i VIETNAM NATIONAL UNIVERSITY — HO CHI MINH CITY ‘ HO CHI MINH CITY UNIVERSITY OF TECHNOLOGY Ss ZIOB eo NGUYEN THI LE LIEN METAL-ORGANIC FRAMEWORKS IRMOE-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 ) L SOc 22 SCOP ee VIETNAM NATIONAL UNIVERSITY — HO CHI MINH CITY HO CHI MINH CITY UNIVERSITY OF TECHNOLOGY NGUYEN THI LE LIEN METAL-ORGANIC FRAMEWORKS IRMOE-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. Phan Thanh Son Nam Independent examiner 1: Assoc. Vu Anh Tuan Independent examiner 2: Assoc. Pham Thanh Huyen Examiner 1: Assoc.
Tran Dai Lam Examiner 2: Dr. Nguyen Quoc Chinh Examiner 3: Assoc. Pham Thanh Quan DECLARATION OE 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 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 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. 11 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. TABLE OF CONTENTS I9) 0. viii LIST OF FIGURES 000.
ix LIST OF ABBREVIATION. ccc ccsesecsceeseecsesesscsesescseesseseessssesesesseseeeeaeed xi INTRODUCTION o. 1 CHAPTER 1 LITERATURE REVIEWS. occ cccceseceseeesescseseescsesessseseeeseneees 4 IV rI00yi li (01.--¿- <6 + 1S S1 TT HT TH TH TH HT Hit 4 1.
6 + 111v TT HT TH TH HT HH ni 5 1.- ánh TH TH HH HT HH TH Hàn Hit 6 1. cà 1S TT HH TH TH Tàn, 7 1.2 The application of MOEs In catfaÏyS1S. 1 MOEs with Metal Active S1(€S.2 MOEs with Reactive Eunctional GTOUpS .3 Grafted species as an aCfV€ SI{€. 6 ng, 20 CHAPTER2 _EXPERIMENTAL.1 Materials and InstrumentafIOI.
Án HT HT HT HT HH HH Hit 33 2.1 The Eriedel-Crafts acylation reaCtOI1.2 The Knoevenagel TeaCfIOI. ¿1k HT TH Hi, 34 2.3 Aza-Michael ReaCtOI.- óc vn ng HH ngư 35 PT N0 x 106 00ái. 35 CHAPTER 3 RESULTS AND DISCUSSIONS.1 Catalyst CharaC{€TIZAf1OT. 6 HT TH HH TH TH nghiệt 37 kh c0.
Án HH TH TH HT HT HT HH Hit 53 3.1 The Friedel-Crafts acylation reaCfiON.2 The Knoevenagel TeaCfIOTI.3 The aza-Michael r€aCfIOH. 102 vii LIST OF TABLES Table 1.1: The surface area oŸ some Imaf€T1AÌS .2 Reported catalytic properties of MOF compounds with active metal sites. Reported catalytic properties of MOF compounds with reactive functional ĐTOUDS. SH TH TH HH TH TH ng TH TH TH TH TH HT TH HH TH TH TH TH TH TH Hư 20 Vili LIST OF FIGURES Figure 1.
Examples of inorganic and orgamic SBUs [22].2 The ligand of POSÏT- l.-- -- ¿+ 111 1S 1211 H111 HH TH nghiệt 18 Figure 1. The schematic view of 1,3,5-benzene tricarboxylic acid tris[N-(4- 2594006019102.1 XRD of the IRMOE-8.- LH TnH HH HH TH TH HH nghiệt 39 Figure 3.2 SEM micrograph of the IRMOIE-8.3TEM micrograph of the IRMOIE-8. TGA analysis of IRMOIE-8. ¿+ Làng HH Hit 40 Figure 3.5 FT-IR spectra of the IRMOF-8 (a), and 2,6-napthalenedicarboxylic acid (b).
