一种新型铒镱共掺碲硅酸盐玻璃的光谱性质及荧光俘获效应研究

用高温熔制法制备了系列Er^3＋／Yb^3＋共掺碲硅酸盐玻璃样品，测试和分析了玻璃样品的吸收光谱、荧光光谱、上转换发光光谱及热稳定性。结果表明：这种玻璃具有较宽的荧光半高宽、较大的受激发射截面，较好的热稳定性。970nm泵浦下该系列玻璃在可见光525，546和658nm这3处存在明显的上转换现象，它们分别由Er^3＋离子^2H11/2→^4 I15/2，4S3/2→^4 I15/2和^4 F9/2→^4 I15/2辐射跃迁产生。另外，测试和讨论了在不同样品厚度下玻璃的光谱特性，如荧光光谱、荧光寿命和上转换发光光谱等。结果表明，荧光俘获效应对Er^3＋离子1．5μm波段荧光及上转换发光都有着较大的影响，并随着玻璃厚度的增加而增大，导致测量值与实际值产生较大的偏差。     

CaS：Ce，Sm的制备及性能表征

采用碳还原法制备了CaS：Ce，Sm样品，并研究了反应机理、还原原理以及灼烧温度对CaS晶格形成和光激励发光的影响。样品的XRD测试表明，采用碳还原法制备的CaS：Ce，Sm样品，具有纯CaS的面心立方结构，晶格常数a=0.569 4 nm，样品的激发光谱是峰值分别位于295 nm和461 nm的宽带谱，样品的荧光光谱是峰值位于503 nm、560 nm、600 nm和655 nm带谱，光激励发光光谱是峰值分别位于500 nm，565 nm和605 nm的宽带谱，光激励激发光谱是峰值位于1 150 nm的宽带谱。     

Exploring the Phase-Selective,Green, Hydrothermal Synthesis of Upconverting Doped Sodium Yttrium Fluoride: Effects of Temperature,Time, and Precursors

The aim of this work was i) to develop a hydrothermal, low-temperature synthesis protocol affording the upconverting hexagonal phase NaYF₄ with suitable dopants while adhering to the “green chemistry” standards and ii) to explore the effect that different parameters have on the products. In optimizing the synthesis protocol, short reaction times and low temperatures (below 150 °C) were considered. Yb³⁺ and Er³⁺ ions were chosen as dopants for the NaYF₄ material. Within the context of the second goal, parameters including nature of the precursors, treatment temperature, and treatment time were investigated to afford a pure hexagonal crystalline phase, both in the doped and undoped materials. To fully explore the synthesis results, the prepared materials were characterized from a structural (XRD), compositional (XPS, ICP-MS), and morphological (SEM) point of view. The upconverting properties of the compounds were confirmed by photoluminescence measurements.     

Assembly-enhanced triplet-triplet annihilation upconversion in the aggregation formed by Schiff-base Pt(Ⅱ) complex grafting-permethyl-β-CD and 9,10-diphenylanthracence dimer

Water-soluble triplet sensitizer with permethyl-β-cyclodextrin(PMCD) grafting on a Schiff-base Pt(Ⅱ)complex(Pt-2),in which PMCD unit serves as a host for binding the acceptors and the Schiff-base Pt(Ⅱ)complex serves as a triplet sensitizer,was synthesized to investigate the effect of supramolecular complexation and assembly on the triplet-triplet annihilation upconversion emission in water.9,10-Diphenylanthracence(DPA) carboxylate(A-1) and its dimer(A-2) in which two DPA carboxylate were covalently linked with an alkyl chain were synthesized as triplet acceptors which also play a role of guest molecules for PMCD.A-1 and A-2 showed high affinity with PMCD,and A-2 can readily aggregate in water and form micron sized assemblies due to the hydrophobic effect and π-π stacking of anthracene core in A-2.The efficiency of TTA-UC was demonstrated to be enhanced by a synergistic effect of host-guest complexation of Pt-2 with A-2 and the self-aggregation of the acceptor A-2,which facilitated the energy transfer and energy fusion among donor and acceptor.     

