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新型硼酸盐和K2NaNbO2F4的合成、结构及性能研究
李俊杰
学位类型硕士
导师潘世烈
2011-05-28
学位授予单位中国科学院研究生院
学位授予地点北京
学位专业材料物理与化学
关键词硼酸盐 合成 X-射线衍射 晶体结构 空间群
摘要随着激光技术和半导体技术的发展,对功能晶体材料提出了各种各样新的要求,对现有的晶体的质量要求也越来越高。因此,现在除了对已有的功能晶体设法继续提高质量或掺质改性外,研究功能晶体的组成,结构与性能间相互关系,探索寻找新型功能晶体始终是一个热门课题。 本论文采用高温溶液法探索新型硼酸盐晶体,主要合成了两种新型的硼酸盐晶体Pb6B2WO12 和Pb2Bi2AlB3O11,并通过单晶衍射对它们的结构进行了解析。同时,在对Pb2Bi2AlB3O11 化合物中铅离子的元素替代实验中发现了一个新的四元系硼酸盐化合物,Sr18Bi3.14Al2.86B18O54。解析了其单晶结构。 此外,在对KF–NaF–Nb2O5 体系的研究中,获得了化合物K2NaNbO2F4 可用于结构解析的单晶,解析了其单晶结构。 1. Pb6B2WO12 化合物。在PbO–Bi2O3–WO3–H3BO3 体系中,在Bi2O3 : PbO : WO3 : H3BO3 = 3 : 12 : 2 : 2 (摩尔比) 时,其单晶通过缓慢降温法可以得到。单晶结构解析的结果表明,Pb6B2WO12 结晶于正交晶系,空间群为Cmcm (No. 63),晶胞参数:a = 18.4904(5) Å,b = 6.35980(10) Å,c = 11.6789(2) Å,Z = 4。Pb6B2WO12 的结构由 链通过BO3 基团形成 层,该铅硼氧层与WO4 基团交替排列,通过长的Pb–O 键[2.74(2)–2.79(1) Å] 相互连接形成。Pb6B2WO12 的红外光谱研究证实了分子中含有BO3 基团。对Pb6B2WO12 化合物的热分析表明,该化合物为一同成分熔融化合物,熔点为749 °C。 2. Pb2Bi2AlB3O11 化合物。在PbO–Bi2O3–Al2O3–H3BO3 体系中,PbO : Bi2O3 : Al2O3: H3BO3 : PbF2 = 2 : 1 : 1 : 2 : 1 (摩尔比) 时,其单晶通过缓慢降温法可以得到。单晶结构解析的结果表明,Pb2Bi2AlB3O11 结晶于单斜晶系,空间群为C2/c (No. 15),晶胞参数:a = 17.263 (2) Å,b = 8.7322 (11) Å,c = 6.8081 (9) Å,β = 90.566°, Z = 4。该化合物呈现为一个三维网络状结构,由OPb2BiAl 四面体通过共享顶点形成的[Pb6Bi6Al3O6]∞ 层与BO3 基团所构成。Pb2Bi2AlB3O11 的红外光谱研究证实了分子中含有BO3 基团。对Pb2Bi2AlB3O11 化合物的热分析表明,该化合物为一同成分熔融化合物,熔点为693 °C。 对Pb2Bi2AlB3O11 化合物中的二价铅离子用Mg2+,Ca2+,Sr2+,Ba2+,Cd2+,Zn2+,Cu2+ 进行的替代实验表明。在SrCO3–Bi2O3–Al2O3–H3BO3 体系中,存在一个新的四元系硼酸盐化合物,Sr18Bi3.14Al2.86B18O54。该化合物结晶于三方晶系,空间群为 (No.148),a = 12.2577 (13) Å,b = 12.2577 (13) Å,c = 9.1387 (13) Å。 3. K2NaNbO2F4 化合物。采用高温溶液法,在KF∙2H2O – NaF – Nb2O5 – NH4F体系中,KF•2H2O : NaF : Nb2O5 : NH4F = 2 : 2 : 1 : 10 (摩尔比) 时,其单晶通过高温溶液法可以得到。单晶结构解析的结果表明,K2NaNbO2F4 为立方晶系,空间群为 (No. 225),晶胞参数:a = 8.4726(4) Å,Z = 4。该化合物由(010) 方向的[Na2Nb2O4F8]∞ 层堆砌形成三维网络结构,层与层之间通过共享O 原子或者F 原子进行连接。此外,在K2NaNbO2F4 的结构中形成了一个少见的[NbO2F4]3- 阴离子基团。K2NaNbO2F4 的红外光谱研究证实了分子中存在NbO2 基团和NbF4 基团。对K2NaNbO2F4 化合物的热分析表明,该化合物为一非同成分熔融化合物,分解温度为899 °C。
其他摘要The continuously development of laser technology puts forward all kinds of new request to optical materials. High quality of crystals is required. Besides improving the quality of the present optical crystals through doping, the investigation of the relations between properties, structures, and compositions of optical crystals as well as exploratory syntheses of new types of optical crystal has always been a hot topic. In this dissertation, two novel lead-containing borates have been prepared by solid-state reactions, including Pb6B2WO12 and Pb2Bi2AlB3O11. Their structures were characterized by single-crystal X-ray diffraction measurements. Meanwhile, we obtained the single crystal of K2NaNbO2F4 in the KF–NaF–NH4F–Nb2O5 system, and solved its structure. 