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题名: (卤素)铅硼酸盐及复合阴离子化合物的合成、结构和性能研究
作者: 董凌云
答辩日期: 2014-05-26
导师: 潘世烈
专业: 材料物理与化学
授予单位: 中国科学院大学
授予地点: 北京
学位: 博士
关键词: 硼酸盐 ; 二阶姜 -泰勒畸变 ; 非线性光学晶体 ; 非线性光学晶体 ; OPb 4四面体 ; 复合阴离 子基团
摘要: 本论文的研究工作分为三部分:第一部分是三种铅硼酸盐化合物Pb4B6O13、Pb4B8O16和Pb6B10O21的结构、线性及非线性光学性能的研究;第二部分是五种卤素铅硼酸盐化合物Pb6B3O10X (X = F, Cl, Br)、Pb2(O4Pb8)(BO3)3Br3及Pb2(O8Pb12)(BO3)2Br6的合成、结构和物化性能的研究;第三部分是两种含有复合阴离子基团的化合物Rb5BS4O16及BaPbSi2O6·BaSO4的设计、合成及物化性能的研究。
1. 将含有立体活性孤对电子而导致易发生二阶姜-泰勒畸变的Pb2+金属阳离子与硼氧功能基团进行结合,采用高温溶液法合成了三种铅硼酸盐化合物Pb4B6O13、Pb4B8O16及Pb6B10O21,同时对三种化合物的结构进行了解析。化合物Pb4B6O13结晶于单斜晶系,非中心对称的空间群Cc(No. 9);化合物Pb4B8O16结晶于三斜晶系,空间群为P(No. 2);化合物Pb6B10O21结晶于单斜晶系的空间群C2/c(No. 15)。在三种铅硼酸盐化合物的结构中,BO3和BO4基团均通过共顶点连接形成二维层状结构,其中非中心对称化合物Pb4B6O13的粉末倍频效应与LiB3O5(LBO)相当并且能够实现相位匹配。
2. 采用高温溶液法在PbO-PbX2-H3BO3(X = F, Cl, Br)体系中合成了五种卤素铅硼酸盐化合物Pb6B3O10X(X = F, Cl, Br)、Pb2(O4Pb8)(BO3)3Br3及Pb2(O8Pb12)(BO3)2Br6。化合物Pb6B3O10X(X = F, Cl, Br)结晶于正交晶系,空间群为Pbcm(No. 57),化合物Pb2(O4Pb8)(BO3)3Br3及Pb2(O8Pb12)(BO3)2Br6结晶于单斜晶系,空间群均为C2/c(No. 15)。五种卤素铅硼酸盐均含有OPb4和BO3基本结构单元,在化合物Pb6B3O10X(X = F, Cl, Br)中,孤立的OPb4和BO3基本结构单元通过共顶点连接形成“Zig-Zag”型∞1[(OPb4)(BO3)3]链状结构;而在化合物Pb2(O4Pb8)(BO3)3Br3和Pb2(O8Pb12)(BO3)2Br6中,OPb4四面体通过共边连接分别形成“Zig-Zag”型∞1[OPb2]链状和∞1[O2Pb3]带状结构,此类链状和带状结构在目前所有含铅氧合化合物中均属首次报道。对以上五种化合物的光学以及物化性能进行了研究。
3. 通过对Rb2CO3-H3BO3-(NH4)2SO4体系的研究,采用高温溶液法合成了含有零维[B(SO4)4]5-复合阴离子基团的化合物硼硫酸铷,Rb5BS4O16。该化合物结晶于四方晶系,手性空间群P43212(No. 96),红外光谱测试结果验证了结构中阴离子基团的存在;紫外-可见-近红外漫反射光谱测试结果表明化合物Rb5BS4O16的截止边低于230 nm,差热/热重分析结果表明Rb5BS4O16是非一致熔融的化合物;首次以非卤素化合物BaSO4盐为模板,BaPbSi2O6为基础化合物,成功合成了含有复合阴离子基团的化合物BaPbSi2O6·BaSO4,红外光谱测试结果验证了结构中SiO4及SO4阴离子基团的存在;紫外-可见-近红外漫反射光谱测试结果表明BaPbSi2O6·BaSO4和基础化合物BaPbSi2O6的带隙相当;差热/热重分析结果表明BaPbSi2O6·BaSO4的热稳定性略高于BaPbSi2O6。
英文摘要:
This dissertation was divided into three parts. In the first part, the crystal structures, linear and nonlinear optical (NLO) properties of three lead borates, Pb4B6O13, Pb4B8O16 and Pb6B10O21, were investigated. In the second part, the syntheses, crystal structures, chemical and physical properties of five lead borate halides were carried out. In the last part, the design, syntheses, chemical and physical properties of two mixed anionic compounds were reported for the first time. 1. Through the combination of the B-O functional group and Pb2+ cation, in which the stereochemically active lone pairs exist and the second-order Jahn-Teller (SOJT) distortion can easily occur, we have obtained three lead borates, Pb4B6O13, Pb4B8O16, and Pb6B10O21, by the high temperature solution method. The structures of three compounds were solved by direct methods. Pb4B6O13 crystallizes in the monoclinic crystal system with the noncentrosymmetric space group Cc (No. 9), Pb4B8O16 crystallizes in the