臺灣博碩士論文加值系統

摘要

本篇論文是在超高真空系統（Ultrahigh vacuum, UHV）中，利用程序控溫反應/脫附（Temperature-programmed reaction/desorption, TPR/D）、反射-吸收紅外光譜學（Reflection-absorption infrared spectroscopy, RAIRS）和X-光光電子譜學（X-ray photoelectron spectroscopy, XPS）探討2-chloropyrimidine在Cu(100)和O/Cu(100)的吸附與熱反應。
在Cu(100)表面，2-chloropyrimidine在140 K會以N原子的孤對電子和Cu表面產生作用進行吸附。在約200 K，此分子的C-Cl鍵開始斷鍵，形成中間物2-pyrimidyl，透過N原子和C2原子化學鍵結於表面。升溫至480 K左右，發現有pyrimidine的脫附，此結果進一步支持有未發生環破裂的2-pyrimidyl中間物存在，但大於480 K，XPS和RAIRS的結果指出pyrimidyl的芳香環以開環。在587 K，測得H2產生，應該來自開環物種的C-H鍵斷裂，然後H原子互相反應形成H2，升溫到~740 K產生HCN，繼續加熱到900 K以上則有C2N2的脫附。
140 K時，2-chloropyrimidine在O/Cu(100)表面與在Cu(100)表面的吸附模式一樣。約200 K，此分子的C-Cl開始斷鍵，表面上的O原子似乎會和C2原子產生鍵結,形成不同於pyrimidyl的新中間物。在227 K有水的產生，是因為銅表面的OH耦合產生。在約480 K，測得H2O、CO2的脫附，表示氧原子的存在，造成熱反應路徑的改變，環破裂提早發生，500 K開始有H2的產生，是環破裂且分解後碎片分子斷C-H鍵之結果。在700 K左右，這些碎片中間物持續反應，生成NO、HCNO、HCN、CO2、CO、N2。超過900 K以上，C2N2生成並脫附。

SUMMARY

The thermal chemistry of 2-chloropyrimidine on Cu(100) and O/Cu(100) surfaces was studied by using temperature-programmed reaction/desorption (TPR/D), X-ray photoelectron spectroscopy (XPS) and reflection-adsorption infrared spectroscopy (RAIRS) conducted in an ultrahigh vacuum chamber.

2-chloropyrimidine is molecularly adsorbed on Cu(100) at 140 K. When the copper is heated to 200 K, cleavage of C-Cl bond occurs and 2-pyrimidyl is generated on the surface. Upon heating to ~480 K, pyrimidine evolves, which further supports the presence of the pyrimidyl intermediate, with the aromatic ring remaining intact. However XPS and RAIRS results suggest that opening of the pyrimidyl ring occurs at a temperature higher than 480 K. H2 desorbs mainly at 587 K, which due to C-H bond dissociation of the ring-opening species. Further heating to ~740 K results in the formation of HCN. C2N2 desorption is observed above 900 K, due to coupling of CN groups.

On oxygen-precovered Cu(100), 2-chloropyrimidine is also molecularly absorbed at 140 K. At 200 K, the C-Cl bond begins to break and the adsorbed O atoms seem to chemically attach to the C2 atoms, forming a new intermediate different from 2-pyrimidyl. Desorption of H2O and CO2 is measured around 480 K, indicating ring breakage occurs on O/Cu(100) is easier than on Cu(100), showing that there is a change in the thermal reaction path of the pyrimidine ring. The surface fragments resulted from the ring-opening of the oxygen-containing pyrimidyl intermediate continue to react on the surface, producing H2 at 500 K and producing NO, HCNO, HCN, CO2, CO and N2 at ~700 K. Above 900 K, C2N2 desorb from surface.

