臺灣博碩士論文加值系統

本論文利用高溫高壓水熱法及熔鹽法合成兩系列的化合物，第一系列過渡金屬矽酸鹽化合物Rb2(Nb2O4)(Si2O6)．H2O (A1) 、Rb2(Nb2O4)(Si2O6) (A2) 、 Rb2(Ta2O4)(Si2O6)．H2O (A3)；第二系列是鑭系金屬矽酸鹽化合物Rb2YFSi4O10 (B1)、Rb2GdFSi4O10 (B2)、Rb2TbFSi4O10 (B3)、Rb2Tb0.9Eu0.1FSi4O10 (B4)、Rb2Eu0.67Tb0.33FSi4O10 (B5)。這兩系列的化合物利用單晶X光繞射儀定出結構，並以粉末X光繞射圖譜，比對理論圖譜確定樣品純度後再進行物理性質的量測。
A系列中的A1及A3互為等結構化合物，其具有新穎的結構，鈮(鉭)氧多面體以共角的形式連接成二維的層狀結構，再經由以矽氧四面體共角連接而成的[Si4O12]8- 四員環單元，以共角的形式連接，進而形成三維的骨架結構。將A1加熱至500 oC，留停一小時，可將孔洞內水分子移除可得A2，且降回室溫後，停留數小時，待水分子重新吸附回孔洞中，結構再次轉變回A1，此為一可逆的吸附行為，我們更進一步將化合物A2加熱至900 oC，發現結構仍穩定存在，顯示其熱穩定很高。
B系列中的所有化合物皆為等結構化合物，金屬氧多面體共角連接形成無限延伸鏈，而鏈與鏈之間則是經由以矽酸鹽四面體共角連接所組成的鋸齒鏈來連接形成一個新穎的三維結構。在本研究中，針對此系列化合物之中心金屬的發光特性，進行放光光譜的研究與探討，並合成混金屬化合物B4、B5，以探討金屬離子間能量轉移的現象。

Two series of transition metal and lanthanide silicates. Three metal silicates were synthesized by the high-temperature, high-pressure hydrothermal method. The series A denotes transition metals silicates, Rb2(Nb2O4)(Si2O6)·H2O (A1), Rb2(Nb2O4)(Si2O6) (A2) and Rb2(Ta2O4)(Si2O6)．H2O (A3). Five metal silicates were synthesized by the flux-growth method. The series B denotes lanthanide silicates, Rb2YFSi4O10 (B1), Rb2GdFSi4O10 (B2), Rb2TbFSi4O10 (B3), Rb2Tb0.9Eu0.1FSi4O10 (B4) and Rb2Eu0.67Tb0.33FSi4O10 (B5). All structures of those compounds are determined by single-crystal X-ray diffraction. The purity of each compound was confirmed by the good agreement between observed powder X-ray pattern and the calculated pattern based on single-crystal X-ray diffraction. The properties of these compounds were further characterized by different physical measurements respectively according to their structural features : the dehydration of A1 by thermogravimetric analysis (TGA) and the luminescence spectra of lanthanide silicates.
A1 and A3 are isostructural, representing a novel structure. Upon heating to 500 oC, A1 loses the lattice water molecules, while the framework structure retains to give the anhydrous compound A2. If A2 is exposed to air for several hours, the water molecules can be restored based on powder X-ray diffraction, and structure will be changed into A1.
All compounds of series B have similar structures, representing a novel structure. These materials have been characterized by photoluminescence spectroscopy, including emission and excitation spectra. Mixed lanthanide samples B4 and B5 have also been prepared and efficient Tb →Eu energy transfer has been observed for B4.

