Studies on Upconversion Mechanism of ZrO2∶Er3+,Yb3+ Nanocrystals Under Excitation at 488 and 980 nm

Erbium, Ytterbium-codoped ZrO2 nanoparticles(ZrO2∶Er3 ,Yb3 ) were prepared by the sol-emulsion-gel technique. The purpose of the present study is the application of upconversion phosphor in the biological label. In order to make out the mechanism of upconversion under 980 nm excitation the 488 nm pump was used. The influence of temperature on the crystallite phase was studied. The results confirm the upconverted mechanism in ZrO2∶Er3 ,Yb3 nanocrystals is due to an energy transfer upconversion(ETU).     

ZnWO4:Er3+,Yb3+纳米棒的制备及发光性能

采用水热法以聚乙二醇为分散剂合成了Er3+,Yb3+共掺的ZnWO4纳米棒.X射线衍射、透射电子显微镜分析结果表明:所得产物为直径约20 nm的ZnWO4纳米棒.在激发波长为980 nm的半导体激光器做光源激发下,确定样品的3个发射峰的发光中心位于532、553和656 nm,分别对应于铒离子2H11/2→4I15/2,4S3/2→4I15/2和4F9/2→4I15/2的跃迁.     

Facile and mass production synthesis of β-NaYF4:Yb3+, Er3+/Tm3+ 1D microstructures with multicolor up-conversion luminescence

Well defined, pure hexagonal-phased NaYF(4):Yb(3+),Er(3+)/Tm(3+) microtubes and microrods were first prepared by a facile and mass production molten salt method without using any surfactant, which offers a new alternative in synthesizing such materials and opens the possibility to meet the increasing commercial demand.     

NaYF4:Yb3+/Er3+单颗粒微米棒偏振上转换发光及其取向示踪※

稀土掺杂微/纳材料的偏振上转换发光在单颗粒示踪和生物医学等领域具有广泛的应用前景. 稀土离子的偏振上转换发光主要取决于其局域态的电子结构和激发态动力学. 利用单颗粒偏振上转换光学测试平台对β-NaYF₄:Yb³⁺/ Er³⁺微米棒的偏振上转换发光进行了系统研究. 随发射偏振角的变化, 单个微米棒的上转换发光强度发生周期性改变, 且来自Er³⁺同一光谱支项的不同晶体场子能级跃迁的偏振方向不同. 与光谱支项整体的上转换发光相比, 其晶体场子能级上转换发光表现出更大的发射偏振度. 利用Er³⁺高度偏振的晶体场跃迁谱线, 实现了对单个微米棒空间取向的动态分析, 揭示了NaYF₄:Yb³⁺/Er³⁺微米棒作为偏振各向异性的上转换荧光探针在单颗粒取向示踪方面的潜在应用.     

Metal complexes with Alizarin complexone—I: Physiocochemical characters and stability constants of the Sc3+, Y3+, La3+, Ce3+, Gd3+ and Yb3+ complexes

Complexes of Alizarin complexone with Sc³⁺, Y³⁺, La³⁺, Gd³⁺, Ce²⁺ and Yb³⁺ have been synthesized and characterized by, pH titrations, conductance measurements, UV, visible and IR spectral studies.     

Er3+, Yb3+:Y2O3激光陶瓷粉体制备与性能研究

以Y2O3,Yb2O3和Er2O3为原料,控制溶液的pH值为3-4左右,采用柠檬酸溶胶-凝胶法制备出Er,Yb∶Y2O3倍半氧化物激光陶瓷前驱粉体。对所得到的粉体进行XRD测试,结果表明最佳煅烧温度为1000℃,并且晶化完全。经过差热-热重分析表明,粉体在1000℃煅烧后不再失重。荧光光谱分析发现,荧光发射的最强峰位于1530 nm处,是Er^3＋的4^I13/2-4^I15/2谱相导致的荧光发射。     

