the pristine ZnO nanotube array.The recombination of photogenerated electrons and holes was increasingly suppressed with the addition of WO3to ZnO.The high relative content of defects on the surface of the ZnO–WO3composites was beneficial to their photocatalytic activity in the degradation of chlorinated phenoxyacetic acid.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.

Effects of Metal Oxide Modifications on Photoelectrochemical Properties of Mesoporous TiO2 Nanoparticles Electrodes for Dye-Sensitized Solar Cells

Mesoporous TiO2 （m-TiO2） nanoparticles were used to prepare the porous film electrodes for dye-sensitized solar cells, and a second metal oxide （MgO, ZnO, A1203, or NiO） modifi- cation was carried out by dipping the m-TiO2 electrode into their respective nitrate solution followed by annealing at 500 ℃. Experimental results indicated that the above second metal oxide modifications on m-TiO2 electrode are shown in all cases to act as barrier layer for the interracial charge transfer processes, but film electron transport and interfacial charge recombination characteristics under applied bias voltage were dependent significantly on the existing states and kinds of these second metal oxides. Those changes based on sec- ond metal oxide modifications showed good correlation with the current-voltage analyses of dye-sensitized solar cell, and all modifications were found to increase the open-circuit photo- voltage in various degrees, while the MgO, ZnO, and NiO modifications result in 23%, 13%, and 6% improvement in cell conversion efficiency, respectively. The above observations indi- cate that controlling the charge transport and recombination is very important to improve the photovoltaic performance of TiO2-based solar cell.

First principles study on electronic structure and optical properties of quaternary arsenide oxides YZnAsO and LaZnAsO

The electronic structure and optical properties of the tetragonal phase quaternary arsenide oxides YZnAsO and LaZnAsO were studied using density-functional theory(DFT) within generalized gradient approximation(GGA).The band structure along the higher symmetry axes in the Brillouin zone,the density of states(DOS) and the partial density of states(PDOS) were presented.The calculated energy band structures show that both YZnAsO and LaZnAsO are indirect gap semiconductors with band gap of 1.173 1 eV and 1.166 5 eV,respectively.The DOS and PDOS show the hybridization of Y-O/La-O atom orbits and Zn-As atom orbits.The dielectric function,reflectivity,absorption coefficient,refractive index,electron energy-loss function and optical conductivity were presented in an energy range from 0 to 25 eV for discussing the optical properties of YZnAsO and LaZnAsO.

Stability and electronic spectra of C_(76) N_2 isomers

Study of geometries of 16 possible isomers for C76N2 based on C78(C2v) by intermediate neglect of differential overlap (INDO) series of methods indicated that the most stable geometry 25,78-C76N2 where two nitrogen atoms substitute two apexes C(25) and C(78) near the shortest X axis and Y axis formed by two hexagons and a pentagon. Electronic structures and spectra of C76N2 were investigated. The reason for the red-shift for absorptions of C76N2 compared with that of C78(C2v) is discussed.

Effects of Sintering Atmosphere on the Microstructure and Surface Properties of Symmetric TiO2 Membranes

The effects of sintering atmosphere on the properties of symmetric TiO2 membranes are studied with regard to sintering behavior, porosity, mean pore size, surface comPosition. and surface charge properties. The exerimental results show that the symmetric TiO2 membranes display better sintering activity in the air than in argon, and the mean pore diameters and porosities of the membrane sintered in argon are higher than those of the membrane sintered in the air at the same temperature. The surface compositions of the symmetric TiO2 membrane sintered in the air and in argon at different temperatures, as studied by X-ray photoelectron spectroscopy, are discussed in terms of their chemical composition, with particular emphasis on the valence state of the titanium ions. The correlation between the valence state of the titanium ions at the surface and the surface charge properties is examined.It is found that the presence of Ti^3＋, introduced at the surface of the symmetric TiO2 membranes by sintering in a lower partial pressure of oxygen, is related to a significant decrease in the isoelectric point. TiO2 with Ti^4＋ at the interface has an isoelectric point of 5.1, but the non-stoichiometric TiO2-x with Ti^3＋ at the interface has a lower isoelectric point of 3.6.

