ZnGa2Se4:V3+ 光谱的理论研究

应用区分t₂和e轨道共价性的差异(包含静电部分和晶场部分)并考虑了低对称场的能量矩阵, 在考虑和忽略静电参量B₀₀的条件下, 分别研究了t₂和e轨道共价性的差异对三元半导体ZnGa₂Se₄:V ³⁺能级以及低对称分裂的影响; 计算了ZnGa₂Se₄:V ³⁺晶体的能级的低对称分裂, 并与实验值进行比较. 计算结果与实验值符合很好. 研究发现: 在对ZnGa₂Se₄:V ³⁺晶体的光学性质进行理论研究时, 在能量矩阵的静电和晶场部分同时考虑t₂和e轨道共价性的差异是非常有必要的; 晶场参量B₀₀对ZnGa₂Se₂4:V ³⁺的能级有重要影响, 因此不能忽略.     

The concentration quenching characteristics of 5D3-7FJ and 5D4-7FJ (J=0―6) transitions of Tb3+ in YBO3:Tb3+ phosphor

The photoluminescence quenching behaviors of ^5D3-^7Fj and ^5D4-^7Fj （J = 0—6） transitions of Tb^3＋ in YBO3：Tb under 130—290 nm excitation were systematically investigated. The results revealed that the quenching concentrations of both ^5D3-^7Fj and ^5D4-^7Fj transitions of Tb^3＋ in YBO3：Tb were mainly dependent on excitation wavelength. Particularly, the quenching concentrations of ^5D4-^7Fj transitions of Tb^3＋ under 130—290 nm excitation were correlated with excitation bands of YBO3：Tb. The quenching concentrations of ^5D3-^7Fj transitions remained at low concentration （2%） under 186—290 nm excitation and then increased gradually with energy of incoming excitation photon when excited at 130—186 nm. This dependence should be involved in their excitation mechanisms and quenching pathway in particular excitation region.[第一段]     

葡萄糖-BrO3--Mn2+-H2SO4-丙酮体系的振荡反应

以葡萄糖为有机底物，与－ＢｒＯ３－－Ｍｎ２＋－Ｈ２ＳＯ４－丙酮组成振荡反应体系，在恒温条件下进行振荡反应。结果表明：反应有诱导期，体系电导（Ｌ）不随时间（ｔ）变化；振荡周期，Ｌ随ｔ发生周期变化，溶液颜色在粉红色与无色之间交替变化，有典型的振荡波型。诱导期及振荡周期反应的表观活化能分别为８４．２７５ｋＪ／ｍｏｌ和９８．１５３ｋＪ／ｍｏｌ。体系振荡反应物浓度范围［葡萄糖］０．０１～０．０２ｍｏｌ／Ｌ，［ＢｒＯ３－］０．０３～０．０４５ｍｏｌ／Ｌ，［Ｍｎ２＋］０．０６～０．０８ｍｏｌ／Ｌ，［丙酮］０．２７～０．３０ｍｏｌ／Ｌ，［Ｈ２ＳＯ４］０．８～１．２ｍｏｌ／Ｌ。振荡反应有Ｂｒ２产生，Ｂｒ２准一级消耗速率常数ｋＢｒ２＝１．６×１０－５Ｓ－。对温度、反应物浓度、丙酮、Ｍｎ２＋、Ｃｌ－、底物对振荡反应的影响作了探讨。     

Bi~(3+)/Yb~(3+)共掺GdVO_4近红外发光性能研究

使用高温固相法制备了一种新的Bi3+,Yb3+共掺杂GdVO4量子裁剪近红外发光材料,该材料在波长为250~400nm的紫外光激发下发射出很强的近红外光(900~1100nm).由于体系中Bi3+离子的引入,相对于Gd0.9Yb0.1VO4,Gd0.87Yb0.1Bi0.03VO4在989nm处的近红外发光强度提高近120%,且其激发峰也从323nm红移至341nm,整个激发谱带更宽,更有利于实际应用.由于Yb3+离子既可以利用基质中的VO3-4电荷迁移态跃迁的能量,也可以同时利用Bi3+的1S0-3P1能级跃迁传递能量,相对于目前报道的理论量子裁剪效率最高的YVO4:Bi3+,Yb3+,GdVO4:Bi3+,Yb3+无论其近红外发光强度还是可见光发光强度强度皆有提升,是一种很有希望的紫外宽带激发近红外发光材料.     

