Functionalised nanostructured dendritic rhodium catalysts for styrene hydroformylation reactions

FUNCTIONALISED NANOSTRUCTURED DENDRITIC RHODIUM CATALYSTS FOR STYRENE HYDROFORMYLATION REACTIONS LI PENG (B. Eng., Tianjin University) A THESIS SUBMITTED FOR THE DEGREE OF PH. D. OF ENGINEERING DEPARTMENT OF CHEMICAL & BIOMOLECULAR ENGINEERING NATIONAL UNIVERSITY OF SINGAPORE 2008 Acknowledgement Acknowledgements First of all, I would like to express my heartfelt thanks to my supervisor, Prof. Sibudjing Kawi, for his tremendous help and constructive suggestions throughout all my Ph. D. candidate period. I appreciate his constant encouragement and precious guidance. His meticulous style influences me profoundly on the way of pursing research. I also want to take this opportunity to thank all our group members who share the laboratories and their knowledge with me, Dr. Shen Shoucang, Zhang Sheng, Yong Siekting, Tang Yunpeng, Zeng Houxu, Luan Deyan, Song Shiwei, Yang Jun, Sun Gebiao, Malik, Warintorn Thitsartarn and Wu Xusheng. They are my good teachers and helpful friends. From them, I experience the pleasure and importance of cooperation. Special thanks should go to Mdm Jamie, Mr. Chia, Mdm Samantha, Mr. Toh and Dr. Yuan for all the help they have offered throughout my research. Their professional skills help me solve technical problems quickly and effectively. In addition, I also wish to thank National University of Singapore for offering me financial support for my Ph. D. studies. This thesis is dedicated to my parents who hide mom’s sickness from me for not disturbing my thesis completion. And it is also a special gift to my wife, Haixia. i Table of Contents Table of Contents Acknowledgements i Table of Contents ii Summary vii Abbreviation .ix List of Figures .xi List of Tables and Scheme . xiii Chapter 1. Introduction .1 1.1 Background of Hydroformylation 1.1.1 Promising Supports .3 1.2 Project Objectives .5 1.3 Thesis Organization .7 Chapter 2. Literature Review .8 2.1 Homogeneous Hydroformylation 2.1.1 The Progress of Homogeneous Hydroformylation Catalysts 2.1.2 Mechanism of Rhodium-Catalyzed Hydroformylation .10 2.1.2.1 Unmodified Rhodium-Catalyzed System 11 2.1.2.2 Modified Rhodium-Catalyzed System .13 2.1.2.3 Rate Determing Step .18 2.1.3 Kinetics of Rhodium-Catalyzed Hydroformylation 19 2.1.4 Parameters and Their Effects .21 2.1.4.1 Effect of CO .21 2.1.4.2 Effect of H2 .22 2.1.4.3 Ligand Effects 23 2.1.4.4 Temperature Effects 26 ii Table of Contents 2.1.4.5 Substrate Structure Effects 27 2.1.4.6 Solvent Effects 28 2.2 Heterogeneous Hydroformylation .29 2.2.1 MCM-41 .31 2.2.2 SBA-15 .36 2.2.3 Dendrimer .39 2.2.4 Nanoscale Catalysis .44 Chapter 3. Experimental .48 3.1 Preparation of Catalysts .48 3.1.1 Chemicals 48 3.1.2 Synthesis of MCM-41 48 3.1.3 Pre-treatment of MCM-41 49 3.1.4 Passivation of MCM-41 and Functionalization inside Pores 50 3.1.5 Functionalization of MCM-41 without Passivation .50 3.1.6 Preparation of MCM-41 Supported PAMAM Dendrimer .51 3.1.7 Passivation of MCM-41 Tethered Rhodium Catalysts .52 3.1.8 Synthesis of SBA-15 54 3.1.9 Synthesis of SBA-15 Supported Dendritic Catalysts .54 3.1.10 Synthesis of Nanoparticles of Al2O3 .56 3.1.11 Synthesis of Nano-Al2O3 Supported Dendritic Catalysts .56 3.1.12 Synthesis α-Al2O3 and γ-Al2O3 Supported Dendritic Catalysts 57 3.2 Hydroformylation Reactions 57 3.2.1 Equipment 57 3.2.2 Reaction Procedure 58 3.3 Characterizations .59 iii Table of Contents 3.3.1 X-ray Diffraction (XRD) 59 3.3.2 BET Analysis .60 3.3.3 FTIR Analysis 61 3.3.4 Inductively Coupled Plasma Atomic Emission (ICP) 62 3.3.5 Gas Chromatograph 62 3.3.6 XPS Analysis .63 3.3.7 Thermal Analysis .64 3.3.8 C, H, N, Elemental Analysis .64 3.3.9 FE-SEM Analysis .64 3.3.10 TEM Analysis 65 Chapter 4. Dendritic SBA-15 Supported Wilkinson's Catalysts for Hydroformylation of Styrene .66 4.1 Preface 66 4.2 Characterizations 68 4.2.1 FTIR Analysis .68 4.2.2 TGA Analysis .70 4.2.3 XRD Analysis .73 4.2.4 TEM Analysis .74 4.2.5 ICP Analysis .76 4.3 Catalytic Run .78 4.3.1 Activity .78 4.3.2 Regio-selectivity .81 4.4 Conclusions 85 Chapter 5. Dendritic SBA-15 Supported HRh(CO)(PPh3)3 for Hydroformylation of Styrene .87 iv Table of Contents 5.1 Preface 87 5.2 Characterizations 89 5.2.1 BET Analysis 89 5.2.2 XPS Analysis 94 5.2.3 FTIR Analysis .96 5.2.4 TEM Analysis .97 5.2.5 Elemental Analysis 100 5.3 Catalytic Run .101 5.3.1 Activity .101 5.3.2 Regio-selectivity .105 5.4 Characterization of Used Catalysts………………………………………… 108 5.5 Conclusions .113 Chapter 6. Dendritic MCM-41 Supported RhCl(PPh3)3 for Hydroformylation of Styrene .114 6.1 Preface 114 6.2 Characterizations 116 6.2.1 XRD Analysis .116 6.2.2 Thermal Analysis 118 6.2.3 FTIR Analysis .121 6.2.4 C, H, N, Elemental Analysis 123 6.2.5 XPS Spectra of Rhodium Complexes on Functionalized MCM-41 124 6.2.6 Hydroformylation of Styrene .126 6.2.6.1 Activity 126 6.2.6.2 Regio-selectivity .130 6.2.7 TEM Image .134 v Table of Contents 6.2.8 ICP Analysis .135 6.3 Conclusions 136 Chapter 7. Dendritic Nano-Alumina Supported RhCl(PPh3)3 for Hydroformylation of Styrene .137 7.1 Preface 137 7.2 Results and Discussions 139 7.2.1 FE-SEM Analysis .139 7.2.2 Comparison of the Nano-Alumina Support and α-Alumina Support…….141 7.2.2.1 Activity………………………………………………………… 142 7.2.2.2 Regio-selectivity……………… .……………………… .………143 7.2.3 Comparison of the Nano-Alumina Support and γ-Alumina Support…….145 7.2.3.1 Activity………………………………………………………… 145 7.2.3.2 Regio-selectivity.… .…………………………………………… 147 7.2.4 Comparison of the Nano-Alumina Support and SBA-15 Support .…… 149 7.2.4.1 Activity……………………………………………………… 149 7.2.4.2 Regio-selectivity…… …… …………………………………… 151 7.2.5 Exploration of Higher PAMAM Dendrimers on Nano-Alumina….…… 153 7.2.5.1 Activity………………………………………………………… 153 7.2.5.2 Regio-selectivity…… .…………………………………… .……155 7.3 Conclusions………………………………………………………………… 158 Chapter 8. Conclusions and Future Work 159 8.1 Conclusions 159 8.2 Future Work 163 References .164 Appendix………………………………………………………………………… …187 vi Nomenclature Summary This thesis reports the study of hydroformylation of styrene catalyzed by heterogenized rhodium complexes. Three types of solid supports have been employed: SBA-15, MCM-41 and nano-Al2O3. The supports’ surfaces are modified with amine (NH2) ligands as starting points for growing PAMAM dendrimers up to third generation. These dendritic supports are used to tether RhCl(PPh3)3 or HRh(PPh3)3, for producing the heterogenized rhodium catalysts. The combination of the highly ordered mesoporous material SBA-15 or MCM41 with the highly branched dendrimer creates a distinct architecture which is both helpful for the dispersion of rhodium due to the high surface areas of supports, the multiple binding sites of dendrimer and the promotional regioselectivity due to the dendrimer and pore effects. The nano-alumina supported PAMAM dendrimer tethered rhodium catalysts exhibit superior catalytic performances due to the special properties