The Preparation, Characterization, H2-sorptionand ,Catalytic Activity of Pt- and Pd-containing Mesoporous silicas

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研究生：	王律之 Wang, Lu-Chih
論文名稱：	The Preparation, Characterization, H2-sorptionand ,Catalytic Activity of Pt- and Pd-containing Mesoporous silicas 含鉑及鈀金屬之中孔洞二氧化矽之製備,鑑定,催化與儲氫性質研究
指導教授：	趙桂蓉 Chao, Kuei-Jung
口試委員:
學位類別：	博士 Doctor
系所名稱：	理學院 - 化學系 Department of Chemistry
論文出版年：	2009
畢業學年度：	97
語文別：	英文
論文頁數：	141
中文關鍵詞：	中孔洞二氧化矽、鉑金屬、鈀金屬、儲氫、催化
外文關鍵詞：	Mesoporous silicas, Catalytic Activity, Platium, H2-sorption, Palladium
相關次數：	點閱：2 下載：0
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This study includes the preparation and characterization of platinum and palladium nanoparticles incorporated on mesoporous silicas as well as the hydrogen sorption on Pd nanoparticles.
Two methods were preceded to prepare the metal incorporated mesoporous silicas, i.e., one-pot synthesis under the control of pH value in reactant mixtures and CVD in SC-CO2 medium. The formations of Pd(0) nanoparticles and mesophases were expected to occur simultaneously in basic media in one-pot synthesis. Pt incorporated mesoporous silicas were synthesized by contacting calcined MCM-48 with Pt(hfac)2 and Pt(acac)2 in SC-CO2 medium, and then, their Pt precursors were reduced by hydrogen at room temperature or 200 oC.
Due to the confinement effect of metal nanoparticles inside the mesochannels, the enhancement on catalytic activity and selectivity of trans/cis 1,4-dimethylcyclohexanes ratio in the hydrogenation of p-xylene was observed on Pd/MCM-41 and Pt/MCM-48 prepared by using Pt(acac)2 as Pt precursors through SC-CO2 treatment.
In addition, the hydrogen sorption on Pd nanoparticles stabilized by surfactant containing in mesoporous silicas was compared with that on Pd nanoparticles stabilized only by surfactant and on Pd membrane. The Pd-Pd bond distances were found to be increased after hydrogen sorption, with the amount of bond expansion increased with metal size and amount of hydrogen adsorption.

Abstract...................................................I
Contents..................................................II
Figure Captions..........................................III
Table Captions...........................................XVI
Chapter 1. Introduction...............................................1
1.1 Metal containing mesoporous silicas....................1
Mesoporous silicas.........................................1
Preparation................................................1
Characterization...........................................3
1.2 X-ray Absorption Spectroscopy (XAS)....................4
Synchrotron radiation......................................4
XAS........................................................6
Data analysis of XAS .....................................11
References................................................15
Chapter 2. Pd incorporated mesoporous silicas.............20
2.1. Experimental..............................................21
2.1.1. Sample preparation...............................................21
MCM-41....................................................21
Pd/MCM-41.................................................21
MCM-48....................................................21
Pd/MCM-48.................................................22
Pd-M485M-r................................................22
2.1.2 Characterization..........................................22
PXRD, TEM and porosity measurements.......................22
XAS measurement...........................................23
TPR.......................................................23
Thermal gravimetric analysis (TGA)........................23
2.1.3 The catalytic tests.................................24
2.2. Results and discussion...............................25
2.2.1 Mesoporous silicas..................................25
2.2.2 Pd nanoparticles in Pd/MCM-41.......................29
Pd species in Pd/MCM-41...................................29
In-situ XAS of the PdO reduction..........................35
Formation mechanism of Pd nanoparticles in Pd/MCM-41......37
2.2.3 Pd nanoparticles in Pd/MCM-48.......................40
2.2.4 Hydrogenation of CALD...............................40
2.2.5 Hydrogenation of p-xylene...........................44
2.3 Conclusion............................................48
References................................................49
Chapter 3. Pt incorporated mesoporous silicas.............52
3.1 Experimental..............................................53
3.1.1 Sample preparation...............................................53
Pt(hfac)2/MCM-48..........................................53
Pt(acac)2/MCM-48..........................................55
3.1.2 Characterization..........................................55
PXRD, TEM and XAS measurements............................55
N2 adsorption and ICP-AES.................................56
CO chemisorption..........................................57
Catalytic test............................................57
3.2 Results and discussion................................58
3.2.1 Mesostructured phase................................58
3.2.2 Pt/MCM-48 synthesized by using Pt(hfac)2 as Pt precursor.................................................62
Pt species in Pt/MCM-48...................................62
Pt complex clusters in mesoporous silica..................71
3.2.3 Pt/MCM-48 synthesized by using Pt(acac)2 as Pt precursor.................................................75
Pt species in Pt/MCM-48...................................75
3.2.4 Hydrogenation of p-xylene...........................77
3.3 Conclusion............................................80
References................................................81
Chapter 4. Hydrogen sorption of Pd/Mesoporous SiO2........83
4.1 Experimental..........................................84
4.1.1 Sample preparation..................................84
Pd/MCM-41.................................................84
Pd/MCM-48.................................................84
Pd/CTAB...................................................85
Pd membrane...............................................85
4.1.2 Characterization..........................................86
4.2 Results and Discussion................................88
4.2.1 Mesoporous silicas...................................................88
4.2.2 Pd species in Pd/MCM-41 and Pd/MCM-48...............92
Pd/MCM-41.................................................92
Pd/MCM-48.................................................96
4.2.3 Hydrogen sorption...................................99
4.3 Conclusion...........................................113
References...............................................114
Conclusion...............................................116
Chapter 5.
Appendix A...............................................117
Appendix B...............................................120
Appendix C...............................................123
Appendix D...............................................125
Appendix E...............................................128
Appendix F...............................................129

                                

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