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研究生： 廖偉傑
Liao, Wei-Chieh
論文名稱： 陽離子對二氧化碳還原電催化選擇性和反應介面影響
The influence of cation on the electrocatalytic selectivity and reaction interface of carbon dioxide reduction
指導教授： 潘詠庭
Pan, Yung-Tin
口試委員: 胡啟章
Hu, Chi-Chang
王冠文
Wang, Kuan-Wen
陳翰儀
Chen, Han-Yi
學位類別： 碩士
Master
系所名稱： 工學院 - 化學工程學系
Department of Chemical Engineering
論文出版年： 2021
畢業學年度： 109
語文別： 中文
論文頁數： 72
中文關鍵詞： 電催化 、二氧化碳還原 、酸性環境 、陽離子半徑 、反應介面 、水合離子效應
外文關鍵詞： Electrocatalysis, Carbon dioxide reduction, Acidic environment, Cation radius, Reaction interface, Hydrate ion effect
相關次數： 點閱：2  下載：0 
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    • 電化學二氧化碳還原反應(Carbon dioxide reduction reaction,CO2RR)，由於具有高效率的將二氧化碳轉化成可利用化學品之巨大潛力而成為研究的重點領域之一。然直到今日，該反應在催化劑材料以及系統參數研究方面仍有許多改善的空間。
    在本研究中，我們使用質子交換膜燃料電池模組作為反應器，並利用1.5 M的鹼金屬陽離子溶液將商用的質子交換膜的質子置換出來，反應系統的酸鹼度因而產生了變化，從而為陰極創造了一個近似中性的環境，不同鹼金屬族的陽離子會對離子交換膜的濕潤程度產生影響，進而導致了系統質子輸送能力的落差，決定了系統最終的選擇率差異。
    除了對反應界面以及系統的質子輸送能力進行探討之外，觸媒的溶解以及電沉積也會受到陽離子影響。電沉積的觸媒形貌以及粗糙度也是決定選擇率的關鍵因素之一。鋰、鈉等小半徑的陽離子系統推測由於強烈的產氫反應造成觸媒溶解以及限制了電沉積的反應，鉀、銫等較大尺寸的離子系統因為較少的質子競爭吸附，有更多的觸媒能夠在被沉積到基材上，同時也產生不同的形貌以及晶型。這說明了系統的選擇率是由反應界面以及觸媒的性質共同決定的。

    The electrochemical carbon dioxide reduction reaction (CO2RR) has become one of the key areas of research due to its great potential for highly efficient conversion of carbon dioxide into usable chemicals. Until today, however, there is still room for improvement in the research and development of catalyst materials and system components.
    In this study, we used the proton exchange membrane fuel cell module as the reactor, and used alkali metal cation substituted the commercial proton exchange membrane (Nafion XL) to control the pH of the reaction system, thus creating an approximately neutral environment for the cathode. The cations of different alkali metal groups showed apparent effect on the ability of the ion exchange membrane to uptake water, which in turn the proton conductivity from anode to cathode. The regulated proton transport is proposed to be responsible for the observed significant difference in CO2RR selectivity over hydrogen production.
    In addition to the discussion of reaction interface and the proton transport of the system, the dissolution and impact of membrane cations to catalyst dissolution and deposition is also revealed. It is observed that the cation system with small radius such as lithium and sodium have caused severe dissolution of the Cu catalyst while the largest Cs cation on the other hand, appeared to influence the restructuring into well define crystals. Such cation dependent dissolution/redeposition is also considered to contribute significantly to the observed variations in CO2RR faradaic efficiencies.

    目錄 摘要 I ABSTRACT II 誌謝辭 III 圖目錄 VII 表目錄 X 第一章 緒論 1 第二章 文獻回顧 2 2.1 薄膜電極 2 2.1.1 氣體擴散媒介 (gas diffusion media) 3 2.1.2 離子交換膜 3 2.2 研究背景 4 2.6 二氧化碳還原反應 5 2.3.1 二氧化碳還原反應介紹 5 2.4 電催化二氧化碳還原反應介紹 6 2.4.1 電化學反應系統 6 2.4.2 續式反應電池模組介紹 8 2.5 電催化二氧化碳還原機制 9 2.5.1 Sabatier principle 10 2.5.2 電催化二氧化碳還原觸媒介紹 12 3.6 影響電催化二氧化碳還原反應介面的因素 14 2.6.1 水的參與 14 2.6.2 反應介面的pH質影響 15 2.6.3 電解液陽離子對反應介面的影響 16 2.6.4 固態電解液層(Nafion layer) 17 2.7 研究動機 18 第三章 實驗方法與儀器 20 3.1. 實驗藥品及耗材 20 3.2. 實驗儀器 23 3.3 分析儀器 24 3.3.1 X射線繞射分析儀 (X-ray diffraction analysis, XRD) 24 3.3.2 熱重分析儀 (Thermogravimetric analysis, TGA) 24 3.3.3 氣相層析儀 (Gas chromatography, GC) 25 3.3.4 掃描式電子顯微鏡 (Scanning electro microscope, SEM) 25 3.4 實驗方法 26 3.4.1 Cu/C觸媒製備 26 3.4.2 Cu/MgO 觸媒製備 26 3.4.3 陽極觸媒漿料製備 26 3.4.5 Cu/C觸媒漿料製備 27 3.4.6 Cu/MgO觸媒製備 27 3.4.7 sodium form 質子交換膜製備 27 3.4.8 電極製備 28 3.4.9 電化學測試裝置 28 3.4.10 電化學分析方法 29 線性掃描伏安法 29 定電位放電法 29 法拉第定律 29 第四章 結果與討論 31 4.1 Cu/C觸媒分析 31 4.2 二氧化碳還原之反應界面討論 35 4.3 薄膜陽離子以及銅觸媒流失 40 4.4 不同陽離子對觸媒溶解的效應 46 第五章 結論 49 第六章 未來工作 50 第七章 參考文獻 56 第八章 附錄 62

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