TABLE OF CONTENTS LIST OF TABLES viii LIST OF FIGURES ix LIST OF ABBREVIATION xii INTRODUCTION CHAPTER LITERATURE REVIEWS 1.1 Metal organic framework 1.1.1 Introduction 1.1.2 MOF properties 1.1.3 MOF synthesis .6 1.1.4 MOF application 1.2 The application of MOFs in catalysis 1.2 MOFs with Metal Active Sites 1.2.2 MOFs with Reactive Functional Groups .18 1.2.3 Grafted species as an active site 20 CHAPTER EXPERIMENTAL .30 2.1 Materials and instrumentation 30 2.2 MOF synthesis 31 2.2.1 IRMOF-8 31 2.2.2 ZIF-9 31 2.2.3 MOF-199 32 2.2.4 IRMOF-3 32 2.3 Catalytic studies 32 vi 2.3.1 The Friedel-Crafts acylation reaction 32 2.3.2 The Knoevenagel reaction 33 2.3.3 Aza-Michael Reaction 34 2.3.4 The Paal-Knorr reaction .34 CHAPTER RESULTS AND DISCUSSIONS 36 3.1 Catalyst characterization 36 3.1.1 IRMOF-8 36 3.3.2 ZIF-9 40 3.3.3 MOF-199 44 3.3.4 IRMOF-3 48 3.2 Catalytic studies 52 3.2.1 The Friedel-Crafts acylation reaction 52 3.2.2 The Knoevenagel reaction 61 3.2.3 The aza-Michael reaction 72 3.2.4 The Paal-Knorr reaction .85 CHAPTER CONCLUSIONS 97 LIST OF PUBLICATIONS 99 REFERENCES 100 vii LIST OF TABLES Table 1.1: The surface area of some materials Table 1.2 Reported catalytic properties of MOF compounds with active metal sites Table 1.3 Reported catalytic properties of MOF compounds with reactive functional groups 20 viii LIST OF FIGURES Figure 1.1 Examples of inorganic and organic SBUs [22] Figure 1.2 The ligand of POST-1 18 Figure 1.3 The schematic view of 1,3,5-benzene tricarboxylic acid tris[N-(4pyridyl)amide] .20 Figure 3.1 XRD of the IRMOF-8 38 Figure 3.2 SEM micrograph of the IRMOF-8 38 Figure 3.3TEM micrograph of the IRMOF-8 39 Figure 3.4 TGA analysis of IRMOF-8 39 Figure 3.5 FT-IR spectra of the IRMOF-8 (a), and 2,6-napthalenedicarboxylic acid (b) 40 Figure 3.6 XRD of the ZIF-9 42 Figure 3.7 SEM micrograph of the ZIF-9 42 Figure 3.8 TEM micrograph of the ZIF-9 .43 Figure 3.9 TGA analysis of ZIF-9 43 Figure 3.10 FT-IR spectra of the ZIF-9 (a) and benzimidazole (b) 44 Figure 3.11 XRD of the MOF-199 45 Figure 3.12 SEM micrograph of the MOF-199 46 Figure 3.13 TEM micrograph of the MOF-199 46 Figure 3.15 FT-IR spectra of the MOF-199 (a) and the 1,3,5-benzenetricarboxylic acid (b) 47 Figure 3.14 TGA analysis of MOF-199 47 Figure 3.16 XRD of the IRMOF-3 49 Figure 3.17 SEM micrograph of the IRMOF-3 50 Figure 3.18 TEM micrograph of the IRMOF-3 50 Figure 3.19 TGA analysis of IRMOF-3 51 Figure 3.20 FT-IR spectra of the IRMOF-3 (a) and the 2-amino-1,4- benzenedicarboxylic acid (b) 51 ix Figure 3.21 Effect of temperature on reaction conversion 53 Figure 3.22 Effect of benzoyl chloride: toluene molar ratio on reaction conversion 53 Figure 3.23 Effect of catalyst concentration on reaction conversion 57 Figure 3.24 Leaching test indicated no contribution from homogeneous catalysis of active acid species leaching into reaction solution 57 Figure 3.25 Catalyst recycling studies 59 Figure 3.26 Effect of substituents on reaction conversion 59 Figure 3.27 Effect of benzaldehyde : malononitrile molar ratio on reaction conversion .65 Figure 3.28 Effect of catalyst concentration on reaction conversion 65 Figure 3.29 Leaching test indicated no contribution from homogeneous catalysis of active species leaching into reaction solution 66 Figure 3.30 Effect of solvent on reaction conversion 66 Figure 3.32 Catalyst recycling studies 68 Figure 3.31 Catalytic recycling study 68 Figure 3.33 Effect of different substituents on reaction conversion 71 Figure 3.34 FT-IR spectra of the reused (a) and fresh (b) ZIF-9 71 Figure 3.35 NH3-TPD spectra of the MOF-199 measured between 100 oC and 400 oC .74 Figure 3.36 Effect of benzylamine: ethyl acrylate molar ratio on reaction conversion 74 Figure 3.37 Effect of catalyst concentration on reaction conversion 75 Figure 3.38 