中文摘要························································································I
英文摘要······················································································Ⅱ
謝誌······························································································Ⅲ
目錄······························································································Ⅳ
圖目錄··························································································Ⅷ
表目錄··························································································XI
附錄之表目錄··········································································XI
第一章緒論····················································································1
1-1簡介······················································································1
1-2 合成方法···········································································7
1-2-1 水熱反應······································································7
1-2-2 助熔劑長晶法····························································11
1-2-3 藥品一覽表································································14
1-3 鑑定方法···········································································15
1-3-1 儀器測量簡介····························································15
1-3-2 單晶X光繞射與結構解析·······································16
1-3-3 粉末X光繞射分析(PXRD)······································19
1-3-4 熱重量分析(TGA)·····················································20
1-3-5 螢光儀········································································20
1-3-6 固態核磁共振分析(Solid-State NMR)······················20
1-4 研究成果···········································································22
第二章 高溫高壓水熱法合成鈮、鉭矽酸鹽·····························23
2-1 前言···················································································23
2-2 實驗部份···········································································25
2-2-1A Rb2(Nb2O4)(Si2O6)．H2O (A1)的合成·····················25
2-2-1B Rb2(Nb2O4)(Si2O6) (A2)的合成································25
2-2-1c Rb2(Ta2O4)(Si2O6)．H2O (A3)的合成······················25
2-2-2A Rb2(Nb2O4)(Si2O6)．H2O (A1)的晶體結構解析·····27
2-2-2-B Rb2(Nb2O4)(Si2O6) (A2) 的晶體結構解析············28
2-2-3A Rb2(Nb2O4)(Si2O6)．H2O (A1)的粉末繞射分析·····30
2-2-3B Rb2(Nb2O4)(Si2O6) (A2)的粉末繞射分析················31
2-2-3C Rb2(Ta2O4)(Si2O6)．H2O (A3)的粉末繞射分析·····32
2-3 結果與討論·······································································33
2-3-1A 化合物A1與A3的結構描述與討論····················33
2-3-1B 化合物A2的結構描述與討論·······························37
2-3-2A 化合物A1的熱重分析(TGA)································41
2-3-2B 化合物A2的熱重分析(TGA)································42
2-3-3 化合物A1固態NMR光譜分析····························43
2-3-4 水分子吸附與去吸附研究········································46
第三章助熔劑長晶法合成鑭系金屬矽酸鹽·······························51
3-1-1 簡介············································································51
3-1-2 螢光體簡介································································54
3-1-3發光原理·····································································56
3-1-4銪離子發光原理·························································58
3-1-5鋱離子發光原理·························································59
3-2實驗部分············································································60
3-2-1A Rb2YFSi4O10 (B1)的合成·········································60
3-2-1B Rb2GdFSi4O10 (B2)的合成·······································60
3-2-1C Rb2TbFSi4O10 (B3)的合成········································61
3-2-1D Rb2Tb0.9Eu0.1FSi4O10 (B4) 和Rb2Eu0.67 Tb0.33FSi4O10(B5)的合成······················································································61
3-2-1E Rb2LnFSi4O10 (Ln = La, Pr, Nd, Sm, Eu, Dy~ Lu)的合成 ······························································································62
3-2-2A Rb2YFSi4O10 (B1)的晶體結構解析··························63