SH TT TT TT TH HH TT TT TT TT TT TT TH TH TT nh 41 Figure 3.6 XRD of the ZZIE-Ó. -- + 11111911 11010 HT HT HT HH 43 Figure 3.7 SEM micrograph of.-- «6 + + ST HH ngư, 43 Figure 3.8 TEM micrograph of the Z2IEE-.-¿-¿- + 6S HH HH tiệt 44 Figure 3.9 TGA analysis Of Z2IEE~.- ¿+ k1 TH HT HT HH nghiệt 44 Figure 3.10 FT-IR spectra of the ZIF-9 (a) and benzimidazole (b).11 XRD of the MOIE-1190.- 4 k1 T HH TH TH TH nghiệt 46 Figure 3.12 SEM micrograph of.13 TEM micrograph of the MOIE-190.15 FT-IR spectra of the MOF-199 (a) and the 1,3,5-benzenetricarboxylic acid (D) cee .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 IRIMOIE-3.--¿- «6kg HH, 52 Figure 3.20 FT-IR spectra of the IRMOF-3 (a) and the 2-amino-1,4- IDowO050016:00094)11021065ã0000011207e.21 Effect of temperature on reaCfIOn COTIV€TSIOII.22 Effect of benzoyl chloride: toluene molar ratio on reaction conversion.23 Effect of catalyst concentration on reac(Ion COIIV€TSION.24 Leaching test indicated no contribution from homogeneous catalysis of acfive acid species leaching 1nto reaction sOÏUfiOH.25 Catalyst recycling StU(1S.---- ‹ + 11k 1v HT HT Hư, Figure 3.26 Effect of substituents on reaction conversion Figure 3.27 Effect of benzaldehyde : malononitrile molar ratio on reaction conversion Figure 3.28 Effect of catalyst concentration on reac(Ion COIIV€TSION.29 Leaching test indicated no contribution from homogeneous catalysis of acfIve species leaching 1nfo reacfiOn SOÏUfIOT1.30 Effect of solvenf on reactiOn CORV€TSIOH1 .32 Catalyst recycling StU(1€S.---- ‹ + 1k1 1v HH HT Hư, 69 Figure 3. Catalytic recycling StUY. --¿- «+ + + 12k HT HT HH Hư, 69 Figure 3.33 Effect of different substituenfs on reacfion COnVerSIOI.34 FT-IR spectra of the reused (a) and fresh (b) Z⁄IF-9.
NH3-TPD spectra of the MOF-199 measured between 100 °C and 400 °C SH TH TT TT TT TT HH HT TT TT TT TT TT TH TH T111 T114 TT TT Tnhh 75 Figure 3.36 Effect of benzylamine: ethyl acrylate molar ratio on reaction conversion 75 Figure 3.37 Effect of catalyst concentration on reac(Ion COIIV€TSION.38 Effect of different catalysts on reaction cOnVeTrSiOI. Effect of solvent on reacfiOn COTV€TSIOII. 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 acfIve species leaching 1nfo reacfiOn SOÏUfIOT1.43 Catalyst recycling studies of the aza-Michael reacfion. Effect of different amines on reaction CORV€TSIOH.45 Effect of benzylamine:2,5-hexanedione molar ratio on reaction conver- Figure 3. Effect of catalyst concenfratlon on reacfion CORV€TSIOH. Leaching test indicated no contribution from homogeneous catalysis of acfIve species leaching 1nfo reacfion SOÏUIOH.
Effect of different cafalysts on reac(lon COTIVeTSIOH.49 Effect of different solvents on reaction CORV€TSIOH.50 Effect of different amines on reaction COTIV€TSIOH.51 Effect of different dikefones on reaction COInV€TSIOH.52 Catalyst recycling studies of the Paal Knorr reaction.53 FT-IR spectra of the fresh (a) and reused (b) IRMOE-3.54 X-ray powder diffractogram of the fresh (a) and reused (b) IRMOF-3.97 xi LIST OF ABBREVIATION 1,4-dicb 2,3-pydca 2,4-pydca 2-pymo 4,5-idc 5-mipt AAS BDC BTC DCM DLS DMF FT-IR H;BTC HKUST 1m IRMOE MCM MIL MOF NDC NDCH oba phen PIZA pz pzdc 1,4-diisocyanobenzene pyridine-2,3-dicarboxylate pyridine-2,4-dicarboxylate 2-hydroxypyrimidinolate 4,5-imidazoledicarboxylate 5-methylisophthalate atomic absorption spectrophotometry benzenedicarboxylate benzenetricarboxylate dichloromethane dynamic laser light scattering dimethylformamide Fourier transform infrared spectroscopy 1,3,5-benzenetricarboxylic acid Hong Kong University of Science and Technology imidazolate isorecticular metal organic framework Mobil Composition of Matter Mate riauxs de |’ Institut Lavoisier Metal organic framework 2,6-napthalenedicarboxylate 2,6-naphthalenedicarboxylic acid 4,42-oxybis(benzoate) 1,10-phenanthroline Porphyrinic Illinois Zeolite Analogue pyrazine pyrazine-2,3-dicarboxylate xii salenMn SBUs SEM t-BuOOH TEM TGA T-H THF TOF T-OOH tpepp XRD ZIF (R,R)-(-)-1,2-cyclohexanediamino-N,N2-bis(3-tertbutyl-5-(4- pyridyl)salicyli-dene)MnCl Secondary Building Units scanning electron microscopy tert-butylhydroperoxide transmission electron microscopy thermogravimetric analysis tetralin tetrahedrohydrofuran turnover frequency R-tetralinhydroperoxide tetra(p-carboxyphenyl)porphyrin X-ray powder diffraction 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].