Effect of different catalysts on reaction conversion 78 Figure 3.39 Effect of solvent on reaction conversion 79 Figure 3.40 FT-IR spectra of the fresh (a) and reused (b) MOF-199 82 Figure 3.41 X-ray powder diffractogram of the fresh (a) and reused (b) MOF-199 82 Figure 3.42 Leaching test indicated no contribution from homogeneous catalysis of active species leaching into reaction solution 84 Figure 3.43 Catalyst recycling studies of the aza-Michael reaction 84 Figure 3.44 Effect of different amines on reaction conversion 85 Figure 3.45 Effect of benzylamine:2,5-hexanedione molar ratio on reaction conversion 86 x Figure 3.46 Effect of catalyst concentration on reaction conversion 87 Figure 3.47 Leaching test indicated no contribution from homogeneous catalysis of active species leaching into reaction solution 88 Figure 3.48 Effect of different catalysts on reaction conversion 90 Figure 3.49 Effect of different solvents on reaction conversion 91 Figure 3.50 Effect of different amines on reaction conversion 92 Figure 3.51 Effect of different diketones on reaction conversion 94 Figure 3.52 Catalyst recycling studies of the Paal Knorr reaction 94 Figure 3.53 FT-IR spectra of the fresh (a) and reused (b) IRMOF-3 96 Figure 3.54 X-ray powder diffractogram of the fresh (a) and reused (b) IRMOF-3 96 xi LIST OF ABBREVIATION 1,4-dicb 1,4-diisocyanobenzene 2,3-pydca pyridine-2,3-dicarboxylate 2,4-pydca pyridine-2,4-dicarboxylate 2-pymo 2-hydroxypyrimidinolate 4,5-idc 4,5-imidazoledicarboxylate 5-mipt 5-methylisophthalate AAS atomic absorption spectrophotometry BDC benzenedicarboxylate BTC benzenetricarboxylate DCM dichloromethane DLS dynamic laser light scattering DMF dimethylformamide FT-IR Fourier transform infrared spectroscopy H3BTC 1,3,5-benzenetricarboxylic acid HKUST Hong Kong University of Science and Technology im imidazolate IRMOF isorecticular metal organic framework MCM Mobil Compostion of Matter MIL Mate´riauxs de l’Institut Lavoisier MOF Metal organic framwwork NDC 2,6-napthalenedicarboxylate NDCH 2,6-naphthalenedicarboxylic acid oba 4,4-oxybis(benzoate) phen 1,10-phenanthroline PIZA Porphyrinic Illinois Zeolite Analogue pz pyrazine pzdc pyrazine-2,3-dicarboxylate xii salenMn (R,R)-(-)-1,2-cyclohexanediamino-N,N-bis(3-tertbutyl-5-(4pyridyl)salicyli-dene)MnCl SBUs Secondary Building Units SEM scanning electron microscopy t-BuOOH tert-butylhydroperoxide TEM transmission electron microscopy TGA thermogravimetric analysis T-H tetralin THF tetrahedrohydrofuran TOF turnover frequency T-OOH R-tetralinhydroperoxide tpcpp tetra(p-carboxyphenyl)porphyrin XRD X-ray powder diffraction ZIF zeolitic immidazole framework xiii INTRODUCTION During the past decade, thousands works on several aspects of MOFs have been published on refereed ISI journals of Science, Nature, American Chemical Society, Royal Society of Chemistry, ScienceDrect, WileyInterscience ect MOFs are extended porous structures composed of transition metal ions or clusters that are linked by organic bridges Compared to conventionally used microporous and mesoporous inorganic materials, these metal-organic structures have the potential for more flexible rational design, through control of the architecture and functionalization of the pores [1] Conventional storage of large amounts of hydrogen in its molecular form is difficult and expensive because it requires employing either extremely high pressures as a gas or very low temperatures as a liquid [2] The desire to store hydrogen with sufficient efficiency to allow its use in stationary and mobile fueling applications is spurring a worldwide effort in new materials development [3, 4] The Department of Energy, has set performance targets for on-board automobile storage systems to have densities of 60 mg H2/g (gravimetric) and 