双稀土有机配合物转光剂的制备与表征

发布时间：2018-11-16 15:29

【摘要】：稀土转光剂是一种具有光转换能力的新型功能材料,可以广泛应用于光纤通讯、农用薄膜、生物分析传感器及激光技术等领域。稀土铕(Eu)元素在光、电、磁等方面的性能突出,被广泛应用于稀土转光剂制备中;但铕的价格昂贵,且其发射光谱单一,与植物光合作用匹配度不高,不适合在农膜中广泛应用。本文以稀土铕、钐(Sm)为中心,A1203、H3BO3为基质,合成了稀土无机转光剂;以稀土铕为中心,掺杂钐、钇(Y)等其它低价格稀土离子和水杨酸(Hsal)、邻菲罗啉(Phen)有机配体,合成了一系列稀土有机配合物转光剂,并成功制备聚乙烯转光膜,主要研究内容如下:1)稀土无机转光剂。采用高温固相法合成Al18B4033:Sm3+、Al18B4033:Eu3+稀土无机转光剂,用X射线衍射、荧光光谱和粒度和粒径分布对其进行表征。当反应原料中 n(Al) / n(B) =4.5:1 时,Al18B4O33:Sm3+转光剂可以由 200-400 nm的光激发,发射波长为580-710nm的红光,其最强荧光强度为735 (a.u.),荧光强度较弱;Al18B4033:Eu3+转光剂可以由200-500 nm的光激发,发射波长为585-720 nm的特征红光,其荧光强度为3032 (a.u.),明显优于Al18B4033:Sm3+稀土无机转光剂的荧光强度,但低于双稀土有机配合物转光剂的荧光强度。2)双稀土有机配合物转光剂。以低成本钐、钇(Y)部分分别取代高价格铕合成与植物吸收光谱更匹配的双稀土有机配合物转光剂EuxSm1-x(Hsal)3Phen、EuxY1-x(Hsal)3Phen。用X射线光电子能谱、红外光谱、荧光光谱、热失重、粒度和粒径分布对转光剂进行表征。EuxSm1-x(Hsal)3Phen转光剂在394 nm紫光处和465 nm蓝绿光处的激发峰强度达到最大值;当Sm3+的摩尔用量为70 %时,转光剂Eu0.3Sm0.7(Hsal)3Phen在646 nm处发射峰强度达到最大值,646 nm处的发射光与植物吸收光谱吻合性好。当Y3+的摩尔用量为70 %时,转光剂Eu0.3Y0.7(Hsal)3Phen在200-465 nm处激发光谱强度达到最大值,在585-665 nm处发射光谱强度达到最大值,转光性能良好。3) 转光膜的制备。选取 Eu(Hsal)3Phen、Eu0.9Sm0.1(Hsal)3Phen、Eu0.6Sm0.4(Hsal)3Phen、Eu0.5Sm0.5(Hsal)3Phen、Eu0.5Y0.5(Hsal)3Phen、Eu0.2Y0.8(Hsal)3Phen和Eu0.1Y0.9(Hsal)3Phen转光剂分别加入低密度聚乙烯,制备转光膜。用荧光光谱仪对转光膜的荧光性能进行表征。结果表明,所得到的转光膜可以将太阳中的紫外光和紫光转化为植物光合作用所需的红光。
[Abstract]:Rare earth optical conversion agent is a new functional material with optical conversion ability. It can be widely used in optical fiber communication, agricultural film, biosensor and laser technology. The rare earth europium (Eu) is widely used in the preparation of rare earth conversion agent because of its outstanding properties in light, electricity and magnetism. However, europium is not suitable for wide application in agricultural film because of its high price, single emission spectrum and poor matching with plant photosynthesis. In this paper, rare earth inorganic optical conversion agent was synthesized with rare earth europium, samarium (Sm) as the center and A1203H3BO3 as the matrix. A series of rare earth organic complexes have been synthesized with rare earth europium as the center, doped with other low price rare earth ions such as samarium, yttrium (Y) and (Hsal), o-phenanthroline salicylate (Phen) organic ligands, and polyethylene photoconversion films have been successfully prepared. The main research contents are as follows: 1) rare earth inorganic light transfer agent. Al18B4033:Sm3 and Al18B4033:Eu3 rare earth inorganic transmitters were synthesized by high temperature solid state method and characterized by X-ray diffraction, fluorescence spectra, particle size and particle size distribution. When n (Al) / n (B) = 4.5: 1, the conversion agent of Al18B4O33:Sm3 can be excited by 200-400 nm, emitting red light at the wavelength of 580-710nm, the strongest fluorescence intensity is 735 (a.u.), and the fluorescence intensity is weak. The fluorescence intensity of Al18B4033:Eu3 conversion agent is 3032 (a.u.), which is obviously better than that of Al18B4033:Sm3 rare earth inorganic conversion agent, which can be excited by 200-500 nm, and the emission wavelength is 585-720 nm, and its fluorescence intensity is 3032 (a.u.). But it is lower than the fluorescence intensity of the light conversion agent of the double rare earth organic complex. 2) the light transfer agent of the double rare earth organic complex. Low-cost samarium and yttrium (Y) were used to replace the high price europium in the synthesis of EuxSm1-x (Hsal) _ 3Pheno _ (EU _ XY _ (1-x) (Hsal) _ (3) Phen), which is more suitable for plant absorption spectra. X-ray photoelectron spectroscopy (XPS), infrared spectroscopy (IR), fluorescence spectrum, thermogravimetric analysis, particle size and particle size distribution were used to characterize the transmitters. The intensity of excitation peaks of EuxSm1-x (Hsal) 3Phen transmitters at 394 nm violet and 465 nm blue-green light reached the maximum. When the molar amount of Sm3 was 70%, the emission peak intensity of Eu0.3Sm0.7 (Hsal) 3Phen reached the maximum at 646 nm, and the emission light at 646 nm coincided well with the plant absorption spectrum. When the molar content of Y3 is 70%, the excitation spectral intensity of Eu0.3Y0.7 (Hsal) 3Phen reaches the maximum at 200-465 nm and the emission intensity at 585-665 nm. 3) the optical conversion film is prepared. Eu (Hsal) 3Pheno Eu0.9Sm0.1 (Hsal) 3Pheno Eu0.6Sm0.4 (Hsal) 3Pheno Eu0.5Sm0.5 (Hsal) 3Pheno Eu0.5Y0.5 (Hsal) 3Phen. Low density polyethylene (LDPE) was added to Eu0.2Y0.8 (Hsal) 3Phen and Eu0.1Y0.9 (Hsal) 3Phen to prepare the conversion film. The fluorescence properties of the film were characterized by fluorescence spectrometer. The results show that the UV and UV light in the sun can be transformed into red light for plant photosynthesis.
【学位授予单位】：合肥工业大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4

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