鹼金屬配位聚合物之合成、結構解析與性質探討

Synthesis, Crystal Structures and Properties of Alkali Metal Coordination Polymers

張廷光(Ting-Kuang Chang)

指導教授 ： 林嘉和

中原大學/理學院/化學研究所/碩士(2013年)

https://doi.org/10.6840/cycu201300252

摘要

在此論文研究中，我們成功了利用鹼金族陽離子與苯六羧酸(Benzenehexacarboxylic acid ，H6BHC) 與四氫呋喃-2,3,4,5-四羧酸(Tetrahydrofuran-2,3,4,5-tetracarboxylic acid ，H4TFTA)藉由中溫水熱合成法合成出11個不同的新穎金屬配位聚合物。其中以鋰、鈉、鉀作為中心金屬與H6BHC之有機配位基合成出四種配位聚合物，並應用於離子電池電極材料研究分析。本文中所合成出的化合物如下：
[ Li4(H2BHC)(H2O)4 ]·2H2O (1)
[ Li6(BHC)(H2O)8 ] (2)
[ Li4(H2BHC)(H2O)4 ] (3)
[ Na3(H3BHC)(H2O)4 ] (4)
[ K3(H3BHC)(H2O)2 ] (5)
[ Rb2(BHCA) ] (6)
[ Rb3(H3BHC)(H2O)2 ] (7)
[ Li6(HTFTA)2(H2O)3 ]·3H2O (8)
(NH4)[Na13(HTFTA)2(TFTA)2]·4H2O (9)
[ K(H3TFTA) ] (10)
[ Rb(H3TFTA) ] (11)
第一部份主要是利用苯六羧酸(H6BHC)為有機配位基與鹼金族合成出化合物1-7。另外，也利用四氫呋喃-2,3,4,5-四羧酸(H4TFTA) 與鹼金族合成出化合物8-11。經由X光單晶繞射鑑定結果顯示化合物1-11皆為三維網狀結構。以上化合物1-11除了使用單晶X光繞射儀來鑑定其結構外，也利用
II
了粉末X光繞射儀、元素分析儀、熱重分析儀、紫外-可見光吸收光譜儀、螢光放光光譜儀和紅外光共振光譜儀來探討其特性。
第二部份則將化合物1、3、4、5應用於鋰離子二次電池負極材料性能研究，並經由粉末X光繞射儀、並與循環伏安法、充放電測試等電化學分析進ㄧ步探討之間的相關性。研究結果顯示，化合物1、3、4、5，於0.1C放電速率下第一圈的電容量皆可達100 mAh/g以上，且經30個循環壽命測試發現有良好的穩定性，但電容量逐漸下降。

關鍵字

苯六甲酸 ； 四氫呋喃四羧酸

並列摘要

For Elevent new coordination polymers have been synthesized under hydrothermal reactions and characterized by single crystal analysis. The reaction of benzenehexacarboxylic acid and tetrahydrofuran-2,3,4,5-tetracarboxylic acid with alkali metal ions. In addition, three new lithium coordination polymers were also synthesized between aromatic carboxylic acids and lithium ions. Moreover , metal coordination polymers were tested as anode materials for lithium ion batteries. The chemical formula of 1 to 11 are as follows:
[ Li4(H2BHC)(H2O)4 ]·2H2O (1)
[ Li6(BHC)(H2O)8 ] (2)
[ Li4(H2BHC)(H2O)4 ] (3)
[ Na3(H3BHC)(H2O)4 ] (4)
[ K3(H3BHC)(H2O)2 ] (5)
[ Rb2(BHCA) ] (6)
[ Rb3(H3BHC)(H2O)2 ] (7)
[ Li6(HTFTA)2(H2O)3 ]·3H2O (8)
(NH4)[Na13(HTFTA)2(TFTA)2]·4H2O (9)
[ K(H3TFTA) ] (10)
[ Rb(H3TFTA) ] (11)
In section one, eleven new coordination compounds 1-11 were synthesized by two different carboxylic acids and alkali metal ions. The single crystal structure analysis showed that all compounds are 3-D metal-organic framework. All compounds were further characterized by powder
X-ray, elemental analysis, thermogravimetric analysis, UV-VIS
spectra, photoluminescence and IR spectroscopy.
In section two, the compounds 1、3、4 and 5 were tested as anode materials for lithium ion batteries. All new electrodes were characterized by powder X-ray, elemental analysis, cyclic voltammetry and charge-discharge test.These new anode materials display discharge capacity of above 100mAh/g at 0.1C rate and a stable cycle performance within thirty cycles, but capacity was decreased.

並列關鍵字

benzenehexacarboxylic acid ； tetrahydrofuran ； tetracarboxylic acid

參考文獻

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