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研究生: 陳昭穎
Chern, Zhao-Ying
論文名稱: 燃料轉換效率於多元金屬催化劑之理論計算研究:硫毒化反應與甲醇氧化反應
Computational Study of Heterogeneous Catalysis in Fuel Cell Applications: Sulfur Poisoning Reactions and Methanol Oxidation Reactions
指導教授: 王禎翰
Wang, Jeng-Han
學位類別: 碩士
Master
系所名稱: 化學系
Department of Chemistry
論文出版年: 2019
畢業學年度: 107
語文別: 中文
論文頁數: 75
中文關鍵詞: 密度泛函理論鈣鈦礦石墨烯三元合金硫毒化反應甲醇氧化反應甲酸氧化反應固態氧化物燃料電池直接甲醇燃料電池直接甲酸燃料電池
英文關鍵詞: Density Functional Theory (DFT), Ruthenium (Ru), Titanium (Ti), ternary alloy, sulfur-poison reaction, methanol oxidation reaction (MOR), formic acid oxidation reaction (FAOR), Solid Oxide Fuel Cells (SOFCs), Direct Formic Acid Fuel Cells (DFAFCs)
DOI URL: http://doi.org/10.6345/NTNU201900141
論文種類: 學術論文
相關次數: 點閱:170下載:13
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  • 本篇論文以第一性原理計算幾個不同的異質催化反應在燃料電池的應用,包括 (1) 第二章討論硫毒化與移除於BaZrO3陽極的反應, (2) 第三章討論甲醇裂解反應於鉑—石墨烯之性質, (3) 第四章討論甲醇氧化反應 (MOR) 與甲酸氧化反應 (FAOR) 於鉑三元合金 (PtRuM, M=Fe, Ti) 陽極之性質。
    第二章節中,計算結果發現燃料中含有的H2S(g)會毒害催化劑表面,此為強放熱反應,然而,移除硫化物為吸熱反應。表示硫毒化為一自發性發生且難避免的反應。研究發現水的加入可以幫助硫化物的移除。除此之外,我們還列出了反應熱與自由能以及電池電動勢之間的關聯性,以此探討電池偏壓以及H2S(g)與H2O(g)的氣體分壓對於硫化反應的影響。第三章討論以石墨烯為擔體之鉑催化劑對於甲醇吸附的性質差異。根據石墨烯與鉑的結合角度可分為0o和30o角,研究結果發現甲醇可吸附在鉑團簇上,但對於鉑層吸附較弱。此種差異可以應用於材料的保護層。第四章討論配位基效應與雙官能基效應對於MOR與FAOR於鉑釕三元合金 (PtRuM, M=Fe, Ti) 上造成的反應差異。鐵的加入可使周圍電子離域化,而鈦的加入可使電子更局域化。總體來看,PtRuTi可以幫助MOR與FAOR更容易進行反應,而鐵的加入幫助不大。

    Our present work utilized the first-principle calculations to investigate several important heterogeneous catalytic reactions in the fuel cells applications, including (1) sulfur poisoning and removal reactions on BaZrO3 based anodes in Chapter 2, (2) Methanol decomposition reaction on Pt layers and Pt clusters supported by graphene in Chapter 3, (3) Methanol oxidation reaction (MOR) and formic acid oxidation reaction (FAOR) on PtRuM (M=Fe, Ti) trimetallic anode in Chapter 4.
    In Chapter 2, our computational results found that the poisoning reaction from gas-phase H2S, fuel contamination, to bulk sulfide formation in highly exothermic, while the sulfur removing reaction from sulfide to gas-phase SO2 formation by small amount of H2O is endothermic, indicating the poisoning behavior is spontaneous and rapid and hard to avoid. Additionally, we utilized the thermodynamic corrections for the Gibbs free energy calculation to reveal the effects of bias potential and partial pressures of H2S and H2O. In Chapter 3, we initially constructed Pt layers and clusters on graphene supporter and found two types of models as the beneath graphene has 0o and 30o rotations, G0-Pt (or G0-Pt37) and G30-Pt (or G30-Pt37). Furthermore, we examined methanol adsorption on them and found that methanol can tightly adsorbed on the Pt clusters while is loose on Pt layers, in comparing with their (111) surfaces. The results explain the inertness of graphene supported Pt layers that is applicable for the protection-layer materials. In Chapter 4, we examined the ligand and bifunctional effects of MOR and FAOR between PtRuM (M=Fe, Ti) ternary materials. Introducing Fe in PtRu makes the neighboring electrons more delocalized; in contrast, Ti makes PtRu more localized. As a result, PtRuTi can assist MOR and FAOR, but PtRuFe cannot.

    致謝 ii 摘要 iii Abstract iv 目錄 vi 表目錄 ix 圖目錄 x 前言 xiii 第一章 理論計算原理 1 1-1 密度泛函理論 ( Density Functional Theory ) 1 1-1-1 Hohenberg-Kohn 定理 1 1-1-2 Kohn-Sham 方程 2 1-1-3 交換關聯泛函:不同級別的近似法 3 1-2 固態材料計算之理論基礎 4 1-2-1 Basis set 4 1-2-2 Pseudopotential 5 1-2-3 Reciprocal lattice 5 1-2-4 布洛赫定理 (Bloch’s Theorem) 6 1-2-5 自洽過程(Self-consistent calculation) 8 1-3 系統設定 9 1-3-1 VASP計算設定 9 1-3-2 系統與軟體 9 第二章 硫毒化反應在SOFC陽極材料Y & Yb-doped BaZrO3上之反應機制探討 10 2-1 緒論 10 2-2 計算參數設定 11 2-3 結果與討論 12 2-3-1 Y & Yb-doped BaZrO3表面模型建立 12 2-3-2 硫化產物在BaZrO3(001)之吸附表現 12 2-3-3 硫化物在BaZrO3(001)之氧化與還原反應機構 16 2-3-4 電池電動勢對於陽極硫毒化反應之影響 20 2-3-5 摻雜Y與Yb在BaZrO3(001)對硫毒化反應之影響 22 2-4 結論 25 第三章 甲醇在鉑層覆蓋及鉑團簇修飾石墨烯的吸附機構探討 26 3-1 緒論 26 3-2 計算參數設定 27 3-3 結果與討論 29 3-3-1 Pt-layer/Graphene與Pt-cluster/Graphene表面結構建立 29 3-3-2 甲醇在Pt-layer/Graphene表面之吸附特性 33 3-3-3 甲醇在Pt-cluster/Graphene表面之吸附特性 37 3-3-4 以態密度與電荷差異分析Pt/Graphene吸附活性 38 3-3-5 甲醇第一步脫氫反應於Pt/Graphene之反應性 42 3-4 結論 46 第四章 探討鉑釕與第三元金屬合金在甲醇與甲酸氧化反應性上的差異 47 4-1 緒論 47 4-2 計算參數設定 48 4-3 結果與討論 49 4-3-1 PtRu(111)與PtRuM(111)表面建立 49 4-3-2 MOR與FAOR於PtRuM上反應物與產物之吸附結構 51 4-3-3 MOR與FAOR於PtRuM上之反應探討 59 4-4 結論 70 第五章 參考書目 71

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