Single Unit Cell Bismuth Tungstate Layers Realizing Robust Solar CO2 Reduction to Methanol

Solar CO₂ reduction into hydrocarbons helps to solve the global warming and energy crisis. However, conventional semiconductors usually suffer from low photoactivity and poor photostability. Here, atomically‐thin oxide‐based semiconductors are proposed as excellent platforms to overcome this drawback. As a prototype, single‐unit‐cell Bi₂WO₆ layers are first synthesized by virtue of a lamellar Bi‐oleate intermediate. The single‐unit‐cell thickness allows 3‐times larger CO₂ adsorption capacity and higher photoabsorption than bulk Bi₂WO₆. Also, the increased conductivity, verified by density functional theory calculations and temperature‐dependent resistivities, favors fast carrier transport. The carrier lifetime increased from 14.7 to 83.2 ns, revealed by time‐resolved fluorescence spectroscopy, which accounts for the improved electron‐hole separation efficacy. As a result, the single‐unit‐cell Bi₂WO₆ layers achieve a methanol formation rate of 75 μmol g^?1 h^?1, 125‐times higher than that of bulk Bi₂WO₆. The catalytic activity of the single‐unit‐cell layers proceeds without deactivation even after 2 days. This work will shed light on designing efficient and robust photoreduction CO₂ catalysts.     

Ion implantation of zinc sulphide

The passivation of argon sputter-etch induced electrically active defects on Ge, Si, and GaAs surfaces by reaction with atomic hydrogen has been observed using deep level transient spectroscopy. A broad band of defect states, giving rise to non-linear Arrhenius plots, appears to be associated with the induced damage centres. For n-type Ge and p-type Si, a 20-min exposure to atomic hydrogen at 180°C is shown to neutralize the damage created by a 5-min, 6 kV (DC), Ar gas sputter-etch. For n-type GaAs a 1-h exposure at 250°C was sufficient, whilst n-type Si required a 1-h exposure to the hydrogen plasma at 300°C to passivate the damage. In each case, to remove the sputter-etch damage by thermal annealing required temperatures approximately 100°C higher, for periods of approximately 2 h.     

掺Co钨酸镉单晶体的坩埚下降生长及光谱特性

应用坩埚下降法,采用70℃.cm-1的固液界面温度梯度与0.50 mm.h-1生长速度,生长出了初始Co掺杂摩尔百分浓度为0.5 mol%、尺寸为Ф25 mm×120 mm的钨酸镉单晶体。晶体呈透明深蓝色。用XRD表征了获得的晶体。观测到518,564和655 nm三个可见波段吸收带以及发光中心1 863 nm(1 323～2 220 nm)的超宽吸收带。可见波段的吸收归属于Co2+在八面晶格场中4T1(4F)→4A2(4F),4T1(4F)→4T1(4P)跃迁叠加,而红外波段的宽带吸收则为八面体场Co2+的4T1(4F)→4T2(4F)能级跃起所致。从吸收特性表明,Co离子掺杂于畸变的氧八面体中,呈现+2价态。根据吸收光谱计算出晶格场参数Dq=990 cm-1,Racah参数BC=726.3 cm-1。在520 nm波长光的激发下,观察到778 nm波段的荧光发射,归属于八面体晶格场中Co2+的4T1(4P)→4T1(4F)能级的跃迁。从吸收与荧光强度的变化推断:沿着晶体生长方向,Co2+浓度逐渐增加,有效分凝系数小于1。     

Electronic band structures and photovoltaic properties of MWO4 (M=Zn, Mg, Ca, Sr) compounds

Divalent metal tungstates, MWO₄, with wolframite (M=Zn and Mg) and scheelite (M=Ca and Sr) structures were prepared using a conventional solid state reaction method. Their electronic band structures were investigated by a combination of electronic band structure calculations and electrochemical measurements. From these investigations, it was found that the band structures (i.e. band positions and band gaps) of the divalent metal tungstates were significantly influenced by their crystal structural environments, such as the W-O bond length. Their photovoltaic properties were evaluated by applying to the working electrodes for dye-sensitized solar cells. The dye-sensitized solar cells employing the wolframite-structured metal tungstates (ZnWO₄ and MgWO₄) exhibited better performance than those using the scheelite-structured metal tungstates (CaWO₄ and SrWO₄), which was attributed to their enhanced electron transfer resulting from their appropriate band positions.     

Eu3+掺杂CaWO4红色荧光粉发光性质的浓度依赖关系研究

采用共沉淀法制备了不同Eu³⁺掺杂浓度的CaWO₄荧光粉材料.通过X射线衍射和场发射扫描电镜技术对样品的结构和形貌进行了表征.测量了各样品的激发光谱、发射光谱和荧光衰减曲线, 计算了各样品的部分Judd-Oflet (J-O)参数和^5D_0 (Eu³⁺)能级量子效率,以及荧光粉的色坐标, 讨论了样品电荷迁移带相对强度、J-O参数、量子效率与掺杂浓度的依赖关系.对Eu³⁺掺杂的CaWO₄ 发光材料的光致发光性质的研究表明,在CaWO₄: Eu³⁺中⁵D₀→⁷F₂跃迁的616~nm 红色发光能被394.5~nm和465~nm的激发光有效激发,具有近紫外(或蓝光)激发效率高和猝灭浓度大的优点, 有潜力成为高效的近紫外(或蓝光)激发白光发光二极管用红色荧光粉材料.     