Highly-ordered dye-sensitized TiO_2 nanotube arrays film used for improving photoelectrochemical electrodes

Thin titanium oxide nanotube arrays (TNAs) films were synthesized by anodization of titanium foil in an aqueous dimethyl sulfoxide solution using a platinum foil counter electrode.TNAs up to 6.8 μm in length,120 nm in inner pore diameter,and 20 nm in wall thickness were obtained by 40 V potentials anodization for 24 h.Their microstructures and surface morphologies were characterized by XRD,TEM,SAED and UV-vis spectroscopy.The photoelectrochemical properties of as-prepared unsensitized and dye-sensitized TNAs electrodes were examined under simulated solar light (AM 1.5,100 mW/cm2) illumination.The results showed that the photocurrent of the dye-sensitized TNAs electrodes reached 6.9 mA/cm2,which was 6 times more than that of the dye-sensitized TiO2 nanoparticles (TNPs) electrodes.It implied that the electron transport process and the charge recombination suppression within TNAs electrodes were much more favorable in comparison with that in the TNPs electrodes.Electrodes applying such kind of titania nanotubes will have a potential to further enhance the efficiencies of TNAs-based dye-sensitized solar cells.

Integration of supertetrahedral cluster with reduced graphene oxide sheets for enhanced photostability and photoelectrochemical properties

Supertetrahedral zinc-gallium-tin sulfide cluster modified with reduced graphene oxide protective layer was first synthesized, which exhibited an excellent photoelectrochemical performance and enhanced stability in comparison to supertetrahedral clusters.

Au doping effects on electrical and optical properties of vanadium dioxides

Vanadium dioxides were fabricated on normal glass substrates using reactive radio frequency （RF） magnetron sputtering. The oxygen flow volume and annealed temperatures as growth parameters are systematically investigated. The electrical and opti- cal properties of VO2 and Au：VO2 thin films with different growth conditions are discussed. The semiconductor-metal phase transition temperature decreased by -10~C for the sample with Au doping compared to the sample without Au doping. How- ever, the optical transmittance of Au：VO2 thin films is much lower than that of bare VO2. These results show that Au doping has a marked effect on the electrical and optical properties.

Nickel-coated silicon photocathode for water splitting in alkaline electrolytes

Photoelectrochemical （PEC） water splitting is a promising approach to harvest and store solar energy [1]. Silicon has been widely investigated for PEC photoelectrodes due to its suitable band gap （1.12 eV） matching the solar spectrum [2]. Here we investigate employing nickel both as a catalyst and protecting layer of a p-type silicon photocathode for photoelectrochemical hydrogen evolution in basic electrolytes for the first time. The silicon photocathode was made by depositing 15 nm Ti on a p-type silicon wafer followed by 5 nm Ni. The photocathode afforded an onset potential of -0.3 V vs. the reversible hydrogen electrode （RHE） in alkaline solution （1 M KOH）. The stability of the Ni/Ti/p-Si photocathode showed a 100 mV decay over 12 h in KOH, but the stability was significantly improved when the photocathode was operated in potassium borate buffer solution （pH ≈ 9.5）. The electrode surface was found to remain intact after 12 h of continuous operation at a constant current density of 10 mA/cm^2 in potassium borate buffer, suggesting that Ni affords good protection of Si based photocathodes in borate buffers.

First-principles study on electronic structures and optical properties of the single-walled (n, 0) ZnO nanotubes

Using the first-principles calculations, we studied the geometric structures, electronic structures and optical properties of the single-walled (n, 0) ZnO nanotubes (NTs). The calculated results show that all the bind energies of the single-walled (n,0) ZnO NTs are of negative values, which indicate that the ZnO NTs can exist stably as single-walled NTs. While the calculated results of electronic structure indicate that the single-walled (n,0) ZnO NTs are a type of direct wide band-gap semiconductor materials, the whole valence bands are spread and drift to low-energy direction with the increase of the NT diameter. The defect energy levels caused by quantum size and surface effects emerge on the top of the valence bands. Furthermore, the calculated results of optical properties reveal that the dielectric peaks have a blue shift and the edge of absorption band corresponds to ultraviolet band with the decrease of the NT diameter. The single-walled (n, 0) ZnO NTs can be applied to ultraviolet semiconductor systems.

Electronic structure and optical properties of Sn_(2x)Ga_(2(1-x))O_3 compounds

Band structure, density of states, electron density difference, and optical properties of intrinsic β-Ga2O3 and Sn2xGa2(1-x)O3 (x= 3.125%-6.25%) compounds are studied using first-principle calculations based on the density functional theory. The anisotropic optical properties are investigated by means of the complex dielectric function, which are explained by the selection rule of band-to-band transitions. All the calculation results indicate that the conductivity of Sn2xGa2(1-x)O3 is super to β-Ga2O3, and the calculated results consist with experiments that have been reported.

