VIETNAM NATIONAL UNIVERSITY – HO CHI MINH CITY HO CHI MINH CITY UNIVERSITY OF TECHNOLOGY NGUYEN THI LE LIEN METAL-ORGANIC FRAMEWORKS IRMOF-8, ZIF-9, MOF199 AND IRMOF-3 AS CATALYSTS FOR THE FRIEDEL– CRAFTS ACYLATION, KNOEVENAGEL, AZA-MICHAEL AND PAAL-KNORR REACTIONS PhD THESIS HO CHI MINH CITY 2013 VIETNAM NATIONAL UNIVERSITY – HO CHI MINH CITY HO CHI MINH CITY UNIVERSITY OF TECHNOLOGY NGUYEN THI LE LIEN METAL-ORGANIC FRAMEWORKS IRMOF-8, ZIF-9, MOF199 AND IRMOF-3 AS CATALYSTS FOR THE FRIEDEL– CRAFTS ACYLATION, KNOEVENAGEL, AZA-MICHAEL AND PAAL-KNORR REACTIONS Major: Organic chemical Technology Major code: 62527505 Supervisor : Assoc.Prof.Dr Phan Thanh Sơn Nam Independent examiner 1: Assoc.Prof.Dr Vu Anh Tuan Independent examiner 2: Assoc.Prof.Dr Pham Thanh Huyen Examiner 1: Assoc.Prof.Dr Tran Đai Lam Examiner 2: Dr Nguyen Quoc Chinh Examiner 3: Assoc.Prof.Dr Pham Thanh Quan DECLARATION OF ORIGINALITY I hereby declare that this is my own research study The research results and conclusions in this dissertation are true, and are not copied from any other resources The literature references have been quoted with clear citation as requested Dissertation Author i THESIS SUMMARY The thesis consists of four chapters, including the literature reviews in chapter one, which provide brief introduction of metal organic framework materials, their properties, and their application Besides, in chapter one, we will collect and summary information from international researcher’s publication on the field of MOF application in organic synthesis reaction as heterogeneous catalyst, which are directly related to our study The main part of this thesis is written in Chapter and Chapter In Chapter 2, the materials, equipment and methodology which are used in our study are presented Our experiment consisted of two parts: (1) Synthesize and characterization of MOFs, and (2) Study the ability of these materials to catalyze organic reactions Chapter will present the experimental results and discussions Chapter is to summarize our significant results with conclusion Four different MOF materials such as IRMOF-8, ZIF-9, MOF-199, IRMOF-3 are synthesized by solvothermal methods in the existent laboratory conditions The yielded materials were analyzed and characterized by modern analytical methods to confirm their structure and properties The analysis techniques included X-ray powder diffraction, SEM micrography and TEM micrography to confirm the crystalline and porous structure of the synthesized catalyst materials Metal concentration in the solid MOFs was determined by AAS techniques, and their functional groups were characterized by FT-IR spectrometer The surface areas of MOFs were determined by Nitrogen physisorption measurements, given the high surface area materials of the four MOFs synthesized in this study The four MOFs: IRMOF-8, ZIF-9, MOF-199, IRMOF-3 were applied as catalysts in the four organic reactions: Friedel- Craft acylation of toluene with benzoyl chloride, Knoevenagel reaction between benzaldehyde and malononitrile, aza-Michael reaction of benzylamine with ethyl acrylate and the Paal-Knorr reaction of benzyl amine with 2,5-hexanedione, respectively Different reaction conditions were ii investigated included the effect of catalyst concentration, reagent ratio, solvents, and the effect of substituents of the reagents on the efficiency of the MOF based catalysts The results show that catalytic properties of the MOFs were good as compared to other solid catalysts The most important experiment was to investigate the leaching of active site of the solid catalysts into the reaction solution Experimental results show that there was no any leaching or homogenous catalytic occurred in the four examined reaction Lastly, the feasibility for the catalyst recyclability was tested and results show that the four catalysts were able to be reused up to five times without any significant degradation Based on the results obtained in this study, it can be concluded that MOF materials can be applied as catalysts in various reactions with advantages such as high efficiency, environment-friendly, and recyclability iii ABSTRACT Highly porous metal-organic framework such as IRMOF-8, ZIF-9, MOF-199 and IRMOF-3 were synthesized by a solvothermal method, and used as an efficient heterogeneous catalyst for the Friedel-Crafts acylation