研究生: |
葉 瑋 Yeh, Wei |
---|---|
論文名稱: |
以均質與異質同步成核法合成具有鉑原子團修飾之鈷錫鈀多尺度觸媒以用於氧還原反應 Pt-clusters decorated Co/SnO2/Pd hierarchical structure nanocatalysts by simultaneously homogeneous and heterogeneous nucleation for ORR application |
指導教授: |
陳燦耀
CHEN, TSAN-YAO |
口試委員: |
陳柏均
Chen, Po-Chun 林滄浪 LIN, TSANG-LANG |
學位類別: |
碩士 Master |
系所名稱: |
原子科學院 - 工程與系統科學系 Department of Engineering and System Science |
論文出版年: | 2019 |
畢業學年度: | 107 |
語文別: | 中文 |
論文頁數: | 156 |
中文關鍵詞: | 奈米觸媒 、氧氣還原反應 、異質 、白金 |
外文關鍵詞: | nanocatalyst, ORR, heterogeneous, platinum |
相關次數: | 點閱:1 下載:0 |
分享至: |
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為了滿足不斷增長的能源需求、降低汙染水平、發展乾淨且可持續再生的能源是現代社會不可避免的議題。燃料電池由於其高轉換效率而成為最有前景的能量轉換裝置之一。陰極的氧氣還原反應 (Oxygen Reduction Reaction) 在燃料電池所有組件中佔有最高的能障 (energy barrier) ,因此需要奈米觸媒 (NCs) 來增強緩慢的反應動力學。鉑基奈米觸媒的高製造成本和電化學活性是開發需要高可靠度及符合成本效益的燃料電池會面臨到的主要瓶頸。因此,為了有效降低奈米觸媒成本並同時提高ORR性能,我們開發了一系列的奈米碳管承載四元多尺度混合金屬奈米觸媒,使其具有鈷錫鈀三元層次結構與原子級鉑團簇修飾結構缺陷。另外,使用簡單快速的濕式化學還原法,並利用不同比例的鉑 (0.5 - 3 wt%) 進行修飾。透過交叉參考X光光譜 (XRD及XAS) 和電化學分析的結果,我們證明了添加錫 (Sn) 會增加原子半徑與表面能,因此鉑 (Pt) 原子會傾向於填充多金屬界面或表面缺陷等表面能較高的位置,同時表面修飾的鉑團簇會從鄰近電負度較低的原子得到電子。這些效應能有效地提升四元多層次結構奈米觸媒 (NCs) 的質量活性 (MA) 和0.85 V的動力學電流值 (Jk) ,且與商業用鉑觸媒 (J.M.Pt/C) 性能相比,當鉑 (Pt) 為1 wt%時,MA提高了20倍 (2146.2 mAmgPt -1) 。
本研究製備出的原子級鉑團簇修飾鈷錫鈀層次結構之四元混合金屬奈米觸媒,藉由調整鉑修飾比例、錫鈀比例與厚度、鈷與酸化奈米碳管之擴散溫度,瞭解鉑原子團簇在不同結構上的變化與對氧氣還原反應活性之間的關聯。如此一來,便能有效地增加催化電流與觸媒反應活性,並減少鉑金屬使用量以降低成本,這種具有預期性能的材料設計方式可以加速發展具有高活性的鉑金屬修飾過渡金屬基觸媒的開發。
In order to meet the growing energy demand, reduce pollution levels, and develop clean and sustainable renewable energy is an inevitable issue in modern society. Fuel cells are one of the most promising energy conversion devices due to their high conversion efficiency. The Oxygen Reduction Reaction of the cathode occupies the highest energy barrier in all components of the fuel cell, so nanocatalysts (NCs) are required to enhance the slow reaction kinetics. The high manufacturing cost and electrochemical activity of platinum-based nanocatalysts are the main bottlenecks faced by fuel cells that require reliability and cost. Therefore, in order to effectively reduce the cost of nanocatalysts and improve the performance of ORR, a series of acidic carbon nanotubes are loaded with a quaternary hierarchical mixed metal nanocatalyst, which has a cobalt-tin-palladium ternary hierarchical structure with atomic platinum cluster modified structural defects. By using a simple but rapid wet chemical reduction method, Co/SnO2/Pd hierarchical structure nanocatalysts with different amount of platinum (0.5 - 3 wt%) can be synthesized. Through cross-reference X-ray spectroscopy (XRD and XAS) and electrochemical analysis, we show that the addition of tin (Sn) increases the atomic radius and surface energy, so platinum (Pt) atoms tend to grow on polymetallic interfaces or surface defects, which has a higher surface energy. Surface-decorated platinum clusters will receive electrons from adjacent atoms with lower electronegativity. These effects can effectively improve the mass activity (M.A.) of quaternary multi-layer nanocomposites (NCs) and the kinetic current value (Jk) of 0.85 V, compared to commercial platinum catalyst (J.M.Pt/C) performance. When the platinum loading is 1 wt%, the MA is increased by 20 times (1345.9 mAmgPt -1) .
The atomic platinum clusters prepared in this experiment modify the cobalt-tin-palladium hierarchical quaternary mixed metal nanocatalyst by adjusting the platinum modification ratio, the ratio of tin to palladium and the thickness, and the diffusion temperature of cobalt and acidic carbon nanotubes. The relationship between platinum atomic clusters in different structures and the activity of oxygen reduction reaction can effectively increase the kinetic current and catalyst activity, and reduce the usage of platinum metal to reduce the cost. Identifying materials design with expected properties can accelerate the development of highly active and abundant transition-metal-based catalysts with low platinum loading
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