臺灣博碩士論文加值系統

本論文所載的研究為使用超高真空表面科學技術以及電化學方法研究有機化合物在金單晶表面的化學反應。
第二章為利用同步輻射光源為基礎的高解析度內核電子能譜術( core level spectroscopy)研究利用溶液浸泡以及氣相吸附的方式製備所得到不同的覆蓋率、吸附在Au(111) 表面上的1-decanethiol薄膜。不論使用何種製備方法所得到的薄膜其S 2p 的內核電子能譜皆有相同的spin-orbit doublet而其S 2p3/2 束縛能（binding energy）位於162.1 eV電子伏特，顯示兩種製備方法所得到的薄膜其硫與金化學鍵結相同。然而C 1s的電子能譜於低覆蓋率時在284.0電子伏特有一個能譜峰，增加覆蓋率的時候在高束縛能的那一邊出現另一個能譜峰，當繼續增加覆蓋率的時候終於變成在285.0電子伏特的單一能譜峰。基材內層能譜的角解析(angle resolved) X光電子能譜分析提供了測量薄膜厚度的方法。在低覆蓋率時在284 電子伏特的C 1s能譜峰關連到比較薄的薄膜，其厚度為4.0埃，而285電子伏特的C 1s能譜峰關連到較厚的薄膜，其厚度為12.6埃，對應到在高覆蓋率時碳鏈全部伸展開來的分子薄膜。C 1s 束縛能的差異是來自於在完全伸展的碳鏈中所造成的不完全的終態靜弛（final state relaxation）。此外，所觀測到的S 2p能譜中的單一能譜峰與基於X光駐波（x-ray standing wave）以及掠角入射X光散射（grazing incidence x-ray scattering）方法所提出的二聚（dimer）模型不合。
第三章所述為利用熱脫附（thermal desorption spectroscopy, TDS）以及高解析X光電子能譜術研究decanethiol吸附在乾淨的Au(111)表面以及其熱反應。實驗的結果顯示decanethiol在低於250 K時化學吸附在Au(111)表面，而且其可能可以隔離出來。繼續加熱，在低於350 K時 S-H鍵結斷裂形成硫醇化物（thiolate）。物理吸附的decanethiol其S 2p的束縛能為163.2電子伏特，化學吸附的decanethiol為161.7-161.9電子伏特，硫醇化物為162.1電子伏特以及吸附的硫原子為161.0電子伏特。在高於400 K時decanethiolate 會開始分解而會釋放出癸烯decene，decanethiol，H2S到氣相中而在金表面上留下吸附的硫原子。分解反應的反應機制推測為以相鄰硫化物之間的直接自身氧化還原反應（dis-proportionation reaction）開始的。
第四章為利用熱脫附方法（TDS）低能量電子繞射（Low energy electron diffraction, LEED），高解析X光電子能譜以及X光吸收邊緣細微結構光譜（near-edge x-ray absorption fine structure spectroscopy, NEXAFS）方法研究S2分子在Au(111) 的吸附作用。不同的Sn( n = 2 to 8)同素異購物在Au(111)表面形成而在200 K到400 K之間脫附，化學吸附的硫原子在不同的覆蓋率時形成不同的結構：覆蓋率在0.36以及0.47 之間形成一個複雜的結構，而覆蓋率等於0.33時形成(O3 x O3) R30°結構。化學吸附的硫原子脫附時成為S2以及S。X光電子能譜顯示硫覆蓋率在0.47與0.85之間時有第三種硫的存在，我們推測為化學吸附的S2分子。對應於物理吸附的硫分子其S 2p3/2- 束縛能為162.9 ± 0.05 eV，化學吸附的S2為181.82~162.05 eV，化學吸附的硫原子為161.13 ± 0.05 eV.。計算得到的硫原子與Au(111)之間的鍵結能為139 kj/mol。
第五章所述為使用循環伏安譜（cyclic voltammetry）研究硝基苯在Au(111)，Au(100)，Au(110)，Au(210)黃金單晶電極以及黃金多晶電極上面於稀過氯酸水溶液中的電化學還原反應。我們發現硝基苯的循環伏安譜對不同的晶面非常敏感。值得注意的是硝基苯在-(110), -(210), 以及多晶間表面於0.33 V vs. SCE的電位處會形成一個未曾報導過，穩定吸附的氧化還原反應中間體（redox intermediate），我們發現此反應中間體所具有不尋常的穩定性可以關連到吸附在表面上水分子的位相（orientation），而水分子的位相是由外加的電位以及黃金電極的零電電位（potential of zero charge）所決定。