10Be/7Be implies the contribution of stratosphere-troposphere transport to the winter-spring surface O3 variation observed on the Tibetan Plateau

10Be/7Be is a stratospheric sensitive tracer.In this paper,measurements of 10Be/7Be and surface O3 from October 2005 to May 2006 at Mt.Waliguan (hereafter WLG,100.898°E,39.287°N,3810 m,a.s.l.),China global atmospheric watch (GAW) observatory,are introduced and used to investigate the stratosphere-troposphere transport (STT) and its impact on surface O3 on the Tibetan Plateau.The results show that the magnitude of STT is weak in winter,followed by strengthening from the end of winter to the middle of spring (from mid February to mid April) with large increases in 10Be,7Be,10Be/7Be and surface O3.At the end of spring (from the end of April to mid May in this paper),the STT weakened,and the continuous increase of surface O3 at WLG is produced by tropospheric photochemistry reactions.     

Effects of Yb^3＋ codoping on visible and near infrared emissions of Er^3＋-Yb^3＋ codoped Al2O3 powders by the sol-gel method

The 0.1 mol% Er^3＋ and 0-2 mol% Yb^3＋ codoped Al2O3 powders were prepared by the sol-gel method, and the phase structure, including only two crystalline types of doped Al2O3 phase, γ-（Al,Er, Yb）2O3 and θ-（Al,Er, Yb）2O3, was detected at the sintering temperature of 1000℃. The visible and near infrared emissions properties depended strongly on the Yb^3＋ codoping, and the corresponding maximal peak intensities centered at about 523, 545, 660 and 1533 nm were obtained respectively for the 0.1 mol% Er^3＋ and 0.5 mol% Yb^3＋ codoped Al2O3 powders, which were composed of θ-（Al,Er,Yb）2O3 and a small amount of γ-（Al,Er, Yb）2O3 phases. The two-photon absorption process was responsible for the visible up-conversion emissions, and the one-photon absorption process was involved in the near infrared emissions of the Er^3＋-yb^3＋ codoped Al2O3 powders.     

Eu~(3+)掺杂纳米TiO_2的制备及光催化性能的研究

通过溶液法制备了不同铕(Eu3+)掺杂量Ti O2纳米颗粒(Eu3+/Ti O2),利用XRD、TEM、XPS对其进行了表征.在可见光照射下,以光催化降解常用的工业染料为目标反应,探讨了Eu3+掺杂量、催化剂用量、溶液p H值和催化剂重复利用对催化活性的影响,以优化光催化条件.结果表明:煅烧温度为500℃,Eu3+/Ti O2光催化剂晶型为锐钛矿型,其晶粒尺寸为14 nm;Eu3+离子的最佳掺杂摩尔比r(Eu3+︰Ti O2)=3%,样品加入量为1.25 mg/m L,p H=10.75时样品光催件性能最佳;其3次循环降解甲基紫,60 min内降解率仍保持在约96%,说明Eu3+/Ti O2光催化剂具有良好的稳定性.     

基于LED的LaBr_3:Ce~(3+)闪烁γ谱仪稳谱技术研究

针对基于LED的LaBr_3:Ce~(3+)闪烁γ谱仪稳谱技术进行研究,介绍了稳谱原理,搭建了硬件测量系统,利用计算机编程控制,通过标定保持待测能区不变时参考峰位随温度变化曲线,达到了非线性稳谱目的,实测稳谱效果在温度0~50℃变化时偏离不超过±1道.     

Theoretical study of partial oxidation of ethylene by vanadium trioxide cluster cation

Density functional theory （DFT） study of reaction between vanadium trioxide cluster cation （VO3^＋） and ethylene （C2H4） to yield VO2^＋ ＋ CH3CHO （acetaldehyde） and VO2CH2^＋ ＋ HCHO （formaldehyde） is carried out. Structures of all reactants, products, intermediates, and transition state in the reaction have been optimized and characterized. The results show unexpected barriers in the reaction due to the existence of a η^2-O2 moiety in the ground state structure of VO3^＋. The initial reaction steps combining ethylene adsorption, C=C activation and O-O cleavage are proposed as rate limiting processes. Comparison of reactions of VO3^＋ ＋ C2H4 with VO3 ＋ C2H4 and VO2^＋ ＋ C2H4 in the previous studies is made in detail. The results of this work may shed light on the understanding of C=C bond cleavage in related heterogeneous catalysis.     

