本文選題：金屬-有機骨架 + 等級孔　； 參考：《河南師范大學》2017年碩士論文

【摘要】：金屬-有機骨架配合物(Metal-Organic Frameworks,MOFs)是近年來人們非常關(guān)注的一類化合物,由于其變化豐富的孔道結(jié)構(gòu)和可調(diào)變的組成與性質(zhì),在氣體吸附、存貯與分離、能量儲存/轉(zhuǎn)化、化學傳感、非均相催化、藥物傳輸?shù)阮I(lǐng)域具有重要用途。早期對于金屬-有機骨架材料的研究主要集中于新型配位結(jié)構(gòu)和孔道結(jié)構(gòu)配合物的合成與性能,近年來人們的研究重點逐漸轉(zhuǎn)移到了等級孔金屬-有機骨架配合物。研究表明,等級孔的形成能夠為金屬-有機骨架材料帶來許多單一孔道MOFs所不具備的特殊性質(zhì),不同形狀結(jié)構(gòu)和不同大小尺度孔道的共存能夠賦予金屬-有機骨架材料在催化、分離、吸附等領(lǐng)域的更多的優(yōu)越性能,所以得到具有等級孔結(jié)構(gòu)的MOFs材料成為人們關(guān)注的熱點。目前用于合成等級孔MOFs的方法主要有模板法、后合成修飾法、擾動輔助納米融合法、水解轉(zhuǎn)化法、等離子體刻蝕及配體刻蝕法等,但這些方法往往實驗條件比較苛刻且后續(xù)處理較為繁瑣,且所得等級孔大多孔道結(jié)構(gòu)不規(guī)則,分布無序,基本上都屬于由微粒無序堆積而形成的孔,而規(guī)則有序等級孔結(jié)構(gòu)的MOFs還很少,而孔的結(jié)構(gòu)直接影響到所得MOFs材料的性能,因此合成新型等級孔結(jié)構(gòu)的金屬-有機骨架配合物及探索簡單可靠的合成等級孔結(jié)構(gòu)的方法具有重要意義。本論文主要進行了以下工作:(1)銅-TATAB等級孔金屬-有機骨架的可控合成、表征、合成機理及性能的研究。以硝酸銅為銅鹽、H3TATAB(H3TATAB:4,4′,4′′-s-三嗪-1,3,5-三對氨基苯甲酸)為配體、DMF為溶劑,通過簡單的原位自組裝合成了具有有序等級孔結(jié)構(gòu)的Cu-TATAB金屬-有機骨架(記為MM-CuTATAB),利用掃描電鏡、透射電鏡、X-射線粉末衍射儀、場發(fā)射掃描電鏡和傅里葉紅外等儀器對所得配合物進行了表征,探索了影響孔結(jié)構(gòu)的合成條件,對其在不同溶劑條件下的穩(wěn)定性進行了研究。同時,以MM-CuTATAB為基礎(chǔ),通過在不同溫度和氣氛下的碳化處理,得到了金屬摻雜的碳基材料,測試了其電催化氧還原反應(yīng)的性能。結(jié)果表明,所得MM-CuTATAB同時具有介孔(37.3nm)和大孔(55.2nm),呈規(guī)則分布;合成反應(yīng)中H2O2加入量的不同和不同的靜置時間是影響等級孔結(jié)構(gòu)形成的重要因素。在不同溶劑中的穩(wěn)定性測試表明其在有機溶劑CH3OH、C2H5OH和CH2Cl2中穩(wěn)定性較大,在水、HCl及NaOH等介質(zhì)中穩(wěn)定性較差。273K和298K下對CO2的吸附實驗表明,MM-CuTATAB表現(xiàn)出了273K下對CO21.18mmol/g的吸附量和298K下0.7mmol/g的吸附量。(2)Zn~(2+)、Co~(2+)、Ni~(2+)摻雜的等級孔Cu/M-TATAB配合物的合成、表征及電催化氧還原性能研究。以H3TATAB為配體、DMF為溶劑,分別與硝酸銅、硝酸鋅、氯化鈷和氯化鎳等原位自組裝合成了不同比例、不同量的Zn~(2+)、Co~(2+)、Ni~(2+)分別摻雜和Zn~(2+)/Co~(2+)共摻雜的配合物等級孔金屬-有機骨架,并進一步進行不同溫度的碳化,進行了其電催化氧還原性能研究。結(jié)果表明:進行Zn~(2+)、Co~(2+)和Ni~(2+)摻雜后仍然可以保持配合物的等級孔結(jié)構(gòu);同時銅鋅摩爾比3:1及700℃下碳化、銅鈷摩爾比4:1及800℃下碳化、銅鎳摩爾比5:1及700℃下碳化和銅鋅鈷摩爾比2:2:2、700℃下碳化所得碳基材料電化學性能較好。(3)三維花狀配合物F-Zn-TATAB的合成、表征及染料吸附性能研究。以硝酸鋅為鋅鹽、H3TATAB為配體、DMF為溶劑,通過水熱反應(yīng)合成了具有三維花狀結(jié)構(gòu)的Zn-TATAB配合物(記為F-ZnTATAB),利用掃描電鏡、透射電鏡、X-射線粉末衍射儀、場發(fā)射、傅里葉紅外等儀器對合成的樣品進行表征,研究了三維花狀結(jié)構(gòu)形成的機理和其應(yīng)用于染料吸附的性質(zhì)。結(jié)果表明所得三維花狀結(jié)構(gòu)由納米片狀結(jié)構(gòu)組裝形成。染料吸附性能測試表明F-ZnTATAB對亞甲基藍(MB)、孔雀石綠(MG)具有較高的的吸附效率:5min可達到82.57%和83.23%。
[Abstract]:Metal-Organic Frameworks (MOFs) is a kind of compound in recent years. Due to its rich pore structure and its composition and properties, it has important applications in the fields of gas adsorption, storage and separation, energy storage / conversion, chemical sensing, heterogeneous catalysis, drug transmission and so on. The research of metal organic skeleton materials is mainly focused on the synthesis and performance of new coordination structures and pore structure complexes. In recent years, the focus of research has gradually shifted to the hierarchical metal organic framework complexes. The study shows that the formation of grade holes can bring many single channel MOFs for metal organic skeleton materials. The coexistence of different shapes and structures and channels of different sizes can give the metal organic skeleton materials more superior performance in the fields of catalysis, separation and adsorption, so the MOFs material with hierarchical structure becomes the hot point of attention. The main methods used to synthesize the grade hole MOFs at present are mainly The template method, the post synthesis modification method, the perturbation assisted nano fusion method, the hydrolysis transformation method, the plasma etching and the ligands etching method, etc., these methods often have more harsh experimental conditions and the subsequent treatment is more complicated, and most of the pores are irregular in the pore structure and the distribution is unordered, basically all belong to the pores formed by the disordered accumulation of particles. But the MOFs of the regular ordered pore structure