双掺Er3+,Yb3+离子KY(WO4)2晶体的光谱性质

研究分析了用助熔剂法生长的Er^3 /Yb^3 :KY(WO4)2晶体在室温下的吸收光谱和发射光谱，在吸收谱的350－1750nm区域，除了900－1050nm的谱带是Er^3 ,Yb^3 的共同谱带，其他的都属于Er^3 的谱带，用266nm激发时产生540－560，660－680，850－870，1450－1600nm四个发射带，用976nm激发时产生的主要是Er^3 的1450－1600nm发射带，这两 的能量转移机制不相同。     

Monitoring the Discontinuous Dodecamer–Icosamer Transition of a Calix[4]arene-Derived Surfactant by Time-Resolved Small-Angle X-ray Scattering

Calix[4]arene-derived surfactants form monodisperse micelles with a well-defined aggregation number (N_agg) of 4, 6, 8, 12, or 20, corresponding to the Platonic solids. This feature is in strong contrast to conventional micelles. In this study, a transition from a dodecamer (N_agg=12) to an icosamer (N_agg=20) was induced by a rapid increase in the NaCl concentration (C_NaCl) using a stopped-flow device and directly observed by time-resolved small-angle X-ray scattering. The N_agg remained unchanged during the first 60 s after the increase in C_NaCl , and then abruptly increased to 20. This feature resembles phase transitions in supersaturated or supercooled states, or highly cooperative phenomena. We surmise that this finding may be due to the fact that only a few N_agg values are thermodynamically allowed when N_agg is sufficiently small. This is the first observation of such an induction time in micellar aggregation.     

Re-dispersion and film formation of GdVO4 : Ln3+ (Ln3+ = Dy3+, Eu3+, Sm3+, Tm3+) nanoparticles: particle size and luminescence studies

GdVO(4)?:?Ln(3+) (Ln(3+) = Dy(3+), Eu(3+), Sm(3+), Tm(3+)) nanoparticles are prepared by a simple chemical route at 140 °C. The crystallite size can be tuned by varying the pH of the reaction medium. Interestingly, the crystallite size is found to increase significantly when pH increases from 6 to 12. This is related to slower nucleation of the GdVO(4) formation with increase of VO(4)(3-) present in solution. The luminescence study shows an efficient energy transfer from vanadate absorption of GdVO(4) to Ln(3+) and thereby enhanced emissions are obtained. A possible reaction mechanism at different pH values is suggested in this study. As-prepared samples are well dispersed in ethanol, methanol and water, and can be incorporated into polymer films. Luminescence and its decay lifetime studies confirm the decrease in non-radiative transition probability with the increase of heat treatment temperature. Re-dispersed particles will be useful in potential applications of life science and the film will be useful in display devices.     

Does Thermochemical Mimicry Extend to Gibbs Energies? The Differences of K+ and NH4 +, and of Na+ and H3O+

Structural Chemistry -     

Yb3+,Er3+掺杂的NaGd(MoO4)2纳米晶的制备及发光性能

采用水热合成技术成功制备了一种新型的上转换发光纳米晶体NaGd(MoO4)2:Yb3+,Er3+.采用X射线粉末衍射分析、透射电镜和光谱分析对不同条件下所得样品的结构和发光性能进行了表征.NaGd(MoO4)2:Yb3+,Er3+和NaGd(MoO4)2具有相同的晶体结构,属于四方晶系;透射电镜观察表明,所得晶体为直径约为20 nm的纳米棒;在980 nm红外激光器的激发下,观察到了3个明显的上转换发射峰,发光中心分别位于531,552和656 nm,分别对应于Er3+2H11/2→I15/2,4S3/2→I15/2和4F9/2→4I15/2的跃迁.     