Determination of some carbonyl carboxylic acids using chemiluminescent reaction of Ru(bipy)3 2+−Ce(IV)

A coupled chemiluminescence method for the determination of some carboxylic acids was developed, based on their enhancement the chemiluminescence light emission of the reaction of tirs (2,2′-bipyridine) ruthenium(II) and Ce(IV) in sulfuric acid medium. The conditions for their determination were optimized. The following detection limits were obtained: oxalic acid, 2.67×10⁻⁸ mol/L; propandioic acid, 1.20×10⁻⁶ mol/L; pyruvic acid, 1.35×10⁻⁸ mol/L; citric acid, 5.10×10⁻⁸ mol/L; barbituric acid, 2.48×10⁻⁷ mol/L. The proposed method was successfully applied to determination of oxalic acid. The coupled chemiluminescent reaction mechanism and rate equation are proposed. Foundation item: Supported by the National Natural Science Foundation of China and the Natural Science Foundation of Hubei Province Biography: HAN He-you (1962-), male, Associate professor, phD, graduate candidate     

流动注射分析法测定水样中的NO2--N和NO3--N

采用流动注射技术测定水样中的NO-/2-N和NO-/3-N.以N-(1-萘基)乙烯二胺盐酸盐和对氨基苯磺酸为显色剂,在540nm下比色测定NO-/2-N的含量.水样中的NO-/3-N,在稀醋酸条件下用锌粉将其预还原成NO-/2-N后,也在上述相同的条件下测定其含量.NO-/2-N的检出限为0.005×10-/6,NO-/3-N的检出限为0.05×10-/6,分析速度为65次/小时.     

Pu(H2O)53+和Pu(H2O)54+ 团簇的相对论密度泛函研究

用TPSSTPSS密度泛函方法, Pu离子和H₂O分子分别采用相对论有效原子实势(RECP)和6-31g基组, 研究了Pu(H₂O)₅³⁺和Pu(H₂O)₅⁴⁺ 团簇溶剂化和非溶剂化效应中的几何结构及紫外可见吸收光谱. 计算结果表明: 水溶剂环境对Pu(H₂O)₅³⁺及Pu(H₂O)₅⁴⁺ 团簇的几何结构影响都比较明显. NBO电荷分析表明水分子与钚离子之间没有直接的电荷转移. 所研究团簇的未配对电子都占据5f轨道. 在气相及水溶剂环境下, 所研究团簇的紫外可见吸收光谱存在较大差距. 主要的吸收峰大都源于f电子之间的跃迁.     

Vegetation evolution on the central Chinese Loess Plateau since late Quaternary evidenced by elemental carbon isotopic composition

There are many controversial issues in loess studies such as natural vegetation types on the Chinese Loess Plateau during the historical periods and the spatial and temporal evolution of C3/C4 plants. Elemental carbon isotopic composition （δ^13Cec） in the loess section may offer new evidence for these problems. Elemental carbon （EC） is produced by incomplete combustion of vegetation, and its carbon isotopic composition has a very small difference from that of the formal vegetation, then δ^13Cec can be used as a record to recover the changes of vegetation. Elemental carbon was extracted by applying the oxidation method from the Ioess-paleosol sequence in the central Chinese Loess Plateau, and its car- bon isotope composition was analyzed by the isotope mass spectrometer. The results showed that the vegetation in this region was a mixed type of C3 and C4 plants, dominated with C3 plants in most of the time. Since late Quaternary, C3/C4 plants may not follow a simple glacial-interglacial cycle mode on the Chinese Loess Plateau, but showing fluctuations. C3 plants increased gradually in L4 period, and more C3 plants occurred during $3 period, and C4 plants increased again during L3-- L2 periods, after that, Cs plants dominated again during S1 --S0 periods. During periods of paleosol development, C3 plants were abundant in S3 and S1, and there were more Ca plants in S2 and SO. During periods of loess sedimen- tation, there were more C3 plants in L4 and L1, and there were more C4 plants in L3 and L2. On the orbital timescale, the vegetation variations revealed by δ^13Cec record are consistent with the results of pollen data and also similar to the results obtained by organic carbon isotopic composition since the last glacial period.     

