Syntheses and catalytic study of zr and hf based metal organic frameworks

VIETNAM NATIONAL UNIVERSITY HCMC UNIVERSITY OF SCIENCE ĐOÀN LÊ HOÀNG TÂN SYNTHESES AND CATALYTIC STUDY OF Zr- AND Hf-BASED METAL-ORGANIC FRAMEWORKS PhD THESIS: CHEMISTRY HOCHIMINH CITY - 2017 VIETNAM NATIONAL UNIVERSITY HCM CITY UNIVERSITY OF SCIENCE ĐOÀN LÊ HOÀNG TÂN SYNTHESES AND CATALYTIC STUDY OF Zr- AND Hf-BASED METAL-ORGANIC FRAMEWORKS Major: Theoretical and Physical Chemistry Specialization: Molecular and NanoArchitecture (MANAR) Major Code: 62 44 01 19 Reviewer 1: GS.TS Phan Thanh Sơn Nam Reviewer 2: TS Phạm Cao Thanh Tùng Reviewer 3: PGS.TS Nguyễn Tiến Công Independent reviewer 1: PGS.TS Nguyễn Đình Tuyến Independent reviewer 2: TS Nguyễn Quốc Thiết SUPERVISOR: Prof Dr Lê Ngọc Thạch HOCHIMINH CITY - 2017 PhD Thesis ACKNOWLEDGEMENTS I would like to especially thank my advisor, Prof Le Ngoc Thach to whom I am extremely indebted Not only did he give me the opportunity to expand my mind but he also gave my life direction and discipline I have learned a great amount under his guidance I sincerely thank Prof Le Ngoc Thach for continued support and advice throughout my career Also I want to thank Kyle E Cordova and Dr Hiroyasu Furukawa for their valuable advice and insightful discussions Even though we have had our difficult moments, I will always respect you for pushing me to the limit and for having been a great mentor I am grateful to all members of MANAR both past and present for truly making my stay at MANAR an unforgettable experience In particular, I wish to thank Nguyen Ho Thuy Linh for her support during my research and my lab mates, Nguyen Lac Ha, Truong Nguyen Bao, and Tu Ngoc Thach for their friendship and enjoyable moments in room 302 I would like to express our gratitude to Assoc Prof Hoang Dung, Nguyen Thi Tuyet Nhung, Mai Toan, Nguyen Thi Diem Huong, Nguyen Thanh Binh, Nguyen Thi Kieu Phuong, Nguyen Thi Thanh Thao, Dinh Nguyen Dai Trang, Assoc Prof Nguyen Thai Hoang, Dr Le Viet Hai, Dr Nguyen Thi Le Anh, and Dr Anh Phan I really appreciate their discussion and help I would like to thank Dr Tran Hoang Phuong and Dr Nguyen Tran Nguyen Nguyen for their collaboration in my research I would also like to especially thank Prof Omar M Yaghi (UC Berkeley) for starting and supporting MANAR i PhD Thesis Finally, I would like to thank my family for their encouragement and support in my life I gratefully acknowledge my parents for working hard at providing a great life for their sons and having instilled in me invaluable work and personal ethics Again thank you all of you ii PhD Thesis TABLE OF CONTENTS List of tables vi List of schemes .vii List of figures viii Glossary of terms and abbreviations xiii Abstract Literature review 2.1 2.1.1 Structure of MOFs 2.1.2 Synthesis of MOFs 2.1.3 Structural analysis and characterization of MOFs 2.2 Zr- and Hf-based metal-organic frameworks 10 2.2.1 Chemistry of Zr-MOFs 12 2.2.2 Chemistry of Hf-MOFs 15 2.2.3 Syntheses of Zr- and Hf-MOFs 16 2.3 Zr- and Hf-MOFs used as heterogeneous catalysts 19 2.3.1 Photocatalysis 20 2.3.2 Lewis acid catalysis of Zr- and Hf-MOFs 27 2.4 Introduction of metal-organic frameworks (MOFs) Scope of this dissetation 32 Results and discussion 34 3.1 Objectives 34 3.2 Syntheses of two novel stable Zr- and Hf-MOFs 36 3.2.1 Synthesis of long, slim ethynyl-containing linker, 1,4-bis(2-[4-carboxyphenyl]ethynyl)benzene (H2CPEB) 36 3.2.2 Synthesis of microcrystal of VNU-1 and VNU-2 (VNU-1-P and VNU-2-P, respectively) 38 iii PhD Thesis 3.2.3 Synthesis of single crystals of VNU-1 and VNU-2 (termed VNU-1-SC and VNU-2-SC, respectively) 52 3.3 Structural analyses and characterization of VNU-1 and VNU-2 58 3.3.1 Structural analyses of VNU-1-SC and VNU-2-SC 58 3.3.2 Characterization of VNU-1 and VNU-2 63 3.3.3 Evaluation of Brønsted acidity in VNU-1-P and VNU-2-P 75 3.3.4 Investigation of