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研究生:朱筱鈞
研究生(外文):Siau-Jyun Jhu
論文名稱:有序中孔碳材改質及其儲氫研究
論文名稱(外文):Study on Hydrogen Storage of Modified Ordered Mesoporous Carbon
指導教授:黃振家黃振家引用關係
指導教授(外文):Chen-Chia Huang
學位類別:碩士
校院名稱:國立雲林科技大學
系所名稱:化學工程與材料工程研究所
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2009
畢業學年度:97
語文別:中文
論文頁數:112
中文關鍵詞:氫溢流序中孔碳材儲氫
外文關鍵詞:hydrogen spilloverhydrogen storageordered mesoporous carbon
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本研究利用有序中孔矽材作為模板製備有序中孔碳材,並作為儲氫材料。將
合成的有序中孔碳材以幾丁聚醣、氨水進行碳材的表面修飾,探討碳材表面含氮
官能基對於儲氫效能的影響。另一方面,利用溼式浸染法將有序中孔碳材以奈米
金屬鈀觸媒修飾,藉由過渡金屬在碳材上所產生的氫氣溢流(Hydrogen Spillover)現
象,增加儲氫效果。利用小角度X-光繞射(SAXS)、穿透式電子顯微鏡(TEM)及氮
氣吸附法鑑定所合成出來的有序中孔材料的結構特性。改質後之有序中孔碳材,
並利用熱重分析(TGA)分析儀、X-射線光電子能譜儀(XPS)、Boehm 表面官能基滴
定分析及原子吸收光儀鑑定改質前後特性差異。儲氫量分別在溫度為77、90 、195
K 及壓力0.1MPa 與在溫度303 K 及壓力4 MPa 下,以定體積法量測。
研究結果顯示,經過改質後的有序中孔碳材,含氮官能基的增加,對於儲氫
效能確實有所助益;由幾丁聚醣及氨水改質後的效果分別由原本的1.17wt.%提升
至1.29wt.% (C-Chi-b)及1.32wt.% (CN-323-32),大約增加10%。利用金屬鈀觸媒改
質之有序中孔碳材,由TEM 分析結果顯示出,鈀觸媒顆粒大小約2-5nm。原子吸
收光譜(AA)分析有序中孔碳材上所含鈀觸媒的含量,約有7.10 wt.%。其對於儲氫
效果有正面效益,在室溫及40 大氣壓下,吸附量從原本的0.14 wt.% 提升至0.25
wt.%,增加78 %。
In this study, an ordered mesoporous carbon (OMC) was synthesized by using
ordered mesoporous silica as template, and was used as hydrogen storage materials. The
synthesized OMC were modified by immersion with chitosan and ammonia water to
enhance surface nitrogen functional groups. The effect of OMC surface modification on
hydrogen storage was investigated. In addition, palladium (Pd) nanoparticles were
impregnated in the OMC via a wet method. The Pd particles in the carbon material
might generate hydrogen spillover phenomenon and enhance hydrogen storage capacity.
The OMC texture characteristics were determined by using small angle X-ray scattering
analysis, transmission electron microscope and nitrogen adsorption analysis. The
physical and chemical properties of the OMC before and after modification were
determined by thermo gravimetric analyzer, X-ray photoelectron spectroscope, Boehm
titration and atomic absorption spectrometer. Hydrogen capacity of the OMC was
obtained by a volumetric adsorption apparatus at 77, 90 and 195 K under 0.1MPa and at
303 K up to 4 MPa.
Experimental results revealed that nitrogen functional groups of the OMC
increased after modification and the hydrogen storage capacity also enhanced.
Hydrogen storage capacity of the chitosan and ammonia modified OMC increased by
about 10% from 1.17 wt.% to 1.29 wt.% (C-Chi-b) and to 1.32 wt.% (CN-323-32).
