| 研究生: |
林予晴 Yu-Qing Lin |
|---|---|
| 論文名稱: |
含三價銪鋱離子配位聚合物內能量轉移之動力學研究 |
| 指導教授: |
張伯琛
Bor-Chen Chang |
| 口試委員: | |
| 學位類別: |
碩士 Master |
| 系所名稱: |
理學院 - 化學學系 Department of Chemistry |
| 論文出版年: | 2016 |
| 畢業學年度: | 104 |
| 語文別: | 中文 |
| 論文頁數: | 80 |
| 中文關鍵詞: | 稀土元素 、銪鋱離子能量轉移 、放光光譜 、時間解析光譜 |
| 相關次數: | 點閱:14 下載:0 |
| 分享至: |
| 查詢本校圖書館目錄 查詢臺灣博碩士論文知識加值系統 勘誤回報 |
本論文使用中溫水熱法合成R2(C8H10O4)3配位聚合物,其中R= Y, Eu, Tb,分別以不同莫耳比例組成配位中心,而配位基C8H10O4為1, 4-cyclohexanedicarboxylate (CHDC)。合成之晶體以單晶及粉末X光繞射鑑定其結構及純度,而配位中心的元素比例則以感應耦合電漿原子發射光譜分析儀(ICP-AES)進行確認。本論文主要針對EuxTb2-x(CHDC)3化合物進行探討,測量了一系列樣品之光致放光光譜、激發光譜及時間解析光譜。進行分析後再次確認Eu3+與Tb3+之間能量傳導會與相鄰機率有關,且發現敏化配位基CHDC會影響到Eu3+與Tb3+之間能量傳導效能。本論文對Eu3+訊號上升時間及Tb3+放光衰退時間進行動力學模型的分析,發現Eu3+與Tb3+之間是個三維能量傳導的模式,並由分析數據得到能量轉移速率常數與相關物理參數,其結果成功地解釋Tb3+→Eu3+之能量轉移效能。
This work adopted mid-temperature hydrothermal method to synthesize coordination polymers, R2(C8H10O4)3, (R= Eu or Tb, and C8H10O4: 1, 4-cyclohexanedicarboxylate, CHDC). Single-crystal and powder x-ray diffraction (XRD) data were collected for confirming their structure and purity. Inductively Coupled Plasma Atomic Emission Spectra (ICP-AES) were also obtained to verify the compositions of Eu3+ and Tb3+. We have acquired the photoluminescence (PL), excitation, and time-resolved spectra of several EuxTb2-x(CHDC)3 compounds. The analysis of these spectra shows that the energy transfer is indeed correlated to the contact probability between Eu3+ and Tb3+ as well as to the sensitization of CHDC ligands. Kinetics models were used to fit the rising temporal profiles of Eu3+ and the decay curves of Tb3+. The results indicate the energy transfer is three dimensional (3D). The rate constants and related parameters were successfully determined. The energy transfer efficiency can be well explained by these results.
1.Evans, R. C.; Carlos, L. D.; Douglas, P.; Rocha, J. Tuning the emission colour in mixed lanthanide microporous silicates: energy transfer, composition and chromaticity. J. Mater. Chem. 2008, 18, 1100-1107.
2.Carnall, W. T.; Goodman, G. L.; Rajnak, K.; Rana, R. S. A systematic analysis of the spectra of the lanthanides doped into single crystal LaF3.
J. Chem. Phys. 1989, 90, 3443-3457.
3.An, Y.; Schramm, G. E.; Berry, M. T. Ligand-to-metal charge-transfer quenching of the Eu3+ (5D1) state in europium-doped tris (2,2,6,6-tetramethyl-3,5-heptanedionato)gadolinium (III). J. Lumin. 2002, 97, 7-12.
4.Blasse, G.; Grabmaier, B. C. Luminescence Materials 1994, Springer-Verlag, Berlin, New York.
5.Huber, G.; Syassen, K.; Holzapfel, W. B. Pressure dependence of 4f levels in europium pentaphosphate up to 400 kbar. Phys. Rev. B 1977, 15, 5123-5128.
6.Cotton, S, Dr. Lanthanide and Actinide Chemistry 2006, John Wiley & Sons, Inc., Chichester, England.
7.陳孟琳, 國立中央大學化學系碩士論文. (2013).
8.蕭郁如, 國立中央大學化學系碩士論文. (2014).
9.李穗美, 國立中央大學化學系碩士論文. (2015).
10.Ferreira, A.; Ananias, D.; Carlos, L. D.; Morais, C. M.; Rocha, J. Novel microporous lanthanide silicates with tobermorite-like structure. J. Am. Chem. Soc. 2003, 125, 14573-14579.
11.Wang, S. L.; Richerson, J. W., Jr. Neutron powder diffraction study of the mixed-valence vanadium pyrophosphate RbV3P4O17. Z. Kristallogr. 1992, 202, 227-236.
12.Barbara M. W. The flux growth of single crystals of rare earth perovskites (orthoferrites, orthochromites and aluminates) J. Cryst. Growth 1969, 5, 323-328.
13.West, A. R. Solid State Chemistry and Its Applications 1984, Wiley, Chichester, West Sussex.
14.Johnson, J. W.; Jacobson, A. J. Redox intercalation reactions of VOPO4·2H2O. Angew. Chem. Int. Ed. Engl. 1983, 22, 412-413.
15.陳逸翔, 國立中央大學化學系碩士論文. (2012).
16.Blasse, G. Luminescence of inorganic solids: from isolated centres to concentrated systems. Prog. Solid St. Chem. 1988, 18, 79-171.
17.Yokota, M.; Tanimoto, O. Effects of diffusion on energy transfer by resonance. J. Phys. Soc. Jpn. 1967, 22, 779-784.
18.Kellendonk, F.; Blasse, G. Luminescence and energy transfer in EuAl3B4O12. J. Chem. Phys. 1981, 75, 561-571.
19.Wu, Z. C.; Shi, J. X.; Wang, J.; Gong, M. L.; Su, Q. A novel blue-emitting phosphor LiSrPO4: Eu2+ for white LEDs. J. Solid State Chem. 2006, 179, 2356-2360.