reaction, Knoevenagel reaction, Aza Micheal reaction and Pal Knorr reaction The solid catalyst was characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR), atomic absorption spectrophotometry (AAS), and nitrogen physisorption measurements High conversions were achieved in the presence of a catalytic amount of the MOFs without the need for an inert atmosphere The solid catalyst could be facilely separated from the reaction mixture by simple centrifugation, and could be reused without a significant degradation in catalytic activity No contribution from homogeneous catalysis of active acid species leaching into the reaction solution was detected iv ACKNOWLEDGMENT First and foremost I offer my sincerest gratitude to my supervisor, Prof Phan Thanh Son Nam, who has supported me throughout my thesis with his patience, motivation, enthusiasm and immense knowledge His guidance helped me in all the time of research and writing of this thesis Besides my advisor, I would like to thank Dr Le Thi Hong Nhan for her encouragement, insightful comments My sincere thanks also go to my fellow labmates and students in Organic Chemistry division and Manar lab for the stimulating discussions, which helps me a lot in laboratory work Also thank to my colleagues in Division of Equipment and Chemical Process for their encouragement Last but not the least; I would like to thank my family for supporting me spiritually throughout my life v 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 .31 2.1 Materials and instrumentation 31 2.2 MOF synthesis 32 2.2.1 IRMOF-8 32 2.2.2 ZIF-9 32 2.2.3 MOF-199 33 2.2.4 IRMOF-3 33 2.3 Catalytic studies 33 vi 2.3.1 The Friedel-Crafts acylation reaction 33 2.3.2 The Knoevenagel reaction 34 2.3.3 Aza-Michael Reaction 35 2.3.4 The Paal-Knorr reaction .35 CHAPTER RESULTS AND DISCUSSIONS 37 3.1 Catalyst characterization 37 3.1.1 IRMOF-8 37 3.3.2 ZIF-9 41 3.3.3 MOF-199 45 3.3.4 IRMOF-3 49 3.2 Catalytic studies 53 3.2.1 The Friedel-Crafts acylation reaction 53 3.2.2 The Knoevenagel reaction 62 3.2.3 The aza-Michael reaction 73 3.2.4 The Paal-Knorr reaction 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the known active catalysts The selectivity for the condensation products was 100 % Consequently, the aromatic 18 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,... Examples of inorganic and organic SBUs [22] 5 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 39 Figure 3. 2 SEM micrograph of the IRMOF- 8 39 Figure 3. 3TEM micrograph of the IRMOF- 8 40 Figure 3. 4 TGA analysis of IRMOF- 8 40 Figure 3. 5 FT-IR... 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 ] Over the past 10 years, the use of MOFs as solid catalysts was particularly interesting because the pore size and functionality of the framework could be adjusted over a range for a variety of catalytic reactions The catalytic properties of MOF. .. 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 1 LITERATURE REVIEWS 1.1 Metal organic framework 1.1.1 Introduction Metal organic frameworks (MOFs) are crystalline coordination polymers built from organic linkers (bridging ligands) and inorganic... (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... guest desorption and framework decomposition With all of these advantages, MOFs is highly promising material for gas separation, gas storage and catalysis 1.1 .3 MOF synthesis MOFs are synthesized by mixing organic ligands and metal salts under solvothermal reaction conditions at relatively low temperatures (typically, below 30 0°C) The properties of organic ligands (bond angles, the ligand chain length,... and organic ligand, solubility of the reactants in the solvent, and pH of the solution In addition, the direct mixing method has been developed, which is adapted, at present, for the synthesis of MOF_ 5 and a number of homologous metal_ organic frameworks (IRMOFs) [28] A number of synthetic methods developed for the production of MOFs also include premixing of immiscible solvents One of the most promising... 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. .. transition metal carboxylates in some processes mostly as Lewis acids and oxidation catalysts [18] Considering the simplicity of the synthesis of MOFs and their affordability, it will be important to know if MOFs can outperform in large-scale 2 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