金屬有機凝膠的合成與碳化對氣體吸附的特性研究

Synthesis and carbonization of metal-organic gels with gas adsorption properties

謝亞耘(Ya-Yun Hsieh)

指導教授 ： 林嘉和

中原大學/理學院/化學研究所/碩士(2015年)

https://doi.org/10.6840/cycu201500357

摘要

摘要
在本論文中，第一部分利用過渡金屬Cr(NO3)3.9H2O和有機配位基：4,4'-磺醯基二苯甲酸(4,4'-sulfonyldibenzoic acid, H2SBA)、4,4'-羥基二苯甲酸(4,4'-oxybis(benzoic acid, H2OBA)、二苯基甲烷-4.4-二羧酸(diphenylmethane-4.4-dicaboxylic acid, H2MBA)、糠酸2,5-二甲酸(Furan-2,5-dicarboxylic Acid, H2FDA)、4-(2-羧基乙烯基)苯甲酸(4-(2-carboxyvinyl)benzoic acid, H2CVB)、硫苯二羧酸(2,5-thiophenedicarboxylic acid, H2TDC)、1,3,5-苯三甲酸(1,3,5-benzenetricarboxylic acid, H3BTC)、1.4-苯二甲酸(1,4-benzenedicarboxylic acid, H2BDC)、2-硝基對苯二甲酸(2-aminoterephthalic acid, H2BDC-NH2) 由水熱合成法合成出新穎金屬有機凝膠金屬(metal-organic gels, MOGs)，其孔洞結構可應用在儲存或分離CO2氣體上。他們的代號命名分別為：
Cr-SBA.................. MOG1
Cr-OBA.................. MOG2
Cr-MBA.................. MOG3
Cr-FDA.................. MOG4
Cr-CVB.................. MOG5
Cr-TDC.................. MOG6
Cr-BTC.................. MOG7
Cr-BDC...................MOG8
Cr-BDC-NH2...........MOG9
實驗結果以粉末X-射線繞射儀(PXRD)來鑑定其分子結構及證實產物的純度，利用掃描式電子顯微鏡(SEM)觀察形貌以及大小；傅立葉轉換紅外線光譜儀(FT-IR)、紫外光-可見光分光光譜儀(UV-Vis)、熱重分析儀(TGA)探討化合物的性質；再藉由孔徑分析儀測量其對於一些氣體上的吸脫附，並加以分析化合物的特性。
在本論文中的第二部分則是將第一部分合成的MOG1~9，藉由直接碳化(direct carbonization)的方式，在惰性氣體N2的環境下高溫鍛燒800 oC、900 oC、1000 oC形成奈米顆粒的金屬氧化物Cr2O3碳化材料，此九種MOGs碳化產物編號分別表示1C~9C。在性質鑑定上，利用PXRD初步的鑑定化合物的結構；SEM、EDS、孔測分析儀，探討化合物的特性。
第三部分則是探討在實驗合成條件上的不同，可合成出兩種不同的金屬有機化合物。以Cr-MBA為例，進行一系列性質測試並比較碳化前後對於氮氣氣體上的吸脫附性質與孔洞特性。

關鍵字

無機化學 ； 碳化材料 ； 金屬有機化合物

並列摘要

Abstract
In this dissertation, the first part describes the preparation and characterization of a series of new chromium metal organic gels (MOGs) which are synthesized by reacting Cr(NO3)3.9H2O with various organic ligands namely, 4,4'-sulfonyldibenzoic acid (H2SBA), 4,4'-oxybis(benzoic acid) (H2OBA), diphenylmethane-4,4'-dicaboxylic acid (H2MBA), furan-2,5-dicarboxylic acid (H2FDA), 4-(2-carboxyvinyl) benzoic acid (H2CVB), 2,5-thiophenedicarboxylic acid (H2TDC), 1,3,5-benzenetricarboxylic acid (H3BTC), 1,4-benzenedicarboxylic acid (H2BDC), and 2-aminoterephthalic acid (H2BDC-NH2) under hydrothermal conditions. The resulting MOGs are listed as followings,
Cr-SBA.................. MOG1
Cr-OBA.................. MOG2
Cr-MBA.................. MOG3
Cr-FDA.................. MOG4
Cr-CVB.................. MOG5
Cr-TDC.................. MOG6
Cr-BTC.................. MOG7
Cr-BDC...................MOG8
Cr-BDC-NH2...........MOG9
The structure, bulk purity and homogeneity of the newly synthesized MOGs have been analyzed using powder X-ray diffraction (PXRD) measurements; The scanning electron microscope (SEM) was used to observe the morphology and particle size; Fourier transform infrared spectroscopy (FT-IR), Ultraviolet - Visible (UV-Vis) Spectrophotometer, and thermal gravimetric analysis (TGA) were used for further characterizations. Finally, gas sorption measurements have been used to study the porous properties of the MOG compounds.
In the second part, carbon materials with nanoparticles metal oxides were prepared by utilizing the synthesized MOGs (MOG1 ~ 9) by direct carbonization in an inert (N2) atmosphere with calcination temperatures are 800 ºC, 900 ºC, 1000 ºC. The resulting carbon materials (which are denoted as 1C ~ 9C) were characterized by PXRD, SEM, Energy-dispersive X-ray spectroscopy, and gas sorption measurements.
In the third part, evaluates experimentally the synthesis conditions, can be synthesized two different metal-organic compounds. For example to Cr-MBA, the nature of the test series and compare before and after the carbonization gas for the nitrogen adsorption-desorption properties of the hole feature.

並列關鍵字

Carbonization ； Inorganic Chemistry ； MOGs

參考文獻

[23] Chaikittisilp, W.; Hu, M.; Wang, H.; Huang, H.-S.; Fujita, T.; Wu K. C.-W.; Chen, L.-C.; Yamauchi, Y.; Ariga, K. Chem. Commun., 2012, 48, 7259.

[14] Xiang, S.; Li, L.; Zhang, J.; Tan, X.; Cui, H.; Shi, J.; Hu, Y.; Chen, L.; Su, C.-Y.; James, S. L. J. Mater. Chem. 2012, 22, 1862.

[36] Wang, L.; Zhang, L.; Song, T.; Li, C.; Xu, J.; Wang, L. Microporous and Mesoporous Materials 2012, 155, 281.

[8] Zhang, J.; Yang, G.; Wang, H.; Chen, Y. New Journal of Chemistry 2009, 33, 1070.

[25] Lo, C.-Y.; Lin, J.-Y.; Chen, W.-Y.; Chen, C.-T.; Chen, Y.-C. J Am Soc Mass Spectrom 2008, 19, 1014.