The Influence of Sulfate‐Doping on the Nature of V Sites in VOx/TiO2 Catalysts

EPR, UV/Vis and FTIR spectroscopy as well as thermal analysis (TA/MS) were applied to study the influence of sulfate species present in the anatase support on the specific nature of VO_x species in supported VO_x/TiO₂ catalysts. Those sulfate species modify the local structure of the supported vanadyl species and lead to the formation of two types of VO²⁺ sites instead of only one type being formed on sulfate‐free anatase. EPR and FTIR spectroscopic measurements revealed that a part of the VO²⁺ species are directly bound to the surface sulfate species. By TA/MS it was found that SO₂ is released at lower temperature from VO_x/TiO₂ in comparison to the vanadium‐free support. The direct bonding between sulfate and VO_x species stabilizes the latter on the surface of VO_x/TiO₂ resulting in three effects: 1) a higher V site dispersion in comparison to sulfate‐free TiO₂, 2) a better resistance of surface vanadyls against diffusion into the bulk of the support and 3) a much faster reoxidation of reduced V sites than observed on sulfate‐free TiO₂.     

富锂掺杂Li1.06Co0.05Cr0.1Mn1.85O4的合成及电化学性能研究

锂离子电池具有比能量高、功率大、使用寿命长、无记忆效应、性能价格比高等优点,从而成为可充式电源的主要选择对象.锰由于资源丰富、价廉、环境友好等优点,使锰酸锂(LiMn2O4)成为最有希望取代钴酸锂的正极材料.但锰酸锂的放电容量相对较低,结构欠稳定,容量衰减严重,作为正极材料还无法与钴酸锂相比,近年来做了大量的研究工作以改善它的电化学性能[1～6].最近Youngjoon Shin等研究发现[7]用少量的Li与Ni共同替代LiMn2O4中的Mn得到的LiMn2-2yLiyNiyO4的电化学性能要优于单元素替代的LiMn2-xMxO4(M=Li,Cr,Fe,Co,Ni)的电化学性能.     

Hydrogen-Related Paramagnetic Centers in Ge-Doped Sol-Gel Silica Induced by γ-Ray Irradiation

We have studied the generation mechanisms of H(II) paramagnetic centers in Ge-doped silica by investigating up to 10⁴ mol ppm sol-gel Ge-doped silica materials. We have considered materials with the same concentrations of Ge but that are produced by two different densification routes that give rise to different concentrations of Ge-related oxygen deficient centers (GeODC(II)). These centers are characterized by an optical absorption band at ∼5.2 eV (B_2β band) and two related emissions at ∼3.2 eV and ∼4.3 eV. The GeODC(II) content was estimated by absorption and emission measurements. The H(II) centers were induced by room temperature γ-ray irradiation and their concentration was determined by electron paramagnetic resonance measurements. The comparison between the two kinds of materials, obtained by different preparations, shows that the GeODC(II) concentration increases with the Ge content and is enhanced by vacuum densification. The comparison of irradiated samples shows that beyond the already known process of conversion of preexisting GeODC(II) into H(II) centers, another generation process of H(II) centers is effective that involves irradiation induced GeODC(II).     

Infrared spectra of two sexithiophenes in neutral and doped states: a theoretical and spectroscopic study

The FT-infrared spectra of two sexithiophenes having their end ,′-positions substituted by n-hexyl or -thiohexyl groups, in neutral and doped states, are studied with the main aim of deriving information about the π-electrons delocalization and about the electronic structure of the charged defects created upon doping with iodine. The analysis of the experimental data is aided by Density Functional Theory calculations. The modifications in the electronic structure of the sexithiophene backbone induced by the n-thiohexyl encapsulation are discussed from the point of view of single molecule interactions in thiol-terminated π-conjugated oligomers bound to metallic or cluster electrodes.     

Partial P-Type Metal Ions Doping Induced Variation of Both Crystal Structure and Oxygen Vacancy Within Cu/SnO2 Metastable Solid Solution Nanofibers for Highly Sensitive C2H2 Sensor

Partial P-type metal ions doping(PPMID) is an alternative method to further enhance the gas sensing performance of N-type metal oxides(NMOs) in contrast to that of P-N metal oxides heterojunctions, but the influences of the introduction of PPMID on the grain size and oxygen vacancies of NMOs have been rarely investigated. Herein, a simple and effective route has been demonstrated to address this problem with Cu²⁺-doped SnO₂ metastable solid solution nanofibers(CSMSSNs) as model and C₂H₂ as target molecule by combining electrospinning and calcination technique. It seems that the introduction of PPMID can also affect crystal structure and oxygen vacancies of NMOs, proven by combining X-ray diffraction(XRD) and X-ray photoelectron spectra(XPS). Thus, PPD, crystal structure and oxygen vacancies have been combined to clarify the enhanced sensing performance of Cu-doped SnO₂ metastable solid solution nanofibers angainst C₂H₂.     