Described in this thesis are studies of selected reaction on gold single crystal surface utilizing UHV surface science techniques and electrochemical method.
Described in Chapter 2 is a report of synchrotron-based, high resolution core level spectroscopy study of 1-decanethiol thin film on Au(111) single crystal prepared from both gas-phase dosing and solution immersion to vary the coverage in a wider range. S 2p core level exhibits a single, well-characterized spin-orbit doublet with S 2p2/3 at 162.0 eV, irrespective of the preparation methods for the films, indicating the identical chemical interaction between sulfur and gold atoms. However, C 1s core level starts from 284.0 eV at low coverage, develops a high-binding shoulder at intermediate coverage and eventually becomes a single peak at 285.0 eV for solution phase preparation. Angle-resolved XPS measurements of substrate core level signals provide a measure of the film thickness. The C 1s peak at 284.0 eV for the low coverage phase is associated with the film of thinner dimension of 4.0 A, presumably due to the stripe phase of the film. The C 1s peak at 285.0 eV is associated with a thicker film of 12.6 A in thickness, corresponding to a fully-extended, trans molecular thin film at high coverage. The difference of C 1s binding energy is attributed to the incomplete final-state relaxation of the carbon atoms in a fully extended configuration. Moreover, the observation of a clear, well-defined, single-peak S 2p signal does not collaborate with the sulfur dimer model proposed based on x-ray standing wave and glazing incidence x-ray scattering results.
Described in Chapter 3 is the adsorption and thermal reaction of decanethiol on clean Au(111) studied by using thermal desorption spectra (TDS) and synchrotron- based high-resolution XPS. The results show that gas-phase dosed decanethiol chemisorbs on Au(111) at below 250 K. A further S-H bond breaking leads to the formation of decanethiolate at below 350 K. Binding energy of S 2p3/2 core level for different species is assigned as 163.2 eV for physisorbed decanethiol, 161.7~161.9 eV for chemisorbed decanethiol, 162.1 eV for thiolate formation and 161.0 eV for atomic sulfur. Decanethiolate is stable up to 350 K, and starts to decompose upon further annealing to above 400 K, releasing decene, decanethiol, H-2S into gas phase and leaving adsorbed sulfur atom on surface. The reaction mechanism was proposed to be initiated by direct disproportionation reaction between adsorbed decanethiolate. The lying-down configuration is essential for long chain alkane thiolate decomposition and decanethiolate in the upright configuration in the dense c(4 x 2) phase initially desorbed as decanethiol or decyl disulfide, and then follow the same decomposed reaction.
In Chapter 4, The adsorption of molecular S-2 on Au(111) surface has been studied by thermal desorption spectroscopy (TDS), low energy electron diffraction (LEED), synchrotron radiation based x-ray photoelectron spectroscopy (XPS) and sulfur K-edge near-edge x-ray absorption fine structure spectroscopy (NEXAFS). For sulfur multilayer, sulfur allotropes of composition Sn (n = 2 to 8) are formed on the Au(111) surface and thermal desorption, occurring between 200 and 400 K, produces various sulfur species. Chemisorbed sulfur atoms form different adsorption structures at different coverages: a complex adsorption structure at a coverage between 0.36 and 0.47 ML as well as a (O3 x O3) R30° structure at a coverage of 0.33 ML. The desorption of chemisorbed sulfur from Au(111) surface results in the evolution of S2 and S exclusively. The XPS data give evidence of the third sulfur species locating on top of chemisorbed layer at coverages between 0.47 and 0.85. The species is claimed to be a chemisorbed S2 species. The respective S 2p3/2 core level binding energies are 162.90 ± 0.05 eV for physisorption multilayer, 161.82~ 162.05 eV for chemisorbed S2 and 161.13 ± 0.05 eV for atomically adsorbed sulfur. The binding energy of atomic sulfur to Au(111) surface is calculated as 139 kj/mol.
Chapter 5 reports the electroreduction of nitrobenzene studied on Au single crystals of (111), (110), (100), and (210) orientations and on Au polycrystal in dilute aqueous perchlorate solution using cyclic voltammetry. The voltammograms were found to be sensitively dependent on surface orientation. Notably, the reduction on -(110), -(210), and -(poly) electrodes can lead to a stably adsorbed redox intermediate, not reported before, at about 0.33 V vs. SCE and the intermediate is deduced as phenyldihydroxylamine and phenyldihydroxylamine cation redox couple. The unusual stability of the redox intermediate is found to correlate with the orientation of adsorbed water molecule that can be intimately controlled by an applied potential in relationship to the potential of zero charge on the surfaces.

封面
Abstract
List of figures and Tables
Chapter 1. Introduction
Reference
Chapter 2. High resolution X-ray Photoelectron Spectroscopic Study of 1-Decane-thiol on Au(111)
2-1 Introduction
2-2 Experimental
2-3 Results and discussion
2-4 Conclusions
2-5 References
Chapter 3. Reactivity of 1-Decanethiol ith Au(111) Surface: a Combined TDS and High Resolution XPS Study
3-1 Introduction
3-2 Experimental
3-3 Results
3-4 Discussion
3-5 References
Chapter 4. The adsorption of molecular sulfur on Au(111) surface: a TDS, LEED, SR-XPS and NEXAFS study
4-1 Introduction
4-2 Experimental
4-3 Results
4-4 Conclusions
4-5 References
Chapter 5 Reaction of nitrobenzene on gold single-crystal electrodes: surface crystallographic orientation dependence
5-1 Introduction
5-2 Experimental
5-3 Results
5-4 Discussion
5-5 Conclusions
5-6 References
Publication list

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