【摘要】：金屬-有機(jī)框架材料(Metal-Organic Frameworks,簡(jiǎn)稱MOFs)是一種新型有機(jī)-無(wú)機(jī)雜化晶態(tài)多孔材料,具有多樣的三維結(jié)構(gòu)和孔道、尺寸可調(diào)、優(yōu)異的熱穩(wěn)定性以及化學(xué)穩(wěn)定性等優(yōu)點(diǎn),可潛在應(yīng)用于能源氣體存儲(chǔ)、催化、光學(xué)、電學(xué)、磁學(xué)以及生物醫(yī)學(xué)等領(lǐng)域。發(fā)光稀土MOFs材料作為新一代固態(tài)發(fā)光材料,其組成中的稀土離子、有機(jī)配體以及客體分子等組成了豐富的發(fā)光位點(diǎn),可以實(shí)現(xiàn)稀土MOFs材料不同的發(fā)光性能應(yīng)用。同時(shí),結(jié)合結(jié)構(gòu)上的多孔性特點(diǎn),使得發(fā)光稀土MOFs材料具備了無(wú)機(jī)發(fā)光材料和有機(jī)發(fā)光材料所無(wú)法比擬的多功能性優(yōu)勢(shì),因而其在白光發(fā)射材料、離子探測(cè)以及熒光溫度傳感等領(lǐng)域具有十分誘人的發(fā)光功能應(yīng)用前景。采用配體H3TATAB(4,4',4”-三嗪-1,3,5-三氨基對(duì)苯甲酸)與稀土硝酸鹽,通過(guò)溶劑熱反應(yīng)構(gòu)筑了一種具有一維孔道結(jié)構(gòu)的新型MOFs材料LnTATAB (Ln =Dy, Tb, Sm, Eu, Gd)。室溫下,H3TATAB配體能夠有效敏化Eu3+、Tb3+離子,部分敏化Dy3+,發(fā)出其特有的特征發(fā)光峰。其中,TbTATAB對(duì)水中汞離子具有優(yōu)異的熒光探測(cè)性能,并且常見(jiàn)金屬離子對(duì)于TbTATAB的發(fā)光強(qiáng)度的影響非常有限,因而這一材料具有很好的選擇性探測(cè)能力。TbTATAB可以作為優(yōu)異的用于水中汞離子濃度的探測(cè)材料。通過(guò)向材料TbTATAB發(fā)光體系中增加染料C460得到了雙發(fā)光中心熒光溫度探針。TbTATAB(?)C460在低溫范圍(50～300 K)對(duì)溫度具有溫度探測(cè)性能。染料發(fā)光強(qiáng)度、Tb3+發(fā)光強(qiáng)度的比值(IC460/ITb)與溫度具有一定的線性關(guān)系,且相對(duì)靈敏度最高達(dá)Sr=3.33% K-1。改變裝載的染料濃度后,TbTATAB(?)C460在生物溫度范圍(25～70℃)能夠?qū)崿F(xiàn)對(duì)溫度的探測(cè)且相對(duì)靈敏度最大達(dá)到了1.83% K-1。該材料在低溫范圍和生物溫度范圍內(nèi)都具有很好的溫度循環(huán)性能,因而能夠潛在應(yīng)用于多范圍的溫度熒光探測(cè)。本文還制備得到了一種基于三羧酸配體H3BPT的稀土MOFs材料LnBPT, Ln=Eu, Tb, DMF=N,N'-二甲基甲酰胺。配體H3BPT能夠高效地敏化銪、鋱離子并發(fā)出其相應(yīng)特征光。通過(guò)改變?cè)现袖B、鋱比例可以得到一系列發(fā)光顏色不同的混合稀土MOFs材料,隨著Eu3+的濃度從40%減少到1%,整體的MOFs的發(fā)光顏色由紅色轉(zhuǎn)變?yōu)辄S色。Eu0.059Tb0.941BPT中,Eu3+的發(fā)光面積的積分和Tb3+的發(fā)光面積的積分最為接近。在Eu0.059Tb0.941BPT中引入了藍(lán)色熒光染料7-二乙氨基-4-甲基香豆素,為體系增加了藍(lán)光發(fā)射,當(dāng)裝載濃度為13.3%時(shí),在340nm激發(fā)下材料能夠發(fā)出優(yōu)質(zhì)的白光。
[Abstract]:Metal-organic frameworks (MOFs) are novel organic-inorganic hybrid crystalline porous materials with various three-dimensional structures and pores, adjustable size, excellent thermal stability and chemical stability. Potential applications in energy gas storage, catalysis, optics, electricity, magnetism and biomedicine. Luminescent rare earth MOFs as a new generation of solid-state luminescent materials, its composition of rare earth ions, organic ligands and guest molecules constitute a wealth of luminescent sites, which can achieve different luminescent properties of rare earth MOFs applications. At the same time, combined with the porous characteristics of the structure, the luminescent rare earth MOFs materials have the advantages of inorganic luminescence materials and organic luminescent materials, so they can not be compared with organic luminescent materials, so they can be used in white light emitting materials. Ion detection and fluorescence temperature sensing have very attractive luminescent applications. A novel MOFs material LnTATAB (Ln Dy, TB, Sm, EuEU, Gd) with one-dimensional pore structure was prepared by solvothermal reaction of the ligand H3TATAB (4H3TATAB) with rare earth nitrate. At room temperature, H3TATAB ligands can effectively sensitize Eu3 + Tb3, partially sensitize Dy3, and emit its own characteristic luminescence peak. Among them, TbTATAB has excellent fluorescence detection performance for mercury ions in water, and the influence of common metal ions on the luminescence intensity of TbTATAB is very limited. Therefore, this material has a good selective detection ability. TbTATAB can be used as an excellent detection material for mercury ion concentration in water. By adding dye C460 to the material TbTATAB luminescence system, the double luminescence center fluorescence probe. TbTATAB (?) C460 has the temperature detection property at low temperature (50 ~ 300K). The ratio of dye luminescence intensity and Tb3 luminescence intensity (IC460 / ITb) has a linear relationship with temperature, and the highest relative sensitivity is as high as 3.33% K-1. TbTATAB (?) C460 can detect the temperature in the biological temperature range (2570 鈩，

本文編號(hào)：2133226