稀土微孔晶體材料的高溫高壓合成及熒光性質(zhì)的研究
發(fā)布時(shí)間：2018-08-06 14:14
【摘要】：稀土因其優(yōu)良的光學(xué)、電學(xué)、磁學(xué)等物理性質(zhì)，已被廣泛的應(yīng)用于生活中的各個(gè)方面。作為一種傳統(tǒng)材料，硅酸鹽的合成和應(yīng)用研究一直是科研工作者研究的熱點(diǎn)。而作為硅酸鹽材料的新秀，具有規(guī)則孔道結(jié)構(gòu)的硅酸鹽化合物在近幾十年的研究中也表現(xiàn)出許多優(yōu)異的性質(zhì)，并在催化、吸附等方面表現(xiàn)出巨大的應(yīng)用潛力。將稀土元素獨(dú)特的發(fā)光性質(zhì)與微孔硅酸鹽均一的孔道性質(zhì)有機(jī)的結(jié)合在一起，一直是人們感興趣并不斷探索的研究課題。微孔稀土硅酸鹽的合成大多都是采用中溫水熱法在200°C以下的溫度條件下合成的，反應(yīng)容器為不銹鋼反應(yīng)釜。本論文通過Quickpress3.0活塞-圓筒式高壓反應(yīng)裝置和HR-1B-2型LECO高溫高壓水熱反應(yīng)裝置，嘗試在更高的壓力和溫度條件下，對具有新穎結(jié)構(gòu)的微孔稀土硅酸鹽/鍺酸鹽化合物的合成進(jìn)行研究。在0.5~1GPa壓力范圍，300~700°C溫度范圍內(nèi)成功合成出了一系列結(jié)構(gòu)新穎的稀土硅酸鹽及鍺酸鹽化合物，并對它們的晶體結(jié)構(gòu)和熒光性質(zhì)進(jìn)行了研究。 （1）采用高溫高壓合成方法，，成功合成出了一個(gè)新的Na15Eu3Si12O36單晶。通過單晶X射線衍射分析對其晶體結(jié)構(gòu)進(jìn)行了解析，并且用粉末X射線衍射和X射線能譜分析對單晶解析的結(jié)果進(jìn)行了驗(yàn)證。單晶結(jié)構(gòu)解析的結(jié)果表明，該晶體是由[Si6O12]n12n-環(huán)硅酸鹽陰離子和EuO6八面體通過共用頂端O原子而相互連接所構(gòu)筑成的三維開放骨架結(jié)構(gòu)。該結(jié)構(gòu)含有由EuO6八面體和SiO4四面體共同限定組成的沿[010]方向的6元環(huán)孔道結(jié)構(gòu)。同時(shí)，單晶解析的結(jié)果表明，在其結(jié)構(gòu)中Na(2)+和Na(3)+離子的位置分別被Eu(2)和Eu(3)部分占據(jù)，這種按統(tǒng)計(jì)無序的Eu/Na占有率無序?qū)a15Eu3Si12O36的熒光性質(zhì)有著重要的影響，而這一結(jié)果在對其熒光性質(zhì)測試中被驗(yàn)證。 （2）在高溫高壓條件下，成功合成出了具有新結(jié)構(gòu)的銪硅酸鹽，其化學(xué)構(gòu)成為Na3EuSi6O15·1.47H2O。單晶X射線衍射晶體結(jié)構(gòu)解析的結(jié)果表明，該晶體是由波浪形SiO4四面體單層之間通過EuO7多面體相互連接起來而形成的三維開放骨架結(jié)構(gòu)。SiO4四面體所形成的單層沿[010]軸方向具有4，5，6，8元環(huán)孔道結(jié)構(gòu)。Na3EuSi6O15·1.47H2O的三維骨架結(jié)構(gòu)中存在著由EuO7多面體和SiO4四面體限定形成的沿[100]方向的4，8元環(huán)孔道結(jié)構(gòu)，以及沿[001]方向的5，6元環(huán)孔道結(jié)構(gòu)。對其熱穩(wěn)定性和熒光性質(zhì)的研究表明，它的結(jié)構(gòu)在800°C依然可以穩(wěn)定存在，并且表現(xiàn)出紅光發(fā)射。這些結(jié)果證明Na3EuSi6O15·1.47H2O是一種具有良好熱穩(wěn)定性的熒光材料。 （3）采用高溫高壓熔鹽法，以KF·2H2O和KOH作為助熔劑，成功合成出了一個(gè)具有新結(jié)構(gòu)的含氟微孔銪硅酸鹽，其化學(xué)構(gòu)成為K2EuSi4O10F。通過單晶X射線衍射、粉末X射線衍射分析確定了其晶體結(jié)構(gòu)。K2EuSi4O10F的結(jié)構(gòu)是由SiO4四面體所構(gòu)成的沿b軸方向的管狀鏈，以及沿b軸方向排列的EuO4F2八面體無限鏈之間通過共用頂端的氧原子而相互連接形成的沿b軸方向具有6，8元環(huán)孔道結(jié)構(gòu)的三維開放骨架結(jié)構(gòu)。對其熒光性質(zhì)的研究表明，K2EuSi4O10F晶體具有強(qiáng)烈的紅光發(fā)射，是一種具有潛在應(yīng)用價(jià)值的紅光熒光材料。 （4）采用HR-1B-2型LECO高溫高壓水熱反應(yīng)裝置，成功合成出了一系列具有2D層狀結(jié)構(gòu)的稀土鍺酸鹽：K3[LnGe3O8(OH)2]。通過單晶X射線衍射、粉末X射線衍射、EDS、紅外光譜對其結(jié)構(gòu)進(jìn)行了研究。單晶結(jié)構(gòu)分析表明K3[LnGe3O8(OH)2]是由[GdGe3O8(OH)2]n3n陰離子骨架所構(gòu)成的二維層狀結(jié)構(gòu)，其基本結(jié)構(gòu)由GeO4/GeO4H四面體和GdO6八面體通過橋氧相互連接而形成的平行于（010）晶面方向的GdGe3O8(OH)2單層，而單層之間則由O H···O鍵相互連接形成沿b軸方向按[ABAB…]順序排列。對共摻雜樣品K3[Gd1-xTbxGe3O8(OH)2]（x=0.1，0.3）熒光性質(zhì)的研究表明，在其熒光光譜中存在著Gd3+和Tb3+的能量傳遞過程，熒光發(fā)射光譜表現(xiàn)出Tb3+離子的特征發(fā)射，是一種潛在的綠色熒光材料