某些同多酸根与蛋白质相互作用的共振瑞利散射光谱研究

在酸性介质中,钼酸根、钨酸根和偏钒酸根等同多酸根与牛血清白蛋白（BSA）和人血清白蛋白（HSA）等蛋白质反应形成结合产物时,会导致溶液的共振瑞利散射（RRS）急剧增强,最大散射峰均位于470nm。反应的适宜酸度分别为pH0．9～1．3（钼酸根．BSA体系）,pH1．1—1．4（钨酸根-BSA体系）和pH0．6—0．9（偏钒酸根-BSA体系）。在一定的浓度范围内,不同的反应体系RRS强度与蛋白质浓度成正比,均可用于蛋白质的测定。反应具有很高的灵敏度,不同的同多酸对BSA的检出限（30σ／s）介于4．1—30．5μg/L之间,其中钼酸根体系的灵敏度最高。考察了共存物质的影响并研究了方法的分析应用。     

Phase formation in the Ni2+-WO 42? -H+-H2O system (Z = 1.00). Crystal structure and properties of sodium heteropolyhexatunsten nickelate(2+) Na4[Ni(OH)6W6O18]·16H2O

The green crystals of Ni_1.5H[Ni(OH)₆W₆O₁₈]·12.5H₂O and blue crystals of Na₄[Ni(OH)₆W₆O₁₈]·16H₂O were isolated from the acidified (to Z = ν(H⁺)/ν(WO₄²⁻) = 1.00) solutions of Ni(NO₃)₂-Na₂WO₄-HNO₃-H₂O systems. The synthesized salts were identified by chemical analysis, XRPA, and IR spectroscopy. It was shown that the heteropolyanions belonged to the Anderson-Evans type of structure. An X-ray diffraction study of Na₄[Ni(OH)₆W₆O₁₈]·16H₂O was carried out (M _r = 1932.07, triclinic, space group P-1, a = 8.0089(11) ?, b = 10.5758(14) ?, c = 12.1987(16) ?; α = 69.268(13)°, β = 71.069(12)°, γ = 83.816(11)°; V = 914.0(2) ?³ at T = 293 K, Z = 1, ρ_cal = 3.510 g/cm³, F ₀₀₀ = 874, μ = 19.470 mm⁻¹, −16 ≤ h ≤ 16, −21 ≤ k ≤ 21, −24 ≤ l ≤ 24; the final R factors are R _F = 0.0277, wR ² = 0.0469 for the observed reflections (R _F = 0.0606, wR ² = 0.0523 for all independent reflections); S = 0.953; CSD-419883). The structure was solved by direct methods and refined in an anisotropic approximation. Hydrogen atoms were found in a difference synthesis and refined in an isotropic approximation with geometrical limitations. The nature of water in Na₄[Ni(OH)₆W₆O₁₈]·16H₂O was characterized by DTA. XRPA was used to identify the thermolysis products of heteropoly compounds. Original Russian Text Copyright ? 2009 by G. M. Rozantsev, S. V. Radio, N. I. Gumerova, V. N. Baumer, and O. B. Shishkin __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 50, No. 2, pp. 311–319, March–April, 2009.     

Mechanism of defect formation and polyanion transport in solid scandium tungstate type oxides

Abstract  The unique diffusion mechanism in the novel polyatomic anion conductor scandium tungstate is studied by molecular dynamics simulations of systems with artificially induced WO₄ ²⁻ defects and compared to our previous simulations of defect-free structure models. The diffusion activation energy obtained from structures with built-in defects is smaller than for the defect-free models and in the case of tungstate vacancies close to the experimental value, suggesting that extrinsic tungstate vacancies due to the volatility of WO₃ are important for the experimental conductivity. The validity of the force field used for the molecular dynamics simulations is further verified by investigating the orthorhombic to monoclinic phase transition of Sc₂(WO₄)₃ under compression. The lattice compressibility in both phases and the phase transition is qualitatively reproduced, though the simulated phase transition pressure occurred is about 0.55 GPa higher than the experimental one. Graphical abstract        

Cd2+掺杂ZnWO4纳米棒的合成和光致发光性能研究

采用简单的水热法合成了Cd2+掺杂ZnWO4纳米棒.通过SEM、TEM、EDX和XRD等手段对产物进行了表征.实验结果表明,产物为直径约20 nm.长300～500 nm的Cd2+掺杂ZnWO4纳米棒.研究了Cd2+掺杂量对ZnWO4纳米棒的光致发光性能的影响,随着Cd2+掺杂量的增加,ZnWO4纳米棒的光致发光强度随之增强.     

聚天冬氨酸与钨酸钠复配对黄铜缓蚀作用的光电化学研究

应用光电化学的方法研究了两种环境友好型缓蚀剂聚天冬氨酸(PASP)和钨酸钠(Na2WO4)的单一配方及其复配对黄铜在含硼砂硼酸缓冲溶液的模拟水中的缓蚀作用. 结果表明, 在光电流循环伏安测试中, 单一的PASP与Na2WO4均能够使黄铜表面Cu2O膜引起的p-型光电流响应增大, 这说明缓蚀剂增大了Cu2O膜的厚度, 使黄铜的腐蚀速率减小. 单一的PASP与Na2WO4的最佳添加浓度分别为20与25 mg•L－1. 若以总浓度为20 mg•L－1时对两者进行复配, 当PASP与Na2WO4的质量比为1∶1时, 两者复配比单一使用时的p-型电流光响应都更大, 黄铜的腐蚀更小, 即缓蚀剂的效果更好.