本研究以密度泛函理論及分子動力學探討物理與化學吸附兩種不同的氫分子吸附機制，由於鉑奈米粒子可將氫分子解離，屬於化學吸附，然而鋰原子不會有將氫分子解離的現象，則是屬於物理吸附；因此本研究希望藉由分子動力學模擬探討上述兩種方式以及儲氫結構排列對於儲氫效率之影響，以達到Department of Energy US (DOE) 在2015年所預訂定的標準，並且其壓力小於100 atm，操作溫度介於-30~50℃，並使得儲氫重量百分比達到(System Gravimetric Density)9.0 wt%。
本研究將分為三部份探討：
第一部分：
因為目前文獻中的勢能未必可以完整的符合研究所需， 為了得到準確且符合研究所需的模擬參數，首先藉由第一原理分子動力學理論(Density functional theory - Molecular dynamics, DFT-MD)獲得結構與相對應能量的資訊，接著藉由Force-matching method 的方法獲得分子動力學(Molecular dynamics, MD)所需的勢能參數值，最後藉由獲得的新勢能參數執行高效率的分子動力學模擬。
第二部份：
由於氫分子解離會牽涉到電子之間的轉移，所以無法以分子動力學模擬斷鍵情形，因此本研究僅探討在不同溫度下不同尺寸鉑奈米粒子在(5,5)及(9,0)單壁奈米碳管下的動態行為，並藉由吸附能、平方位移圖、平均平方位移圖分析鉑奈米粒子在奈米碳管的運動行為，並分析溫度效應對鉑奈米粒子在奈米碳管上的影響，進而找出最適合儲氫的鉑奈米粒子結構與相對應溫度。
第三部份：
將研究鋰原子散佈在單壁奈米碳管上儲氫的現象，首先建立純碳管與散佈鋰之碳管的系統，將此系統均勻散佈氫分子，而系統壓力分別為1 atm、 50 atm、 100 atm 與200 atm，並模擬溫度在77K與300K定溫下之氫分子吸附的狀況，並藉由氫氣分子在碳管周圍數量的分佈圖及重量百分比(wt%)觀察分析吸附的現象。最後本研究將以週期性邊界條件去模擬一個較大的系統，並探討碳管陣列的形式，以此方式研究將可找到合適的儲氫系統。

In this study, we used the Density functional theory (DFT) and Molecular dynamics (MD) to obtain the suitable hydrogen storage of platinum nanoclusters on the (5,5) and (9,0) carbon nanotubes (CNTs) and Li atoms on the (5,5) carbon nanotube. platinum nanoclusters on the CNT is chemisorption because hydrogen molecules dissociated. Li atoms on the CNT is physisorption due to hydrogen molecule do not dissociated. We hope that two different hydrogen storage models can achieve the goal which was set by Department of Energy US. There are three parts in this study. There were three parts in this study:
The first part:
It is very important for obtaining the suitable potential parameters in the Molecular dynamics simulation to reflect the interaction between materials. However, we can not find the suitable parameters from the references to simulate our system. Hence, we use the Force-matching method and Density functional theory to obtain the potential parameter in our system. The Molecular dynamics simulation is utilized to simulate the hydrogen adsorption qith the modified potential parameters.
The second part:
The dynamics behavior of different platinum nanopartilces on the (5, 5) and (9, 0) CNTs at different temperature are investigated by the Molecular dynamics simulation when new parameters are obtained. The migration trajectory, square displacement and mean square displacement of the mass center of platinum nanoclusters are used to analyze to find what sizes of platinum nanoparticle and temperature are the best for hydorgen storage.
The third part:
Density functional theory simulation is utilized to simulate hydrogen molecules adsorbed on the (5, 5) pristine CNT and CNT with lithium atoms. The pressure and temperature effects are used to analyze the hydrogen storage system. Moreover, the different arrangements of CNTs array are also studied, such as, Van der Waals distance (VDW) and shape of array (triangular and square arrangement). Finally, the adsorbed and released phenomenon are also analyzed by the gravimetric capacity (wt%) of hydrogen molecule for hydrogen.

中文摘要……………………………………………………………………. .. .I
英文摘要………………………………………………………………..….....III
目錄………………………………………………………………………….V
圖目錄……………………………………………………………………...VII
表目錄………………………………………………………………………...XI
第一章 緒論 1
1.1 研究動機 1
1.2 奈米碳管與奈米粒子儲氫簡介 4
1.3 奈米碳管與奈米粒子應用於儲氫文獻回顧 7
1.4 本文架構 13
第二章 模擬方法及理論介紹 14
2.1 勢能參數取得之方法 15
2.1.1 Basin-Hopping計算法 16
2.1.2 Force-matching method 18
2.1.3 勢能介紹 19
2.2 密度泛函理論簡介 28
2.3 分子動力學理論 36
2.3.1 週期性邊界 43
2.4 第一原理分子動力學理論 44
2.5 數值分析 45
2.5.1 吸附能(Adsorption Energy) 45
2.5.2 重量百分比(wt%) 46
2.5.3 平方位移(Square Displacement)和平均平方位移(Mean Square Displacement) 47
第三章 結果與討論 48
3.1 欲模擬系統勢能參數之獲得方法 49
3.1.1 物理模型之建構 49
3.1.2 勢能參數取得之過程 50
3.1.3 各勢能參數結果分析 51
3.2 鉑奈米粒子於單壁奈米碳管之運動行為分析 58
3.2.1 模擬模型之建構 58
3.2.2 運動行為分析 63
3.3 鋰原子散佈在單壁奈米碳管與陣列之儲氫分析 73
3.3.1 物理模型之建構 73
3.3.2 模擬單一碳管添加鋰原子對儲氫之影響 79
3.3.3 模擬鋰原子在碳管陣列形式不同對儲氫的影響 87
3.3.4 模擬矩陣儲氫與釋放過程 90
結論 96
參考文獻 99

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