含鉛離子和三價金屬陽離子之混亞磷酸 -磷酸鹽化合物合成及結構和性質探討

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姓名

李天予(Tian-Yu Lii) 查詢紙本館藏

畢業系所

化學學系

論文名稱

含鉛離子和三價金屬陽離子之混亞磷酸 -磷酸鹽化合物合成及結構和性質探討
(Synthesis and Characterization of Mixed Phosphite-Phosphates Containing Lead Cation and Trivalent Metal Cations)

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摘要(中)

本論文利用中溫水熱合成法合成出三個含鉛離子和三價金屬陽離子之
混亞磷酸 -磷酸鹽化合物， Pb2Al(HPO3)3(H2PO4) (A1)、 Pb2Ga(HPO3)3(H2PO4) (A2)和 Pb2Fe(HPO3)2(HPO4)(H2PO4) (A3)。三個化合物皆由單晶 X光繞射實
驗解析出化合物的晶體結構，再用 EDS 確定化合物元素組成，而當中化合
物 A1、 A2有進一步測量紅外光光譜和固態核磁共振來進行定性及光學性
質的分析。化合物 A1、 A2和 A3 三個化合物皆為透明片狀的三維網狀結構
且三個化合物為等結構化合物，三個化合物的空間群皆為中心對稱的 Cmcm
三個化合物的結構都具有三價陽離子的亞磷酸層狀結構和磷酸二氫鉛層狀
結構。兩種層狀結構在以共享氧原子的方式互相連接形成三維的網狀結構。
A1和 A2化合物的紅外光光譜儀的測量，顯示化合物結構中有 P-H鍵結存
在因此確認兩個化合物具有亞磷酸基團，兩個化合物在經由固態核磁共振
的測量確認鋁、鎵和磷原子的配位環境。本論文三個化合物皆為混亞磷酸 -磷酸鹽化合物，這類型的化合物在現有的文獻中相當稀少，顯示中溫水熱合
成法可以合成新結構的化合物。

摘要(英)

mixed phosphite-phosphates containing lead cation and trivalent metal cations, Pb2Al(HPO3)3(H2PO4) (A1), Pb2Ga(HPO3)3(H2PO4) (A2) and Pb2Al(HPO3)2(HPO4)(H2PO4) (A3), were synthesized in a Teflon-lined autoclave under middle-temperature hydrothermal conditions. Their structures were characterized by single-crystal X-ray diffraction and their contents were verified by energy dispersive spectroscopy. The purity was confirmed by powder X-ray diffraction. The presence of the P-H group in [HPO3] and the hydrogen bonding interactions in the structures were studied by infrared spectroscopy. In addition solid state NMR spectra of A1 and A2 were measured to study the coordination environments of P, Al, and Ga atoms. The three compounds are isostructural with the centrosymmetric orthorhombic space group Cmcm. The structure contains [MO6] (M=Al、Ga、Fe) octahedra which are linked by phosphite and dihydrogen phosphate ligands to from 2D layers with the eight-coordinate lead ions being located in the interlayer region. Few well-characterized trivalent metal phosphite-phosphates have been documented. A comparison with related compounds in the literature will also be reported.

關鍵字(中)

★ 水熱合成法
★ 混亞磷酸-磷酸鹽

關鍵字(英)

