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类SBBO型硼酸盐和含有多种孤立P-O基团磷酸盐的合成 、结构和性能研究
张香玉
Subtype硕士
Thesis Advisor潘世烈
2016-05-26
Degree Grantor中国科学院大学
Place of Conferral北京
Degree Discipline材料物理与化学
Keyword硼酸盐 磷酸盐 晶体结构 维度减小理论 孤立p-o基团
Abstract

基于硼酸盐和磷酸盐丰富的结构类型,本论文在磷酸盐和硼酸盐中探索合成结构新颖的化合物。在M2O-CaO-B2O3 (M = Rb, Cs)体系探索并合成了类SBBO型的Rb2Ca3B16O28 和 Cs2Ca3B16O28;在Li2O-PbO-P2O5和Li2O-PbO-BaO-P2O5体系中探索并合成了含有多种孤立P-O基团的Pb12[Li2(P2O7)2(P4O13)2](P4O13) 和Pb3Ba6[Li2(P2O7)2(P4O13)2],确定了这四种化合物的晶体结构,并表征其性能。1. 类SBBO型硼酸盐在M2O-CaO-B2O3 (M = Rb, Cs)体系中,通过高温溶液法获得该体系的第一例化合物,两个同构的中心对称化合物Rb2Ca3B16O28和Cs2Ca3B16O28。他们均结晶于单斜晶系C2/c (No. 15)空间群。Rb2Ca3B16O28的晶胞参数为a = 21.64(2) ?,b = 7.731(9) ?,c = 13.399(15) ?,β = 91.701(14)°,Z = 4;Cs2Ca3B16O28的晶胞参数为a = 21.703(7) ?,b = 7.717(3) ?,c = 13.456(5) ?,β = 91.095(4)°,Z = 4。该化合物具有类似Sr2Be2B2O7 (SBBO) 的结构:它的基本构筑单元为船型的[B8O18]基团,每个[B8O18]基团与周围的六个相同的基团连接形成二维层,相对排列的两个层通过共用氧原子连接形成三维开放框架层,Rb或Cs原子填充在层内的三维孔中,Ca原子连接三维开放框架层形成三维网状结构。紫外-可见-近红外透过光谱测试表明,它们的光学透过截止边分别为242 nm和234 nm。热学性能测试表明他们为非同成分熔融化合物。2. 含有多种孤立P-O基团的磷酸盐以维度减小理论为指导,通过高温溶液法获得两种结构非常新颖的磷酸盐,Pb12[Li2(P2O7)2(P4O13)2](P4O13)和Pb3Ba6[Li2(P2O7)2(P4O13)2]。其中,Pb12[Li2(P2O7)2(P4O13)2](P4O13)中存在三种孤立的P-O基团,P2O7和两种对称性不同的P4O13,这在磷酸盐体系是首次发现;Pb3Ba6[Li2(P2O7)2(P4O13)2]中存在两种孤立P-O基团,P2O7和P4O13。两个化合物的晶胞参数及结构特征如下:(a) Pb12[Li2(P2O7)2(P4O13)2](P4O13) 结晶于三斜晶系P (No. 2)空间群。晶胞参数为a = 7.3723(4) ?,b = 11.4425(6) ?,c = 14.2163(7) ?,α = 73.020(3)°,β = 81.998(3)°,γ = 85.325(3)°,Z = 1。该晶体结构中,P4O13基团分为两类:一类与LiO4四面体和P2O7基团连接形成零维的[Li2(P2O7)2(P4O13)2]18-阴离子簇;另一类是孤立的。零维的[Li2(P2O7)2(P4O13)2]18-阴离子簇和孤立的[P4O13]6-基团通过PbOn 多面体相互连接形成三维整体结构。(b) Pb3Ba6[Li2(P2O7)2(P4O13)2] 结晶于三斜晶系P (No. 2)空间群。晶胞参数为a = 7.5293(4) ?,b = 7.8246(4) ?,c = 15.7265(9) ?,α = 80.356(3)°,β = 84.680(3)°, γ = 78.446(3)°,Z = 1。在晶体结构中,LiO4四面体连接P2O7和P4O13基团形成零维的[Li2(P2O7)2(P4O13)2]18-阴离子簇,Pb-O和Ba-O多面体连接零维的阴离子簇形成三维的网络结构.