Ru、Rh、Pd掺杂GaSb的电子结构和光学性质

运用第一性原理计算方法研究了过渡族金属TM(TM=Ru、Rh、Pd)掺杂GaSb的电子结构和光学性质,结果表明:TM掺杂GaSb主要以TM替代Ga(TM @Ga)缺陷存在,并可增强GaSb半导体材料对红外光区光子的响应,使体系光学吸收谱的吸收边红移;TM@Ga所引入的杂质能级分布于零点费米能级附近,这极大地增强了体系的介电性能,促进了电子-空穴对的产生和迁移,因而提升了掺杂体系的光电转换效率;Ru 掺杂对GaSb光学性质的改善最为明显,当掺杂浓度为6.25%(原子数分数)且均匀掺杂时,Ru掺杂GaSb体系对红外光区光子的吸收幅度最大,有效提升了GaSb光电转换效率和光催化活性。     

铕取代的锆硼钨多金属氧酸盐的制备和发光特性

制备了高发射效率的稀土多金属氧酸盐BPOM:Eu及ZrPOM:Eu荧光体,并对其结构及发光性质进行了研究。结果表明样品具有Keggin结构,Eu在两类样品中均有肉眼可见的在红光区的强发射。但在BPOM:Eu中以⁵D₀→⁷F₁磁偶极跃迁发射为主,在ZrPOM:Eu中以⁵D₀→⁷F₂电偶极跃迁发射为主。铕在ZrPOM:Eu中的对称性低于在BPOM:Eu中的对称性。这种差异也使铕离子的激发光谱具有不同的特征。铕在两种多金属氧酸盐中均有浓度猝灭,在BPOM:Eu中浓度为2.0%时发射强度最大;在ZrPOM:Eu中浓度为2.4%时发射强度最大。在ZrPOM:Eu中有较弱的配体到中心铕离子的能量传递,而在BPOM:Eu中却未观测到能量传递现象。     

Enhancement of photosensitivity in bismuth doped Cu2ZnSnS4 thin films

In this paper, the effect of bismuth doping on the structural, morphological, optical and electrical properties of Cu₂ZnSnS₄ (CZTS) films has been investigated. The undoped and bismuth doped CZTS films (0, 0.5, 1, 1.5 and 2 mol%) were deposited on glass substrates by solution based method. The XRD result shows a significant improvement in the crystallinity of the films with increase in bismuth concentration. The Raman spectra of the films show the dominant peak at 334 cm^–1 corresponding to A₁ vibrational mode of CZTS kesterite phase. The FESEM micrographs of the films show an enhancement in the grain size and densification with the addition of bismuth ion concentration. The optical bandgap of the films was found to vary (1.59–1.40 eV) with the doping of bismuth ions. The I –V characteristics indicate twofold increment in the photoconductivity for the bismuth doped CZTS films under 100 mW/cm² illumination suggesting their potential application in photovoltaic devices. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Mo掺杂调控电子结构增强NiS电催化固氮性能

以泡沫镍为骨架,通过水热法制备了Mo掺杂的NiS多级纳米花状结构(Mo-NiS).在偏压为-0.7 V(vs RHE)下,2 h内,0.83 Mo-NiS(制备时钼、镍物质的量之比为0.83)的电催化固氮速率平均可达4.21μg·cm-2·h-1,法拉第效率平均为18％.XPS测试和DFT计算表明,Mo掺杂增加了Ni活...     

分层掺B和吸附H2O碳纳米管的结构稳定性及电子场发射性能

运用基于第一性原理的密度泛函理论,系统研究了处于外电场中分层掺B并吸附不同数目H₂O碳纳米管体系的结构稳定性和电子场发射性能. 研究表明:第3层掺B并吸附5个H₂O的B₃CNT+5H₂O体系结构最稳定,管帽处Mulliken电荷最密集,尤其与单独掺B的B₃CNT和单独吸附H₂O的B₃CNT+5H₂O相比,其Fermi能级处态密度分别