is very few, and the structure of the hole directly affects the properties of the obtained MOFs material. Therefore, it is of great significance to synthesize the metal organic framework complex of the new class pore structure and to explore the simple and reliable synthetic grade hole structure. The main work of this paper is as follows: (1) copper -TATAB grade hole The controllable synthesis, characterization, synthesis mechanism and properties of the metal organic framework, with copper nitrate as copper salt, H3TATAB (H3TATAB:4,4 ', 4' '-s- three azine -1,3,5- three p-aminophenic acid) as ligands and DMF as the solvent, have synthesized a Cu-TATAB metal organic skeleton with an ordered hierarchical structure by simple in situ self-assembly (recorded as MM-CuTATAB). By means of scanning electron microscopy, transmission electron microscopy, X- ray powder diffractometer, field emission scanning electron microscope and Fourier infrared instrument, the synthetic conditions of the pore structure are explored, and the stability of the structure under different solvent conditions is studied. At the same time, MM-CuTATAB is based on different temperatures and atmospheres. The carbon based material doped with metal was obtained. The performance of the electrocatalytic oxygen reduction reaction was tested. The results showed that the MM-CuTATAB had a regular distribution of mesoporous (37.3nm) and large pores (55.2nm), and the difference in the amount of H2O2 added and the different stationary time in the synthesis reaction were important factors affecting the formation of the structure of the grade hole. The stability test in different solvents showed that the stability of the organic solvent CH3OH, C2H5OH and CH2Cl2 was larger. The adsorption experiments on CO2 under the low stability.273K and 298K in water, HCl and NaOH showed that MM-CuTATAB showed the adsorption amount of CO21.18mmol/g under 273K and the amount of adsorption under 298K. (2) 2+) synthesis, characterization and electrocatalytic oxygen reduction properties of doped grade hole Cu/M-TATAB complexes, with H3TATAB as the ligand and DMF as solvent, respectively, with copper nitrate, zinc nitrate, cobalt chloride and nickel chloride in different proportions, different amounts of Zn~ (2+), Co ~ (2+), Ni~ (2+) and Zn~ (2+) Co doped complexes Zn~ (2+), Co~ (2+) and Ni~ (2+) can still maintain the grade pore structure of the complex; at the same time, the molar ratio of copper and zinc mole to 3:1 and 700 C, copper and cobalt molar ratio 4:1 and 800 C, copper and nickel at the same time The carbon based carbon based materials obtained by carbonization at mole ratio 5:1 and 700 C and Cu ZnCo molar ratio 2:2:2700 C are better. (3) synthesis, characterization and dye adsorption properties of three dimensional flower like complex F-Zn-TATAB, with zinc nitrate as zinc salt, H3TATAB as ligand and DMF as solvent, by hydrothermal reaction to synthesize a three-dimensional flower like structure of Zn- TATAB complex (F-ZnTATAB) was used to characterize the synthesized samples by scanning electron microscopy, transmission electron microscopy, X- ray powder diffractometer, field emission, Fourier infrared and other instruments. The mechanism of the formation of three-dimensional flower structure and the properties of its application to dye adsorption were studied. The results showed that the three-dimensional flower structure was assembled by nano sheet structure. Dye adsorption tests showed that F-ZnTATAB had high adsorption efficiency for methylene blue (MB) and malachite green (MG): 5min could reach 82.57% and 83.23%..
【學位授予單位】：河南師范大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O641.4

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