有機-無機混成之金屬磷酸鹽/亞磷酸鹽骨架化合物的合成與性質研究;Synthesis and Properties of Inorganic-Organic Hybrid Frameworks of Metal Phosphates and Phosphites

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题名:	有機-無機混成之金屬磷酸鹽/亞磷酸鹽骨架化合物的合成與性質研究;Synthesis and Properties of Inorganic-Organic Hybrid Frameworks of Metal Phosphates and Phosphites
作者:	陳彥杰;Chen,Yen-Chieh
贡献者:	化學學系
关键词:	金屬磷酸鹽;金屬亞磷酸鹽;無機骨架
日期:	2016-08-11
上传时间:	2016-10-13 12:47:04 (UTC+8)
出版者:	國立中央大學
摘要:	本論文利用有機胺作為模板在中溫水熱法合成四個金屬磷酸鹽/亞磷酸鹽，以上化合物均能獲得單晶產物，並藉由單晶X光繞射方法收集數據後進行鑑定結構，並以粉末X光圖譜(PXRD)和理論圖譜比對後和元素分析比對確保樣品純度以供後續分析。　　我們將四個化合物分為A和B兩系列： A為具有鋅磷酸骨架、有機雙胺膜板(Diamine, DA1)、對苯二甲酸(L)的結構，並得到配為基L分別利用順式和反式的方式與中心金屬鍵結：(H2DA1)Zn2(cis-L)(HPO4)2 (A1) 和(H2DA1)Zn2(trans-L)(HPO4)2 (A2)。B為含鋅亞磷酸骨架和鈷亞磷酸骨架，使用有機胺(DA2)和對苯二甲酸(L)作為配位基合成結構相同的：Zn3(L)0.5(DA2)(HDA2)(HPO3)2 (B1)和Co3(L)0.5(DA2)(HDA2)(HPO3)2 (B1)。　　A系列有Na+離子交換、Eu3+和Tb3+離子吸附並進行光激發螢光譜(photoluminescence spectroscopy, PL)的測試得到具有放光能力的A-Eu和A-Tb。B1可以當作Cu2+的離子感測器，B2則是使用鈷金屬當作中心金屬，並與B1具有相同結構，並利用超導量子干涉磁量儀(Superconducting Quantum Interference Device Magnetometer, SQUID)，測量B2之磁性。 ;Two series of metal phosphate and phosphites structural, A and B, were shown as follows：(DA1)Zn2(Lcis)(HPO4)2 (A1)、(DA1)Zn2(Ltrans)(HPO4)2 (A2)、Zn3(L)0.5(DA2)(HDA2)(HPO3)2 (B1) and Co3(L)0.5(DA2)(HDA2)(HPO3)2 (B2). A1 and A2 were synthesized with the same reactants under the mild hydrothermal conditions. B1 and B2 had a similar structure with different metal center (B1 for Zn and B2 for Co). All of these structures were determined by single-crystal X-ray diffraction. Purity determined by PXRD, EA, XRF and EDX. 　　A1 and A2 are similar structure. BDC(L) bonded to Zn center with two different phases (cis and trans coordinate with metal). This is the first time we find in OMPO (organic-metallophosphate). By soaking A1 and A2 in Na+ solution, we found that DA1 were partially replaced by Na+ ion and ethanol. By the results of Element Analysis、Thermogravimetry Analysis and FTIR, we determined the new structure ：(DA1)0.5Na(C2H5OH)0.5Zn2(L)(HPO4)2. A1 and A2 had no luminescence properties. However, by soaking Eu3+ and Tb3+ ions solution, A1-Eu/Tb and A2-Eu/Tb had luminescence properties (green light for A1/A2-Tb and red light for A1/A2-Eu). 　　Soaking in Cu(NO3)2, powder color of B1 would turn white to blue by exchanging Cu ion for only an hour. B1 was also a good sensor for Cu2+ ion. The metal center of B2 was Co, which showed good magnetism. Determined by SQUID, B2 has paramagnetism in high temperature and antiferromagnetism in low temperature.
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