SiO2包覆Gd2O3:Er3+,Yb3+纳米粉的制备、结构及发光性能

用微乳液法合成出SiO2包覆的Yb3+,Er3+离子舣掺杂的Gd2O3粉体,X射线衍射结果表明所制备粉体为立方Gd2O3结构.透射电镜照片显示其颗粒形状近似为球形,粒径为10～40 nm;该粉体在波长为980 nm的半导体激光器激发下发射出中心波长为562 nm的绿色和660 m的红色上转换荧光,分别对应于Er3+离子的4S3/2/2H11/2→4I15/2跃迁和4F9/2→4I15/2跃迁.发光强度和激发功率关系的研究揭示其均为双光子过程,能量传递和激发态吸收是上转换发光的主要机制.由于其具有高效的上转换发光性能,而经过纳米复合后制成的纳米Gd2O3(核)/SiO2(壳),容易溶于水并易于和有机物结合,能与生物分子结合.     

Temperature-induced Evolution of Micro-structure and Chain Dynamics in Thermoplastic Polyurethane with Low Hard Segment Content as Studied by In Situ Synchrotron SAXS and Time-Domain NMR Experiments

The microstructural evolution of a thermoplastic polyurethane(TPU) with low hard segment content has been monitored utilizing in situ real-time synchrotron small angle X-ray scattering(SAXS) and time-domain nuclear magnetic resonance(NMR) measurements. The TPU is composed of 23 wt% of [4,4-methylenediphenyl diisocyanate(MDI)]-[1,4-butanediol(BD)] chain segments, which form hard domains, as[polytetrahydrofuran(PTHF)] forming soft domains. The number and distribution of monomer units in hard block...     

Characterization of TcCl4 and β-TcCl3 by X-ray absorption fine structure spectroscopy

Technetium tetrachloride and β-TcCl₃, synthesized from the reaction of Tc metal and Cl_2(g) in sealed tubes, were characterized by X-ray absorption fine structure spectroscopy. Extended X-ray absorption fine structure (EXAFS) spectroscopy measurements are in good agreement with the X-ray diffraction structures of the two compounds. For TcCl₄, the absorbing Tc atom is surrounded by Cl atoms at 2.34(2) Å and Tc atoms at 3.66(4) Å. For β-TcCl₃, the absorbing Tc atom is surrounded by Cl atoms at 2.40(2) Å and Tc atoms at 2.81(3), 3.66(4) and 5.71(6) Å. EXAFS spectroscopy indicates that the TcCl₄ and β-TcCl₃ samples obtained by sealed tube reactions are single phase. The X-ray absorption near edge structure spectra of TcCl₄ and β-TcCl₃ were recorded; the positions of the Tc K-edges of β-TcCl₃ (21,050.5 eV) and TcCl₄ (21,053.0 eV) are compared to the ones measured for α-TcCl₃ (21,051.0 eV) and TcCl₂ (21,048.8 eV). A correlation between the positions of the Tc K-edges and the oxidation state of the Tc atom in technetium binary chlorides was determined.     

A general approach for selective enhancement of green upconversion emissions in Er3+ doped oxides by Yb3+–MoO4 2− dimer sensitizing

In this paper, we report a general approach to enhance the upconversion (UC) luminescence of Er³⁺ doped oxides phosphors by Yb³⁺–MoO₄ ^2? dimer sensitizing, which induced strong green UC emissions under the 976 nm laser diode excitation. By codoping of Yb³⁺ and Mo⁶⁺ in the Er³⁺ doped TiO₂ and ZnO, the green UC emissions intensity can be selectively increased about 10 and 500 times than those of Er³⁺–Yb³⁺ codoped TiO₂ and ZnO, respectively. The high excited state energy transfer between |²F_7/2, ³T₂> state of Yb³⁺–MoO₄ ^2? dimer and ⁴F_7/2 level of Er³⁺ significantly avoids the nonradiative decay processes happened at lower energy levels of Er³⁺, and then increases the green UC emissions efficiently. The proposed Yb³⁺–MoO₄ ^2? dimer sensitizing has been realized as an efficient way to enhance the green UC emissions in other Er³⁺ doped oxides phosphors. It is expected that the selective enhanced green UC emissions sensitized by Yb³⁺–MoO₄ ^2? dimer in Er³⁺ doped oxides phosphors can greatly extend their scope of applications.     