triclinic crystal system with the centrosymmetric space group P (No. 2), and Pb6B10O21 crystallizes in the centrosymmetric space group C2/c (No. 15) of the monoclinic system. The BO3 and BO4 groups are connected through corners to form two dimensional layers in the structures of three compounds. Pb4B6O13 produces the second harmonic generation (SHG) intensity as strong as LiB3O5 (LBO) and is phase-matchable. 2. Five lead oxyborate halides, Pb6B3O10X (X = F, Cl, Br), Pb2(O4Pb8)(BO3)3Br3 and Pb2(O8Pb12)(BO3)2Br6, were synthesized by the high temperature solution method in the PbO-PbX2-H3BO3 (X = F, Cl, Br) system. Pb6B3O10X (X = F, Cl, Br) crystallize in the space group Pbcm (No. 57) of the orthorhombic system, while the last two compounds, Pb2(O4Pb8)(BO3)3Br3 and Pb2(O8Pb12)(BO3)2Br6, crystallize in the space group C2/c (No. 15) of the monoclinic system. The five compounds have the same fundmental building units (FBUs), the OPb4 anion-centered tetrahedra and BO3 triangles. The crystal structures of Pb6B3O10X (X = F, Cl, Br) are dominated by one-dimensional ∞1[(OPb4)(BO3)3] “Zig-Zag”-chain, which is formed by the isolated OPb4 tetrahedra and BO3 triangles. Pb2(O4Pb8)(BO3)3Br3 consists of the single ∞1[OPb2] chains, while Pb2(O8Pb12)(BO3)2Br6 possesses the ∞1[O2Pb3] ribbons in “Zig-Zag” fashion. It should be noted that those chains and ribbons, which are formed by the edge-sharing OPb4 tetrahedra, are rarely found in other lead-containing oxysalts. The optical, chemical and physical properties of the above lead oxyborate halides were carried out. 3. A new chiral rubidium borosulfate, Rb5BS4O16, has been successfully synthesized by the high temperature solution method in the Rb2CO3-H3BO3-(NH4)2SO4 system. It crystallizes in the chiral space group P43212 (No. 96) of the tetragonal system. Zero-dimensional anion groups, [B(SO4)4]5-, exist in the compound. Its UV cut off edge is below 230 nm. The TG-DSC analysis suggests that Rb5BS4O16 is an incongruent melting compound. We firstly developed BaSO4 salt as anion group provider and structure template, and BaPbSi2O6 as the basic compound, to synthesize mixed anionic material, BaPbSi2O6?BaSO4. The anion groups presented in the sample were identified by IR spectra. BaPbSi2O6?BaSO4 and BaPbSi2O6 own nearly the same band gaps. The TG-DSC analysis suggests that BaPbSi2O6?BaSO4 has higher thermal stability than BaPbSi2O6.
内容类型: 学位论文
URI标识: http://ir.xjipc.cas.cn/handle/365002/3410
Appears in Collections:材料物理与化学研究室_学位论文

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作者单位: 中国科学院新疆理化技术研究所

Recommended Citation:
董凌云. (卤素)铅硼酸盐及复合阴离子化合物的合成、结构和性能研究[D]. 北京. 中国科学院大学. 2014.
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