臺灣博碩士論文加值系統

本論文以不同方法製備金屬-氧化物複合觸媒材料，第一種方法利用固態反應法合成尖晶石氧化物形成銅或鎳金屬觸媒應用於甲醇蒸氣重組反應；另外一種方法針對金屬間化合物或非晶質合金所製備之金、鉑觸媒進行一氧化碳氧化反應測試。上述研究方法皆根據熱力學中Ellingham 自由能平衡圖概念，了解不同金屬於不同溫度範圍下之氧化還原能力。
首先以固態反應法製備銅基尖晶石化合物CuX2O4 (X=Fe, Mn, Al, La)，探討在氫氣還原後之微結構變化及其觸媒特性。由程序升溫還原量測儀所得到之結果顯示，銅基尖晶石化合物之還原能力取決於尖晶石結構中B位元素而影響，其觀察到銅鐵氧化物出現最低還原溫度，並且於190°C開始產生還原反應，依序分別為銅鋁氧化物(267°C)、銅錳氧化物(270°C)、銅鑭氧化物(326°C)。還原後之銅鋁氧化物具有最佳觸媒特性與熱穩定性，深入研究其表面形貌與相成分變化，發現到銅鋁氧化物於360°C氫氣還原後，其觀察到細微銅顆粒(50.9 nm)析出於表面氧化鋁擔體，形成穩定之金屬-氧化物複合觸媒。同時，銅金屬氧化物複合材料之觸媒活性亦優於傳統商業型觸媒，此研究方法證實由銅基尖晶石化合物經還原處理後，具備潛力作為極佳活性與高熱穩定性之觸媒。
第二部分，將銅-鎳鐵氧體(Ni1-xCuxFe2O4)透過氫氣還原法製備銅-鎳氧化鐵擔體觸媒。所有鐵氧體於還原處理前皆呈現表面平滑之顆粒型態。銅鐵氧體、銅-鎳鐵氧體及鎳鐵氧體分別於溫度240、300及400°C進行還原處理，其表面形成奈米銅金屬和(或)奈米鎳金屬粒子(5-32 nm)及微孔洞(5-30 nm)分散於四氧化三鐵擔體表面上。將鎳鐵氧體還原溫度升高至500°C時，由於鐵-鎳合金生成覆蓋於四氧化三鐵擔體表面，因此原先擔體表面之鎳金屬顆粒及微孔皆消失。銅鐵氧體於溫度240°C氫氣還原處理後，在反應溫度360°C得到最高氫氣產率，其最高值達到149 ml STP/min．g-cat。銅-鎳鐵氧體中生成鎳金屬會增強反向水煤氣轉化反應，以至於增加一氧化碳副產物進而減少二氧化碳產率，當隨著還原溫度升高，其鐵-鎳合金會直接影響甲醇蒸氣重組反應之氫氣產率。
最後，為了要開發新製程製備新型奈米金與鉑觸媒於鋯基氧化物擔體中，嘗試以金屬間化合物與非晶質合金作為前驅物，將氧化鋯作為擔體製備金屬-氧化物複合觸媒(Au, Pt/ZrO2-Fe2O3)，以探討奈米金與鉑於鋯基氧化物擔體對其一氧化碳氧化反應活性之影響。利用真空電弧熔煉法將純鋯、鐵、金、鉑等元素，以不同化學計量配比於氬氣氣氛中熔製成鋯基金屬合金錠並經由擊碎、研磨製成金屬間化合物粉末，接著將部分金屬合金錠以單輥熔射旋淬法製備非晶質合金薄帶。藉由熱分析數據，了解隨著溫度的變化並分別進行不同溫度的氧化處理，進而形成奈米金與鉑觸媒穩定且均勻分散於鋯基氧化物擔體中，進一步解析金、鉑金屬觸媒顆粒與擔體間之交互作用。另一方面，以鈰鎳金屬間化合物為前驅物，藉由添加少量金或白金金屬取代結構中之鎳金屬，製備形成金屬-氧化物複合觸媒(Au, Pt/CeO2-NiO)。當金屬間化合物經由氧化過程時，其結構中的鈰金屬較容易形成二氧化鈰，造就金或白金金屬顆粒逐漸析出於表面，進而促進整體觸媒活性。尤其將Ce50Ni45Au5金屬間化合物直接置於反應床中，經過五次升降溫測試後，其表面會析出均勻的金與鎳金屬顆粒分散於二氧化鈰擔體。

There are two different approaches in this thesis. One approach is to synthesize spinel-type oxides as a precursor preparing Cu or Ni catalysts for steam reforming of methanol (SRM). The other approach focuses on preparation of Au or Pt catalysts from intemetallic compounds or amorphous alloys to perform CO oxidation reaction. These approaches in terms of the ellingham diagram which is usually used to evaluate the ease of reduction of metal oxides or oxidation of metal.
