Effect of CO_2 on the structural variation of Na_2WO_4/Mn/SiO_2 catalyst for oxidative coupling of methane to ethylene

In this work,the influence of CO2 on the structural variation and catalytic performance of Na2WO4/Mn/Si O2 for oxidative coupling of methane to ethylene was investigated. The catalyst was prepared by impregnation method and characterized by XRD,Raman and XPS techniques. Appropriate amount of CO2 in the reactant gases enhanced the formation of surface tetrahedral Na2WO4 species and promoted the migration of O in MOx,Na,W from the catalyst bulk to surface,which were favorable for oxidative coupling of methane. When the molar ratio of CH4/O2/CO2 was 3/1/2,enriched surface tetrahedral Na2WO4 species and high surface concentration of O in MOx,Na,W were detected,and then high CH4 conversion of 33.1% and high C2H4 selectivity of 56.2% were obtained. With further increase of CO2 in the reagent gases,the content of active surface tetrahedral Na2WO4 species and surface concentration of O in MOx,Na,W decreased,while that of inactive species(Mn WO4 and Mn2O3) increased dramatically,leading to low CH4 conversion and low C2H4 selectivity. It could be speculated that Na2WO4 crystal was transformed into Mn WO4 crystal with excessive CO2 added under the reaction conditions. Pretreatment of Na2WO4/Mn/Si O2 catalyst by moderate amount of CO2 before OCM also promoted the formation of Na2WO4 species.     

Antimony(III)-doped PbWO4 crystals with enhanced photoluminescence via a shape-controlled sonochemical route

Sb(III)-doped lead tungstate single crystals with controlled shapes and enhanced green emission have been synthesized via a facile, Pluronic P123 (EO(20)PO(70)EO(20))-assisted, sonochemical method. The surfactant Pluronic P123 was found to play a crucial role in the morphology control of the final products. The growth process was investigated by carefully following time-dependent experiments, and the oriented attachment process accompanying Ostwald ripening was proposed for the possible formation mechanism. The optical properties, such as the Raman spectra and PL spectra, of doped PbWO(4) were studied. Room-temperature photoluminescence of doped PbWO(4) samples with different morphologies at desired Sb doping concentrations showed greatly enhanced luminescence intensity compared to the undoped PbWO(4).     

聚天冬氨酸与钨酸钠复配对白铜B10的缓蚀作用

应用光电化学的方法研究了两种环境友好型缓蚀剂聚冬天氨酸(PASP)和钨酸钠(Na2WO4)的单一配方及其复配对白铜B10在硼砂-硼酸缓冲溶液中的缓蚀作用援研究表明, 在光电流循环伏安测试中, 单一的PASP与Na2WO4均能够使B10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B10的腐蚀速率减小. 单一的PASP与Na2WO4的最佳添加浓度分别为3和5 mg·L-1, 单一的Na2WO4比单一的PASP使p型光电流响应增大趋势更大. 若以总浓度为5 mg·L-1时对两者进行复配, 当PASP与Na2WO4的质量浓度比为1:1和1:3时, 两者复配比单一使用时的p型电流光响应都更大, B10的腐蚀更小, 即缓蚀剂的效果更好. 交流阻抗测试结果与光电化学测试相一致.     

对甲烷氧化偶联W－Mn／SiO＿2催化剂Na＿2WO＿4的流失及其影响的考察

用ＸＲＤ、ＦＴ－ＩＲ、ＥＳＲ、Ｈ２－ＴＰＲ和ＴＰＯ等方法，对Ｎａ２ＷＯ４－Ｍｎ２Ｏ３／ＳｉＯ２催化剂和其经水煮处理的一系列样品进行了表征．实验发现该催化剂中的结晶态Ｎａ２ＷＯ４易于流失，单层分布的Ｎａ２ＷＯ４在苛刻的处理条件下也有可能流失．依此，探讨了上述流失现象与Ｎａ２ＷＯ４－Ｍｎ２Ｏ３／ＳｉＯ２催化剂的催化活性及该催化剂在长时间反应中发生的ＳｉＯ２相变之间的关系，证明了结晶态Ｎａ２ＷＯ４的流失对该催化剂甲烷氧化偶联反应的催化活性只有轻微的影响，单层分布Ｎａ２ＷＯ４的流失可造成催化剂中Ｍｎ从Ｍｎ３＋转变为Ｍｎ２＋，并使催化剂的催化活性明显降低．但在水煮条件下，无论是结晶态的还是单层分布，Ｎａ２ＷＯ４的流失都没有对ＳｉＯ２的α－方石英结构产生影响     

