【摘要】：分子篩由于其獨特的結(jié)構(gòu),在催化、吸附、離子交換等方面具有重要應(yīng)用。分子篩的特殊結(jié)構(gòu)能夠為一些發(fā)光中心提供良好的環(huán)境,例如稀土離子、量子點、Ag等,其復(fù)合材料在白光照明、紅外光放大、隨機激光、防偽編碼、氣體探測等領(lǐng)域具有潛在應(yīng)用。發(fā)光中心(離子)經(jīng)過離子交換后在分子篩孔道內(nèi)的分布與狀態(tài),將極大地影響發(fā)光中心間的相互作用(能量傳遞)及發(fā)光特性,且分子篩骨架結(jié)構(gòu)的負(fù)電性也是一個不可忽視的因素,因此有必要研究這些因素對發(fā)光的影響,并探索其潛在的應(yīng)用。本論文的主要研究結(jié)果如下:通過離子交換法獲得Yb~(3+)/Mn~(2+)摻雜的分子篩復(fù)合材料,并用ICP、XRD、SEM、BET、固體核磁、X射線吸收、熒光光譜等手段表征了其組成、結(jié)構(gòu)、離子分布狀態(tài)和光學(xué)性質(zhì)。結(jié)果表明Yb~(3+)/Mn~(2+)盡可能多地占據(jù)孔道內(nèi)不同格位,且Yb~(3+)優(yōu)先占據(jù)孔道內(nèi)格位,總摻雜量受限于格位數(shù)量。Yb~(3+)-Mn~(2+)間的能量傳遞(Stokes光譜和上轉(zhuǎn)換光譜)和X射線吸收譜說明兩種離子在濃度較高時才出現(xiàn)在近鄰位。一個有趣的現(xiàn)象是,共摻時Mn~(2+)發(fā)光壽命隨著Mn~(2+)濃度的增加而顯著增加(3~4倍),而Yb~(3+)發(fā)光壽命變化不明顯,可能的原因有:(a)隨著[MnCl2]的引入,Yb~(3+)/Mn~(2+)周圍的缺陷減少;(b)分子篩骨架的負(fù)電性對Mn~(2+)的d-d躍遷比對Yb~(3+)的f-f躍遷影響大。研究了Y型分子篩摻Ag-Eu復(fù)合材料在不同光源照射下的發(fā)光行為。XRD、SEM和拉曼光譜結(jié)果均表明Y型分子篩摻Ag,Eu系列樣品的晶型未發(fā)生變化。利用Ag、Eu~(3+)之間的能量傳遞,可以實現(xiàn)對光譜的調(diào)控,獲得白光發(fā)射。相比于氙燈激發(fā)的樣品,266 nm激光激發(fā)的樣品Eu~(3+)的發(fā)光相對于Ag的發(fā)光有明顯的增強,且~5D_0→~7F_0的躍遷發(fā)光的半峰寬變小,~5D_0→~7F_0與~5D_0→7F_2躍遷發(fā)光強度的比值變小,而~5D_0→7F_1與~5D_0→7F_2躍遷發(fā)光強度的比值變大。原因可能是在266 nm激光的作用下,相比于氙燈光源,激光可到達樣品更深的內(nèi)部,從而激發(fā)處于對稱位置(SI、SU)的Eu~(3+)。~5D_0→7F4相對~5D_0→7F_2躍遷發(fā)光強度的增強可能是由于激光誘導(dǎo)Eu~(3+)配體極化的動態(tài)耦合效應(yīng)所導(dǎo)致的。
[Abstract]:Because of its unique structure, molecular sieve has important applications in catalysis, adsorption and ion exchange. The special structure of molecular sieve can provide a good environment for some luminous centers, such as rare earth ions, quantum dots, Ag, etc. The composite materials are illuminated by white light, amplified by infrared light, random laser, anti-counterfeiting coding, etc. Gas detection and other fields have potential applications. The distribution and state of luminescent centers (ions) in molecular sieve channels after ion exchange will greatly affect the interaction (energy transfer) and luminescence characteristics between the luminescent centers. The negative electricity of molecular sieve skeleton is also a factor that can not be ignored. Therefore, it is necessary to study the influence of these factors on luminescence and explore its potential application. The main results of this thesis are as follows: Yb~ (3) / Mn2 doped molecular sieve composites were obtained by ion exchange method, and their composition and structure were characterized by ICP,XRD,SEM,BET, solid-state NMR X-ray absorption and fluorescence spectra. Ion distribution and optical properties. The results show that Yb~ (3) / Mn2 occupies as many different lattice positions in the pore as possible, and Yb~ (3) preferentially occupies the lattice in the pore. The total doping amount is limited by the energy transfer (Stokes spectrum and upconversion spectrum) and X-ray absorption spectrum between the lattice number. Yb3 -Mn2. The results show that the two ions appear in the near neighbor only when the concentration is high. An interesting phenomenon is that the luminescence lifetime of co-doped Mn~ (2) increases significantly with the increase of Mn~ (2) concentration (3 ~ 4 times), but Yb~ (3) luminescence lifetime does not change obviously. The possible reason is that with the introduction of [MnCl2], the defects around Yb3 / Mn2 decrease the negative charge of; (b) molecular sieve skeleton. The d-d transition of Mn~ (2) is greater than the f-f transition of Yb~ (3). The luminescence behavior of Y type molecular sieve doped Ag-Eu composite under different light sources was studied. The results of SEM and Raman spectra showed that the crystal structure of Y type zeolite doped Ag,Eu series was not changed. Using the energy transfer between Ag,Eu~ (3), the spectrum can be regulated and the white light emission can be obtained. Compared with the sample excited by xenon lamp, the luminescence of Eu~ (3) was obviously enhanced compared with that of Ag, and the half-peak width of transition luminescence of 5D0 / 7F0 was smaller than that of sample Eu~ (3) stimulated by xenon lamp. However, the ratio of luminescence intensity of 7F_2 transition between 7F_1 and 5D _ 0 is increased. The reason may be that the laser can reach deeper inside the sample than a xenon light source under the action of a 266 nm laser. Thus, the enhancement of the luminescence intensity of Eu~ (3). 5 D tit 0 7F4 in symmetric position (SI,SU) relative to 5 D 0 7F_2 transition may be due to the dynamic coupling effect of Eu~ (3) ligand polarization induced by laser.
【學(xué)位授予單位】：華南理工大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2016
【分類號】：TB33

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