From TEM observations, the particle size of Pd on the OMC is about 2-5 nm. The
content of palladium catalyst on the OMC was determined as 7.10 wt. % by using an
atomic absorption spectrometer. A positive effect on hydrogen storage is found by Pd
impregnation on the OMC. Hydrogen storage capacity on Pd impregnated OMC was
determined as 0.27 wt.% at 303 K and 4 MPa, and was 78 % higher than that on the
pristine OMC (0.14 wt.%).
中文摘要…………………………………………………………………………… i
英文摘要..………………………………………………………………………….. ii
誌謝………………………………………………………………………………… iii
目錄………………………………………………………………………………… iv
表錄………………………………………………………………………………… vii
圖錄………………………………………………………………………………… viii
一、 緒論……………………………………………………………………….. 1
二、 文獻回顧…………………………………………………………………. 3
2.1 分子篩簡介………………………………………………………… 3
2.2 吸附與脫附………………………………………………………… 9
2.2.1 等溫吸附模式……………………………………………… 10
2.2.2 孔洞大小分布圖…………………………………………… 11
2.3 碳材表面官能基…………………………………………………… 13
2.4 碳材儲氫文獻回顧………………………………………………… 15
2.5 氫氣溢流效應(Hydrogen Spillover effect)………………………... 18
三、 實驗………………………………….............................. 21
3.1 實驗藥品及材料………………………………………………… 21
3.1.1 實驗藥品……………………………………………… 21
3.1.2 吸附質………………………………………………… 22
3.2 儀器設備…………………………………………………………… 23
3.3 有序中孔分子篩合成………………………………………….... 26
3.3.1 有序中孔矽分子篩SBA-15合成………………………. 26
3.3.2 有序中孔碳材CMK-3合成…………………………….. 26
3.4 CMK-3改質…………………………………………………...... 27
3.4.1 氨水(NH3.H2O)表面改質……………………………. 27
3.4.2 幾丁聚醣表面改質…………………………………… 27
3.4.3 Pd觸媒改質…………………………………………... 28
3.5 有序中孔碳材定體積儲氫分析…………………………………… 30
3.5.1 常壓低溫氣體吸附系統……………………………… 30
3.5.2 He 系統體積校正…………………………………….. 31
3.5.3 H2 吸附測量步驟…………………………………….. 32
四、 結果與討論……………………………………………………………… 35
4.1 基本性質鑑定……………………………………………………… 35
4.1.1 粉末X-光繞射結構鑑定分析………………………... 35
4.1.2 穿透式電子顯微鏡 TEM分析…………………………. 41
4.1.3 BET量測………………………………………………… 41
4.1.4 SEM表面形態觀察…………………………………... 48
4.1.5 TGA熱重分析………………………………………... 50
4.2 表面官能基分析…………………………………………………… 53
4.2.1 FTIR光譜分析………………………………………... 53
4.2.2 XPS分析………………………………………………… 55
4.3 有序中孔碳材CMK-3儲氫效能………………………………….. 63
4.3.1 儲氫量測準確性分析…………………………….... 63
4.3.2 氫氣等溫吸附曲線分析………………………….... 63
4.3.3 含氮官能基之有序中孔碳材儲氫效能分析………… 67
4.3.4 Boehm表面官能基滴定分析……………………….... 72
4.4 吸附特性分析………………………………………………….... 74
4.4.1 吸附熱探討…………………………………………… 74
4.4.2 Dubinin-Radushkevitch (D-R)吸附分析………... 78
4.5 有序中孔碳材以金屬奈米鈀觸媒改質儲氫效能………………… 86
4.5.1 添加鈀觸媒TEM分析圖……………………………... 86
4.5.2 原子吸收光譜(AA)分析鈀觸媒在有序中孔碳材上的含
量…………………………………………………………86
4.5.3 鈀觸媒改質之有序中孔碳材儲氫效能分析………… 86
五、 結論……………………………………………………………………….. 90
參考文獻…………………………………………………………………………. 92
自傳………………………………………………………………………………... 97
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