正极添加Na2WO4对镍氢电池高温性能的影响

研究了添加不同比例的Na2WO4对镍正极高温性能的影响, 结果表明, Na2WO4可提高镍氢电池的高温充电效率. 70 ℃条件下, 添加1.0%(w)的Na2WO4时镍正极的充电效率达到85%以上. 此外, Na2WO4的加入也可提高镍氢电池的放电容量、循环寿命和荷电保持率. 研究表明: Na2WO4可以促进镍正极高温下充电正反应的进行, 提高析氧过电位.     

甲烷氧化偶联Mn_2O_3-Na_2WO_4/SiO_2催化剂——Ⅱ.表面氧种和结构

本文用XPS详细考察了Mn_2O_3-Na_2WO_4/SiO-2催化剂的表面氧种,提出了该催化剂表面活性相在SiO_2表面分散的一种可能的表面结构模型。 实验部分详见另文,这里需要指出。所有催化剂样品在XPS分析前,均经在能谱仪预处理室(～10~(-3)Pa)和超高真空测试室(基础真空6.7×10~(-8)Pa)递次的450C和700C原位加热处理,以使在大气中吸附的水分和气体脱附。各元素的特征谱峰由联机计算机以多道模式同时录取(通能50eV),并累加1 h以获取高信噪比数据。Ols峰的解迭用联机计算机以高斯函数拟合,为考察该解迭结果的可靠性,曾对1.9wt％Mn_2O_3-5wt％Na_2WO_4/SiO_2催化利的     

W掺杂SiO2介孔材料的制备与表征

以非离子表面活性剂三嵌段共聚物P123为模板剂、正硅酸乙酯(TEOS)为硅源、钨酸钠(Na2WO4·2H2O)为钨源, 通过水热法一步合成了W掺杂的二氧化硅介孔材料W-SiO2, 并通过XRD、HRTEM、EDX、FT-IR、N2吸附-脱附等表征手段, 考察了随着W含量增加, W-SiO2介孔材料结构的变化规律以及钨物种在材料中的存在状态. 结果表明, 当WO3含量w(WO3)约为10%时, W-SiO2中的钨物种是高度分散进入介孔骨架,形成W-O-Si 键; 当w(WO3)=20%时, 样品中开始有未掺入到SiO2骨架中WO3的结晶出现; 当w(WO3)约60%时, W-SiO2 样品能保持很好的介孔孔道结构, 更高含量WO3掺入将破坏二氧化硅介孔结构.     

3-氨基-1,2,4-三氮唑和Na_2WO_4复合缓蚀剂对黄铜的缓蚀协同作用

应用交流阻抗和极化曲线测试3-氨基-1,2,4-三氮唑(ATA)和钨酸钠复合缓蚀剂对黄铜在3%NaCl溶液中的缓蚀作用.结果表明,ATA对黄铜有缓蚀作用,并以7.5 mg.L-1ATA的缓蚀效果最好,缓蚀率为87.46%,以7.5 mg.L-1ATA和0.15 mg.L-1Na2WO4配成复合缓蚀剂则对黄铜具有很好缓蚀协同效应,缓蚀效率达91.82%,属阴极型缓蚀剂.     

Oxidative coupling of methane over （Na2WO4＋Mn or Ce）/SiO2 catalysts： In situ measurement of electrical conductivity

The effects of manganese oxide or ceria promoters on the performance of Na2WO4/SiO2 catalysts for oxidative coupling of methane (OCM) are reported. The OCM reaction was performed in a continuous-flow microreactor at 800 ℃, atmospheric pressure and under GHSV = 13200 ml gC-1at h-1. Catalysts were characterized by in situ conductivity measurement, FT-IR spectroscopy, XRD, SEM and temperature programmed reduction analysis. Manganese oxide promoted Na2WO4/SiO2 is considered as one of the active and selective ca...     

