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题名: 新型硼磷酸盐和磷酸盐化合物的合成、结构及性能研究
作者: 史云晶
答辩日期: 2013-05-28
导师: 周忠祥、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: 硕士
关键词: Na3Cd3B(PO4)4 ; Pb3B(PO4)3 ; LiNa3P2O7 ; Rb2CdP2O7 ; Cs2CdP2O7 ; 晶体结构 ; 性质
摘要: 本文在Na2O-CdO-B2O3-P2O5、PbO-B2O3-P2O5、Li2O-Na2O-P2O5、Rb2O-CdO-P2O5和Cs2O- CdO-P2O5体系中探索合成了Na3Cd3B(PO4)4,Pb3B(PO4)3,LiNa3P2O7,Rb2CdP2O7和Cs2CdP2O7五种 化合物,确定了5种化合物的晶体结构,并表征其性能。 1. 化合物Na3Cd3B(PO4)4 Na3Cd3B(PO4)4单晶是从高温熔液中自发成核结晶得到的。Na3Cd3B(PO4)4属于正交晶系,Pmc21空间群,a = 13.6854(3) ?,b = 5.3346(11) ?,c = 18.2169(4) ?,Z = 4。该化合物具有零维的[B(PO4)4]9-阴离子基团;该化合物吸收边是360 nm;Na3Cd3B(PO4)4有相对较强的粉末倍频效应,相当于1.1倍的KDP,并且能够实现相位匹配。 2. 化合物Pb3B(PO4)3 采用顶部籽晶法获得了Pb3B(PO4)3晶体,尺寸为18 mm × 7 mm × 9 mm。Pb3B(PO4)3属于正交晶系,Ibca空间群,a = 7.0080(2) ?,b = 14.2286(4) ?,c = 21.5469(6) ?,Z = 8。该化合物的[B(PO4)3]6-阴离子基团通过共用O原子排列形成围绕a方向的“之”字型链;Pb3B(PO4)3是一致熔融化合 物;Pb3B(PO4)3的吸收边为276 nm。 3. 化合物LiNa3P2O7 LiNa3P2O7单晶是从高温熔液中自发成核结晶得到的。LiNa3P2O7属于正交晶系,C2221空间群,a = 5.4966(2) ?,b = 9.1365(4) ?,c = 12.2764(5) ?,Z = 4。LiNa3P2O7的结构中有ab平面上二维的[Li3P2O7]3-层;LiNa3P2O7是一致熔融化合物;吸收边是233 nm。 4. 化合物Rb2CdP2O7 和Cs2CdP2O7 Rb2CdP2O7 和Cs2CdP2O7单晶是从高温熔液中分别自发成核结晶得到的。Rb2CdP2O7和Cs2CdP2O7分别属于单斜晶系的P21/c空间群和正交晶系 的Pnma空间群。Rb2CdP2O7晶胞参数为a = 5.3818(6) ?,b = 9.8723(11) ?,c = 15.6308(15) ?,β = 92.140(7)°,Z = 4;Cs2CdP2O7晶胞参数为a = 16.341(5) ?,b = 5.4772(15) ?,c = 10.019(3) ?,Z = 4。两种化合物具有相似的结构,在空间呈三维网络结构。3个P2O7基团与3个CdO5多面体交替连接,形成了二维的有孔隙的层状结 构;Rb2CdP2O7和Cs2CdP2O7都是一致熔融化合物;Rb2CdP2O7和Cs2CdP2O7的吸收边分别是204 nm和280 nm。
英文摘要:
In this paper, lots of researches in Na2O-CdO-B2O3-P2O5, PbO-B2O3-P2O5, Li2O-Na2O-P2O5, Rb2O-CdO-P2O5 and Cs2O-CdO-P2O5 systems have been studied, and Na3Cd3B(PO4)4, Pb3B(PO4)3, LiNa3P2O7, Rb2CdP2O7 and Cs2CdP2O7 have been synthesized. The crystal structures and properties of these compounds have been described. 1. Na3Cd3B(PO4)4 The single-crystal of Na3Cd3B(PO4)4 has been obtained by high tempurature solution method. Na3Cd3B(PO4)4 crystallizes in orthorhombic space group Pmc21 with unit cell parameters of a = 13.6854(3) ?, b = 5.3346(11) ?, c = 18.2169(4) ?, Z = 4. Na3Cd3B(PO4)4 has zero-dimensional [B(PO4)4]9- anionic groups. The absorption edge is 360 nm. Na3Cd3B(PO4)4 exhibits 1.1 times SHG effect as large as that of KDP and is phase-matchable. 2. Pb3B(PO4)3 The crystal of Pb3B(PO4)3 with crystal dimension of 18 mm × 7 mm × 9 mm has been obtained by top seeded growth method. Pb3B(PO4)3 crystallizes in orthorhombic space group Ibca with the unit cell parameters of a = 7.0080(2) ?, b = 14.2286(4) ?, c = 21.5469(6) ?, Z = 8. The [B(PO4)3]6- anionic groups connect with each other to form a one-dimensional zigzag chain along a axis. Pb3B(PO4)3 is a congruent melting compound. The absorption edge of Pb3B(PO4)3 is 276 nm. 3. LiNa3P2O7 The single-crystal of LiNa3P2O7 has been obtained by high tempurature solution method. LiNa3P2O7 crystallizes in orthorhombic space group C2221 with unit cell parameters of a = 5.4966(2) ?, b = 9.1365(4) ?, c = 12.2764(5) ?, Z = 4. LiNa3P2O7 consists of a two-dimensional [LiP2O7]3- layer. LiNa3P2O7 is a congruent melting compound. The absorption edge is 233 nm. 4. Rb2CdP2O7 and Cs2CdP2O7 The single-crystal of Rb2CdP2O7 and Cs2CdP2O7 have been obtained by high tempurature solution method. Rb2CdP2O7 and Cs2CdP2O7 crystallize in the monoclinic space group P21/c and orthorhombic space group Pnma, respectively. The unit cell parameters are a = 5.3818(6) ?, b = 9.8723(11) ?, c = 15.6308(15) ?, β = 92.140°(7) for Rb2CdP2O7 and a = 16.341(5) ?, b = 5.4772(15) ?, c = 10.019(3) ? for Cs2CdP2O7, respectively. Two compounds feature two-dimensional [CdP2O7]2- layers, which are composed by CdO5 polyhedra and diphosphate groups. Both Rb2CdP2O7 and Cs2CdP2O7 are congruent melting compounds. The absorption edges of Rb2CdP2O7 and Cs2CdP2O7 are 204 and 280 nm, respectively.
内容类型: 学位论文
URI标识: http://ir.xjipc.cas.cn/handle/365002/2465
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作者单位: 中国科学院新疆理化技术研究所

Recommended Citation:
史云晶. 新型硼磷酸盐和磷酸盐化合物的合成、结构及性能研究[D]. 北京. 中国科学院大学. 2013.
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