3-2-2B Rb2GdFSi4O10 (B2)的晶體結構解析························64
3-2-3A 化合物B1、B2的粉末繞射分析··························66
3-2-3B 化合物B4和B5的粉末繞射分析························66
3-2-3C Rb2LnFSi4O10 (Ln = La, Pr, Nd, Sm ~ Lu)的粉末繞射分析 ······························································································66
3-3 結果與討論·······································································72
3-3-1A Rb2YFSi4O10 (B1) 和Rb2GdFSi4O10 (B2)的結構描述與討論······························································································72
3-3-2固態NMR 光譜分析·················································78
3-3-3發光性質研究·····························································79
3-3-3A化合物 B3 之光激放光與激發光譜······················80
3-3-3B化合物 B4 之光激放光與激發光譜······················82
3-3-3C化合物 B5 之光激放光與激發光譜······················86
第四章 結論················································································89
第五章 參考文獻········································································92
附錄······························································································98
圖目錄
圖1具有二十四環的類沸石結構·················································2
圖2 (a)鍺酸鹽SU-M沿 [111] 方向的結構圖(b)隧洞上的三十環開口通道································································································3
圖3 (a)未經熱處理之 ETS-10(b)經熱處理後之 ETS-10···········4
圖4 (a) Rb3In(H2O)Si5O13 矽酸鹽骨架(b) CdSO4 結構··············5
圖5 K(UO)Si2O6 結構示意圖·······················································6
圖6 中溫水熱反應器(a)外觀 (b)內部透視圖 (c)零組件············9
圖7. 高溫、高壓水熱反應器(a)外觀與反應容器(金管)(b)內部透視圖········································································································9
圖8. 密閉容器內水的填充度與溫度壓力的關係圖·················10
圖9 (a)同成份熔化(congruent melting) (b)非同成份熔化(incongruent melting)相圖·················································································13
圖10 Bruker-AXS SMART APEX與X8 APEX 單晶繞射儀的(a) 外觀 (b) SMART APEX組成(含低溫裝置) (c) X8 APEX 組成·········16
圖11 化合物A1之理論與實測與實測粉末繞射圖·················30
圖12 化合物A2之理論與實測粉末繞射圖·····························31
圖13 化合物A3之理論與實測粉末繞射圖·····························32
圖14 化合物A1的組成單元50%電子密度分布橢圓球圖·····34
圖15 (a) 化合物A1中NbO6八面體共角連接形成無限延伸鍊，而鍊與鍊之間經由共邊連接形成一個二維的陣列 (b)化合物A1中silicate 的連接方式······················································································35
圖16 化合物A1沿著b軸觀察的多面體圖·····························36
圖17 化合物A2的組成單元50% 電子密度分布橢圓球圖···38
圖18 (a)化合物 A1 沿 a 軸方向結構圖 (b)化合物 A2 沿(1, 1, 0)面方向結構圖··················································································39
圖19 (a) [Si4O12]8- 四聚體排列方式(b) NbO6 四聚體排列方式···40
圖20 化合物A1的熱重分析·····················································41
圖21 化合物A3的熱重分析·····················································42
圖22 (a)化合物A1的固態29Si MAS NMR圖譜(b) Rb4(NbO)2(Si8O21)結構示意圖(左，中)及其29Si MAS NMR圖譜(右)····················45
圖23 化合物A2在室溫之下放置不同時間之粉末繞射圖·····48
圖24 化合物A2不同時間下的粉末繞射圖(局部放大圖)·······49
圖25 化合物A3除水前後比較圖·············································50
圖26 化合物A3除水前後比較(局部放大)······························50
圖27 Na5Eu0.75Tb0.25Si4O12 和Na5Eu0.25Tb0.75Si4O12的激發光譜···
······································································································52
圖28 Na5Eu0.75Tb0.25Si4O12 和Na5Eu0.25Tb0.75Si4O12的室溫放光光譜
······································································································52
圖 29 Cs3EuSi6O15 結構示意圖(a)沿著 a 軸 (b)沿著 c 軸·····53
圖 30 K5Eu2FSi4O13 結構示意圖(a)沿著a軸(b)沿著b軸············53
圖 31 以 147 nm 激發 PDP 電漿電視三色螢光粉之放光圖······································································································55
圖32 具有 4fn 電子組態之三價稀土離子能階分佈圖············57
圖33 三價銪離子之能階分佈····················································58
圖34 三價鋱離子之能階分佈圖················································59
圖35 化合物B1的粉末繞射分析·············································67
圖36 化合物B2的粉末繞射分析·············································67
圖37 化合物B4的粉末繞射分析·············································68
