探索二氧化碳加氫製甲醇的活性位點：透過調控氧化亞銅尺寸與晶面揭示尺寸效應與金屬–載體界面作用

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題名:	探索二氧化碳加氫製甲醇的活性位點：透過調控氧化亞銅尺寸與晶面揭示尺寸效應與金屬–載體界面作用
作者:	蕭語晴;Hsiao, Yu-Ching
貢獻者:	化學學系
關鍵詞:	異相催化;二氧化碳;甲醇
日期:	2025-08-18
上傳時間:	2025-10-17 11:36:03 (UTC+8)
出版者:	國立中央大學
摘要:	近年來，二氧化碳的移除因其對環境保護的重要性而備受關注。將二氧化碳加氫轉化為甲醇是一種兼具環境與能源效益的關鍵技術，其中銅基催化劑因展現良好的活性與選擇性而廣受研究。然而，目前工業上所使用的銅基催化劑多為共沉澱法製備，具備高度複雜且不均勻的形貌，導致其表面暴露的活性位點類型難以明確界定，亦使反應機制研究面臨挑戰。為解決上述問題，本研究旨在透過精確控制氧化亞銅的粒徑，並量化不同位點的數量，深入探討二氧化碳加氫反應的主要活性位點。我們成功合成出不同尺寸的氧化亞銅立方體，並以此為基礎，藉由液相吸附法製備了一系列具有不同銅粒徑的 Cu/ZrO2 催化劑。隨後，採用含浸法與再吸附法在 Cu/ZrO2 催化劑上附載鋯，形成 ZrO2/Cu/ZrO2 結構。同時，我們也製備了兩種以氧化鋁為載體的催化劑作為對照組。活性測試顯示，Cu/ZrO2 與兩種氧化鋁載體催化劑呈現相似的活性趨勢，且活性差異不顯著。進一步量化產物生成速率與銅位點數量後，我們觀察到，對於含浸法製備的 ZrO2/Cu/ZrO2 催化劑而言，其活性變化與銅立方體的邊緣原子佔總暴露原子數的比例呈現高度相關性。相較之下，含浸法製備的氧化鋁載體催化劑並未表現出相同的活性趨勢。綜合實驗結果推測二氧化碳加氫反應的活性位點可能位於銅與鋯的界面且須以離子態的鋯與銅原子協同形成特定的鍵結結構，才能構成有效的活性位點。本研究為深入理解銅基催化劑在二氧化碳加氫反應中的活性機制提供了關鍵性的實驗證據，並強調了金屬-載體界面在催化性能調控中的重要作用。;The removal of CO2 has garnered significant attention in recent years due to its environmental implications. Copper-based catalysts have emerged as promising materials for CO2 hydrogenation. This study aims to identify the primary active sites for this reaction by controlling the size of Cu2O and quantifying the number of different site types. We synthesized Cu2O nanocubes of varying dimensions, which were utilized to prepare a series of Cu/ZrO2 catalysts via a toluene adsorption method. Zirconium was loaded onto these Cu/ZrO2 catalysts using impregnation and re-adsorption methods, respectively, to form the ZrO2/Cu/ZrO2 structure. Two alumina-supported catalysts were prepared as reference materials. Preliminary activity tests revealed similar activity trends and no significant differences between the Cu/ZrO2 and the two alumina-supported catalysts. Further quantification of product formation rates and the number of copper site types revealed a strong correlation between the catalytic activity of the impregnated ZrO2/Cu/ZrO2 catalysts and the proportion of edge atoms on the cuprous oxide nanocubes relative to the total exposed copper atoms. In contrast, the alumina-supported catalysts prepared by impregnation did not exhibit the same trend. These findings strongly suggest that the active sites for CO2 hydrogenation are likely located at the copper-zirconia interface. We assume that the synergistic formation of specific bonding configurations involving ionic zirconium and copper atoms is essential for creating effective active centers. This research provides crucial experimental evidence for a deeper understanding of the active mechanism of copper-based catalysts in CO2 hydrogenation, underscoring the critical role of the metal-support interface in tuning catalytic performance.
顯示於類別:	[化學研究所] 博碩士論文

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