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Ionothermal Synthesis Of Metal-organic Frameworks Based On1,4-naphthalenedicarboxylic Acid

Posted on:2014-09-21Degree:MasterType:Thesis
Country:ChinaCandidate:J L WangFull Text:PDF
GTID:2251330401975854Subject:Inorganic Chemistry
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The ionothermal synthesis is a new method of preparing porous metal-organic frameworks (MOFs)with novel structures and specially appointed functions. Ionic liquids as solvents not only can provide apure ionic environment, but also can guide the construction of structure by the template effects of ionstructure, which greatly improves the production rate and controllable of porous materials. Moreover, thestructure, size, polarity and hydrophilic of ionic liquids will all directly affect the synthesis of targetproducts. Therefore, the design and construction of multifunctional metal-organic frameworks byionothermal synthesis methods based on the concept of supermolecular chemistry and the diversity and themodifiability of complexes structure, and studying the assemble laws and influencing factors of thestructure compositions and properties, which is one of the distinctive research subjects of coordinationchemistry and supramolecular chemistry, and is also a new trend of the development of material chemistry.In this paper,24MOFs have been synthesized by ionothermal method and structurally characterized by IR,thermogravimetric (TG) analyses, powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction.Some factors such as the types and size of ionic liquids, the radius and oxidation state of the metal ion,which can all affect the structure of MOFs. The magnetic properties of some MOFs were studied.Moreover, the connections of structures and magnetic behaviors were also researched.This paper has divided into five chapters which were introduced as follows:1, Nine cobalt metal-organic frameworks:(EMIm)[Co(1,4-NDC)Br](E=ethyl, MIm=N-methylimidazolium)(CoMOF-1),(PMIm)2[Co7(1,4-NDC)6(OH)4](P=propyl)(CoMOF-2),(BMIm)2[Co6(1,4-NDC)6(OH)2](B=butyl)(CoMOF-3),(AMIm)4[Co4Na5(1,4-NDC)8Br](A=amyl) (CoMOF-4),[C3(MIm)2][Co(1,4-NDC)Br]2(CoMOF-5),[C4(MIm)2][Co(1,4-NDC)Br]2(CoMOF-6),[C5(MIm)2][Co(1,4-NDC)Br]2(CoMOF-7),[C6(MIm)2][Co(1,4-NDC)Br]2(CoMOF-8) and(EMIm)2[Co3(1,4-NDC)4(EIm)2(H2O)2](CoMOF-9) have been ionothermally synthesized and structurallycharacterized by TG, PXRD and complete X-ray single-crystal diffraction analyses, where1,4-NDC2andCnare1,4-naphthalenedicarboxylic acid anion and saturated alkyl chain with the numbers of carbon atomsof n, respectively.2, Six nickel MOFs:(EMIm)2[Ni3(1,4-NDC)4(EIm)2(H2O)2](NiMOF-10),(PMIm)[Ni2(1,4-NDC)2(CH3COO)](NiMOF-11),(BMIm)[Ni2(1,4-NDC)2(CH3COO)](NiMOF-12),(C7-MIm)2[Ni3(1,4-NDC)4(H2O)2](NiMOF-13),[C4(MIm)2][Ni(1,4-NDC)Br]2(NiMOF-14) and[Ni3(1,4-NDC)4(MIm-C5Im)2(H2O)2](NiMOF-15) have been synthesized based on Ni(AC)2and1,4-H2NDC.3, Four Mn-MOFs:(EMIm)[Mn(1,4-NDC)Br](MnMOF-16),(PMIm)[Mn2(1,4-NDC)2(Ac)](MnMOF-17),(BMIm)[Mn2(1,4-NDC)2(Ac)](MnMOF-18) and [C6(MIm)2][Mn(1,4-NDC)Br]2(MnMOF-19) have been synthesized derived from Mn(AC)2and1,4-H2NDC.4, Three Ln-MOFs (EMIm)2[Pr2(1,4-NDC)4](PrMOF-20),(EMIm)2[Er2(1,4-NDC)4](H2O)<sub>4.75(ErMOF-21) and (EMIm)2[Ho2(1,4-NDC)4](H2O)5.50(HoMOF-22) have been synthesized from Ln(NO33and1,4-H2NDC (Ln=Pr, Er, Ho), in which both ErMOF-21and HoMOF-22exhibit3D porous channels.5, Two novel3D MOFs (EMIm)8Br8[Sr20(1,4-NDC)20](SrMOF-23) and [Zn7(1,4-NDC)6(OH)2](ZnMOF-24) have been synthesized with Sr(NO32or Zn(NO3)2and1,4-H2NDC, respectively.
Keywords/Search Tags:Ionic liquids, Metal-organic frameworks, Crystal structure, Magnetic properties
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