Carbon isotopic composition,turnover and origins of soil CO<Subscript>2</Subscript> in a monsoon evergreen broadleaf forest in the Dinghushan Biosphere Reservoir,South China

Carbon isotopic compositions of soil CO2 in rainy season (July) from two natural soil profiles (DHLS & DHS) in the monsoon evergreen broadleaf forest in the Dinghushan Biosphere Reservoir (DBR), South China, are presented. Turnover and origins of soil CO₂ are preliminarily discussed in this paper. Results show that the content of soil CO2 varies between 6120 and 18718 ppmv, and increases with increasing depth until 75 cm, and then it declines. In DHLS, soil CO₂ δ¹³C ranges from −24.71‰ to −24.03‰, showing a significant inverse correlation (R²＝0.91) with the soil CO₂ content in the same layer. According to a model related to soil CO₂ δ¹³C, the soil CO₂ is mainly derived from the root respiration (>80%) in DHLS. While in DHS, where soil CO₂ ? 13C ranges from −25.19‰ to −22.82‰, soil CO₂ is primarily originated from the decomposition of organic matter (51%–94%), excluding the surface layer (20 cm, 90%). Radiocarbon data suggest that the carbon in soil CO₂ is modern carbon in both DHLS and DHS. Differences in ¹⁴C ages between the “oldest” and “youngest” soil CO₂ in DHLS and DHS are 8 months and 14 months, respectively, indicating that soil CO₂ in DHLS has a faster turnover rate than that in DHS. The ¹⁴C values of soil CO₂, which range between 100.0‰ and 107.2‰ and between 102.5‰ and 112.1‰ in DHLS and DHS, respectively, are obviously higher than those of current atmospheric CO₂ and SOC in the same layer, suggesting that soil CO₂ is likely an important reservoir for Bomb-¹⁴C in the atmosphere.     

非饱和煤矸石淋滤仪改进及应用

为提升非饱和煤矸石室内淋滤试验的可靠性与准确性,对传统非饱和煤矸石淋滤仪的降雨模拟系统进行改良,实现了随机降雨路径的模拟,并增大了煤矸石有效淋滤体积。同时,以韩城桑树坪煤矿煤矸石为研究对象,揭示了不同降雨强度和风化程度组合条件下煤矸石淋滤特征,试验结果是：(1)淋滤液电导率(EC)及SO4_^2-浓度(c)均随淋滤时间呈整体下降趋势,且可划分为快速下降和缓降趋稳两个阶段;(2)采用指数型函数、傅里叶函数及幂函数对不同试验条件下EC-t和c-t关系曲线进行拟合,拟合函数R_²介于0.87~1.00;(3)167mm/h降雨强度下,淋滤液电导率及SO_4^2-浓度对风化程度的敏感性指数最大,分别为3.14和7.64;(4)相较其它条件下淋滤液电导率及SO_4^2-浓度,83mm/h降雨强度和风化3a矸石条件下淋滤液EC值和c值更高。分析得到三点结论：(1)煤矸石可溶元素释放量主要呈指数型函数衰减,并在试验进行3~5h后趋于稳定;(2)风化程度为影响煤矸石可溶元素释放能力的主控因素;(3)较小的降雨强度和较高的风化程度有利于煤矸石元素持续淋滤释放。     

CaCl_2-NaCl熔盐中Fe~(3+)电化学行为的循环伏安分析

利用ZrO_2(Y_2O_3)固体电解质管集成构建Pt,O_2(air)|ZrO_2作为参比电极的电化学电池,采用循环伏安法在1273、1323、1373、1393K温度下对溶解0.5%Fe2O3的CaCl2-NaCl共晶熔盐中Fe~(3+)的电化学行为进行研究,分析了Fe~(3+)在Pt电极上的还原机理,并计算了电极反应交换电子数、Fe~(3+)扩散系数与Fe~(3+)扩散活化能等电化学参数。结果表明,在实验温度范围内,熔盐中Fe~(3+)在Pt电极上还原为Fe的反应是一步还原并受扩散控制的可逆过程;随着温度升高,Fe~(3+)扩散系数增大,Fe~(3+)扩散活化能为97.91kJ·mol-1。另外,本实验测得的Fe~(3+)扩散系数与文献值基本相符,因此,可以认为利用该电化学电池装置研究溶解有Fe2O3的CaCl2-NaCl溶盐的电化学行为是可行的。     

