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研究生： 劉哲維
Liu, Che-Wei
論文名稱： 中空碳球生成機制研究與MgO作為鑄模合成中孔洞碳材方法之研究
Studies on Formation Mechanism of Carbons Hollow Spheres and the Syntheses of Mesoporous Carbon by Using MgO as Cast
指導教授： 林弘萍
Lin, Hong-Ping
學位類別： 碩士
Master
系所名稱： 理學院 - 化學系
Department of Chemistry
論文出版年： 2007
畢業學年度： 95
語文別： 中文
論文頁數： 112
中文關鍵詞： 中孔洞碳材 、高分子混掺
外文關鍵詞： mesoporous carbon, polymer blending
相關次數： 點閱：85  下載：2 
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    • 中孔洞碳材之所以受到許多關注及其廣泛的應用，主要是由於具有高的比表面積和大的孔洞體積，以及熱穩定度及良好的導電度。有別於以往需要繁雜的實驗步驟以及耗費許多時間的含浸法，以高分子混掺來合成中孔洞碳材則提供了一個簡單又迅速的實驗方法，但其實驗過程中的合成機制一直沒有被推測及證明出來，因此本研究利用改變不同的變因，藉由實驗結果不斷地推測以及證明，嘗試推導將最有可能的合成機制，而這也將有助於未來對於合成中孔洞碳材的研究以及應用。
    然而，以高分子混掺法合成中孔洞碳材，必須在碳化過後利用氫氟酸來移除氧化矽模板，而氫氟酸對人以及環境皆有一定的危害。因此研究上也嘗試以可被一般無機酸移除之氧化鎂來取代氧化矽，利用氧化鎂作為隔板來合成出中孔洞碳材，並且控制不同的實驗變因來找出最適當的實驗步驟和藥劑比例，合成出具有良好孔洞性以及高表面積的中孔洞碳材。
    此外，中孔洞碳材可做為導電以及電容材料，而碳材必須同時具有高表面積以及高石墨化程度，才可成為一個良好的導電以及電容材料。於是在實驗過程中加入了硝酸鐵，藉由在碳化的過程中以鐵奈米顆粒來催化碳材之石墨化，使合成出的碳材具有一定的石墨化程度，並且調整不同的實驗變因，以維持碳材仍然具有高表面積的特性。

    Mesoporous carbons of high surface area, large pore volume, high thermal stability and good electric conduction have attracted much attention of chemists and material scientists. Distinct from the typical nano-casting method including complicated and time-consuming synthetic steps, we proposed a new synthetic method by using PF containing polymer blends as template of porous silicas. After a fast sol-el reaction in the acidified silicate aqueous solution, we found the PF-PEO-silica composite in hollow sphere were prepared. The mesoporous carbon hollow spheres can be obtained from high-temperature pyrolysis and HF-etching and the mesoporous silica hollow spheres can be synthesized by calcination in air.
    In addition to the synthesis of the mesoporous silica and carbon hollow spheres, we also studied the effects of several experimental factor on the physical properties of the mesoporous carbons. According to the experimental results, we tried to propose a formation mechanism of the mesoporous carbon hollow spheres from PF-PEO polymer blend. Then, the mechanism provides mush information to help ones to control the diameter and properties of the hollow spheres.
    Although the polymer blending method is convenient to prepare the mesoporous carbons, the HF-etching process is essentially required to remove the silica framework. However, HF is hazardous to environment and the health of human. Therefore, we tried to use MgO nanoparticles as spacer that could be easily removed by inorganic acids to substitute SiO2. We tried many chemical compositions to find the most appropriate experimental steps and the composites for the synthesis of mesoporous carbons with high surface area and large porosity.
    To expand the application of the Mesoporous carbons in electrode materials and supercapacitor, the mesoporous carbon must have both high surface area and high electric conductivity. For improving the conductivity of the mesoporous carbon, we added a proper amount of Fe(NO3)3 into the PF-F127-MgO composite. During the pyrolysis, the iron nanoparticle can catalyze the increase the graphite extent of the mesoporous carbons. According to our experiments, the mesoporous carbons of high surface area and graphite content have been synthesized with a well control on the synthetic compositions.

    第一章 序論 1 1.1 孔洞材料介紹 1 1.1.1 中孔洞碳材(Mesoporous Carbon)簡介 1 1.1.2 中孔洞氧化矽(Mesoporous Silica)材料簡介 2 1.1.3 孔洞性材料的研究範疇 3 1.2 界面活性劑性質簡介 5 1.2.1 界面活性劑的分類 6 1.2.2 微胞的形成 7 1.3 矽酸鹽的基本概念 9 1.4 微乳液 12 1.5高分子混摻(polymer blends) 13 1.5.1 混摻的方法 14 1.6 研究動機與目的 16 第二章 實驗部份 21 2.1 化學藥品 21 2.2中孔洞碳材的合成方法 22 2.2.1利用高分子混掺法合成中孔洞碳材之合成步驟 22 2.2.2以MgO做為隔板合成中孔洞碳材之合成步驟 23 2.2.3利用Fe(NO3)3合成高石墨化程度中孔洞碳材之合成步驟 25 2.3 產物的鑑定 25 2.3.1穿透式電子顯微鏡(TEM) 25 2.3.2氮氣等溫吸附/脫附測量 26 2.3.3熱重分析儀 (TGA ) 29 2.3.4 X-射線粉末繞射光譜 (PXRD) 29 2.3.5掃描式電子顯微鏡 (SEM) 30 2.3.6拉曼光譜 (Raman) 30 第三章 以高分子混掺法製備中孔洞中空碳球 33 3.1 研究動機及目的 33 3.2實驗結果與討論 35 3.2.1 PEO高分子分子量對孔洞性碳材性質之影響 37 3.2.2溶劑對於合成中空碳球之影響 39 3.2.3酚醛樹酯含量對於碳材之影響 43 3.2.4矽酸鈉溶液pH值之探討 48 3.2.5矽酸鈉溶液熟化時間之探討 53 3.3結論 58 第四章利用MgO取代Sodium Silicate合成中孔洞碳材 61 4.1 研究動機與目的 61 4.2實驗結果與討論 62 4.2.1氧化鎂添加量對於碳材性質之影響 63 4.2.2酸鹼對於以MgO合成碳材的影響 69 4.2.3酚醛樹酯添加量對於合成碳材的影響 74 4.2.4合成系統中水量對於合成碳材的影響 77 4.3結論 79 第五章 合成具有高石墨化程度的中孔洞碳材 83 5.1 研究動機與目的 83 5.2 實驗結果與討論 84 5.2.1以硝酸鐵合成中孔洞碳材 85 5.2.2氧化鎂作為隔板以及利用硝酸鐵合成碳材 89 5.2.3酚醛樹酯添加量對於合成碳材之影響 92 5.2.4酸鹼對於以硝酸鐵和氧化鎂合成碳材的影響 97 5.2.5中孔洞碳材石墨化程度的探討 99 5.3 結論 103 第六章 結論 105 參考資料 107

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