臺灣博碩士論文加值系統

本論文主要內容為製備及鑑定鈀(II)-咪唑 (Pd(II)-Imidazole) 錯合物之
LB 分子薄膜，所使用之鈀(II)-咪唑錯合物分子包括[Pd(imCnH2n+1)2Cl2] (n =
12, 14, 16, 18) 與 [Pd(imCm(2-OH))2Cl2] (m = 10, 12, 14, 16, 18)，為同時具有
親水與疏水部份之兩性分子。當分子於軟鏈端之烷鏈不含氫氧基(-OH)時，
不論碳鏈長短皆無液晶相；當於咪唑基長碳鏈二位置碳上引入氫氧基時，
可藉由官能基產生氫鍵而有較強的分子間作用力，使之產生液晶性質。
鈀(II)-咪唑錯合物於氣/液界面具有自組裝性質，我們使用藍穆爾槽
(Langmuir trough) 透過機械擠壓並由等溫壓力-面積曲線圖(π-A isotherm)
觀察氣/液界面上二維分子薄膜之排列。烷鏈間之凡德瓦爾力使分子形成有
序排列之單層膜，烷鏈越長單層膜分子越趨穩定，當烷鏈上引入-OH 基，
可使分子單層膜更穩定。再運用LB 技術將氣/液界面分子薄膜轉移至固體
基材上，利用AFM 觀察不同分子薄膜的表面形貌、接觸角觀察薄膜之表面
親/疏水性質、FT-IR 鑑定LB 膜的官能基以及低角度X-光繞射分析LB 多
層膜的層間關係。
此外將具十六碳長烷鏈並含-OH 基之鈀(II)-咪唑LB 薄膜經高溫燃燒
除去有機部份後，可得分散性良好且粒徑均勻之奈米金屬顆粒吸附於固體
基材上，此種方法可應用於製備奈米顆粒方面之相關研究。

This thesis focuses on the preparation and characterization of molecular
monolayers and multilayers of palladium(II)-imidazole complexes prepared by
Langmuir-Blodgett (LB) technique. The Pd(II)-imidazole complexes used in
this study, including [Pd(imCnH2n+1)2Cl2] (n = 12, 14, 16, 18) and
[Pd(imCm(2-OH))2Cl2] (m = 10, 12, 14, 16, 18), are amphiphilic molecules
which contain both hydrophilic and hydrophobic moieties. All of the
compounds [Pd(imCnH2n+1)2Cl2] do not exhibit liquid crystalline behaviors,
which may be attributed to a too small anisotropy to have sufficient core-core
interaction to stabilize the mesophase. When a lateral hydroxyl group is
incorporated at the 2-position of the alkyl chain in imidazole, the complexes
[Pd(imCn(2-OH))2Cl2] show properties of liquid crystals.
The Pd(II)-imidazole complexes form molecularly thin films at the air/water
interface through self-assembly. By mechanical compression with barriers in a
Langmuir trough, the molecular ordering at the air/water interface can be studied
by surface pressure-area (π-A) isotherms. Molecules with longer alkyl chains
produce more stable monolayer films. Incorporation of lateral hydroxyl group
in the alkyl chain enhances the stability of the films via intramolecular hydrogen
bonding interactions. The monolayers at the air/water interface are transferred
onto solid substrate using vertical dipping LB technique. The LB films are
comprised of monolayers or multilayers of Pd(II)-imidazole complexes, which
are controlled by the number of deposition cycles. The surface morphology,
the hydrophilicity/hydrophobicity, the surface functionalities, and the interlayer
spacings of the LB films are characterized by atomic force microscope (AFM),
contact-angle goniometer, reflective absorption infrared spectrometer (RAIR)
and grazing-angle x-ray diffractometer (XRD), respectively.It is found that after high-temperature combustion of the LB monolayer of
[Pd(imC16(2-OH))2Cl2], fairly uniform and well dispersed Pd nanopartciles are
formed on the solid substrate. Further studies can be conducted to explore the
applicability of this method in preparation of nanoparticles.

中文摘要…………………………………………………………………………i
英文摘要………………………………………………………………………...ii
總目錄…………………………………………………………………………..iv
第一章 序論…………………………………………………………………….1
1-1 前言…………………………………………………………………….1
1-2 研究動機……………………………………………………………….3
第二章 文獻回顧……………………………………………………………….4
2-1 簡介………………………………………………………………………4
2-1-1 分子單層膜………………………………………………………4
2-1-2 分子多層膜………………………………………………………8
2-2 Pd(II)-Imidazole 錯合物分子……………………………………………..9
2-3 原理………………………………………………………………………10
2-3-1 分子單層膜………………………………………………………10
2-3-1-1 分子單層膜的形成…………………………………….10
2-3-1-2 壓膜過程之壓力–面積等溫線………………………...10
2-3-1-3 分子單層膜的沉積…………………………………….13
2-3-2 分子多層膜性質………………………………………………..14
第三章 實驗方法……………………………………………………………15
3-1 藥品……………………………………………………………………15
3-2 實驗儀器………………………………………………………………16
3-3 實驗步驟………………………………………………………………16
3-3-1 清洗基材………………………………………………………..16
3-3-2 Pd(II)-Imidazole 錯合物分子溶液配置………………………...17
3-3-3 Langmuir 單分子層製備觀察…………………………………...18
3-3-4 LB 膜的製作……………………………………………………..18
3-4 分析方法………………………………………………………………..20
3-4-1 原子力顯微鏡 …………………………………………………20
3-4-2 熱重分析儀 ……………………………………………………21
3-4-3 低角度X-光繞射法…………………………………………….22
3-4-4 自動接觸角測量儀……………………………………………..24
3-4-5 傅立葉轉換紅外光光譜儀……………………………………..26
第四章 結果與討論…………………………………………………………...30
4-1 等溫壓力-面積圖………………………………………………………30
4-2 LB films 的表面形貌鑑定………………………………………………34
4-2-1、在高表面壓條件下製備之LB films 單層膜…………..………34
4-2-2 、在高表面壓條件下製備之LB films 單層膜的接觸角……….36
4-2-3、在低表面壓條件下製備之LB films 單層膜…………………..37
4-2-4 、在低表面壓條件下製備之LB films 單層膜的接觸角………39
4-2-5 、過平台區條件下製備之LB films 單層膜……………………41
4-2-6 、高表面壓條件下，經500℃燒結過後之LB films 單層膜........42
4-3 Pd(II)-Imidazole 錯合物分子LB films 的FT-IR 光譜鑑定…...………....45
4-5、LB films 低角度X-光繞射………..……………………………………48
4-5-1、LB films 的低角度X-光繞射層間關係……….....………......…48
4-5-2、LB films 的X-光繞射之變溫實驗及穩定性……....……….......51
第五章 結論…………………………………………………………………...56
第六章 參考文獻…………………………………………………...57

附錄……………………………………………………………….61

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