Firstly, various Cu-based spinel compounds, i.e., CuFe2O4, CuMn2O4, CuAl2O4 and CuLa2O4 were fabricated by a solid-state reaction method. H2-TPR results indicated that reducibility of Cu-based spinel compounds was strongly dependent on the B-site component where the CuFe2O4 catalyst revealed the lowest reduction temperature (190°C), followed by CuAl2O4 (267°C), CuMn2O4 (270°C) and CuLa2O4 (326°C). The reduced CuAl2O4 catalyst revealed the best performance in terms of catalytic activity. Based on the SEM and XRD results, pulverization of the CuAl2O4 particles due to gas evolution and a high density of nanosized Cu particles (50.9 nm) precipitated on the surfaces of the Al2O3 support were observed after reduction at 360°C in H2. Reduction of Cu-based spinel compounds appear to be a potential synthesis route for preparing a catalyst with high catalytic activity and thermal stability. The catalytic performance of these copper-oxides composites was superior to those of conventional copper catalysts.
Secondly, Fe3O4-supported Cu and Ni catalysts are prepared through reduction of Cu-Ni (Ni1-xCuxFe2O4) ferrites. All ferrites are characterized with granular morphology and a smooth particle surface before reduction. Reduction temperature for the CuFe2O4, Ni0.5Cu0.5Fe2O4 and NiFe2O4 ferrites were 240, 300, and 400°C, respectively, in which nanosized Cu and/or Ni particles (5-32 nm) and mesopores (5-30 nm) are distributed and adhered on the surfaces of Fe3O4 supports. After the reduction treatment at temperature higher than 500°C for NiFe2O4 ferrite, the Ni particles and mesopores disappear from the Fe3O4 surfaces, which is due to the formation of a Fe-Ni alloy covered on the Fe3O4 surfaces. The CuFe2O4 ferrite after H2 reduction at 240°C exhibits the highest activity quoted with H2 production rate of 149 ml STP/min．g-cat at 360°C. The existence of Ni in the Cu-Ni ferrites enhances the reverse water gas shift reaction, raises the CO selectivity and reduces the CO2 selectivity. Formation of the Fe-Ni alloy exaggerates the trend and poisons the H2 production rate.
