Preparation and application of multinuclear rare earth ion doped organic complex light conversion agents
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摘要: 为加快实现农业新旧动能转换,建设现代农业强国,转光农膜一直被作为“光学农业”领域的重要研究方向之一。转光农膜的制备需要具有良好耐候性和优异转光特性的转光剂,但是现有的转光剂存在发射光谱单一和发射范围窄的问题,这导致转光剂的发射光谱与植物光合作用吸收光谱匹配度较差,严重限制了转光农膜的发展。本文合成了一类以水杨酸和邻菲啰啉为配体、多种稀土离子(Sm3+、Eu3+和Y3+)掺杂的有机配合物(转光剂)发光材料。数据表明,通过Sm3+的掺入显著拓宽了该类转光剂的荧光光谱。利用吹塑法将合成的转光剂掺入乙烯-1-己烯共聚物(PO)薄膜中,制备了具有紫外光转红光作用的转光农膜。采用FTIR和XPS确定转光剂的成分和结构组成。同时利用TGA55和组合式瞬态/稳态荧光光谱仪(FLS920)对转光剂和转光农膜的热稳定性和光学性质进行表征。测试结果表明,合成的转光剂可以吸收紫外光(波长λ=250~400 nm)并发射出红光(λ=610~660 nm),该光谱性质与植物光合作用在红光区的吸收光谱匹配性较高,并且利用该类转光剂制备的转光农膜仍旧保持了良好的发光性能,这将有利于转光剂在农膜领域中的推广和应用。本文为拓宽转光剂荧光发射范围,提高与植物光合作用在红光波段吸收光谱的匹配度,提供了一种切实可行的方法,并将转光剂成功应用于制备转光农膜,达到了较好的紫外转红光的目的。Abstract: In order to accelerate the transition to new from old economic engines and build a strong modern agricultural country, light conversion agricultural film has been regarded as one of the important research directions in the field of "optical agriculture". The light conversion agents must have good weather resistance and excellent light conversion characteristics to fabricate the light conversion agricultural film. However, the existing light conversion agents have the problems of single emission spectrum and narrow emission range, which leads to the poor matching between the emission spectrum of light conversion agents and the absorption spectrum of plant photosynthesis, and seriously restricts the development of light conversion agricultural film. In this paper, a kind of organic complex (light conversion agents) doped with a variety of rare earth ions (Sm3+, Eu3+, and Y3+) were synthesized by use salicylic acid and o-phenanthroline as ligands. The results show that the fluorescence spectra of this kind of light conversion agents are significantly broadened by the incorporation of Sm3+. A light conversion agricultural film with the function of converting ultraviolet light to red light was prepared by mixing the synthesized light conversion agent into ethylene-1-hexene copolymer (PO) film by blow molding. The composition and structure of the light conversion agents were determined by FTIR and XPS. At the same time, the thermal stability and optical properties of light conversion agents and light conversion agricultural film were characterized by TGA55 and steady state and transient state fluorescence spectrometer (FLS920). The test results show that the synthesized light conversion agents can absorb ultraviolet light (λ=250-400 nm) and emits red light (λ=610-660 nm). The spectral property is highly matched with the absorption spectrum of plant photosynthesis in the red light region, and the light conversion agricultural film prepared with this kind of light conversion agents still maintains good luminescence performance, which will be conducive to the popularization and application of light conversion agents in the field of agricultural film. This study provides a practical method to broaden the fluorescence emission range of light conversion agents and improve the matching with the absorption spectrum of plant photosynthesis in the red band. The light conversion agents are successfully applied to the preparation of light conversion agricultural film, which achieve the purpose of converting ultraviolet light into red light.
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图 4 转光剂的归一化激发光谱:(a) 转光剂1~5的激发光谱;(b) 转光剂6~10的激发光谱
Figure 4. Normalized excitation spectra of light conversion agents: (a) Excitation spectra of light conversion agents 1-5; (b) Excitation spectra of light conversion agents 6-10
6H5/2, 4L17/2, 4K11/2, 4M19/2—Sm3+ energy level state; 7F0, 5L6, 5D3—Eu3+ energy level state
图 5 转光剂的归一化荧光发射光谱:(a) 转光剂1~10的发射光谱;(b) 转光剂1、4和8的发射光谱
Figure 5. Normalized fluorescence emission spectra of light conversion agents: (a) Emission spectra of light conversion agents 1-10; (b) Emission spectra of light conversion agents 1, 4 and 8
4G5/2, 6H5/2, 6H7/2, 6H9/2—Sm3+ energy level state; 5D0, 7F1, 7F2—Eu3+ energy level state
图 7 转光农膜和转光剂的归一化激发光谱和荧光发射光谱:(a) 转光农膜1、4和8的激发光谱;(b) 转光剂1、4、8和相应转光农膜的荧光发射光谱
Figure 7. Normalized excitation spectra and fluorescence emission spectra of light conversion agents and light conversion agricultural film: (a) Excitation spectra of light conversion agricultural film 1, 4 and 8; (b) Fluorescence emission spectra of light conversion agents 1, 4, 8 and corresponding light conversion agricultural film
表 1 转光剂的实验编号
Table 1. Sample numbers of light conversion agents
Type of light conversion agent X/mmol Y/mmol Products 1 0.1 0.8 Eu0.1Sm0.8Y0.1(Hsal)3Phen 2 0.2 0.7 Eu0.2Sm0.7Y0.1(Hsal)3Phen 3 0.3 0.6 Eu0.3Sm0.6Y0.1(Hsal)3Phen 4 0.4 0.5 Eu0.4Sm0.5Y0.1(Hsal)3Phen 5 0.5 0.4 Eu0.5Sm0.4Y0.1(Hsal)3Phen 6 0.6 0.3 Eu0.6Sm0.3Y0.1(Hsal)3Phen 7 0.7 0.2 Eu0.7Sm0.2Y0.1(Hsal)3Phen 8 0.8 0.1 Eu0.8Sm0.1Y0.1(Hsal)3Phen 9 0.9 0.0 Eu0.9Y0.1(Hsal)3Phen 10 0.0 0.9 Sm0.9Y0.1(Hsal)3Phen Notes: X—Eu3+ millimolar quantity; Y—Sm3+ millimolar quantity. -
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