1. Small single crystals of Pb6B2WO12 were obtained from the solution of Bi2O3 : PbO : WO3 : H3BO3 with molar ratio of 3 : 12 : 2 : 2. The single-crystal X-ray structural analysis showed that Pb6B2WO12 crystallizes in the orthorhombic space group Cmcm (No. 63) with a = 18.4904(5) Å, b = 6.35980(10) Å, c = 11.6789(2) Å, Z = 4. Pb6B2WO12 may be described as a layered structure consisting of 2D sheets and WO4 groups that are held together via long Pb–O [2.74(2)–2.79(1) Å] bonds. The sheets are formed by chains and BO3 groups. The IR spectrum of Pb6B2WO12 confirmed the existence of trigonally coordinated boron atoms. The results of thermal stability suggested that Pb6B2WO12 is a congruently melting compound and its melting point is 749 °C. 2. Small single crystals of Pb2Bi2AlB3O11 were obtained from the solution of PbO : Bi2O3 : Al2O3 : H3BO3: PbF2 with molar ratio of 2 : 1 : 1 : 2: 1. The single-crystal X-ray structural analysis showed that Pb2Bi2AlB3O11 crystallizes in the monoclinic space group C2/c (No. 15) with a = 17.263(2) Å, b = 8.7322(11) Å, c = 6.8081(9) Å,β=90.566°, Z = 4. Its structure may be described as three-dimensional frameworks formed of (100) [Pb6Bi6Al3O6]∞ layers stacked along a-axis. The layers are interconnected via BO3 groups. The IR spectrum of Pb2Bi2AlB3O11 confirmed the existence of trigonally coordinated boron atoms. The results of thermal stability suggested that Pb2Bi2AlB3O11 is also a congruently melting compound and its melting point is 693 °C. Preliminary substitution attempts were made: for Pb2+ by Mg2+, Ca2+, Sr2+, Ba2+, Cd2+, Zn2+, Cu2+. In the SrCO3–Bi2O3–Al2O3–H3BO3 system, a new borate compound, Sr18Bi3.14Al2.86B18O54 was found. The compound is trigonal, space group (No.148), and the unit cell parameters are a = 12.2577 (13) Å, b = 12.2577(13) Å, c = 9.1387(13) Å. 3. Single crystals of K2NaNbO2F4 were grown from the solution of KF∙2H2O : NaF : Nb2O5 : NH4F with molar ratio of 2 : 2 : 1 : 10. The compound is cubic, space group The IR spectra of K2NaNbO2F4confirmed the existence both NbO2 groups and NbF4 groups. The results of thermal stability suggested that Pb2Bi2AlB3O11 is not a congruently melting compound and the decomposition temperature was 899 °C. (No. 225), and the unit cell parameters are a = 8.4726(4) Å, Z = 4. Its structure can be described as three-dimensional frameworks formed of (010) [Na2Nb2O4F8]∞ layers stacked along b axis. The layers are interconnected via the sharing of O or F atoms.
文献类型学位论文
条目标识符http://ir.xjipc.cas.cn/handle/365002/4429
专题材料物理与化学研究室
作者单位中国科学院新疆理化技术研究所
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李俊杰. 新型硼酸盐和K2NaNbO2F4的合成、结构及性能研究[D]. 北京. 中国科学院研究生院,2011.
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