由於奈米碳管(CNTs)之特殊結構，使其具備特異的物理化學性質，尤其在儲氫特性方面，深具研究及實用的潛力。因此，本研究之主要目的為探討最佳多壁CNTs (MWCNTs)合成方法、結構特性鑑定及其儲氫能力。實驗是以溶劑熱法配合使用鉀及鈉金屬為還原劑來合成MWCNTs，經場發掃描式電子顯微鏡(FE-SEM)及穿透式電子顯微鏡(TEM)測試結果為以鉀為還原劑所合成之K-MWCNTs管徑約為30~100 nm，管壁為多層石墨化結構，合成條件為285℃反應12 hr；以鈉為還原劑所合成之Na-MWCNTs管徑約為20~60 nm，管壁為非晶質碳(amorphous carbon)所構成，合成條件為285℃反應20 hr，並可得到碳雜質較少且純度較高之MWCNTs。並以X射線能量散佈分析儀(EDS)、X光粉末繞射儀(XRPD)、拉曼光譜(Raman spectroscopy)、延伸細微結構X光吸收光譜(EXAFS)及X光吸收邊緣結構光譜(XANES)來驗證溶劑熱法合成MWCNTs之反應機構及分析其碳管結構之結晶性。拉曼光譜分析結果顯示K-MWCNTs之G-band強度大於Na-MWCNTs，而D-band的強度大小則相反，顯示K-MWCNTs石墨結晶性較強。XRPD分析結果顯示以溶劑熱法合成之MWCNTs結構結晶性與電弧放電法(arc discharge, AD)或噴霧熱解法(spray pyrolysis, SP)法相異。
為探討MWCNTs經改質處理後對儲氫之能力是否有提昇效果，選擇arc discharge(AD)或apray pyrolysis(SP)合成之MWCNTs及K-MWCNTs或Na-MWCNTs進行比較，並對以上不同製程方法之MWCNTs進行HNO3、KMnO4、及H2O2等改質處理，並添加貴重金屬Pd以及NaAlH4來試圖增加其儲氫量，再以微量天平檢測MWCNTs對H2吸附之效果，接著並以紅外線光譜(FTIR)檢測改質處理後碳管表面結構之變化。結果顯示，經由改質處理過後的奈米碳管，儲存氫氣的效果均有提昇，而經由硝酸處理過後的碳管，其吸附效果最好，吸附量都可以達到0.8 wt%以上；同時也可以發現，經由硝酸改質過後的奈米碳管，在添加了Pd之後，對於氫氣的吸附效果也最好，其儲存氫氣的效果依序為HNO3>KMnO4>H2O2；除此之外，在XRD分析方面，也可以發現到，經過硝酸改質過後的奈米碳管，其晶形強度會消退；此外，Pd在經過分散於碳管上的步驟之後，會發現其晶形改變，也會大量提昇碳管的儲氫效率。而藉由TEM及FE-SEM的觀察，可以發現Pd可以很均勻地分散於碳管之間。為了深入瞭解Pd的精細結構，進一步採用延伸X光吸收光譜及X光吸收邊緣結構(EXAFS/XANES)來分析；顯示經由還原步驟後，PdCl2可以順利地還原成Pd，同時，可以發現Pd-Pd鍵距為2.76±0.02Å，配位數為6±0.25，Pd-Cl鍵距為2.25±0.02Å，配位數為1.8±0.25。此研究顯示Pd分散於碳管上確實可以大量提昇奈米碳管的儲氫效果。