45 g H2/L (volumetric) [5] Yaghi and coworkers previously investigated the synthesis of different MOFs based on Zn4O(COO)6 , Zn3[(O)3(COO)3] , Cu2(COO)4 and carboxylate organic linkers These MOFs were used as adsorbents for hydrogen storage Among these MOFs, MOF-177, constructed from Zn4O(COO)6 and 1,3,5-benzenetribenzoic acid as organic linker, could afford surface areas of 5640 m2/g Moreover, surface areas of 4590 m2/g were achieved for MOF-20, a MOF with thieno[3,2-b]thiophene-2,5-dicarboxylic acid as organic linker [5] Hydrogen storage capacity of these MOFs were investigated, showing that MOF-177 and MOF-20 exhibited highest capacity of up to 7.5% and 6.7% (wt/wt), respectively [6] Furthermore, they found that binding of hydrogen at the inorganic cluster sites was affected by the nature of the organic linkers The sites on the organic link had lower binding energies, but a much greater capacity for increases in hydrogen loading, which demonstrated their importance for hydrogen uptake by these materials [7, 8] Reducing anthropogenic carbon dioxide emission as well as lowering the amount of greenhouse gases in the atmosphere is apparently one of the most crucial environmental issues that should be seriously taken into consideration [9, 10] Yaghi and co-workers previously pointed out that removal of carbon dioxide from flue gas, synthesis gas and other industrial gases by chilling and pressurizing the exhaust or by passing the fumes through a fluidized bed of aqueous base solution was significantly expensive and inefficient Using MOFs for carbon dioxide capture and storage has been one of the best options [11-13] Yaghi and co-workers employed MOF-199 as adsorbent for carbon dioxide storage Silica- and carbon-based physisorptive materials such as zeolites and activated carbons were referenced as benchmark materials Remarkably, they found that, at 35 bar, a container filled with MOF-177 could capture times the amount of carbon dioxide in a container without adsorbent, and about times the amount when filled with benchmark materials [14] Metal open framework materials (MOFs), include zeolitic imidazolate frameworks (ZIFs) exhibit unique and outstanding properties, and therefore can be regarded as a “new” class of catalytic materials The structural nanoporosity of MOF materials places them at the frontier between zeolites and surface 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room temperature Tetrahedron Lett., 2010 51: p 2109-2114 Zhang, Z.-H., J.-J Li, and T.-S Li, Ultrasound-assisted synthesis of pyrroles catalyzed by zirconium chloride under solvent-free conditions Ultrason Sonochem., 2008 15: p 673-676 Yuan, S.Z and L.X Jin Liu, A convenient synthesis of pyrroles catalyzed by acidic resin under solvent-free condition Chin Chem Lett., 2010 21: p 664668 118 [...]... linker The NH2 group is slightly basic due to a free electron pair on nitrogen atom Based on this characteristic, several reactions have been carried out using IRMOF- 3 as a basic catalyst, as the case of Knoevenagel reaction More common, IRMOF- 3 is often used as a supporter for other basic group like some heterocyclic compounds, which contain nitrogen The functionalized IRMOF- 3 also show high activity in... application of MOFs in the area Other studies also demonstrated the MOF s ability in methane storage [21] The inert gases mixtures was separated from each other by continuous adsorption on electrochemically produced Cu-BTC -MOF [30 ].Coordination unsaturated metal sites (MOF- 74 and MOF- 199] and amino functionality (IRMOF- 3) proved effective adsorption contaminants including SO2, NH3, Cl2, C6H6 and CH2Cl2 [31 ]... catalytic activity for tranesterification reactions of 2,4-dinitrophenylacetate with 1-phenyl-2-propanol [79] Figure 1.2 The ligand of POST-1 