臺灣博碩士論文加值系統

本論文是以水熱反應合成了17個新穎的有機銨鎵磷酸鹽與有機銨過渡金屬鎵磷酸鹽化合物。所有的化合物，皆以單晶X-ray繞射方法解析其結構定出化學式；並由感應耦合電漿原子發射光譜儀(ICP-AES) 或電子微探儀(EPMA)測量其金屬元素種類和比例;再由熱重量/微差熱分析(TGA/DTA)觀察化合物的脫水、相轉變及分解之現象，部分化合物並由固態核磁共振光譜儀(MAS NMR)來量測31P與 71Ga的固態核磁共振光譜，以及使用超導量子干涉磁量儀(SQUID)來測量材料之磁性及磁滯曲線或磁化強度。
這些化合物依不同有機銨陽離子(或配位基)分成三個系列：
第一個系列共含有三個以1,2-diaminocyclohexane (DACH) 為有機陽離子化合物，[(1S,2S)-H2DACH][Ga2(1S,2S-DACH)(HPO4)(PO4)2] (1)為layer structure，(H2DACH)2[Zn4Ga2(HPO4)3(PO4)4] (2)為新穎的3D結構化合物，以及(H2DACH)[Zn2Ga2(PO4)4] (3)具有CGS framework。
第二個系列共含有五個以piperazine (PPZ) 為有機陽離子的化合物，(H2PPZ)3[Ga4(OH)2(PO4)2(HPO4)4(H2PO4)2] (4)為chain structure，(H2PPZ)3[Ga8(H2O)4(PO4)10]×2H2O (5)，以及(H2PPZ)3[TixGa8-x(H2O)4(PO4)10]×2H2O (x~2.52) (6)有相同寬闊的layer structure，(H2PIP)[Zn2Ga(PO4)3] (7) 具有SOD framework，以及(H2PIP)[Zn2Ga2(PO4)4]·H2O (8) 具有GIS framework。
第三個系列共含有九個用diethylenetriamine (DIEN) 來反應的化合物，[Ga2(DETA)(PO4)2]·2H2O (9) 為3D framework，有24環的一維大孔道，[CrxGa1-x(DETA)(PO4)2]·yH2O(10)，[Co0.11Ga1.89(DETA)(PO4)2]·0.86H2O(11)，[Co0.19Cr0.21Ga1.6(DETA)(PO4)2]·1.02H2O (12)，[Mn0.2Ga1.8(DETA)(PO4)2]·1.33H2O (13)，[Fe0.2Ga1.8(DETA)(PO4)2]·1.11H2O (14)，以及[Zn0.17Ga1.83(DETA)(PO4)2]·1.17H2O (15)，為過渡金屬取代到化合物9的相同結構
，(H3DETA)[Mn(H2O)2Ga(PO4)2]3 (16) 具有CZP結構的3D chiral framework， 以及(H3DETA)[Zn3Ga(PO4)4]·H2O (17)與UCSB-7有相同的3D chiral framework。
在所有17個化合物中，共合成了一個新穎3D結構的ZnGaPO化合物，五個與文獻已知結果等結構的MGaPO(M = Mn, Zn)，一個等結構chian的GaPO，兩個新穎的layer structure，七個過渡金屬取代的MxGa1-xPOs，以及一個將孔道大小記錄提升到24環的GaPO。

This thesis describes 17 new gallophosphates and transition metal substituted gallophosphates, which were synthesized by hydrothermal reaction. All compounds were characterized by single-crystal X-ray diffraction, powder X-ray diffraction, thermogravimetric analysis, EPMA, ICP-AES, solid-state NMR spectroscopy, and magnetic susceptibility data.
These compounds were divided into three parts by different template or structure directing agent:
The first system: DACH/(M, Ga)/P/O (M= Zn) was contributed by three compounds. There are the two dimensional layer-structure of (1S,2S)-H2DACH][Ga2(1S,2S-DACH)(HPO4)(PO4)2] (1), novel three dimensional structure of (H2DACH)2[Zn4Ga2(HPO4)3(PO4)4] (2), and CGS topology of (H2DACH)[Zn2Ga2(PO4)4] (3).
The second system: PPZ/(M, Ga)/P/O (M = Ti, Zn) was contributed by five compounds. There are the one dimensional chain-structure of (H2PPZ)3[Ga4(OH)2(PO4)2(HPO4)4(H2PO4)2] (4), the same widen layer structure of (H2PPZ)3[Ga8(H2O)4(PO4)10]×2H2O (5) and (H2PPZ)3[TixGa8-x(H2O)4(PO4)10]×2H2O (x~2.52) (6), SOD topology of (H2PPZ)[Zn2Ga(PO4)3] (7), and GIS topology of (H2PPZ)[Zn2Ga2(PO4)4]·H2O (8).
The third system: DIEN/(M, Ga)/P/O (M = Cr, Mn, Fe, Co, Zn) was contributed by nine compounds. There are the three dimensional framework of [Ga2(DETA)(PO4)2]·2H2O (9) with one dimensional 24-membered ring, the chromium substituted [CrxGa1-x(DETA)(PO4)2]·yH2O (x~0.17, y~0.95) (10), the cobalt substituted [CoxGa1-x(DETA)(PO4)2]·yH2O (x~0.11, y~0.86) (11)，the chromium and cobalt substituted [CoxCryGa1-x-y(DETA)(PO4)2]·zH2O (x~0.19, y~0.21, z~1.02) (12)，the manganese substituted [MnxGa1-x(DETA)(PO4)2]·yH2O (x~0.2, y~1.33) (13)，the iron substituted [FexGa1-x(DETA)(PO4)2]·yH2O (x~0.2, y~1.11) (14), the zinc substituted [ZnxGa1-x(DETA)(PO4)2]·yH2O (x~0.17, y~1.17) (15), and 3D chiral framework of (H3DETA)[Mn(H2O)2Ga(PO4)2]3 (16) and (H3DETA)[Zn3Ga(PO4)4]·H2O (17).

第一章 緒論 1-1
1.1 微孔材料簡介 1-1
1.2 論文研究目標 1-6
1.3 合成方法 1-7
1.4 鑑定方法 1-12
1.5 研究成果摘要 1-19
1.6 參考文獻 1-20
第二章 DACH/(M, Ga)/P/O系列 (M = Zn) 2-1
2.1 簡介 2-1
2.2 實驗部分 2-2
2.3 結果與討論 2-8
2.4 結論 2-25
2.5 參考文獻 2-26
第三章 PPZ/(M, Ga)/P/O系列 (M = Zn, Ti) 3-1
3.1 簡介 3-1
3.2 實驗部分 3-2
3.3 結果與討論 3-10
3.4 結論 3-32
3.5 參考文獻 3-33
第四章 DIEN/(M, Ga)/P/O系列 (M = Cr, Mn, Fe, Co, Zn) 4-1
4.1 簡介 4-1
4.2 實驗部分 4-3
4.3 結果與討論 4-15
4.4 結論 4-36
4.5 參考文獻 4-37
第五章 總結 5-1
附錄A. 表附錄 A-1
附錄B. 圖附錄 B-1
附錄C. 博士班研究期間發表的論文 C-1
附錄D. 簡列化合物晶格常數 D-1

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