[Abstract]:Rare earth has been widely used in all aspects of life because of its excellent optical, electrical, magnetic and other physical properties. As a traditional material, the research of the synthesis and application of silicate has always been a hot spot for researchers. As a new show of silicate materials, the silicate compounds with regular pore structure have been used in recent decades. Many excellent properties have also been shown in the study, and great potential applications have been shown in catalysis and adsorption. It is a research subject that people are interested in and continuously explore the unique luminescence properties of rare earth elements and microporous silicate homogeneous pore properties. The medium temperature hydrothermal method was synthesized under the temperature of less than 200 C. The reaction vessel was a stainless steel reaction kettle. In this paper, the Quickpress3.0 piston cylindrical high pressure reactor and the HR-1B-2 LECO high temperature and high pressure hydrothermal reaction device were used to try the microporous rare earth silicate with new structure under higher pressure and temperature. The synthesis of germanate compounds was studied. A series of novel rare earth silicates and germanate compounds were successfully synthesized in the range of 0.5~1GPa pressure and 300~700 C temperature range, and their crystal structure and fluorescence properties were studied.
(1) a new Na15Eu3Si12O36 single crystal was successfully synthesized by high temperature and high pressure synthesis. The crystal structure of the single crystal was analyzed by X ray diffraction analysis of single crystal. The results of the single crystal analysis were verified by powder X ray diffraction and X ray energy spectrum analysis. The crystal structure analysis showed that the crystal was composed of [Si6O12]n1 A three-dimensional open framework constructed by the 2n- ring silicate anions and the EuO6 eight sides by sharing the apical O atoms. The structure contains a 6 membered ring channel structure along [010] direction composed of EuO6 eight and SiO4 tetrahedron. The results of single crystal analysis show that Na (2) + and Na (3) + ions are in its structure. The positions were occupied by Eu (2) and Eu (3), and the statistical disordered Eu/Na occupancy disorder had an important effect on the fluorescence properties of Na15Eu3Si12O36, and this result was verified in the test of its fluorescence properties.