圖38 化合物B5的粉末繞射分析·············································68
圖39 (a) 各化合物的粉末繞射分析疊圖(La~Sm) , (b) 各化合物的粉末繞射分析疊圖(Eu~Ho), (c) 各化合物的粉末繞射分析疊圖(Er~Lu)
······································································································69
圖40 化合物B1的組成單元50% 電子密度分布橢圓球圖···74
圖41 化合物B2的組成單元50%電子密度分布橢圓球圖·····74
圖42 化合物B1的局部多面體圖·············································75
圖43 化合物B1的多面體圖·····················································76
圖44 K2ScFSi4O10的多面體圖····················································76
圖45化合物B1(左)與K2ScFSi4O10(右)矽酸鹽連接形式比較···77
圖46 化合物B1的固態29Si MAS NMR圖譜·····························78
圖47 光激放光光譜研究之示意圖············································79
圖48 化合物 B3 之放光光譜圖···············································81
圖49 化合物 B3 之激發光譜圖···············································81
圖50 化合物 B4之放光光譜圖················································84
圖51 K3[EuSi3O8(OH)2] and K3[Tb0.95Eu0.05Si3O8(OH)2]的室溫放光光
譜··································································································84
圖52 化合物 B4 之激發光譜圖···············································85
圖53 K3[EuSi3O8(OH)2] K3[Tb0.95Eu0.05Si3O8(OH)2]的室溫激發光譜
······································································································85
圖54 化合物 B5 之放光光譜圖···············································87
圖55 化合物 B5 之激發光譜圖···············································88
圖56化合物Na5Eu0.75Tb0.25Si4O12 和Na5Eu0.25Tb0.75Si4O12的室溫激發光譜······························································································88
表目錄
表(1) 研究成果一覽表································································22
表(2) 文獻中具有SHG現象的化合物······································24
附錄之表目錄
表A1-1 Rb2(Nb2O4)(Si2O6)．H2O(A1)之晶體數據資料·············98
表A1-2 Rb2(Nb2O4)(Si2O6)．H2O(A1)原子座標與熱擾動參數
······································································································99
表A1-3 Rb2(Nb2O4)(Si2O6)．H2O(A1) 之部份鍵長·················100
表A2-1 Rb2(Nb2O4)(Si2O6)(A2) 之晶體數據資料····················102
表A2-2 Rb2(Nb2O4)(Si2O6)(A2) 之原子座標與熱擾動參數····103
表A2-3 Rb2(Nb2O4)(Si2O6)(A2) 之部份鍵長····························105
表B1-1 Rb2YFSi4O10 (B1)之晶體數據資料······························108
表B1-2 Rb2YFSi4O10 (B1) 之原子座標與熱擾動參數·············109
表B1-3 Rb2YFSi4O10 (B1)之部份鍵長······································110
表B2-1 Rb2GdFSi4O10 (B2)之晶體數據資料·····························111
表B2-2 Rb2GdFSi4O10 (B2) 之原子座標與熱擾動參數···········112
表B2-3 Rb2GdFSi4O10 (B2) 之部份鍵長···································113

[1] Schuth, F.; Schmidt, W. Adv. Mater. 2002, 9, 629.
[2] Davis, M. E. Nature 2002, 417, 813.
[3] Wilson, S. T.; Lok, B. M.; Messina, C. A.; Cannan, T. R.; Flanigen, E. M. J. Am. Chem. Soc. 1982, 104, 1146.
[4] Lin, C.-H.; Wang, S.-L.; Lii, K.-H. J. Am. Chem. Soc. 2001, 123, 4649.
[5] Guillou, N.; Gao, Q.; Forster, P. M.; Chang, J.-S.; Nogues, M.; Park, S.-E.; Ferey, G.; Cheetham, A. K. Angew. Chem. Int. Ed. 2001, 40, 2831.
[6] Zhou, Y.; Zhu, H.; Chen, Z.; Chen, M.; Xu, Y.; Zhang, H.; Zhao, D. Angew. Chem. Int. Ed. 2001, 40, 2166.
[7] Plevert, J; Gentz, T. M.; Laine, A.; Li, H.; Young, V. G.; Yaghi, O. M.; O’Keeffe, M. J. Am. Chem. Soc. 2001, 123, 12706.
[8] Zou, X.; Conradsson, T.; Klingstedt, M.; Dadachov, M. S.; O’Keeffe, M. Nature 2005, 437, 716.
[9] Wang, X.; Liu, L.; Jacobson, A. J. Angew. Chem. Int. Ed. 2001, 40,
2174.
[10] Wang, X.; Liu, L.; Jacobson, A. J. J. Am. Chem. Soc. 2002, 124,
7812.
[11] Brandão, P.; Valente, A.; Philippou, A.; Ferreira, A.; Anderson, M.
W.; Rocha, J. Eur. J. Inorg. Chem. 2003, 1175.
[12] Nyman, M.; Bonhomme, F.; Teter, D. M.; Maxwell, R. S.; Bu, B.
X.; Wang, L. M.; Ewing, R. C.; Nenoff, T. M. Chem. Mater. 2000,
12, 3449.
[13] Nyman, M.; Bonhomme, F.; Maxwell, R. S.; Nenoff, T. M. Chem.
Mater. 2001, 13, 4603.
[14] Francis, R. J.; Jacobson, A. J. Angew. Chem. Int. Ed. 2001, 40, 2879.
[15] Kao, H.-M.; Lii, K.-H. Inorg. Chem. 2002, 41, 5644.