Effect of alkali-metal ions on the local structure and luminescence for double tungstate compounds AEu(WO4)2 (A = Li, Na, K)

The effect of alkali-metal ions on the local structure and luminescence properties for alkali-metal europium double tungstate compounds AEu(WO(4))(2) (A = Li, Na, K) has been investigated by a dual-space structural technique, atomic pair distribution function (PDF) analysis, and the Rietveld method of powder X-ray diffraction. The compounds AEu(WO(4))(2) (A = Li, Na) crystallize in the isostructure with the tetragonal space group I41/a (No. 88) and show the same luminescence properties in spite of the different doped alkali metals. However, KEu(WO(4))(2) crystallizes in monoclinic symmetry with the space group C2/c (No. 15). Compared with the two other counterparts, KEu(WO(4))(2) exhibits a more effective charge-transfer excitation, a larger Stokes shift, and a broader 612 nm emission band. This phenomenon is ascribed to the lower crystal symmetry in KEu(WO(4))(2), which influences bond distances and the coordination number of Eu(3+). Two complementary methods, the Rietveld method and PDF analysis, reveal that both LiEu(WO(4))(2) and NaEu(WO(4))(2) afford the same local surroundings of Eu(3+). The local structure determined by the Rietveld and PDF methods well account for the observed luminescent properties.     

电感耦合等离子体质谱(ICP-MS)法测定高钨基体样品中稀土元素的含量

准确测定钨矿和钨酸盐晶体等高钨基体样品中稀土元素的含量有助于开展矿床地球化学特征研究及钨酸盐激光晶体材料的制备和性质研究。在高钨基体样品电感耦合等离子体质谱法（ICP-MS）分析时,为了考察高钨及高含量阳离子等基体组成对分析结果的影响,实验针对Na2WO4、CaWO4、NaY(WO4)2、MnWO4和(Fe,Mn)WO4等高钨基体样品,采用硝酸和氢氟酸高压密闭消解,加入稀土元素并用2% HNO3溶液稀释定容配制成稀土元素浓度为1 ng·g-1的基体匹配标准溶液;同时,直接用2% HNO3溶液配制稀土元素浓度相同的非基体匹配标准溶液以对比系统考察两种基体溶液中稀土元素的相对灵敏度系数（RSC）差异。结果显示,基体匹配溶液与2% HNO3溶液中稀土元素的RSC相对偏差基本小于15%,表明基体效应的影响可以忽略不计。进而,为了准确测定常见高钨基体样品中稀土元素的含量,实验建立了基于ICP-MS的高钨基体样品中稀土元素准确定量分析方法,该方法线性关系好（R2 ? 0.9997）,检出限低（0.5 ~ 27.9 pg·g-1）,准确度理想（相对误差-6.25 ~ 10.74%）。采用该方法测定了钨酸钙单晶实际样品中稀土元素的含量并将其与基体匹配法的测定结果进行比对,结果显示两者相对偏差为0.80 ~ 12.75%,说明本文所建立的分析方法可靠,能用于定量测定高钨基体样品中稀土元素的含量。     

棒状结构Pt/PbWO4微米晶的合成、表征及其高光催化性能

PbWO4是一类重要的半导体,广泛运用于高能物理领域无机闪烁晶体.它具有许多独特的物理性能,如衰减时间短(10 ns)、能量密度高(8.28 cm3)、低光产率(300 photons/MeV)、短辐射长度(0.9 cm)和高抗辐照损伤等. PbWO4纳米晶体的激子荧光、热荧光和其它光学性能主要取决PbWO4晶体的形貌和微观结构.目前已经合成了不同结构的PbWO4纳米/微米晶体,如四角双锥微米晶、微米球、纳米棒、纳米纺垂体等.近年来, PbWO4的光催化性能也引起人们的重视.研究发现, PbWO4晶体的光催化性能和其形貌、微观结构密切相关.如在不同形貌的十四面体、三维多尺度微米球和纳米颗粒中, PbWO4微米球表现了极高的光催化活性.此外, PbWO4微米球由于密度大,非常容易分离,从而有利于其回收利用,在循环使用时具有很高的稳定性.因此,合成具有特殊形貌的PbWO4纳米/微米晶体具有重要的理论和现实意义.此外,合成贵金属/半导体复合纳米结构是提高光催化性能的另一有效策略.在贵金属/半导体复合纳米结构中,光生电子(e–)和(h+)的复合可以在很大程度上得到抑制,因为光生e–可以快速地迁移至贵金属颗粒中心,从而加速e–和h+的分离.本文利用水热结合焙烧法首先合成了长度大于1μm的棒状PbWO4微米晶.然后利用光化学沉积法,在PbWO4微米晶表面沉积不同含量(0.5 wt%,1 wt%,和2 wt%)的Pt纳米粒子.利用X射线衍射(XRD)、N2物理吸附、扫描电镜(SEM)、透射电镜(TEM)、光电子能谱(XPS)、光致发光谱(PL)和紫外-可见漫反射吸收光谱(UV-Vis DRS)等手段对所制PbWO4和Pt/PbWO4进行了表征.表征结果表明,合成的PbWO4和Pt/PbWO4的比表面积很小(1.5–1.9 m2/g),沉积的Pt纳米粒子为金属态. UV-Vis DRS测试表明,沉积的Pt纳米粒子在光照下可以产生表面等离子共振,促进可见光的吸收.另外, PL的结果则证实Pt纳米粒子的存在还可抑制PbWO4晶体在光照下产生的光生e–和h+的分离.而XRD和高分辨TEM分析表明PbWO4微米棒的晶体生长方向为(–102)晶体方向.电子选区衍射表明,棒状PbWO4微米晶具有极高的结晶度.以氙灯为光源进行了光催化降解染料酸性橙II的光催化性能测试.结果表明,当沉积1–2 wt%Pt纳米粒子时,可使光催化活性提高2倍左右.另外, Pt/PbWO4微米棒的密度较大,非常容易进行离心分离催化剂及其循环使用.在第一次使用时酸性橙II的降解率为93%,而在第四次使用时酸性橙II的降解率仍维持在88%,表现出很好的光催化稳定性. Pt/PbWO4具有很高的光催化活性的原因,一方面是由于其具有很高的结晶度和独特的棒状结构,另一方面是由于沉积的Pt纳米粒子在光照下可以产生表面等离子共振,促进了可见光的吸收和光生e–与h+的分离.     