the chemical stability 79 3.4 VNU-1-P and VNU-2-P used as heterogeneous photocatalysts 86 3.4.1 Introduction 86 3.4.2 Photosorption analysis of VNU-1-P and VNU-2-P 87 3.4.3 Photocatalytic degradation of organic dye pollutants 90 3.4.4 Structural stability and recyclability of VNU-1-P and VNU-2-P after the photocatalytic reaction 95 3.5 VNU-1-P and VNU-2-P used as heterogeneous catalysts in Friedel–Crafts benzoylation 99 3.5.1 Introduction 99 3.5.2 Optimization of reaction conditions 100 3.5.3 Friedel–Crafts benzoylation of aromatic compounds catalyzed by VNU-1P and VNU-2-P 102 3.5.4 Comparative studies of catalysts and heating methods 105 3.5.5 Recyclability and structural stability of VNU-1-P after reaction 109 Experimental 111 4.1 Chemicals 111 4.2 General methods 111 4.3 Synthesis of 1,4-bis(2-[4-carboxyphenyl]ethynyl)benzene (H2CPEB) 114 4.4 Syntheses of Zr- and Hf-MOFs 115 4.4.1 Synthesis of VNU-1 115 4.4.2 Synthesis of VNU-2 116 4.4.3 Syntheses of UiO-66 or UiO-67 117 iv PhD Thesis 4.4.4 4.5 Procedure of potentiometric titration 118 Photocatalysis of VNU-1 and VNU-2 118 4.5.1 Evaluation of photocatalytic activity 118 4.5.2 Procedure of VNU-1 and VNU-2 recovery after reaction 119 4.6 Procedure of catalyzed Friedel-Crafts acylation of aromatic compounds 120 4.6.1 Procedure for Zr-MOF catalyzed Friedel-Crafts acylation of aromatic compounds 120 4.6.2 Procedure for metal halide catalyzed Friedel-Crafts acylation of aromatic compounds 120 4.6.3 Procedure of VNU-1 recovery after reaction 121 4.6.4 Identification of products 121 Conclusion 127 References 128 v PhD Thesis LIST OF TABLES Table 2.1 Summary of some reported Zr-MOFs 13 Table 2.2 Comparison of BET surface areas Zr-MOF and Hf-MOF in same structures (M: Zr or Hf) 16 Table 2.3 Comparison of BET surface areas of Zr MOFs synthesized under different conditions 19 Table 2.4 Photocatalytic activity of UiO-66-NH2 for organic transformations 25 Table 2.5 Conversions and selectivities of reaction, and jasminaldehyde yield at full heptanal conversion for the solventless reaction of benzadehyde and heptanal in the presence of 10% w/w catalysts 28 Table 2.6 p-Xylene acylation with benzoyl chloride using various acid catalysts 30 Table 2.7 Comparing catalytic ability of MOFs in amidation of benzoic acid 31 Table 2.8 Comparing catalytic ability of MOFs in cycloaddition reaction of CO2 with epoxide 32 Table 3.1 Chacterization and structure analyzis of H2CPEB 37 Table 3.2 Effect of molar ratio of ZrOCl2·8H2O salt to H2CPEB linker on VNU-1-P crystallinity 39 Table 3.3 Effect of concentration of ZrOCl2·8H2O and linker H2CPEB on VNU-1-P crystallinity 41 Table 3.4 Effect of reaction temperature on VNU-1 crystallinity 43 Table 3.5 Effect of reaction time on VNU-1-P crystallinity 45 Table 3.6 Effect of modulator concentration on VNU-1-P crystallinity 47 Table 3.7 Effect of modulators on VNU-1-P crystallinity 49 Table 3.8 Optimizing modulator concentration on VNU-2-P synthesis 51 Table 3.9 Optimizing conditions for VNU-1-SC synthesis 54 Table 3.10 Optimizing conditions for VNU-2-SC synthesis 56 Table 3.11 Summary of crystallographic data for VNU-1-SC and VNU-2-SC 60 vi PhD Thesis Table 3.12 Lower-pressure carbon dioxide adsorption capacities for metal-organic frameworks at 298 K 74 Table 3.13 Lower-pressure methane adsorption capacities for metal-organic frameworks at 298 K 75 Table 3.14 Calculated pKa values for Zr- and Hf-MOFs 76 Table 3.15 Summary of the photoabsorption properties and pertinent structural information of VNU-1, VNU-2, and other related MOF structures 89 Table 3.16 Optimized condition of reaction between mesitylene (1 mmol) and benzoyl chloride (1 mmol) catalyzed by VNU-1 under microwave irradiation 101 Table 3.17 The Friedel–Crafts benzoylation of aromatic compounds using VNU-1-P and VNU-2-P under microwave irradiation 102 Table 3.18 The Friedel–Crafts benzoylation