(2) the new structure of europium silicate is successfully synthesized at high temperature and high pressure. The chemical composition of the Na3EuSi6O15. 1.47H2O. single crystal X ray diffraction crystal structure analysis shows that the crystal is a three dimensional open skeleton structure.SiO4 four formed by the interaction of EuO7 polyhedron between the wavy SiO4 tetrahedron monolayers. The structure of the 4,8 element ring along the [100] direction, formed by the EuO7 polyhedron and SiO4 tetrahedron, and the 5,6 element ring path along the [001] direction in the three-dimensional skeleton structure of the 4,5,6,8 element ring channel structure.Na3EuSi6O15. 1.47H2O along the [010] axis along the surface of the surface, and the study of the thermal stability and the fluorescence properties of the 5,6 element ring along the [001] direction. It shows that its structure is still stable at 800 C and shows red light emission. These results show that Na3EuSi6O15 1.47H2O is a kind of good thermal stability fluorescent material.
(3) a fluorine containing microporous europium silicate with a new structure was synthesized by the high temperature and high pressure molten salt method with KF 2H2O and KOH as the flux. The chemical composition of the structure was K2EuSi4O10F. through the single crystal X ray diffraction. The structure of the crystal structure.K2EuSi4O10F was determined by the powder X ray diffraction analysis. The structure of the crystal structure composed of the SiO4 tetrahedron is along the b axis. A three-dimensional open skeleton structure with a 6,8 ring channel structure along the b axis along the b axis, which is formed between the tubular chain of the direction and the EuO4F2 eight plane infinite chains arranged along the b axis through the sharing of oxygen atoms at the top. Red fluorescent material of value.
(4) a series of rare earth germanate with 2D layered structure were successfully synthesized by HR-1B-2 LECO high temperature and high pressure hydrothermal reaction device. The structure of K3[LnGe3O8 (OH) 2]. was studied by single crystal X ray diffraction, powder X ray diffraction, EDS, and infrared spectroscopy. The single crystal structure analysis showed that K3[LnGe3O8 (OH) 2] was separated from negative Yin. The two-dimensional layered structure of the subskeleton consists of the GdGe3O8 (OH) 2 monolayers parallel to the direction of the (010) crystal plane formed by the GeO4/GeO4H tetrahedron and the GdO6 eight facets connected by the bridge oxygen. The single layer is connected by the O H. O bond to form [ABAB in the direction of b axis. The study of the fluorescence properties of Co doped samples K3[Gd1-xTbxGe3O8 (OH) 2] (x=0.1,0.3) shows that there is a energy transfer process of Gd3+ and Tb3+ in the fluorescence spectrum. The fluorescence emission spectrum shows the characteristic emission of Tb3+ ions and is a potential green fluorescent material.
【學(xué)位授予單位】：吉林大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2015
【分類號】：TQ133.3
本文編號：2167988
[Abstract]:Rare earth has been widely used in all aspects of life because of its excellent optical, electrical, magnetic and other physical properties. As a traditional material, the research of the synthesis and application of silicate has always been a hot spot for researchers. As a new show of silicate materials, the silicate compounds with regular pore structure have been used in recent decades. Many excellent properties have also been shown in the study, and great potential applications have been shown in catalysis and adsorption. It is a research subject that people are interested in and continuously explore the unique luminescence properties of rare earth elements and microporous silicate homogeneous pore properties. The medium temperature hydrothermal method was synthesized under the temperature of less than 200 C. The reaction vessel was a stainless steel reaction kettle. In this paper, the Quickpress3.0 piston cylindrical high pressure reactor and the HR-1B-2 LECO high temperature and high pressure hydrothermal reaction device were used to try the microporous rare earth silicate with new structure under higher pressure and temperature. The synthesis of germanate compounds was studied. A series of novel rare earth silicates and germanate compounds were successfully synthesized in the range of 0.5~1GPa pressure and 300~700 C temperature range, and their crystal structure and fluorescence properties were studied.
