本文選題：金屬有機(jī)配位聚合物　切入點(diǎn)：金屬摻雜　出處：《內(nèi)蒙古大學(xué)》2017年碩士論文　論文類型：學(xué)位論文

【摘要】：基于結(jié)構(gòu)的多樣性及可設(shè)計(jì)性,金屬有機(jī)配位聚合物在氣體存儲與分離、鐵電、非線性光學(xué)、非均相催化和光學(xué)等領(lǐng)域表現(xiàn)出廣闊的應(yīng)用前景。本文選用 H_4btca 和 Htpbpc(H_4btca = biphenyl-2,3,3',5'-tetracarboxylic acid,Htpbpc =4'-[4,2';6',4"]terpyridin-4'-yl-biphenyl-4-carboxylicacid)為主配體,部分實(shí)驗(yàn)過程中引入 phen 和 H_2bdc(phen= 1,10-phenanthroline,H_2bdc = terephthalicacid)作為輔助配體,同金屬離子在水熱/溶劑熱條件下自組裝合成了 20個(gè)配位聚合物。依照配合物不同的結(jié)構(gòu)特性,分別探究了其在熒光調(diào)控、熒光傳感和光催化領(lǐng)域展現(xiàn)出的應(yīng)用潛力。分為以下四部分進(jìn)行介紹:第一部分選用H_4btca和phen配體與LnC13·6H_2O在水熱條件下合成了一系列Ln-MOFs(1-13)。基于配合物6和8同晶結(jié)構(gòu)并分別發(fā)射出明亮的紅色和綠色特征熒光,進(jìn)一步將Eu3+/Tb3+離子組裝進(jìn)同一框架結(jié)構(gòu)中構(gòu)筑了系列混金屬摻雜MOFs[EuxTb1-x(Hbtca)(phen)](0 ≤ x ≤ 1)(14-17)。通過調(diào)控金屬摻雜比及激發(fā)波長實(shí)現(xiàn)了熒光調(diào)控和白光發(fā)射。第二部分選用Htpbpc配體與Eu(Ⅲ)離子在溶劑熱條件下合成一維配合物[Eu2(tpbpc)4·CO3·4H_2O]·DMF·solvent(18),其可以發(fā)射明亮的紅色熒光并兼具優(yōu)異的水穩(wěn)定性、酸堿穩(wěn)定性和熱穩(wěn)定性。配合物18可作為熒光傳感器用于定量檢測Cr3+,CrO42-和Cr2O72-離子,并表現(xiàn)出低檢出限、高靈敏度和高選擇性等優(yōu)勢。此外,基于MOF 18的熒光試紙可在幾秒鐘內(nèi)實(shí)現(xiàn)可視化的對Cr(Ⅲ)和Cr(Ⅵ)離子的識別。值得注意的是,此為第一例可同時(shí)檢測水體系中不同價(jià)態(tài)鉻離子的LMOF材料。第三部分選用Htpbpc配體與不同過渡金屬鹽在溶劑熱條件下合成一系列三維MOFs[M(tpbpc)2]·solvent(19-22)。其中,MOF19作為具有雙熒光發(fā)射機(jī)制的MOF熒光傳感材料,可對Hg~(2+)離子在10-6-10-3 M大范圍內(nèi)進(jìn)行定量檢測。另外,MOF 19還可定量檢測Cr(Ⅵ)離子,并具有檢測限低,響應(yīng)迅速、可循環(huán)利用等特點(diǎn)。第四部分選用Htpbpc和H_2bdc配體與Co(NO3)2·6H_2O在溶劑熱條件下成功構(gòu)筑一個(gè) 2D 大孔 MOF[Co(tpbpc)(bdc)0.5·H_20]·solvent(23),進(jìn)一步在合成過程中用Zn(Ⅱ)離子逐漸替換Co(Ⅱ)離子,構(gòu)筑了一系列同構(gòu)的金屬摻雜MOFs。隨著Co(Ⅱ)逐步被Zn(Ⅱ)取代,MOFs材料作為催化劑在可見光下降解甲基橙的能力也逐漸提高。此工作提供了一個(gè)通過改變MOF中金屬摻雜比例進(jìn)而實(shí)現(xiàn)可控調(diào)節(jié)其光催化性能的方法。
[Abstract]:Based on structural diversity and designability, organometallic coordination polymers in gas storage and separation, ferroelectric, nonlinear optics, In this paper, H4btca and Htpbpc(H_4btca = biphenyl-2bdcPhen are selected as auxiliary ligands Htpbppc 4- [4tpbpc 4"] terpyridin-4-yl-biphenyl-4-carboxyacid. in some experiments, phen and H2bdcphenphen = 110-phenanthropc H2bdc = terephthalicacidd are used as auxiliary ligands. Twenty coordination polymers were synthesized by self-assembly of the same metal ions under hydrothermal / solvothermal conditions. The potential applications in the field of fluorescence sensing and photocatalysis are described in the following four parts: in the first part, a series of Ln-MOFsC1-13O have been synthesized under hydrothermal conditions by using H _ S _ 4btca and phen ligands and LnC13 路6H _ 2O under hydrothermal conditions, based on the isocrystalline structures of complexes 6 and 8. Emitting bright red and green characteristic fluorescence, Furthermore, the Eu3 / TB 3 ions were assembled into the same frame structure to construct a series of mixed metal doped MOFs [EuxTb1-xHbtcaphenin] 0 鈮，

本文編號：1561607