[16] Ferreira, A.; Lin, Z.; Rocha, J.; Morais, C. M.; Lopes, M.;
Fernandez, C. Inorg. Chem. 2001, 40, 3330.
[17] Ferreira, A.; Lin, Z.; Soares, M. R.; Rocha, J. Inorg. Chim. Acta
2003, 356, 19.
[18] Hung, L.-I.; Wang, S.-L.; Szu, S.-P.; Hsieh, C.-Y.; Kao, H.-M.; Lii,
K.-H. Chem. Mater. 2004, 16, 1660.
[19] Hung, L.-I.; Wang, S.-L.; Chen, C.-Y.; Chang, B.-C.; Lii, K.-H.
Inorg.Chem. 2005, 44, 2992.
[20] Ananias, D.; Ferreira, A.; Rocha, J.; Ferreira, P.; Rainho, J. P.;
Morais, C.; Carlos, L. D. J. Am. Chem. Soc. 2001, 123, 5735.
[21] Ferreira, A.; Ananias, D.; Carlos, L. D.; Morais, C. M.; Rocha, J. J.
Am. Chem. Soc. 2003, 125, 14573.
[22] Rocha, J.; Ferreira, P.; Carlos, L. D.; Ferreira, A. Angew. Chem. Int.
Ed. 2000, 39, 3276.
[23] Jeong, H.-K.; Chandrasekaran, A.; Tsapatsis, M. Chem. Commun.
2002, 2398.
[24] Haile, S. M.; Wuensch, B. J. Acta Cryst. 2000, B56, 335.
[25] Haile, S. M.; Wuensch, B. J. Acta Cryst. 2000, B56, 349.
[26] Pei-Yun Chiang ; Tsai-Wei Lin ; Jian-Hung Dai ; Bor-Chen Chang, and Kwang-Hwa Lii , Inorganic Chemistry, 2007, V46, 3619
[27] Meow-Yu Huang ,Yi-Hsiu Chen, Bor-Chen Chang, and Kwang-Hwa Lii , Chem. Mater. 2005, 17, 5743-5747
[28] Wang, X.; Huang, J.; Jacobson, A. J. J. Am. Chem. Soc. 2002, 124,
15190.
[29] Huang, J.; Wang, X.; Jacobson, A. J. J. Mater. Chem. 2003, 13, 191.
[30] Burns, P. C.; Olson, R. A.; Finch, R. J.; Hanchar, J. M.; Thibault, Y.
J. Nucl. Mater. 2000, 278, 290.
[31] Chen, C.-S.; Kao, H.-M.; Lii, K.-H. Inorg. Chem. 2005, 44, 935.
[32] Chen, C.-S.; Chiang, R. K.; Kao, H.-M.; Lii, K.-H. Inorg. Chem.
2005, 44, 3914.
[33] Chen, C.-S.; Lee, S.-F.; Lii, K.-H. J. Am. Chem. Soc. 2005, 127,
12208.
[34] Boudin, S.; Hsieh, C.-Y.; Lii, K.-H. Unpublished research. Crystal
data for Cs2VOSi6O14: orthorhombic, Pmn21, a = 8.834(2) Å, b =
24.774(5) Å, c = 13.877(3) Å, and R1 = 0.0451.
[35] Wang, X.; Liu, L.; Jacobson, A. J. J. Am. Chem. Soc. 2002, 124,
7812.
[36] McGehee, M. D.; Bergstedt, T.; Zhang, C.; Saab, A. P.; O’Regan, M.
B.; Bazan, G. C.; Srdanov, V. I.; Heeger, A. J. Adv. Mater. 1999, 11,
1349.
[37] de Sá, G. F.; Malta., O. L.; de Mello Donegá, C.; Simas, A. M.;
Longo, R. L.; Santa-Cruz, P. A.; da Silva, Jr. E. F. Coord. Chem.
Rev. 2000, 196, 165.
[38] Carlos, L. D.; Messaddeq, Y.; Brito, H. F.; Sá Ferreira, R. A.; de Zea
Bermudez, V.; Ribeiro, S. J. L. Adv. Mater. 2000, 12, 594.
[39] Rabenau, A. Angew. Chem. Int. Ed. 1985, 24, 1026.