4，5-环氧-α-紫罗兰酮的合成研究

研究以H2O2为氧化剂,钨酸钠／磷酸／十六烷基氯化毗啶原位合成的过氧钨配合物催化α-紫罗兰酮合成4,5-环氧-α-紫罗兰酮的反应,考察了催化剂用量、反应温度、反应时间、pH值、溶剂及季铵盐等因素对反应的影响。结果表明,以1,2-二氯乙烷作溶剂,nα-紫罗兰酮：n钨酸钠：n磷酸：n十六烷基氯化吡啶：n过氧化氢=100：0.3：0．1：0．2：120,pH值为4．0,65℃的条件下反应6h,收率可达85％,其结构通过MS、^1H-NMR、IR、EA等检测技术进行表征。     

不同种类羧酸钠对草酸钙结晶过程中晶相的影响

采用X射线衍射法研究了水溶液中不同种类羧酸钠对尿结石主要成份草酸钙结晶的影响，这些羧酸钠分别为含有一、二、三和四个羧基的羟基乙酸钠（NaGly）、酒石酸钠（Na2Tart）、柠檬酸钠（Na3Cit）和EDTA二钠盐（Na2EDTA）.结果表明，随着羧酸钠浓度的增加，草酸钙的晶相均发生规律性的变化：从最稳定的一水草酸钙（COM），到不稳定的二水草酸钙（COD），最后转化为次稳定的三水草酸钙（COT）.不同结构羧酸钠抑制COM生长、促进COD生成的顺序为:Na3Cit >Na2Tart >Na2EDTA >NaGly.该结果将为临床上选择防结石药物提供新的思路.     

沙苑子提取液对不同体系中草酸钙晶体生长影响的研究

通过与水、氯化钠、正常人尿液体系的比较,重点研究了结石患者尿液体系中加入中药沙苑子提取液对草酸钙晶体生长的的影响,利用SEM,FTIR和XRD等测试手段对所得晶体进行表征。结果发现:在结石患者尿液体系中形成的草酸钙晶体为一水草酸钙(COM)晶体,而在这4种体系中加入沙苑子提取液后,只形成二水草酸钙(COD)晶体,表明沙苑子提取液能抑制COM晶体生长,并且随着沙苑子提取液浓度增大,抑制作用增强。沙苑子抑制草酸钙晶体生长的可能机理进行了探讨。     

