研究生: |
楊雅真 Ya-Jen Yang |
---|---|
論文名稱: |
NHx (x= 0 ~ 3)和NOx在RuO2(110)表面吸附和反應之理論計算研究 Theoretical Study of NHx (x= 0 ~ 3) and NOx Adsorption and Reaction on RuO2 (110) surface |
指導教授: |
江志強
Jyh-Chiang Jiang |
口試委員: |
魏金明
none 蔡大翔 Dah-Shyang Tsai 林聖賢 none |
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: | 101 |
中文關鍵詞: | 二氧化釔 、氨 、氮氧化物 、吸附 、反應 、能障 、虛頻 |
外文關鍵詞: | RuO2, NHx, NOx, Adsorption, Reaction, barrier, frequency |
相關次數: | 點閱:308 下載:1 |
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本研究係利用DFT方法模擬0.5 ML和1 ML的NHx (x = 0~3)吸附在純RuO2(110)表面和0.5 ML的NHx (x = 0~3)吸附在富氧表面、NOx吸附在純RuO2(110)表面、NH3氧化反應、1 ML的NHx (x = 1, 2)自身反應、NOx氧化還原反應。計算結果顯示NHx吸附能和表面重建的現象會隨著N原子上的H數目減少而增加,即Ncus有最大的吸附能。NH3分子則考慮兩部分反應: (1) N-H鍵裂解; (2)形成NO或N2分子。N-H鍵裂解反應是H遷移到RuO2(110)表面鄰近的氧原子(Ocus和Obr)上,在表面形成OH或H2O; N-H鍵裂解完後,表面上的N會和鄰近的N原子或氧原子結合。在氨氧化反應中顯示表面Ocus比Obr活性高,在形成OH、H2O及NO反應中,和Ocus或OHcus反應所得能障較低,在這些反應中最大能障1.09 eV,此結果和Wang等人實驗結果吻合[30],而反應後所產生的NOcus的脫附能較高,也和實驗相吻合。高覆蓋率下,NHx (x = 1, 2)在純RuO2(110)表面容易反應成不對稱的吸附方式,顯示自身反應扮演很重要的角色。另外,NOx吸附在純RuO2(110)表面,NO3cus之吸附能最大;而在NOx氧化還原反應中,當表面含Ncus多時,反應路徑傾向形成N2O,而表面含Ocus多時,反應路徑傾向形成NO2。
The adsorption of NHx species (x = 0 ~ 3) on clean RuO2 (110) surface with 0.5 ML and 1 ML coverage, and the adsorption on oxygen-rich surface, and the adsorption of NOx on clean RuO2 (110) surface, and NH3 oxidation reactions, and the self-reactions of NHx (x = 1, 2) with 1 ML coverage, and NOx redox reaction are simulated by density functional theory (DFT). Vienna ab-initio simulation package (VASP) is applied in this work. The binding energies and surface reconstruction of NHx species increase as the number of hydrogen decreased on N atom, i.e. Ncus has the highest binding energy. The NH3 oxidation reaction can be considered two parts, the N-H bond dissociations and the formation of NO or N2 molecule on the surface. In N-H dissociation, the hydrogen atoms migrate to the neighboring oxygen atoms on RuO2 (110) surface (Ocus and Obr), and the OH or H2O forms on the surface; and the second part, after N-H bonds dissociated, the nitrogen atom can combine with another nitrogen atom or the surface oxygen atom. The surface Ocus shows the higher activity than Obr in the ammonia oxidation. In formation of OH, H2O and NO, reactions with Ocus or OHcus have lower reaction barriers, and the highest barrier in these reactions is 1.09 eV. This result consists with the previous experiments by Wang et al. [30]. After the reaction, the higher desorption energy of NOcus also consists with the higher desorption temperature in experiment. The self-reactions of NHx (x = 1, 2) with 1 ML coverage have lower reaction barriers, and that prefer asymmetry adsorption. In addition, the adsorption of NOx on clean RuO2 (110) surface, NO3 has the highest binding energy. In NOx redox reaction, the availability of chemisorbed Ocus or Ncus controls the selectivity towards NO2 or N2O.
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