Keywords: 2-chloropyrimidine, Temperature-programmed reaction/desorption (TPR/D), Reflection-absorption infrared spectroscopy (RAIRS), X-ray photoelectron spectroscopy (XPS), Cu(100)

目錄
第一章 緒論
1.1 表面化學的發展 1
1.2 表面的定義 1
1.3 表面吸附 3
1.4 真空的定義及運用 4
1.5 實驗動機 5
第二章 表面分析的測量技術
2.1 程序控溫反應/脫附（Temperature-programmed reaction/desorption, TPR/D） 9
2.2 反射-吸收紅外光譜學（Reflection-absorption infrared spectroscopy, RAIRS） 12
2.3 X-光光電子譜學（X-ray photoelectron spectroscopy, XPS） 15
第三章 實驗系統與方法
3.1 超高真空系統（Ultrahigh vacuum, UHV） 18
3.2 單晶的前處理 20
3.3 氧化表面製備 20
3.4 藥品的前處理 20
第四章 結果與討論
4.1 2-氯吡嘧啶（2-chloropyrimidine）在銅（100）表面上的熱反應（Thermal reaction）研究
4.1.1 2-氯吡嘧啶在銅（100）單晶表面的程序控溫反應/脫附（TPR/D）研究 22

4.1.2 2-氯吡嘧啶在氧/銅（100）單晶表面的程序控溫反應/脫附（TPR/D）研究 36
4.2 2-氯吡嘧啶（2-chloropyrimidine）在銅（100）表面上的X-光光電子譜儀學（XPS）研究
4.2.1 2-氯吡嘧啶在銅（100）單晶表面的X-光光電子譜學（XPS）研究 44
4.2.2 2-氯吡嘧啶在氧/銅（100）單晶表面的X-光光電子譜學（XPS）研究 49
4.3 2-氯吡嘧啶（2-chloropyrimidine）在銅（100）表面上的反射吸收紅外光譜儀（RAIRS）研究
4.3.1 2-氯吡嘧啶在銅（100）單晶表面的反射吸收紅外光譜儀（RAIRS）研究 52
4.3.2 2-氯吡嘧啶在氧/銅（100）單晶表面的反射吸收紅外光譜儀（RAIRS）研究 60
第五章 結論 62
參考文獻 64
 