★ Hydrothermal synthesis
★ Mixed Phosphite-Phosphates

論文目次

目錄
摘要
v
Abstract vi
謝誌
vii
目錄
viii
圖目錄
xi
表目錄
xiv
附錄之表目錄
xv
第一章
緒論 1
1-1 雷射 1
1-1-1 雷射的原理與歷史 1
1-1-2 雷射的分類 2
1-2 非線性光學 4
1-2-1 非線性光學的原理與歷史 4
1-2-2 非線性光學晶體及其應用 5
1-3 亞磷酸鹽 11
1-4 論文研究動機 13
1-5 研究成果摘要 14
第二章
實驗與結構解析 15
2-1 合成方法 15
ix
2-1-1 水熱合成法水熱合成法 ................................................................................................................................................................ 15
2-1-2 使用設備清單使用設備清單 ........................................................................................................................................................ 19
2-1-3 使用藥品清單使用藥品清單 ........................................................................................................................................................ 19
2-2 鑑定方法鑑定方法 .............................................................................................................................................................................................. 20
2-2-1 使用儀器列表使用儀器列表 ........................................................................................................................................................ 20
2-2-2 單晶單晶X光繞射儀與結構分析光繞射儀與結構分析 ...................................................................................................... 21
2-2-3 粉末粉末X光繞射儀光繞射儀 (PXRD) ................................................................................................................ 28
2-2-4 能量色散能量色散X射線譜射線譜 (EDS) .............................................................................................................. 29
2-2-5 紅外線光譜儀紅外線光譜儀 (IR) .............................................................................................................................. 30
2-2-6固態核磁共振光譜儀固態核磁共振光譜儀 (SSNMR) .............................................................................. 30
第三章
第三章結果與討論結果與討論 ...................................................................................................................................................................................... 34
3-1 實驗部分實驗部分 .............................................................................................................................................................................................. 34
3-1-1 Pb2Al(HPO3)3(H2PO4) (A1)合成條件合成條件 .................................................................................. 34
3-1-2 Pb2Ga(HPO3)3(H2PO4) (A2)合成條件合成條件 ................................................................................ 35
3-1-3 Pb2Fe(HPO3)2(HPO4)(H2PO4) (A3)合成條件合成條件 .......................................................... 36
3-2 單晶單晶X光繞射結構解析光繞射結構解析 ............................................................................................................................................ 37
3-2-1 單晶單晶X光繞射分析光繞射分析 ...................................................................................................................................... 37
3-2-2 Pb2Al(HPO3)3(H2PO4) (A1) 結構解析結構解析 .............................................................................. 38
3-2-3 Pb2Ga(HPO3)3(H2PO4) (A2) 結構解析結構解析 ............................................................................ 40
3-2-4 Pb2Fe(HPO3)2(HPO4)(H2PO4) (A3) 結構解析結構解析 ...................................................... 42
3-3 化合物鑑定與性質測量化合物鑑定與性質測量 .............................................................................................................................................. 44
3-3-1 Pb2Al(HPO3)3(H2PO4) (A1)粉末粉末X光繞射分析光繞射分析 ................................................ 44
3-3-2 Pb2Al(HPO3)3(H2PO4) (A1)能量色散能量色散 X射線譜射線譜 .............................................. 45
3-3-3 Pb2Al(HPO3)3(H2PO4) (A1)紅外線光譜分析紅外線光譜分析 .......................................................... 46
x
3-3-4 Pb2Al(HPO3)3(H2PO4) (A1) 27Al固態核磁共振分析固態核磁共振分析 ................................ 49
3-3-5 Pb2Al(HPO3)3(H2PO4) (A1) 31P固態核磁共振分析固態核磁共振分析 .................................... 50
3-3-6 Pb2Ga(HPO3)3(H2PO4) (A2)粉末粉末 X光繞射分析光繞射分析 ............................................ 52
3-3-7 Pb2Ga(HPO3)3(H2PO4) (A2)能量色散能量色散 X射線譜射線譜 ............................................ 53
3-3-8 Pb2Ga(HPO3)3(H2PO4) (A2)紅外線光譜分析紅外線光譜分析 ........................................................ 54
3-3-9 Pb2Ga(HPO3)3(H2PO4) (A2) 71Ga固態核磁共振分析固態核磁共振分析 .............................. 57
3-3-10 Pb2Ga(HPO3)3(H2PO4) (A2) 31P固態核磁共振分析固態核磁共振分析 .............................. 58
3-3-11 Pb2Fe(HPO3)2(HPO4)(H2PO4) (A3)粉末粉末 X光繞射分析光繞射分析 .................. 60
3-3-12 Pb2Fe(HPO3)2(HPO4)(H2PO4) (A3)能量色散能量色散 X射線譜射線譜 .................. 61
3-4 晶體結構描述晶體結構描述 .............................................................................................................................................................................. 62
3-4-1 Pb2Al(HPO3)3(H2PO4) (A1) 結構描述結構描述 .............................................................................. 64
3-4-2 Pb2Ga(HPO3)3(H2PO4) (A2) 結構描述結構描述 ............................................................................ 69
3-4-3 Pb2Fe(HPO3)2(HPO4)(H2PO4) (A3) 結構描述結構描述 ...................................................... 74
3-5 結構比較結構比較 .............................................................................................................................................................................................. 79
3-2-1 A1、、A2和和A3結構比較與討論結構比較與討論 ................................................................................................ 79
第四章
第四章結論結論 .............................................................................................................................................................................................................. 82
參考文獻
參考文獻 .......................................................................................................................................................................................................................... 83
附錄
附錄 .......................................................................................................................................................................................................................................... 88

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指導教授

李光華(Kwang-Hwa Lii)

審核日期

2020-7-17

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