Design and synthesis of reticular MOFs with high porosity and gas storage

Tan, Chenrong (2013) Design and synthesis of reticular MOFs with high porosity and gas storage. PhD thesis, University of Nottingham.

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Abstract

This thesis comprises six chapters.

Chapter 1 introduces the background to the project. In this chapter, issues of energy problems, the advantages of H2 and materials and methods for storage are introduced and then the subject is focused on porous metal-organic frameworks (MOFs), a new class of porous materials which are good candidates as on-board storage materials combining with the fuel cell technology. Three topics are discussed about porous materials, (i) metal nodes as secondary building units (SBUs) to prepare porous MOFs, (ii) the strategy in design and synthesis for hydrogen storage in MOFs, (iii) review of gas storage by H2, CH4 and CO2 in MOFs.

Chapters 2 to 6 are the results and discussions from my work. They are separated based on different metal cation system.

Chapter 2 describes materials prepared from Mg(II) cations and bi- or tricarboxylate ligands. H2L1, H2L2 were purchased from commercial suppliers and three carboxylate ligands were synthesized. All have been employed in the preparation of MOFs to give five Mg(II) framework materials: {Mg3(L1)3(DMA)4}∞ 1, [Mg3(L2)3(DMF)4]∞ 2, [Mg3(L3)3(DMF)4]∞ 3, {[Mg3(L4)2(DMA)4]•(DMA)4}∞ 4, {[Mg3(L5)2(DMA)4]•(DMA)4}∞ 5. The structures of these compounds obtained from single crystal X-ray diffraction and porosity in network are discussed. H2 adsorption measurement is carried out on {[Mg3(L5)2(DMA)4]•(DMA)4}∞ 5, which gives a uptake of 2.06 wt% at 20 bar at 77 K.

Chapter 3 describes materials prepared from Ni(II) cations and tetracarboxylate ligands. {[Ni2(L6)(H2O)4]•(DMF)3(EtOH)(H2O)5}∞ 6, {[Ni2(L7)(H2O)5]•(DMF)2(EtOH)2(H2O)6}∞ 7, {[Ni2(L8)(H2O)5]•(DMF)3(EtOH)2(H2O)7}∞ 8 are afforded. Analyses of structure, thermal stability and porosity of the compounds are discussed.

Chapter 4 describes MOF materials prepared from Cu(II) cation and tri- or tetracarboxylate ligands. {[Cu2(L12)(H2O)2]•(DMF)3(C2H5OH)3(H2O)5}∞ 13, {[Cu2(L13)(H2O)2]•(DMF)3(C2H5OH)4(H2O)7}∞ 14, {[Cu3(L14)2(H2O)3]•(DMF)2(C4H8O2)4(H2O)5}∞ 15, {[Cu3(L14)2(H2O)3]•(DMF)1.5(DMSO)3(H2O)6}∞ 16, {[Cu2(L15)(H2O)2]•(DMF)(C4H8O2)2(H2O)5}∞ 17, {[Cu2(L16)(H2O)2]•(DMF)(C4H8O2)1.5(H2O)4}∞ 18, {[Cu2(L17)(H2O)2]•(DMF)0.5(C4H8O2)(H2O)3}∞ 19 are affored. Analyses of structure, thermal stability and porosity of the compounds are discussed. Gas adsorption measurements (N2, Ar, H2, CH4 and CO2) are carried out on porous materials.

Chapter 5 describes a new (4,8)-connected polyhedral framework with mixed pores was synthesised based on Cu(II) cation and a tetrabranched octacarboxylate ligand {[Cu4L18(H2O)4]•10DMF•C4H8O2•8H2O}∞ 20. Analyses of structure, thermal stability and porosity of the compounds are discussed. Gas adsorption measurements (N2, Ar, H2, CH4 and CO2) are carried out this compound, which gives a hydrogen uptake of 2.5 wt% at 1 bar and 6 wt% at 20 bar at 77 K.

Chapter 6 summarizes the crystal structure and gas adsorption of the MOF materials obtained in each chapter.

Item Type: Thesis (University of Nottingham only) (PhD)
Supervisors: Schröder, M.
Champness, N.R.
Subjects: Q Science > QD Chemistry > QD241 Organic chemistry
Faculties/Schools: UK Campuses > Faculty of Science > School of Chemistry
Item ID: 13482
Depositing User: EP, Services
Date Deposited: 11 Aug 2016 11:56
Last Modified: 14 Sep 2016 05:54
URI: http://eprints.nottingham.ac.uk/id/eprint/13482

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