Luận án TS: MOF (IRMOF, ZIF, MOF-199) làm xúc tác Friedel-Crafts, Knoevenagel

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, MOF- 199 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, MOF- 199 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. 3KDQ7KDQK6ѫQ1DP Independent examiner 1: Assoc. Vu Anh Tuan Independent examiner 2: Assoc. Pham Thanh Huyen Examiner 1: Assoc.

7UDQĈDL/DP Examiner 2: Dr. Nguyen Quoc Chinh Examiner 3: Assoc. 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 researchHU¶V 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 2 and Chapter 3. 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 3 will present the experimental results and discussions. Chapter 4 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.1 CHAPTER 1 LITERATURE REVIEWS.1 Metal organic framework.2 The application of MOFs in catalysis.

1 MOFs with Metal Active Sites .2 MOFs with Reactive Functional Groups .3 Grafted species as an active site .1 Materials and instrumentation .1 The Friedel-Crafts acylation reaction .2 The Knoevenagel reaction .3 Aza-Michael Reaction .4 The Paal-Knorr reaction.35 CHAPTER 3 RESULTS AND DISCUSSIONS .1 The Friedel-Crafts acylation reaction .2 The Knoevenagel reaction .3 The aza-Michael reaction.4 The Paal-Knorr reaction.98 LIST OF PUBLICATIONS .102 vii LIST OF TABLES Table 1.1: The surface area of some materials .2 Reported catalytic properties of MOF compounds with active metal sites. Reported catalytic properties of MOF compounds with reactive functional groups. 20 viii LIST OF FIGURES Figure 1. Examples of inorganic and organic SBUs [22].2 The ligand of POST-1.

The schematic view of 1,3,5-benzene tricarboxylic acid tris[N-(4- pyridyl)amide] .1 XRD of the IRMOF-8 .2 SEM micrograph of the IRMOF-8 .3TEM micrograph of the IRMOF-8. TGA analysis of IRMOF-8 .5 FT-IR spectra of the IRMOF-8 (a), and 2,6-napthalenedicarboxylic acid (b).6 XRD of the ZIF-9 .7 SEM micrograph of the ZIF-9 .8 TEM micrograph of the ZIF-9 .9 TGA analysis of ZIF-9 .10 FT-IR spectra of the ZIF-9 (a) and benzimidazole (b).11 XRD of the MOF-199 .12 SEM micrograph of the MOF-199 .13 TEM micrograph of the MOF-199 .15 FT-IR spectra of the MOF-199 (a) and the 1,3,5-benzenetricarboxylic acid (b).14 TGA analysis of MOF-199 .16 XRD of the IRMOF-3 .17 SEM micrograph of the IRMOF-3 .18 TEM micrograph of the IRMOF-3 .19 TGA analysis of IRMOF-3.20 FT-IR spectra of the IRMOF-3 (a) and the 2-amino-1,4- benzenedicarboxylic acid (b) .21 Effect of temperature on reaction conversion .22 Effect of benzoyl chloride: toluene molar ratio on reaction conversion.23 Effect of catalyst concentration on reaction conversion .24 Leaching test indicated no contribution from homogeneous catalysis of active acid species leaching into reaction solution .25 Catalyst recycling studies.26 Effect of substituents on reaction conversion .27 Effect of benzaldehyde : malononitrile molar ratio on reaction conversion .28 Effect of catalyst concentration on reaction conversion .29 Leaching test indicated no contribution from homogeneous catalysis of active species leaching into reaction solution .30 Effect of solvent on reaction conversion .32 Catalyst recycling studies. Catalytic recycling study.33 Effect of different substituents on reaction conversion .34 FT-IR spectra of the reused (a) and fresh (b) ZIF-9. NH3-TPD spectra of the MOF-199 measured between 100 oC and 400 oC .36 Effect of benzylamine: ethyl acrylate molar ratio on reaction conversion 75 Figure 3.37 Effect of catalyst concentration on reaction conversion .38 Effect of different catalysts on reaction conversion.

Effect of solvent on reaction conversion. FT-IR spectra of the fresh (a) and reused (b) MOF-199. X-ray powder diffractogram of the fresh (a) and reused (b) MOF-199. Leaching test indicated no contribution from homogeneous catalysis of active species leaching into reaction solution .43 Catalyst recycling studies of the aza-Michael reaction.

Effect of different amines on reaction conversion .45 Effect of benzylamine:2,5-hexanedione molar ratio on reaction conver- sion. Effect of catalyst concentration on reaction conversion. Leaching test indicated no contribution from homogeneous catalysis of active species leaching into reaction solution. Effect of different catalysts on reaction conversion.49 Effect of different solvents on reaction conversion.50 Effect of different amines on reaction conversion.51 Effect of different diketones on reaction conversion.52 Catalyst recycling studies of the Paal Knorr reaction .53 FT-IR spectra of the fresh (a) and reused (b) IRMOF-3.54 X-ray powder diffractogram of the fresh (a) and reused (b) IRMOF-3.97 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 Composition of Matter MIL 0DWHULDX[VGHO¶,QVWLWXW/DYRLVLHU MOF Metal organic framework 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-(4- pyridyl)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 co- workers 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. 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].

1 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.