Metal organic framework structures with uncoordinated amino groups, for example, IRMOF- 3 and MIL- 53, were stable base catalysts for the Knoevenagel condensation of benzaldehyde with ethyl cyanoacetate or ethyl acetoacetate IRMOF- 3 showed the same activity as the known.. .reactions, advantageously replacing the homogeneous processes [19] There is no doubt that, as in the case of zeolites, gradual introduction of MOFs as industrial catalysts will give relevance to this area and will trigger further research in this area [20] The number of publications on MOFs as catalysts was significantly lower than the case of MOFs as adsorbents for gas capture and storage 3 CHAPTER... increases, which was report by Rorig and his group [ 133 ] Second amines were more nucleophilic than primary amines and were therefore more reactive However, it was worth noting that this was highly dependent on the electronic and steric environment of the amine, this was demonstrated by Suathong Goh professor [ 134 ] Various catalysts have been applied to these reactions, as Bronsted [ 135 ], or Lewis acid catalysts. .. as the known active catalysts The selectivity for the condensation products was 100 % Consequently, the aromatic amino group of the MOF was more active than that of the homogeneous catalyst aniline [32 ] The increased basicity of IRMOF- 3 over other amminic catalysts has been explained via the formation of protonated conjugate derivatives, involving hydrogen-bonds and originating quasi-planar 6-term rings... examine the feasibility to use MOFs as efficient heterogeneous catalysts in organic synthesis, according to greener environment The study was scoped in four typical organic synthesis reactions consisted of Friedel -Craft acylation, Knoevenagel reaction, aza-Michael reaction and Paal -Knorr reaction, which will be discussed below Friedel Crafts acylation provides fundamental and useful method for the synthesis... methanol has been carried out using metal organic frameworks (MOFs) as solid heterogeneous catalysts Of the MOFs tested, a copper-containing MOF [Cu3(BTC)2] (BTC=1 ,3, 5- benzenetricarboxylate) showed better catalytic activity than an iron-containing MOF [Fe(BTC)] and an aluminum containing benzenedicarboxylate) [76] 17 MOF [Al2(BDC )3] (BDC=1,4- 1.2.2 MOFs with Reactive Functional Groups There are MOFs with... near future [38 -41] 8 Several published data show that there are some basic approaches to design heterogeneous catalysts based on MOFs such as supports for an active metal, bringing ligands as an active site, inorganic node as an active site, introduction of guest molecules containing an active site and the post synthetic modification of the framework The utilization of MOFs as solid catalysts is particularly... Au(III) -MOF over the rest of the catalysts Soluble gold salts and the gold salen complex were found to suffer from irreversible deactivation, and therefore, the initial reaction rate (TOF) and maximum conversion attained were lower compared to those for the Au(III) -MOF [71] Other reactions Free metal centers in [Cu3(pdtc)L2(H2O )3] .2DMF.10H2O made it had catalytic characteristic and was tested for catalysis ... flue gas, synthesis gas and other industrial gases by chilling and pressurizing the exhaust or by passing the fumes through a fluidized bed of aqueous base solution was significantly expensive and. .. Using MOFs for carbon dioxide capture and storage has been one of the best options [11-13] Yaghi and co-workers employed MOF-199 as adsorbent for carbon dioxide storage Silica- and carbon-based physisorptive... in this area [20] The number of publications on MOFs as catalysts was significantly lower than the case of MOFs as adsorbents for gas capture and storage CHAPTER LITERATURE REVIEWS 1.1 Metal organic