in the presence of zirconium and hafnium catalysts 107 LIST OF SCHEMES Scheme 2.1 Cross aldol condensation of heptanal and benzaldehyde catalyzed by UiO66 or UiO-66-NH2 27 Scheme 2.2 Cyclization of (+)-citronellal catalyzed by UiO-66-X 29 Scheme 2.3 p-Xylene acylation with benzoyl chloride 29 Scheme 2.4 Amidation of benzoic acid catalyzed by Zr-MOFs 31 Scheme 2.5 Cycloaddition reaction of CO2 with epoxide catalyzed by Hf-NU-1000 32 Scheme 3.1 Friedel–Crafts benzoylation of aromatic compounds catalyzed by VNU-1 and VNU-2 35 Scheme 3.2 Synthesis of the ditopic linker, H2CPEB, was accomplished by Sonagashira coupling and hydrolysis reaction 36 vii PhD Thesis LIST OF FIGURES Figure 2.1 Synthesized ultrahigh-porosity MOFs from 1999 to 2012 The values in parentheses represent the pore volume (cm3/g) of these materials Figure 2.2 Number of MOF structures reported in the Cambridge Structural Database (CSD) from 1971 to 2011 Figure 2.3 Some organic linkers used to synthesize MOFs Figure 2.4 Metal containing units used for construction of MOFs Figure 2.5 SBUs presentation of metal containing units and organic linkers Figure 2.6 Possible pathways to formation of a new monolayer on the surface of MOF-5 during the synthesis Figure 2.7 Structure of Zn-MOF (MOF-5) and Cu-MOF (HKUST-1) (HKUST: Hong Kong University of Science and Technology, termed by Williams and co-authors) 11 Figure 2.8 The year-by-year increase of reported Zr-MOFs in the last eight years (by SciFinder) 12 Figure 2.9 The Zr6O4(OH)4(-CO2)12 cluster is presented in stick-and-ball (a) and polyhedron (b) The SBU shape is cuboctahedron (c) 15 Figure 2.10 Powder XRD patterns of Zr-UiO-67 prepared with different amounts of benzoic acid (given as equivalents with respect to ZrCl4) as the modulator SEM images of UiO-67 synthesized in the presence of benzoic acid are also given 18 Figure 2.11 Photoabsorption by transition of electrons in the valence band (VB) to the conduction band (CB) in a semiconductor 20 Figure 2.12 Photophysical processes occur after the irradiation of the MOF-5 solid material 21 Figure 3.1 Comparing PXRD patterns of samples with different molar ratios of ZrOCl2·8H2O to linker H2CPEB 40 Figure 3.2 Comparing PXRD patterns of samples with different concentrations of ZrOCl2·8H2O and linker H2CPEB 42 viii Appendix Nitrogen adsorption isotherms for VNU-2-SC (squares) and VNU-2-P (circles) at 77 K with adsorption and desorption branches represented by closed and open circles, respectively XI Appendix 1H and 13C NMR of 4-methoxybenzophenone XII Appendix 10 1H and 13C NMR of 3,4-dimethoxybenzophenone XIII Appendix 11 1H and 13C NMR of 2,4-dimethoxybenzophenone XIV Appendix 12 1H and 13C NMR of 2,5-dimethoxybenzophenone XV Appendix 13 1H and 13C NMR of 2,4,5-trimethoxybenzophenone XVI Appendix 14 1H and 13C NMR of 4-ethoxybenzophenone XVII Appendix 15 1H and 13C NMR of 4-methylthiobenzophenone XVIII Appendix 16 1H and 13C NMR of 4-ethylbenzophenone XIX Appendix 17 1H and 13C NMR of 2,4-dimethylbenzophenone XX Appendix 18 1H and 13C NMR of 2,4,6-trimethylbenzophenone XXI Appendix 19 1H and 13C NMR of 2-benzoylfluorene XXII Appendix 20 1H and 13C NMR of 1-benzoylnaphthalene XXIII Appendix 21 1H and 13C NMR of 2-benzoylnaphthalene XXIV Appendix 22 1H and 13C NMR of 9-benzoylanthracene XXV ... 2.2 Zr- and Hf- based metal- organic frameworks Among the reported MOF structures, the Zn(II)- and Cu(II) -based metal- organic frameworks (Zn-MOFs and Cu-MOFs, respectively) have been early and. .. MOFs 2.1.3 Structural analysis and characterization of MOFs 2.2 Zr- and Hf- based metal- organic frameworks 10 2.2.1 Chemistry of Zr- MOFs 12 2.2.2 Chemistry of Hf- MOFs... containing linkers.[10] Recently, the synthesis of series of robust and porous Zr- based and Hf- based metal- organic frameworks (Zr- MOFs and Hf- MOFs, respectively) were reported.[8,36] These materials