[40] Kennedy, G. C. Am. J. Sci. 1950, 248, 540.
[41] (a) West, A. R. Solid State Chemistry and Its Applicatons, John Wiley & Sons, New York, 1989.(b) Byrappa, K. ; Ohachi, T. , Crystal Growth Technology , William Andrew Inc. : New York, 2003.
[42] 王素蘭 科儀新知，民國九十四年二月第二十六卷第四期
[43] APEX II software package; Bruker AXS, Madison, WI, 2005.
[44] Sheldrick, G. M. SAINT programs, Release Version 5.1; Bruker AXS, Madison, WI, 1998.
[45] Sheldrick, G. M. SHELXTL programs, Release Version 5.1; Bruker AXS, Madison, WI, 1998.
[46] Brown, I. D.; Altermann, D. Acta Crystallogr. 1985, B41, 244.
[47] 高憲明 中國化學學會, 2004 , 62 , 255
[48] J. Gopalakrishnan, Journal of solid state chemistry , 1999, 148, 75-80
[49] R. A. Wheeler, M.H. Whangbo, T. Hughbanks, R. Hoffmann, J. K.Burdett, and T. A. Albright, J. Am. Chem. Soc. 108, 2222 (1986); S. K.Kang, H. Tang, and T. A. Albright, J. Am. Chem. Soc. 115, 1971 (1993).
[50] M. Kunz and I. D. Brown, J. Solid State Chem. 115, 395 (1995).
[51] N. S. P. Bhuvanesh and J. Gopalakrishnan, J. Mater. Chem. 7, 2297(1997).
[52] S.L. Issler, Journal of Alloys and Compounds, 1995, 229, 54-65
[53] W.j. Schipper, Journal of Alloys and Compounds, 1993, 202, 283-287
[54] L. H. Brixner, J. Phys. Chem. Solids, 1991, 52, 623-627
[55] 單晶結構分析原理與實驗，陳小明編著，科學出版社，page 108
[56] Donnay, G. ; Allmann, R. Am.Mineral. 1970, 55, 1003.
[57] Eur. J. Solid State Inorg. Chem. 27, 435-442 , 1990
[58] Friedrich Liebau. Structural Chemistry of Silicates , 1985
[59] (a)High-Resolution Solid-State NMR of Silicates and Zeolites , Günter Engelhardt , copyright © 1987 by John Wiley＆ Sons Ltd. , page 97 (b) Radeglia, R. ; Engelhardt, G. Chem. Phys. Lett. 1985, 114, 28.
[60] (a) Anto´nio Moreira dos Santos, Fernando M. B. Marques,c Luı´s D. Carlosa and Joa˜o Rocha J. Mater. Chem., 2006, 16, 3139–3144 , 3139 (b) Duarte Ananias, Mariya Kostova, Filipe A. Almeida Paz, Artur Ferreira, Luis D. Carlos, Jacek Klinowski, and Joao Rocha. J.AM.CHEM.SOC. 2004, 126, 10410-10417
[61] Huang, M.-Y.; Chen, Y.-H.; Chang, B.-C.; Lii, K.-H. Chem. Mater. 2005, 17, 5743.
[62] Chiang, P.-Y.; Lin, T.-W.; Dai, J.-H.; Chang, B.-C.; Chang, B.-C.; Lii, K.-H. Inorg. Chem. 2007, 46, 3619.
[63] 郭琬琳，陳宏凱，盧曉琪，鄭炳銘 科學發展 2005, 11.
[64] Carnall, W. T.; Goodman, G. L.; Rajnak, K.; Rana, R. S. J. Chem. Phys. 1989, 90, 343.
[65] Huber, G.; Syassen, K.; Holzapfel, W. B. Phys. Rev. B 1977, 15, 5123.
[66] Carlos, L. D.; Messaddeq, Y.; Beito, H. F.; Sá Ferreira, R.A.; de Zea Bermudez, V.; Ribeiro, S. J. L. Adv. Mater. 2000, 12, 594.
[67] Blasse, G.; Grabmaier, C. Luminescence Materials, Springer, 1994.
[68] Uwe Kolitsch , Eur. J. Mineral.2004, 16, 143-149
[69] Gary L. Miessler, Donald A. Tarr, Inorganic Chemistry, third edition, p. 390