基于层状氢氧化镧的稀土离子激活杂化组装荧光体

doi:10.6023/A21100484

摘要/Abstract

采用水热法制备了十二烷基磺酸根(DS^-)插层的稀土离子(Eu³⁺, Tb³⁺和Ce³⁺)激活的层状氢氧化镧(LLaH), 通过微波法将苯甲酸根(BA^-)与层中DS^-进行离子交换反应, 形成杂化组装. X-射线衍射(XRD)结果表明这些杂化组装具有典型的层状结构, 离子交换反应后层间距由3.2 nm减小为1.9 nm. 光致发光光谱显示稀土Eu³⁺和Tb³⁺掺杂的LLaH均表现出相应的特征红色和绿色发射, 但(Eu/Tb)_0.1La_1.9(OH)₅BA•H₂O的发光强度是(Eu/Tb)_0.1La_1.9(OH)₅DS•H₂O的十几倍, 这得益于BA^-对稀土离子发光产生了很好的敏化作用. 通过超声和离心过程将Tb_0.1La_1.9(OH)₅BA•H₂O, Eu_0.1La_1.9(OH)₅BA•H₂O和Ce_0.08La_1.92(OH)₅DS•H₂O杂化组装样品进行层剥离制成胶体溶液, 发现不同比例的Eu_0.1La_1.9(OH)₅BA•H₂O和Tb_0.1La_1.9(OH)₅BA•H₂O两种胶体混合能够对发光颜色进行调整; 三种胶体混合后通过改变激发波长也可以有效调整发光颜色, 特别是在280~290 nm紫外光激发下, 能够获得白色荧光, 显示出优异的光功能特性.

关键词: 层状氢氧化物, 稀土, 荧光, 发光胶体, 离子交换

The layered rare earth hydroxides (LRHs) have recently been paid attention owing to the adjustable rare earth ions in the host and alterable anions in the gallery, which may be applied in adsorption, catalyst, fluorescence and detection fields. However, as far as we know, the studies of rare earth ions-activated layered lanthanum hydroxide (LLaH) fluorescent systems were seldom reported. In this paper, the hybrid assemblies (Eu/Tb)_0.1La_1.9(OH)₅DS•H₂O and Ce_0.08La_1.92(OH)₅DS• H₂O solid samples were first prepared with Eu(NO₃)₃, TbCl₃, Ce(NO₃)₃•6H₂O and La(NO₃)₃ solutions by hydrothermal process at 140 ℃ for 12 h, in which the interlayer was pillared with dodecyl sulfonate (DS^-) anions. Then, the DS^- anions of the as-prepared (Eu/Tb)_0.1La_1.9(OH)₅DS•H₂O were exchanged with benzoate (BA^-) solution through microwave process, and the hybrid assemblies samples (Eu/Tb)_0.1La_1.9(OH)₅BA•H₂O were obtained. The X-ray diffraction (XRD) results indicate that the solid samples have superior crystallization and layered structure, and the interlayer distance is decreased from 3.2 nm to 1.9 nm after the ion-exchange reaction. The photoluminescence excitation spectra show that the excitation intensities in the ultraviolet (UV) region (≈280 nm) for (Eu/Tb)_0.1La_1.9(OH)₅BA•H₂O are much stronger than those for (Eu/Tb)_0.1La_1.9- (OH)₅DS•H₂O due to the strong absorption peak from BA^- anion. Excited with 280 nm, the emission spectra exhibit the characteristic emission transitions of Eu³⁺ or Tb³⁺ ions, and the intensities of (Eu/Tb)_0.1La_1.9(OH)₅BA•H₂O are more than tenfold of (Eu/Tb)_0.1La_1.9(OH)₅DS•H₂O because of efficient sensitization effect of BA^-. On the other hand, the (Eu/Tb)_0.1La_1.9(OH)₅BA•H₂O and Ce_0.08La_1.92(OH)₅DS•H₂O hybrid assemblies were exfoliated to colloidal solutions through ultrasound and centrifugation process in formamide solvent. It has been observed that the fluorescent color can be adjusted by mixing the colloid solutions of Eu_0.1La_1.9(OH)₅BA•H₂O and Tb_0.1La_1.9(OH)₅BA•H₂O in different volume ratios. Moreover, the fluorescent color can be changed with the three colloid components by varying the excitation wavelength. In particular, the white light can be achieved as excited with 280—290 nm UV light, exhibiting supreme photofunctional performances. The investigation will promote the effective combination of rare earth luminescence with layered materials.

Key words: layered hydroxide, rare earth, fluorescence, luminescent colloid, ion-exchange

引用此文

左翔宇, 许怡飞, 石士考. 基于层状氢氧化镧的稀土离子激活杂化组装荧光体[J]. 化学学报, 2022, 80(2): 133-140.

Xiangyu Zuo, Yifei Xu, Shikao Shi. Rare Earth Ions-Activated Hybrid Assemblies Fluorescent Systems Based on the Layered Lanthanum Hydroxides[J]. Acta Chimica Sinica, 2022, 80(2): 133-140.

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图/表 12

图1. 相关样品的XRD图

Figure 1. XRD patterns of related samples

图式1. 离子交换过程和层间距变化

Scheme 1. Process of ion-exchange and change of interlayer distance

图2. TbDS (a)和TbBA (b)的TG和DSC曲线

Figure 2. TG and DSC curves of TbDS (a) and TbBA (b)

图3. Eu(DS/BA)和Tb(DS/BA)粉末样品的激发光谱

Figure 3. Excitation spectra of Eu(DS/BA) and Tb(DS/BA) powder samples

图4. Eu(DS/BA)和Tb(DS/BA)粉末样品的发射光谱

Figure 4. Emission spectra of Eu(DS/BA) and Tb(DS/BA) powder samples

图5. (Eu/Tb)BA粉末样品的色坐标图和在254 nm紫外光下的照片

Figure 5. CIE chromaticity diagram and photograph irradiated with 254 nm UV light of (Eu/Tb)BA powder samples

图6. Tb(DS/BA)粉末样品的Tb3+荧光衰减曲线

Figure 6. Fluorescent decay curves of Tb3+ in Tb(DS/BA) powder samples

图7. CeDS和CeDS-FM的激发和发射光谱(右下为胶体样品在365 nm紫外光下的照片)

Figure 7. Excitation and emission spectra of CeDS and CeDS-FM (the lower right colloidal photograph under a 365 nm UV light)

图9. EuBA-FM和TbBA-FM的激发光谱

Figure 9. Excitation spectra of EuBA-FM and TbBA-FM

图10. TbBA-FM, EuBA-FM和混合胶体的发射光谱和色坐标图

Figure 10. Emission spectra and CIE chromaticity diagram of TbBA-FM, EuBA-FM and mixed colloid solutions

图11. 4号混合胶体在280~340 nm (Δλ=10 nm)波长激发下的发射光谱和色坐标图

Figure 11. Emission spectra (λex=280—340 nm, Δλ=10 nm) and CIE chromaticity diagram of No. 4 mixed colloid solution

图12. 4号混合胶体在280~290 nm (Δλ=2 nm)波长激发下的发射光谱和色坐标图

Figure 12. Emission spectra (λex=280—290 nm, Δλ=2 nm) and CIE chromaticity diagram of No. 4 mixed colloid solution

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