Investigation of the Ce-Mn conversion coating on 6063 aluminium alloy

In this paper, the sustainable Ce-Mn chemical conversion coating was fabricated on 6063 aluminium alloy by means of Ce(NO₃)₃ and KMnO4 as the inhibitors and NaF as the accelerator. The morphologies, composition and valence state of the coating were analyzed by scanning electron microscopy (SEM), energy dispersive spectrometry (EDS) and X-ray photoelectron spectroscopy (XPS), respectively. The results indicated that the Ce-Mn conversion coating was formed. The anticorrosion of the coating was evaluated in 3.5 wt.% NaCl aqueous solution at room temperature by using polarization curve and electrochemical impedance spectroscopy (EIS). It indicated that the treated surface presented better anticorrosion behavior in chloride media than on the original material surface. The corrosion resistance of Ce-Mn conversion coating was about equal to the trivalent chromium conversion coating.     

Preparation and luminescence characteristics of Sr3SiO5：Eu^2＋ phosphor for white LED

The Sr3SiO5：Eu^2＋ phosphor was synthesized by high temperature solid-state reaction. The emission spectrum of Sr3SiO5：Eu^2＋ shows two bands centered at 487 and 575 nm, which well agree with the theoretic values of emission spectrum. The excitation spectrum for 575 nm emission center has several excitation bands at 365, 418, 458 and 473 nm. And the results show that the emission spectrum of Sr3SiO5：Eu^2＋ is influenced by the Eu^2＋ concentration. The relative emission spectra of the white-emitting InGaN-based YAG：Ce^3＋ LED and Sr3SiO5：Eu^2＋ LED were investigated. The results show that the color development of InGaN-based Sr3SiO5：Eu^2＋ is better than that of InGaN-based YAG：Ce^3＋, and the CIE chromaticity of InGaN-based Sr3SiO5：Eu^2＋ is （x=0.348, y=0.326）.     

NaBH4还原改性TiO2(B)及光催化性能研究

以TiCl₄为原料,在（CH₂OH）₂溶液中通过一步水热法制备单斜相二氧化钛[TiO₂(B)]。使用不同质量含量NaBH₄对TiO₂(B)进行还原改性,调控其内含Ti³⁺的浓度,合成了含Ti³⁺的TiO₂(B)-NaBH₄X样品。采用X射线衍射仪（X-ray diffraction,XRD）、拉曼光谱仪（Raman spectroscopy）、紫外-可见漫反射光谱仪（UV-visible diffuse reflectance spectroscopy,UV-DRS）、X射线光电子能谱仪(X-ray photoelectron spectroscopy,XPS）对材料进行表征。改性后TiO₂(B)-NaBH₄X样品保持其原有晶体结构,并未发生相变,仅有结晶度的改变。原始TiO₂(B)禁带宽度为3.15 eV,通过改性,Ti³⁺的存在改变了禁带宽度,成功地将禁带宽度降低到2.82 eV,将吸光区域扩展到可见光区域。通过可见光光催化分解水制氢与可见光降解甲基橙试验,确立了TiO₂(B)-NaBH₄3样品有最好的可见光光催化活性,产氢速率达到0.58 μmol·h^-1·g^-1,6 h降解率达到40%。     

基于掺铕钨酸盐荧光强度比的非接触温度传感

为了突破传统测温技术应用的局限性,利用NaY （WO₄）₂：Eu³⁺玻璃陶瓷（glass ceramics,GC）实现了具有非接触、实时响应、自校准等优势的双模荧光强度比（luminescence intensity ratio,LIR）测温。采用高温熔融淬灭法制备出含NaY （WO₄）₂：Eu³⁺纳米晶的透明GC样品,并进行系列光谱测量和热敏性能分析。结果表明,样品中Eu³⁺的激发态能级⁵D₁和⁵D₀和基态能级⁷F₂和⁷F₀为两对独立的热耦合能级,可分别基于这两对热耦合能级实现性能优异的双模LIR温度传感。该双模LIR测温技术数据可靠、测温范围广、灵敏度高,再结合GC材料优势,是可用于光纤温度传感器的核心技术材料。