圖目錄
圖1.2.1 面心立方晶體及其(100)面俯視圖 2
圖1.5.1 嘧啶（Pyrimidine）與2-氯吡嘧啶（2-Chloropyrimidine）分子結構圖 5
圖2.1.1 程序控溫反應脫附（TPR/D）實驗裝置示意圖 10
圖2.1.2模擬零級、一級、二級、半級和（1-）級動力學反應的TPD圖譜 11
圖2.2.1反射紅外光實驗的入射平面和s與p極化光定義表示圖 12
圖2.2.2表示光在金屬表面反射的相轉移關係圖，透過計算可以得到s和p極化光的相轉移角度 13
圖2.2.3表示兩種不同的偶極運動方向，藉由基板中的傳導電子（Conduction electrons）形成鏡像偶極（Image dipole） 13
圖2.2.4反射-吸收紅外光譜儀（RAIRS）實驗裝置圖 14
圖2.3.1 ESCA基礎理論圖示 15
圖3.1.1超高真空表面分析系統示意圖 19
圖4.1.1 2-chloropyrimidine不同曝露量下，m/z 114的TPD圖譜 24
圖4.1.2 60 L 2-chloropyrimidine/Cu(100)的主要離子碎片（m/z 79、87、114、116）TPR/D圖譜 25
圖4.1.3 2-chloropyimidine的主要離子碎片和相對強度與NIST資料庫比對 25
圖4.1.4 50 L 2-chloropyrimidine/Cu(100)的m/z 2、26、27、52、53和80的TPR/D圖譜 28
圖4.1.5 50 L 2-chloropyrimidine/Cu(100)的m/z 26、27、53和80的TPR/D圖譜 29
圖4.1.6 Pyrimidine的主要離子碎片和相對強度與NIST資料庫比對 29
圖4.1.7 HCN的主要離子碎片和相對強度與NIST資料庫比對 29
圖4.1.8 50 L 2-chloropyrimidine/Cu(100)的m/z 26、52的TPR/D圖 30
圖4.1.9 C2N2的主要離子碎片和相對強度與NIST資料庫比對 30
圖4.1.10不同2-chloropyrimidine曝露量，m/z 80的TPR/D圖譜 32
圖4.1.11不同2-chloropyrimidine曝露量，m/z 2的TPR/D圖譜 33
圖4.1.12不同2-chloropyrimidine曝露量，m/z 27的TPR/D圖譜 34
圖4.1.13不同2-chloropyrimidine曝露量，m/z 52的TPR/D圖譜 35
圖4.1.14 30 L 2-chloropyrimidine/O/Cu(100)的主要離子碎片（m/z 79、87、114、116）TPR/D圖譜 37
圖4.1.15 2-chloropyimidine的主要離子碎片和相對強度與NIST資料庫比對 37
圖4.1.16 30 L 2-chloropyrimidine/O/Cu(100)的m/z 2、14、17、18、26、27、28、30、43、44和52的TPR/D圖譜 38
圖4.1.17 H2O的主要離子碎片和相對強度與NIST資料庫比對 41
圖4.1.18 30 L 2-chloropyrimidine/O/Cu(100)的m/z 14、28和44的TPR/D圖 42
圖4.1.19 CO2的主要離子碎片和相對強度與NIST資料庫比對 42
圖4.1.20 HCN的主要離子碎片和相對強度與NIST資料庫比對 43
圖4.1.21 C2N2的主要離子碎片和相對強度與NIST資料庫比對 43
圖4.2.1 10 L 2-chloropyrimidine/Cu(100)的C1s、N1s和Cl2p的XPS圖譜 48
圖4.2.2 30 L 2-chloropyrimidine/O/Cu(100)的C1s、N1s、Cl2p和O1s的XPS圖譜 51
圖4.3.1 60 L 2-chloropyrimidine/Cu(100)的RAIRS圖譜 55
圖4.3.2 DFT計算2-chloropyrimidine的結構最佳化的示意圖 57
圖4.3.3 DFT計算2-chloropyrimidine吸附在Cu(100)表面的
結構最佳化的示意圖 58
圖4.3.4 DFT計算2-pyrimidyl吸附在Cu(100)表面的結構最佳化的示意圖 59
圖4.3.5 60 L 2-chloropyrimidine/O/Cu(100)的RAIRS圖譜 61
 
表目錄
表1.3.1物理吸附和化學吸附比較 4
表1.4.1真空壓力區分 4
表3.1.1實驗室常用儀器的廠牌和型號 18
表3.4.1實驗使用的樣品與資訊 21
表4.2.1 C1s、N1s、O1s、Cl2p的XPS束縛能（單位：eV） 47
表4.3.1 2-chloropyrimidine/Cu(100)和2-pyrimidyl/Cu(100)的
振動頻率和模式 54
表4.3.2 DFT計算的2-chloropyrimidine的結構最佳化的鍵長與鍵角 57
表4.3.3 DFT計算2-chloropyrimidine吸附在Cu(100)表面的結構最佳化的鍵長與鍵角 58
表4.3.4 DFT計算2-pyrimidyl吸附在Cu(100)表面的結構最佳化的鍵長與鍵角 59
Scheme目錄
Scheme 1.5.1溴化鈷（CoBr2）作為催化劑，幫助2-氯吡嘧啶和芳香基鹵化物形成有機金屬試劑 17
Scheme 1.5.2嘧啶的熱裂解反應機構。（a）為p-pyrimidyl radical,（b）為o-pyrimidyl radical 17
Scheme 4.1.1生成pyrimidine的兩種可能路徑 27
Scheme 4.1.2 Cu(100)表面上生成的H2O的溫度 41
Scheme 5.1 2-chloropyrimidine/Cu(100)的反應機構 62
Scheme 5.2 2-chloropyrimidine/O/Cu(100)的反應機構 63

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