Spectroscopic and electrochemical properties of Cu-dicyandiamide complex

Dicyandiamide(DICY) is a common ligand that exhibits low toxicity but can irritate the skin and eyes and cause methemoglobinemia on long-term exposure. Crystalline Cu-dicyandiamide(Cu-DICY) was obtained via facile synthesis and its molecular structure and theoretical Raman spectra were simulated by using density functional theory(DFT). The results suggested that the Cu^(2+) coordinates with two H_2 O molecules and two different DICY molecules(an imino DICY and an amino DICY). The stability constants of Cu-DICY were calculated, and the electrochemical properties were studied. Two electrochemical redox processes occur in Cu-DICY in an aqueous solution: a reversible reaction with a formal potential of 0.2 V vs.MSE and an irreversible reaction between –0.4 and –1.2 V vs. MSE. The standard rate constant k0 for the reversible reaction was estimated to be 7.6×10^(-3) cm/s. In addition, based on the reversible reaction of Cu-DICY, square wave voltammetry was used to rapidly determine the concentration of Cu(II) and the detection limit was 66.7 μg/L, which satisfies the detection limit requirements for copper in tap water(2 mg/L) as provided by the World Health Organization.

First-Principles Calculations on Electronic,Chemical Bonding and Optical Properties of Cubic Hf_3N_4

Electronic, chemicM bonding and optical properties of cubic Hf3N4 （ c-Hf3N4 ） are calculated using the first- principles based on the density functional theory （DFT）. The optimized lattice parameter is in good agreement with the available experimental and cedculational values. Band structure shows that c-Hf3N4 has direct band gap. Densities of states （DOS） and charge densities indicate that the bonding between Hf and N is ionic. The optical properties including complex dielectric function, refractive index, extinction coefficient, absorption coefficient, and refleetivity are predicted. Prom the theory of crystal-field and molecular-orbited bonding, the optical transitions of c-Hf3N4 affected by the electronic structure and molecular orbited are studied. It is found that the absorptive transitions of c-Hf3N4 compound are predominantly composed of the transitions from N T2 2p valence bands to Hf T2 （dxy, dxz, dyz） conduction bands.

Theoretical studies of the structures and spectroscopic properties of the photoelectrochemical cell ruthenium sensitizers,C101 and J13

A variety of heteroleptic ruthenium sensitizers have been engineered and synthesized because of their higher light-harvesting efficiency and lower charge-recombination possibility than the well known homoleptic N3 dye. As such, a great deal of atten- tion has been focused on sensitizers with the general formula Ru（ancillary-ligand）（anchoring-ligand）（NCS）2, among which important examples are Ru（4,4＇-bis（5-hexylthiophen-2-yl）-2,2＇-bipyridine）（4,4＇-carboxylic acid-4＇-2,2＇-bipyridine）（NCS）2 （C101） and Ru（N-（4-butoxyphenyl）-N-2-pyridinyl-2-pyridinamine）（4,4＇-carboxylic acid-4＇-2,2＇-bipyridine）（NCS）2 （J13）. In order to simulate experimental conditions with different pH values, the photosensitizing processes of these sensitizers pos- sessing different degrees of deprotonation （2I-I, lit to OH） have been explored theoretically in this work. Their ground/excited state geometries, electronic structures and spectroscopic properties are first calculated using density functional theory （DFT） and time-dependent DFT （TDDFT）. The absorption and emission spectra of all the complexes in acetonitrile solution are also predicted at the TDDFT （B3LYP） level. The calculated results show that the ancillary ligand contributes to the molecular or- bital （MO） energy levels and absorption transitions. It is intriguing to observe that the introduction of a thiophene group into the ancillary ligand leads directly to the increased energy of the absorption transitions in the 380-450 nm region. The calcula- tions reveal that although deprotonation destabilizes the overall frontier MOs of the chromophores, it tends to exert a greater influence on the unoccupied orbitals than on the occupied orbitals. Consequently, an obvious blue shift was observed for the absorptions and emissions in going from 21-1, 1H to OH. Finally, the optimal degree of deprotonation for C101 and J13 has al- so been evaluated, which is expected to lead to further improvements in the performance of dye-sensitized solar cells （DSSCs） coated with such sensitizers.