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研究生： 林冠男
Quan-nan Lin
論文名稱： 密度泛涵理論在Pt15、Pt11Fe4和Pt11Co4團簇上對氧氣還原之研究
DFT Study of Oxygen Reduction Reaction on Pt15, Pt11Fe4 and Pt11Co4 clusters
指導教授： 黃炳照
Bing-Joe Hwang
口試委員: Tse-Chuan Chou
Tse-Chuan Chou
杜景順
Jing-Shan Do
江志強
Jyh-Chiang Jiang
陳俊維
Chen Chun-Wei
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： 2006
畢業學年度： 94
語文別： 英文
論文頁數： 94
中文關鍵詞： DFT 、氧氣還原 、PtCo 、PtFe
外文關鍵詞： PtCo and PtFe
相關次數： 點閱：191  下載：3 
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    • 本研究以密度泛涵理論探討氧氣在Pt15、Pt11Fe4 和Pt11Co4 團簇上的還原反應。為了充分了解Co和Fe對氧氣還原的影響，氧分子及其反應中間體在團簇上的吸附性質亦做了相關的計算。本研究計算了反應中可能產生的物種在團簇上吸附的形態和能量進而得到反應的能量表面輪廓圖及相關反應能量。計算結果發現H2O2在團簇上的生成和吸附較不穩定說明了氧氣在Pt15、Pt11Fe4 和Pt11Co4 團簇上的還原是經由“平行”的反應路徑進行，其中又以“直接”的路徑為主。經由OOH在Pt11Fe4 和Pt11Co4上易分離的特性及團簇上Pt吸附點不易被O和OH 吸附的性質發現 Pt 與Co和Fe的合金對於氧氣還原優於Pt的原因為較容易的O-O斷鍵能力和較多的活性部位。

    Density functional theory is used to study oxygen reduction reaction on Pt15, Pt11Fe4 and Pt11Co4 clusters. In this study, the adsorption properties of O2 molecule and intermediates in ORR are investigated in order to get insight into the influence of Co and Fe towards oxygen reduction reaction. Potential energy profiles and related energetics for ORR on Pt15, Pt11Fe4 and Pt11Co4 clusters are obtained by calculating the possible adsorbed species formed in ORR. The adsorption of H2O2 on Pt15, Pt11Fe4 and Pt11Co4 clusters is relatively unstable indicates that O2 reduction possibly proceed via a parallel pathway with the direct one as the dominant step. Pt forms alloys with Co or Fe benefit oxygen reduction reaction in terms of easy O–O dissociation and available active sites by the lower barrier of OOH dissociation and the dislike of OH and O adsorption on their Pt sites.

    Abstract (Chinese) Abstract (English) Acknowledgement Contents List of Tables List of Figures Chapter 1: Introduction 1.1 General Aspects of Fuel Cell 1.2 Ab Initio Quantum Chemistry Study for Oxygen Reduction on Fuel CellCatalysts 1.2.1 Adsorption of Molecular Oxygen on Fuel Cell Catalysts 1.2.2 Oxygen Reduction Reaction Mechanism 1.2.3 The Motive of the Study Chapter 2: Theoretical Background 2.1 Ab Initio 2.2 Schrödinger Equation and Electron Wavefunction 2.3 Hartree-Fock Method 2.3.1 Hartree Approximation 2.3.2 Hartree-Fock 2.3.3 Self Consistent Field 2.4 Density Functional Theory 2.4.1 Hohenberg and Kohn Theorems 2.4.2 Kohn and Sham Method 2.4.3 Implementations of Kohn and Sham Method 2.5 Perturbation Theory 2.5.1 Rayleigh-Shrödinger Perturbation Theory 2.5.2 Møller-Plesset Pertubation Theory 2.6 Ab Initio Basis Set 2.6.1 Gaussian Type Orbitals 2.6.2 Spilt Valence Basis Set 2.6.3 Polarization and Diffuse Basis Set 2.6.3 Effective Core Potentials 2.7 Transition-State Theory Chapter 3: Computational method Chapter 4: Results and Discussion 4.1 Bare clusters 4.2 The adsorption properties of oxygen and intermediates on Pt15, Pt11Co4 and Pt11Fe4 clusters 4.2.1 O2 adsorption 4.2.2 OOH. Adsorption 4.2.3 O adsorption 4.2.4 OH adsorption 4.3 Reaction pathways of the ORR 4.3.1 ORR on Pt15 cluster 4.3.2 ORR on Pt11Fe4 and Pt11Co4 clusters Chapter 5: Conclusions Reverences

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