博碩士論文 105222010 詳細資訊




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姓名 黃怡誠(Yi-Cheng Huang)  查詢紙本館藏   畢業系所 物理學系
論文名稱
(Oxidative steam reforming of ethanol on rhodium nanoclusters supported by graphene grown on Ru(0001))
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摘要(中) 我們研究以銠(Rhodium)奈米粒子作為催化劑鍍在graphene上用釕(Ruthenium)單晶作為基板,了解水(H2O)及氧氣(O2)在乙醇(Ethanol)的氧化蒸氣重整反應中如何扮演有效改變反應途徑的角色。並藉由熱脫附質譜儀(TPD)、紅外光反射吸收能譜(IRAS)與同步輻射光電子能譜(PES)表面探測技術在超高真空(UHV)的環境下進行表面量測。結果顯示,當有氧原子(O*)預先吸附在銠奈米粒子表面上會促進乙醇的分解並改變反應途徑從純乙醇吸附藉由C-Hβ的斷鍵形成乙醇中間產物oxametallacycle (CH2CH2O*)改變為藉由C-Hα的斷鍵形成乙醛(CH3CHO*),此變大大促進了氫氣(H2)的產生,也生成副產物一氧化碳(CO)及甲烷(CH4)。而隨著高氧原子覆蓋量的表面,反應途徑轉向為生成乙酸(CH3COO*),此改變抑制了氫氣的產生但也促進生成了二氧化碳。水以分子的狀態吸附在銠奈米粒子上並沒有分解且脫附溫度低於200 K。相反的,當氧原子預先吸附於銠奈米粒子金屬表面上,有大部分的水分解形成氫氧根(OH*)及氧原子(O*)且脫附溫度高於常溫300 K。在之後的乙醇的氧化蒸氣重整反應中水與氧的共同吸附對於反應的效率並沒有像氧預先吸附那樣有效且明顯的改變反應途逕及產量。
摘要(英) With rhodium-based catalysts, rhodium nanoclusters supported on graphene grown on Ru(0001) surface, we investigated how oxygen and water play effective roles in the oxidative steam reforming reaction of ethanol, under ultrahigh vacuum conditions and using temperature programmed desorption (TPD), infrared reflection adsorption spectroscopy (IRAS), synchrotron-based photoemission spectroscopy (PES). The result show that the atomic oxygen (O*) on Rh surfaces promoted the decomposition of ethanol and altered the reaction pathway from the one via C-Hβ bond cleavage forming oxametallacycle to that via C-Hα bond cleavage forming acetaldehyde; the alternation high promoted the production of H2 along with the side products of CO, CH4. The reaction pathway shifted to acetate intermediates with higher oxygen content, which suppressed the production of H2 but promoted that of CO2. Water adsorbed molecularly on Rh surface; no water was dissociated and water desorbed below 200 K. In contrast, on atomic oxygen (O*) pre-covered Rh surface, a great fraction of water molecules underwent dissociation into atomic hydrogen and hydroxyl groups (OH*) and desorbed above room temperature 300 K. The OH* on D2O*/O*-Rh clusters surface abstracted H from ethanol, like O* but did not altered the reaction pathway as effectively as O*- the O2 effect in this aspect is more significant than the H2O one.
關鍵字(中) ★ 氧化蒸氣重整
★ 乙醇
★ 銠
關鍵字(英) ★ Oxidative steam reforming
★ Ethanol
★ Rhodium
★ water
★ oxygen
論文目次 摘要 i
Abstract ii
Chapter 1 Introduction 1
Reference 3
Chapter 2 Literature survey 5
2.1 The Characterization of graphene/Ru(0001) 5
2.2 H2O dissociation on oxygen-covered Rh(111) 10
2.3 Ethanol reforming on Rh catalyst 13
2.3.1 Ethanol decomposition on clean Rh(111) 13
2.3.2 Ethanol decomposition on oxygen pre-covered surface 17
2.3.3 Oxidative steam reforming of Ethanol on Rh(111) 21
2.3.4 Ethanol decomposition on clean Rh(100) 23
2.3.5 Ethanol decomposition on oxygen-covered Rh(100) 27
Chapter 3 Experiment Methods and Apparatus 31
3.1 Experiment methods 31
3.1.1 Cleaning Ru(0001) 31
3.1.2 Graphene ultrathin film growth 33
3.1.3 Vapor deposition of Rh 34
3.1.4 Ethanol adsorption and reaction 34
3.2 Temperature programmed desorption (TPD) 36
3.3 Infrared reflection adsorption spectroscopy (IRAS) 41
3.4 Fourier Transform Interferometers 44
3.5 Photoemission Spectroscopy (PES) 47
3.5.1 PES analysis System 47
3.5.2 X-ray Photoelectron Spectroscopy (XPS) 47
Reference 51
Chapter 4 Results and discussions 52
4.1 Adsorbed CO as a probe on Rh clusters/graphene/Ru(0001) 52
4.2 Reaction of ethanol on varied oxidative Rh nanoclusters surface 53
4.2.1 Reaction products of ethanol decomposition on bare Rh clusters surface 53
4.2.2 Reaction products of ethanol decomposition on oxygen pre-adsorbed Rh clusters (O*-Rh) surface 55
4.2.3 Reaction products of ethanol decomposition on oxygen and water co-adsorbed Rh clusters (D2O*/O*-Rh) surface 57
4.2.3.1 Water dissociation on oxygen-covered Rh clusters surface 57
4.2.3.2 Ethanol decomposition on oxygen and water co-adsorbed Rh clusters (D2O*/O*-Rh) surface 61
4.2.4 Reaction pathway analysis for ethanol decomposition on Rh clusters surface 64
4.2.5 Reaction probability of ethanol on oxidative Rh clusters surface 69
Reference 71
Chapter 5 Conclusion 72
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4-1. Caglar, B., et al., The effect of C–OH functionality on the surface chemistry of biomass-derived molecules: ethanol chemistry on Rh(100). Physical Chemistry Chemical Physics, 2016. 18(43): p. 30117-30127.
4-2. Vesselli, E., et al., Ethanol Decomposition: CC Cleavage Selectivity on Rh(111). ChemPhysChem, 2004. 5(8): p. 1133-1140.
4-3. Vesselli, E., et al., Ethanol auto-thermal reforming on rhodium catalysts and initial steps simulation on single crystals under UHV conditions. Applied Catalysis A: General, 2005. 281(1): p. 139-147.
4-4. Syu, C.-Y. and J.-H. Wang, Mechanistic Study of the Oxidative Steam Reforming of EtOH on Rh(111): The Importance of the Oxygen Effect. ChemCatChem, 2013. 5(10): p. 3164-3174.
4-5. Caglar, B., J.W. Niemantsverdriet, and C.J. Weststrate, Modeling the surface chemistry of biomass model compounds on oxygen-covered Rh(100). Physical Chemistry Chemical Physics, 2016. 18(34): p. 23888-23903.
4-6. 夏于耀, Oxidative Reforming of Ethanol on Rh(111): effect of co-adsorbed oxygen and hydroxyl,中央大學碩士論文,桃園縣,民國107年


指導教授 羅夢凡(Meng-Fan Luo) 審核日期 2019-2-26
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