Synthesis of 1,2:4,5-di-O-Isopropylidene-3-C-Cyano-β-D-ribo-hex-2-ulo Pyranose by Phase Transition Catalysis

Introduction The cyano branched carbohydrates are useful, versatil intermediaries for the synthesis of branched sugars having biological activity in nature. Owing to the good yield, mild reaction conditions and high stereospecificity, the phase transition catalysis(PTC)method has been widely used to the syntheses of C-     

Voltage- and Power-Conversion Performance of Bi-functional ZrO2 : Er3+/ Yb3+ Assisted and Co-sensitized Dye Sensitized Solar Cells for Internet of Things Applications

Giant power conversion efficiency is achieved by using bifunction ZrO₂ : Er³⁺/Yb³⁺assisted co-sensitised dye-sensitized solar cells. The evolution of the crystalline structure and its microstructure are examined by X-ray diffraction, scanning electron microscopy studies. The bi-functional behaviour of ZrO₂ : Er³⁺/Yb³⁺ as upconversion, light scattering is confirmed by emission and diffused reflectance studies. The bi-function ZrO₂ : Er³⁺/Yb³⁺ (pH=3) assisted photoanode is co-sensitized by use of N719 dye, squaraine SPSQ2 dye and is sandwiched with Platinum based counter electrode. The fabricated DSSC exhibited a giant power conversion efficiency of 12.35 % with V_OC of 0.71 V, J_SC of 27.06 mA/cm², FF of 0.63. The results, which motivated the development of a small DSSC module, gave 6.21 % and is used to drive a tiny electronic motor in indoor and outdoor lighting conditions. Small-area DSSCs connected in series have found that a V_OC of 4.52 V is sufficient to power up Internet of Things (IoT) devices.     

Global Reaction Pathways in the Photodissociation of I3− Ions in Solution at 267 and 400 nm Studied by Picosecond X-ray Liquidography

The mechanism of a photochemical reaction involves the formation and dissociation of various short-lived species on ultrafast timescales and therefore its characterization requires detailed structural information on the transient species. By making use of a structurally sensitive X-ray probe, time-resolved X-ray liquidography (TRXL) can directly elucidate the structures of reacting molecules in the solution phase and thus determine the comprehensive reaction mechanism with high accuracy. In this work, by performing TRXL measurements at two different wavelengths (400 and 267 nm), the reaction mechanism of I₃⁻ photolysis, which changes subtly depending on the excitation wavelength, is elucidated. Upon 400 nm photoexcitation, the I₃⁻ ion dissociates into I₂⁻ and I. By contrast, upon 267 nm photoexcitation, the I₃⁻ ion undergoes both two-body dissociation (I₂⁻+I) and three-body dissociation (I⁻+2I) with 7:3 molar ratio. At both excitation wavelengths, all the transient species ultimately disappear in 80 ns by recombining to form the I₃⁻ ion nongeminately. In addition to the reaction dynamics of solute species, the results reveal the transient structure of the solute/solvent cage and the changes in solvent density and temperature as a function of time.     

Luminescent core–shell Fe3O4@Gd2O3:Er3+, Li+ composite particles with enhanced optical properties

Bifunctional magneto-optical nanocomposites with Fe₃O₄ nanoparticles as a core and erbium and lithium codoped gadolinium (Gd₂O₃:Er³⁺, Li⁺) as the shell were synthesized successfully using a simple urea homogeneous precipitation method. The fabricated Fe₃O₄@Gd₂O₃:Er³⁺, Li⁺ particles were characterized by X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, photoluminescence spectroscopy and quantum design vibrating sample magnetometry. The upconversion emission intensity was enhanced significantly comparing to that without Li⁺ ions. These bifunctional composites are expected to be potentially applied for drug delivery, cell separation and bioimaging.