Rare Earth Ions-Activated Hybrid Assemblies Fluorescent Systems Based on the Layered Lanthanum Hydroxides

doi:10.6023/A21100484

Abstract

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

Cite this article

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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Fig. & Tab. 12

Figure 1. XRD patterns of related samples

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

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

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

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

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

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

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

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

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

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

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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