Finally, in order to develop a process for preparation of a new form of catalyst where Au, Pt fine particles supported on metal oxides (ZrO2, Fe2O3), Au or Pt–contained Zr2Fe-based intermetallic compounds and amorphous alloys were used as precursors for oxidation treatment. The catalytic properties of Au, Pt/metal oxides catalysts prepared by crystallization or oxidation have been investigated with CO oxidation reaction (CO+1/2O2→CO2). Zr67Fe33, Zr67Fe30Au3 and Zr67Fe30Pt3 alloys were prepared by arc-melting in Ar atmosphere. Amorphous phase was further fabricated by single-roller melt spinning in an Ar atmosphere. The catalysts were obtained by annealing amorphous ribbons at elevated temperatures. After the oxidation process, metal-oxide composite catalysts of Au, Pt/ZrO2-Fe2O3 were obtained. The changes in the intermetallic compounds and amorphous alloy ribbons before and after the oxidation treatment were analyzed, and the effects of the oxidation features and mechanisms on the catalytic activity of the catalyst was investigated. On the other hand, the metal/oxide complex catalyst (Au, Pt/CeO2-NiO) was successfully synthesized using the cerium-based intermetallic compound Ce50Ni50 as a precursor and replacing Ni with a small quantity of Au or Pt. The catalytic properties of CeO2-NiO supported Au and Pt catalysts for the CO oxidation reaction were investigated. The catalysts were obtained by oxidation treatment at elevated temperatures. The cerium metal in the intermetallic compound was easily oxidized to CeO2 during the oxidation process, in which Au or Pt particles precipitated on the surface and promoted the overall catalytic activity. This was especially clear when intermetallic Ce50Ni45Au5 was tested in the reaction bed directly; Au and Ni particles precipitated to the surface of the CeO2 support and were evenly distributed after five cycles of a heating and cooling test.

CHINESE ABSTRACT i
ENGLISH ABSTRACT iv
ACKNOWLEDGEMENTS (CHINESE) vii
CONTENTS ix
LIST OF TABLES xii
LIST OF FIGURES xiii
Chapter 1 1
Introduction 1
1.1 Background 1
1.2 Motivation 3
Chapter 2 5
Literature Review 5
2.1 Oxides as a Precursor 5
2.1.1 Steam Reforming of Methanol 5
2.1.2 Cu-Based Catalysts 7
2.2 Metals as a Precursor 8
2.2.1 Intermetallics 9
2.2.2 Single Roller Melt-Spinning Method 12
2.2.3 Amorphous Alloys 14
2.2.4 Property of Gold and Platinum 16
2.2.5 Methods of Preparation 17
2.2.6 Metal-Supported Interaction 21
2.2.7 Catalytic Mechanism 24
Chapter 3 27
Reduction Behaviors and Catalytic Properties for Methanol Steam Reforming of Cu-based Spinel Compounds CuX2O4 (X=Fe, Mn, Al, La) 27
3.1 Introduction 28
3.2 Experimental Procedure 29
3.3 Results and Discussion 31
3.3.1 Reduction Behaviors of Various Cu-based Spinel Compounds 31
3.3.2 Catalytic Performance of Copper-Oxide Composites Obtained by Reduction of Various Cu-based Spinel Compounds 42
Chapter 4 49
Catalysts Prepared from Copper-Nickel Ferrites for the Steam Reforming of Methanol 49
4.1 Introduction 49
4.2 Experimental Procedure 51
4.3 Results and Discussion 53
Chapter 5 71
Au or Pt Catalysts Prepared from Intermetallic and Amorphous Compounds of Zr67Fe33-xMx (M=Au, Pt) for the Oxidation of Carbon Monoxide 71
5.1 Introduction 72
5.2 Experimental Procedure 73
5.3 Results and Discussion 75
5.3.1. Catalytic activities of Zr67Fe33-xMx (M=Au, Pt) intermetallic compounds 75
5.3.2. Catalytic activities of Zr67Fe33-xMx (M=Au, Pt) amorphous alloys 79
Chapter 6 97
Characterization of New Catalysts Prepared by In-Situ Activation of Ce50Ni50-xMx (M=Au, Pt) Intermetallic Compounds for CO Oxidation 97
6.1 Introduction 98
6.2 Experimental Procedure 99
6.3 Results and Discussion 100
Chapter 7 118
Conclusion and Future Prospect 118
7.1 Conclusion 118
7.2 Future Prospect 119
REFERENCES 121
CURRICULUM VITAE 138
LIST OF ORIGINAL PUBLICATIONS 139

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