研究生: |
莊健峰 Chien-Fang Chuang |
---|---|
論文名稱: |
甲醇分子在氧化銥(110)、銥/氧化銥(110)以及富氧狀態下的氧化銥(110)表面吸附作用與裂解反應之研究 Theoretical Study of methanol adsorption and dehydrogenation on IrO2(110), Ir/IrO2(110) and O/IrO2(110) surface |
指導教授: |
江志強
Jyh-Chiang Jiang |
口試委員: |
林聖賢
Sheng-Hsien Lin 魏金明 Jin-Ming Wei 蔡大翔 Dah-Shyang Tsai |
學位類別: |
碩士 Master |
系所名稱: |
工程學院 - 化學工程系 Department of Chemical Engineering |
論文出版年: | 2008 |
畢業學年度: | 96 |
語文別: | 中文 |
論文頁數: | 136 |
中文關鍵詞: | IrO2 、密度泛涵理論計算 、甲醇分子裂解反應 、Ir/ IrO2 |
外文關鍵詞: | methanol decomposition, DFT, IrO2, Ir/IrO2 |
相關次數: | 點閱:255 下載:2 |
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本論文中主要是利用密度泛涵理論(DFT)計算方法,研究甲醇氣體分子在IrO2(110)、Ir/IrO2(110)以及O/IrO2(110)表面上的吸附以及裂解之反應機制。經過結構最佳化計算後發現,甲醇分子在IrO2(110)表面上,不是以甲醇分子形態吸附,而是經過O—H鍵裂解後,形成甲氧基分子吸附在Ircus上以及H原子吸附在Obr的位置。接著在後續的氫裂解反應中,有三種步驟都有近似的反應能障,分別是甲氧基分子發生氫裂解反應,還有甲醛分子發生氫裂解反應,以及H原子在Obr之間的遷移反應。因此,若考慮計算誤差,這三種反應都有可能為此反應機制之速率決定步驟。另外,甲醇分子吸附在Ir/IrO2表面的研究中,考慮了四種不同的吸附位置,而取了其中兩種較穩定的吸附結構,當作裂解反應的起始點,再比較不同的起始點所發生的裂解反應,發現CHO分子以四元環結構吸附在表面上,會毒化此觸媒表面,造成下一步的裂解反應能障變高,因此若能避免此吸附結構發生,反應能障則大幅降低。接著討論甲醇分子吸附在富氧的IrO2(110)表面,發現甲醇分子是以分子型態吸附在Ircus上,與吸附在IrO2(110)表面不同。而在後續的裂解反應中,其速率決定步驟為CHO分子裂解,其反應能障為1.74 eV。比較甲醇分子在三種不同的表面下之裂解反應,發現在Ir/IrO2表面上,O—H鍵結裂解之反應能障遠遠高於其他表面。另外,在富氧的情形下,並沒有降低甲醇分子裂解反應之能障。
Periodic, Density Functional Theory (PW91-GGA) calculations are used to study competitive paths for methanol decomposition on rutile-type IrO2(110), 1/2ML Ir/ IrO2(110), and Oxygen rich IrO2(110) surface. The energy barriers for all the elementary steps, starting with O—H scission and proceeding via sequential hydrogen abstraction from the resulting methoxy intermediate, are presented here. The minimum energy path is represented by a potential energy connecting methanol with its final decomposition product, carbon monoxide (CO). For methanol decomposition on IrO2(110) surface, the energy barriers of methoxy dehydrogenation, formaldehyde dehydrogenation, and hydrogen diffusion between Obr are very close and those are higher than other reactions. On Ir/IrO2 surface, there are four possible methanol adsorption structures, and the two most stable structures are used to be the initial state of methanol decomposition on Ir/IrO2 surface. The calculated result shows the adsorption of CHO on the surface with four member ring conformation is very close,which may poison the catalytic surface. The structure of methanol adsorption on IrO2 is different from O/IrO2 . The rate determining step of methanol decomposition on O/IrO2 surface is CHO, and decomposition, the energy barrier is 1.74 eV.
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