Er3+单掺、Er3+/Yb3+共掺杂Ca12Al14O32F2的 制备及上转换发光性质

利用高温固相法成功制备了Er~(3+)单掺、Er~(3+)/Yb~(3+)共掺杂Ca_(12)Al_(14)O_(32)F_2上转换发光样品。在980 nm激光激发下,Er~(3+)单掺和Er~(3+)/Yb~(3+)共掺杂样品均呈现出较强的绿光(528,549 nm)和较弱的红光(655 nm)发射,分别归因于Er~(3+)离子的~2H_(11/2),~4S_(3/2)→~4I_(15/2)和~4F_(9/2)→~4I_(15/2)能级跃迁。随着Er离子浓度的增加,单掺杂样品上转换发光强度先增大后减小,最佳掺杂浓度为0.8%。共掺杂Yb~(3+)后,Er~(3+)的发光强度明显增大。还原气氛下合成的样品上转换发光强度增大约两倍,可能和笼中阴离子基团变化有关。发光强度和激发光功率的关系表明所得上转换发射为双光子吸收过程,借助Er~(3+)-Yb~(3+)体系能级结构详细讨论了上转换发射的跃迁机制。     

Synthesis,properties and mechanism of photodegradation of core–shell structured upconversion luminescent NaYF4:Yb3+,Er3+@BiOCl

Microspherical bismuth oxychloride (BiOCl) can only utilize ultraviolet (UV) light to promote photocatalytic reactions. To overcome this limitation, a uniform and thin BiOCl nanosheet was synthesized with a particle size of about 200 nm. As results of UV–visible diffuse reflectance spectroscopy showed, the band gap of this nanostructure was reduced to 2.78 eV, indicating that the BiOCl nanosheet could absorb and utilize visible light. Furthermore, the upconversion material NaYF₄ doped with rare earth ions Yb³⁺ and Er³⁺ emitted visible light at 410 nm following excitation with near‐infrared (NIR) light (980 nm), which could be utilized by BiOCl to produce a photocatalytic reaction. To produce a high‐efficiency photocatalyst (NaYF₄:Yb³⁺,Er³⁺@BiOCl), BiOCl‐loaded NaYF₄:Yb³⁺,Er³⁺ was successfully synthesized via a simple two‐step hydrothermal method. The as‐synthesized material was confirmed using X‐ray diffraction, scanning electron microscopy, X‐ray photoelectron spectroscopy as well as other characterizations. The removal ratio of methylene blue by NaYF₄:Yb³⁺,Er³⁺@BiOCl was much higher than that of BiOCl alone. Recycling experiments verified the stability of NaYF₄:Yb³⁺,Er³⁺@BiOCl, which demonstrated excellent adsorption, strong visible‐light absorption and high electron–hole separation efficiency. Such properties are expected to be useful in practical applications, and a further understanding of the NIR‐light‐responsive photocatalytic mechanism of this new catalytic material would be conducive to improving its structural design and function.     

可见近红外光响应直接Z型异质结光催化剂LaNiO3/CdS的产氢性能

通过冷凝-回流方式制备可见近红外光响应直接 Z型 LaNiO₃/CdS纳米杂化物，在对其进行物理化学表征后将其应用于光解水产氢反应。在可见光照射下，LaNiO₃/CdS光催化剂在5 h的H₂产量达到737 μmol，其H₂产量是CdS的4.3倍(172 μmol)。光电化学测试证实，LaNiO₃/CdS之间异质结的构筑能有效地促进光生载流子在界面的迁移、分离，从而促进其光解水产氢效率和稳定性的提高。同时随着近红外光的引入，其产氢活性提高至996 μmol。在上转换荧光测试中，LaNiO₃在808 nm光激发下在406和628 nm显示出发射荧光，这表明其能在近红外光照射下产生光生载流子，从而进一步提高其光解水产氢效率。     

试验优化设计Er3+-Yb3+共掺杂Gd2Ti2O7上转换发光特性

采用溶胶-凝胶（Sol-gel）法制备了Er³⁺-Yb³⁺共掺杂Gd₂Ti₂O₇纳米晶粉末,通过试验优化设计的理论建立了Er³⁺-Yb³⁺掺杂浓度与发光强度的回归方程,利用遗传算法优化计算出方程的最优解Er³⁺、Yb³⁺掺杂浓度分别为5.60%（物质的量分数）和13.43%。Er³⁺-Yb³⁺共掺杂Gd₂Ti₂O₇纳米晶粉末为单一面心立方Gd₂Ti₂O₇相结构,随Yb³⁺共掺杂浓度增加,X射线衍射峰逐渐向高角偏移。在976 nm激光激发下,Er³⁺-Yb³⁺共掺杂Gd₂Ti₂O₇获得了分别对应于Er³⁺的²H_11/2/⁴S_3/2→⁴I_15/2和⁴F_9/2→⁴I_15/2跃迁的绿色和红色上转换发光,且绿色和红色发光均为双光子吸收过程。研究了最优样品上转换发光与温度之间的关系,发现绿色上转换发光具有优良的温度传感特性,对红色上转换发光的温度猝灭进行了解释。