(1) a new Na15Eu3Si12O36 single crystal was successfully synthesized by high temperature and high pressure synthesis. The crystal structure of the single crystal was analyzed by X ray diffraction analysis of single crystal. The results of the single crystal analysis were verified by powder X ray diffraction and X ray energy spectrum analysis. The crystal structure analysis showed that the crystal was composed of [Si6O12]n1 A three-dimensional open framework constructed by the 2n- ring silicate anions and the EuO6 eight sides by sharing the apical O atoms. The structure contains a 6 membered ring channel structure along [010] direction composed of EuO6 eight and SiO4 tetrahedron. The results of single crystal analysis show that Na (2) + and Na (3) + ions are in its structure. The positions were occupied by Eu (2) and Eu (3), and the statistical disordered Eu/Na occupancy disorder had an important effect on the fluorescence properties of Na15Eu3Si12O36, and this result was verified in the test of its fluorescence properties.
(2) the new structure of europium silicate is successfully synthesized at high temperature and high pressure. The chemical composition of the Na3EuSi6O15. 1.47H2O. single crystal X ray diffraction crystal structure analysis shows that the crystal is a three dimensional open skeleton structure.SiO4 four formed by the interaction of EuO7 polyhedron between the wavy SiO4 tetrahedron monolayers. The structure of the 4,8 element ring along the [100] direction, formed by the EuO7 polyhedron and SiO4 tetrahedron, and the 5,6 element ring path along the [001] direction in the three-dimensional skeleton structure of the 4,5,6,8 element ring channel structure.Na3EuSi6O15. 1.47H2O along the [010] axis along the surface of the surface, and the study of the thermal stability and the fluorescence properties of the 5,6 element ring along the [001] direction. It shows that its structure is still stable at 800 C and shows red light emission. These results show that Na3EuSi6O15 1.47H2O is a kind of good thermal stability fluorescent material.
(3) a fluorine containing microporous europium silicate with a new structure was synthesized by the high temperature and high pressure molten salt method with KF 2H2O and KOH as the flux. The chemical composition of the structure was K2EuSi4O10F. through the single crystal X ray diffraction. The structure of the crystal structure.K2EuSi4O10F was determined by the powder X ray diffraction analysis. The structure of the crystal structure composed of the SiO4 tetrahedron is along the b axis. A three-dimensional open skeleton structure with a 6,8 ring channel structure along the b axis along the b axis, which is formed between the tubular chain of the direction and the EuO4F2 eight plane infinite chains arranged along the b axis through the sharing of oxygen atoms at the top. Red fluorescent material of value.
(4) a series of rare earth germanate with 2D layered structure were successfully synthesized by HR-1B-2 LECO high temperature and high pressure hydrothermal reaction device. The structure of K3[LnGe3O8 (OH) 2]. was studied by single crystal X ray diffraction, powder X ray diffraction, EDS, and infrared spectroscopy. The single crystal structure analysis showed that K3[LnGe3O8 (OH) 2] was separated from negative Yin. The two-dimensional layered structure of the subskeleton consists of the GdGe3O8 (OH) 2 monolayers parallel to the direction of the (010) crystal plane formed by the GeO4/GeO4H tetrahedron and the GdO6 eight facets connected by the bridge oxygen. The single layer is connected by the O H. O bond to form [ABAB in the direction of b axis. The study of the fluorescence properties of Co doped samples K3[Gd1-xTbxGe3O8 (OH) 2] (x=0.1,0.3) shows that there is a energy transfer process of Gd3+ and Tb3+ in the fluorescence spectrum. The fluorescence emission spectrum shows the characteristic emission of Tb3+ ions and is a potential green fluorescent material.
【學(xué)位授予單位】：吉林大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2015
【分類號】：TQ133.3
【參考文獻(xiàn)】
相關(guān)期刊論文 前1條
1 鄧宇航;宋文申;董偉樂;代如成;王中平;張?jiān)雒?丁澤軍;;White light emission of Eu~(3+)/Ag co-doped Y_2Si_2O_7[J];Journal of Rare Earths;2014年09期
本文編號：2167988
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