不同晶型WO3·0.33H2O的结构及性能

以Na2WO4.2H2O为主要原料,采用液相法(80℃)和离子交换-水热法(150℃)分别制备了六方WO3.0.33H2O和以正交相为主的混合晶型WO3.0.33H2O。通过对2种晶型WO3.0.33H2O材料进行X射线衍射(XRD)、场发射电子扫描显微镜(FE-SEM)、红外光谱(FTIR)、X射线光电子能谱(XPS)和循环伏安测试,表征了产物的晶相和结构等。正交WO.30.33H2O结构中由于相邻钨氧八面体层的相互位移而形成空隙,六方WO3.0.33H2O结构中没有位移则形成孔道;正交WO3.0.33H2O具有比六方WO3.0.33H2O更短键长的W=O和更负的导带位置。紫外-可见透射光谱研究表明,六方WO.30.33H2O具有更明显的电致变色效应,可能是因为结构中的孔道使H+易扩散使六方WO.30.33H2O更易发生氧化还原反应。光催化性能研究表明,正交WO3.0.33H2O具有更负的导带位置,价带电子跃迁后易于向电子受体转移,抑制了电子和空穴的复合,使得混合晶型WO3.0.33H2O的紫外光光催化能力相对六方WO.30.33H2O更强。     

纳米WO3粉体的制备与光催化活性研究

报道了以钨酸钠和盐酸为主要原料,通过气液反应制备纳米WO3粉体光催化剂的新方法．在XPS,XRD,TEM等手段对催化剂进行了表征的基础上,又讨论了焙烧温度和乙醇加入量对催化剂粒度大小以及光催化活性的影响．同时对纳米WO3粉体催化剂的光催化重整乙醇制氢反应活性进行了研究,观察了产氢效率和光电化学行为．研究结果表明,气液反应法是一种简单有效的制备纳米WO3粉体催化剂的方法,并显示出较好的光催化活性;该方法所得的三氧化钨粉末粒子平均直径在100nm以下;钨酸钠溶液中乙醇加入量对三氧化钨粉末粒子的尺寸和分散性都有影响,随着乙醇量的增加,粒子尺寸减小,且分散性较好．焙烧温度引起的WO3粒子晶体结构的变化会导致光氧化还原电位变化,是引起光催化活性差异的主要原因．     

Raman spectroscopy as a means for the identification of plattnerite (PbO2), of lead pigments and of their degradation products

The Raman spectra of plattnerite [lead(IV) oxide, PbO2] and of the lead pigments red lead (Pb3O4), lead monoxide [PbO, litharge (tetragonal) and massicot (orthorhombic)], lead white [basic lead carbonate, 2PbCO3.Pb(OH)2] and of their laser-induced degradation products were recorded using a range of different excitation lines, spectrometer systems and experimental conditions. The degradation of PbO2 is more extensive along the pathway PbO2-->Pb3O4-->PbO (litharge)-->PbO (massicot) the shorter the wavelength of the excitation line and the higher its power. The Raman spectrum of PbO2, which is black and of the rutile structure, is particularly difficult to obtain but three bands, at 653, 515 and 424 cm-1, were identified as arising from the b2g, a1g and e(g) modes respectively, by analogy with the corresponding modes of isostructural SnO2 (776, 634 and 475 cm-1). A further oxide was identified, PbO1.55, the Raman spectrum of which does not correspond to that of any of the laser-induced degradation products of PbO2 at any of the wavelengths used. The Raman results are critical to the future use of Raman microscopy for the identification of lead pigments on artworks.     

Hollow PbWO4 nanospindles via a facile sonochemical route

Novel nanosized lead tungstate (PbWO4) hollow spindles were successfully synthesized, for the first time, via a Pluronic P123- (EO20PO70EO20-) assisted sonochemical process. The triblock copolymer acted as a structure-directing agent and played a key role in the formation of the hollow spindles. An in situ micelle templating mechanism has been proposed for the possible formation mechanism of the hollow nanostructure. The optical properties of the final products were investigated. It is exciting that the as-prepared PbWO4 hollow structure shows extraordinarily high room-temperature photoluminescence intensity compared to the solid structures.     

Nd3+:NaLa(WO4)2晶体的生长和光学性质

Nd3+:NaLa(WO4)2 crystals with a dimension up to 7 mm were grown from a high temperature solution using a double-crucible method. Scanning electron microscopy observations of the crystals showed that there were no small cracks on the surface of the crystals although they underwent two phase transitions when cooling down from high temperatures. X-ray diffraction studies indicated that the as-obtained product is pure low- temperature tetragonal Nd3+:NaLa(WO4)2. The absorption and fluorescence spectra for Nd3+:NaLa(WO4)2 were measured at room temperature. The absorption band at 804 nm has a wide full-width half maximum of 23 nm whose origin is discussed. The absorption and emission cross sections were calculated to be 7.24*10-20 cm2 at 804 nm and 6.54*10-20 cm2 at 1057 nm, respectively.