Other Abstract

This dissertation mainly explores and synthesizes the novel structures in phosphate and borate because of their abundant structure types. In M2O-CaO-B2O3 (M = Rb and Cs) system, borates analogous to SBBO (Rb2Ca3B16O28 and Cs2Ca3B16O28) have been synthesized; in Li2O-PbO-P2O5 and Li2O-PbO-BaO-P2O5 systems, two phosphates with multiple isolated P-O groups (Pb12[Li2(P2O7)2(P4O13)2](P4O13) and Pb3Ba6[Li2(P2O7)2(P4O13)2]) have been synthesized. The crystal structures and properties of the four compounds have been investigated.1. Borates analogous to SBBOIn M2O-CaO-B2O3 (M = Rb and Cs) system, the first example of compounds, two isostructural centrosymmetric compounds Rb2Ca3B16O28 and Cs2Ca3B16O28 has been synthesized by high temperature solution method. They crystallize in the monoclinic system space group C2/c (No. 15), with a = 21.64(2) ?, b = 7.731(9) ?, c = 13.399(15) ?, β = 91.701(14)°, Z = 4 for Rb2Ca3B16O28 and a = 21.703(7) ?, b = 7.717(3) ?, c = 13.456(5) ?, β = 91.095(4)°, Z = 4 for Cs2Ca3B16O28. Their structures are similar to Sr2Be2B2O7 (SBBO): the fundamental building block (FBB) is the boat-shaped B8O18 groups, which connects with six neighboring analogues to form a two-dimensional (2D) layer, and two face-to-face 2D layers are further bridged by O atoms to obtain the three-dimensional (3D) open-framework layer. The Rb or Cs atoms fill the in-layer 3D holes, while Ca atoms bridge 3D open-framework layers to form a 3D network structure. UV-Vis-NIR transmission spectrum indicates that the UV cut-off edge is 242 nm for Rb2Ca3B16O28 and 234 nm for Cs2Ca3B16O28. Thermal analysis reveals that they are incongruently melting compounds.2. Phosphates with multiple isolated P-O groupsGuided by dimensional reduction, two novel phosphates, Pb12[Li2(P2O7)2(P4O13)2](P4O13) and Pb3Ba6[Li2(P2O7)2(P4O13)2], were obtained by high temperature solution method. In the Pb12[Li2(P2O7)2(P4O13)2](P4O13), there are three types isolated P-O groups, P2O7 and two types of P4O13 groups with different symmetry, which is first discovered in phosphate; in the Pb3Ba6[Li2(P2O7)2(P4O13)2], there are two types of isolated P-O groups, P2O7 and P4O13. Unit cell parameters and structure characteristics of the two compounds are as follows:(a) Pb12[Li2(P2O7)2(P4O13)2](P4O13) crystallizes in the triclinic system space group P (No. 2), with a = 7.5293(4) ?, b = 7.8246(4) ?, c = 15.7265(9) ?, α = 80.356(3)°, β = 84.680(3)°, γ = 78.446(3)°, Z = 1. In the crystal structure, the P4O13 groups are divied into two types: one type is used to construct the 0D [Li2(P2O7)2(P4O13)2]18- anionic cluster with the LiO4 tetrahedra and P2O7 groups; the other type is isolated. They are connected by PbOn polyhedra to form a 3D framework (b). Pb3Ba6[Li2(P2O7)2(P4O13)2] crystallizes in the triclinic system space group P (No. 2), with a = 7.5293(4) ?, b = 7.8246(4) ?, c = 15.7265(9) ?, α = 80.356(3)°, β = 84.680(3)°, γ = 78.446(3)°, Z = 1. In the crystal structure, the LiO4 tetrahedra connect the P2O7 and P4O13 groups to form zero-dimensional (0D) [Li2(P2O7)2(P4O13)2]18- anion clusters, which are connected by Pb-O and Ba-O polyhedra to form a 3D network structure.

Document Type学位论文
Identifierhttp://ir.xjipc.cas.cn/handle/365002/4591
Collection材料物理与化学研究室
Affiliation中国科学院新疆理化技术研究所
Recommended Citation
GB/T 7714
张香玉. 类SBBO型硼酸盐和含有多种孤立P-O基团磷酸盐的合成 、结构和性能研究[D]. 北京. 中国科学院大学,2016.
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