Carbon nanotubes (CNTs) have attracted increasing attention because of their unique structural, mechanical, and electronic properties. Surface chemistry modifications are also useful and critical to manipulate the adsorptive properties of CNTs and develop their potential of hydrogen storage. Therefore, the main objectives of this study were to investigate the optimal synthesis methods or characteristics identification of multiwall CNTs (MWCNTs) and the abilitiy of hydrogen storage in CNTs. Experimentally, the MWCNTs were produced from the catalytic-assembly benzene-thermal routes to MWCNTs by using reduction of hexachlorobenzene by metallic K or Na in the presence of Co/Ni catalyst precursors at moderate temperatures of 503-623 K. The MWCNTs of well-graphited walls were obtained with reductive K metals of catalytic hexachlorobenzene-thermal routes at 558 K for 12 hrs. Similarly, the amorphous MWCNTs with fewer impurities were also formed from the reductive Na metals of hexachlorobenzene-thermal catalytic pathways at lower temperature of 558 K for 12 hrs. The diameters of K-MWCNTs and Na-MWCNTs ranged of 30-100 and 20-60 nm, respectively by using field-emission scanning microscopy (FE-SEM) and transmission electron microscopy (TEM) microphotos. In addition, the reaction mechanisms, fine structures, surface chemical modification or crystalline properties of MWCNTs were further identified by using energy dispersive spectrometer (EDS), X-ray powder diffractometer (XRPD), thermal gravimetric analyzer (TGA), X-ray absorption near edge structural (XANES) or extended X-ray absorption fine structural (EXAFS) spectroscopy. From Raman spectra of MWCNTs, the G-band peak of K-MWCNTs was more intensive than the one of Na-MWCNTs but for the D-band peak of MWCNTs oppositely. They both indicated that the K-MWCNTs had stronger well-graphited structures than Na-MWCNTs. Moreover, the optimal crystalline or surface modification properties of MWCNTs via solvothermal routes compared with arc discharge (AD) or spray pyrolysis (SP) method were observed by XRPD patterns of MWCNTs.
In order to more thoroughly examine the storage efficiencies of hydrogen for different kinds of AD-MWCNTs, SP-MWCNTs, K-MWCNTs or Na-MWCNTs were used for comparison. The chemical modifications of MWCNTs surfaces for adsorption enhancement included HNO3, KMnO4 and H2O2 processes. Moreover, try the additive just as palladium or NaAlH4 to increase the amount of hydrogen adsorbed on CNTs, then use the microbalance to measure the net weight of CNTs after the processes of hydrogen adsorption, and Fourier transform infrared spectroscopy (FTIR) were performed. Experimentally, after the processes of modification, the efficiency of hydrogen storage of CNTs have great improvement, and the CNTs modified by nitric acid improved the most, even over 0.8 wt％. We can also discover that the CNTs modified by nitric acid after adding palladium(Pd) would increase the efficiency of hydrogen storage the most, it was HNO3 > KMnO4 > H2O2modification processes in series. Besides, by the XRD analysis, after the process of nitric acid, the crystalline of CNTs would reduce. By analysis of TEM and FESEM, we found that Pd particles dispersed on CNTs perfectly. In order to understand the fine structures of Pd particles, XANES and EXAFS were used. The Pd particle with a Pd-Pd bond distance of 2.76±0.02Å, and a coordination number of 5.9±0.25 and PdCl2 particles with a Pd-Cl bond distance of 2.25±0.02Å, and a coordination number of 1.8±0.25 were also measured by EXAFS spectroscopy. This study reveal that Pd particles dispersed on CNTs can improve the amount of hydrogen storage successfully.

中文摘要 I
ABSTRACT III
目錄 XVI
圖 目 錄 X
表 目 錄 XVI
第一章 前言 1
第二章 文獻回顧 4
2.1 奈米碳管發展歷史 4
2.2 奈米碳管的結構 6
2.3 奈米碳管的特性 8
2.3.1 機械特性 8
2.3.2 電傳導性 11
2.3.3 場發射性 14
2.3.4 熱性質 18
2.4 奈米碳管之成長方法 21
2.4.1 電弧放電法 21
2.4.2 雷射蒸發法 23
2.4.3 化學氣相沈積法 24
2.4.4 溶劑熱合成法 26
2.5 奈米碳管的應用 30
2.5.1 場發射源的應用 30
2.5.2 微電子元件的應用 33
2.5.3 複合材料中的強化材料 38
2.6 吸附理論 39
2.7 奈米碳管儲氫理論 42
2.7.1 氫 42
2.7.2 氫能源 42
2.7.3 奈米碳管儲氫量估算 45
2.8 儲氫材料的比較 52
2.9 氫燃料電池 57
第三章 實驗方法與分析 60
3.1 實驗藥品 60
3.2 實驗器材 61
3.2.1 微量天平 62
3.2.2 實驗裝置圖 63
3.3 合成奈米碳管 64
3.3.1 以鉀為還原劑 64
3.3.2 以鈉為還原劑 66
3.4 氫氣吸附實驗 69
3.5 分析方法 74
3.5.1 場發掃描式電子顯微鏡 74
3.5.2 穿透式電子顯微鏡 78
3.5.3 X光粉末繞射儀 80
3.5.4 熱重量分析儀 83
3.5.5 比表面積 85
3.5.6 同步輻射吸收光譜 87
3.5.6.1 同步輻射光吸收實驗 87
3.5.7 拉曼光譜分析 92
3.5.8 傅立葉轉換紅外線光譜分析 94
第四章 結果與討論 98
4.1 合成奈米碳管 98
4.1.1 以鉀為還原劑合成奈米碳管 98
4.1.2 以鈉為還原劑合成奈米碳管 105
4.1.3 不同還原劑所合成之奈米碳管結構差異 112
4.2 奈米碳管特性分析 115
4.2.1 奈米碳管拉曼光譜分析 115
4.2.2 奈米碳管XRPD分析 117
4.3 奈米碳管儲氫能力分析 118
4.3.1 奈米碳管之改質處理 118
4.3.2 將Pd分散於奈米碳管中 125
4.3.3 X光吸收邊緣結構性質分析 129
4.3.4 奈米碳管儲氫效果之比較 132
4.3.4.1 SP-MWCNTs氧化處理後對H2吸附效果之比較 132
4.3.4.2 改質後SP-MWCNTs添加Pd對H2吸附效果比較 134
4.3.4.3 AD-MWCNTs氧化處理後對H2吸附效果之比較 137
4.3.4.4 改質後AD-MWCNTs添加Pd對H2吸附效果之比較 138
4.3.4.5 MWCNT添加NaAlH4後對H2吸附效果之比較 139
第五章 結論及未來研究方向 140
5.1 結論 140
5.2 未來研究方向 142

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