of the support. Generally, passivated SBA-15 or MCM-41 based dendritic catalysts exhibited better stability than the nonpassivated counterparts. This is attributed to the pore confinement of the mesopores of the passivated SBA-15 and MCM-41. Morover, catalytic performances with the passivated SBA-15 or MCM-41 based dendritic catalysts reach highest with certain PAMAM generation. This is attributed to the positive dendrimer effects, because the rhodium complexes are better dispersed on the more perfectly grown dendrimers. vii Nomenclature For the non-passivated SBA-15 supported Wilkinson’s Catalysts, the catalytic performances decrease as the PAMAM dendrimer generation goes up. This is due to the dendrimers growing outside the SBA-15 channels where is similar to the situation of a normal silica. The longer and longer dendrimer arms due to increased generation block the active catalytic centers in this case. In contrast, for the passivated SBA-15 supported Wilkinson’s catalysts, the passivation not only improves the stability of the catalysts but also let the dendrimers develop in a more spacious environment which allows the dendrimers grow with fewer defects. And the catalytic performances not decrease along with the dendrimer generation but reach highest point at an optimal generation which is second. The MCM-41 supported catalysts show much similar behavior to the SBA-15 supported ones yet differ in that the optimal generation of highest catalytic performance is first generation. This is attributed to the smaller pore size distribution of MCM-41 compared to SBA-15. GC, BET, TGA, TEM, FE-SEM, FTIR, XPS, XRD and ICP etc. have been employed for characterization of the as-synthesized hyeterogenized catalysts. The PAMAM dendrimers are shown to be successfully anchored on the supports with spectroscopic evidence and thermal analysis results. XRD and TEM show the mesoprous structures of SBA-15 and MCM-41 are stable during the hydroformylation reactions. The synthesized nano-Al2O3 catalysts are highly active, selective and stable. Keywords: Hydroformylation, styrene, rhodium, Wilkinson’s Catalyst, SBA-15, MCM-41, nano-alumina, PAMAM, dendrimer, heterogeneous catalysis, passivation viii Nomenclature Abbreviation °C Degree Centigrade Å angstrom BET Brunauer Emmett Teller method DTA Differential Thermal Analysis FE-SEM Field Emission Scanning Electron Microscopy FTIR Fourier Transform Infrared Spectroscopy GC Gas Chromatography Gn (n=0,1,2,3) PAMAM Dendrimer of Generation n HSn (n=0,1,2,3) HRh(CO)(PPh3)3 Supported on SBA-15 Functionalized with PAMAM Dendrimer Generation n HPSn (n=0,1,2,3) HRh(CO)(PPh3)3 Supported on Passivated-SBA-15 Functionalized with PAMAM Dendrimer Generation n ICP Inductively Coupled Plasma SEM Scanning Electron Microscopy TEM Transmission Electron Microscopy PAMAM Poly(amidoamine) Dendrimer Passivated MCM-41 Supported PAMAM Dendrimer of PMn (n=0,1,2) Generation n Passivated SBA-15 Supported PAMAM Dendrimer of PSn (n=0,1,2,3) Generation n Sn (n=0,1,2,3) SBA-15 Supported PAMAM Dendrimer of Generation n XPS X-ray Photoelectron Spectroscopy XRD X-Ray Diffraction ix References [98] Coronado, J. 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Kawi. Conference Name: 4th Asis Pacific Congress on Catalysis (APCAT 4) Session: Nanotechnology in Catalysis [3] Li P. and S. Kawi. “Dendritic SBA-15 Supported Wilkinson’s Catalyst for Hydroformylation of Styrene”, Catalysis Today, 131, pp.61-69. 2008. [4] Li P. and S. Kawi. “SBA-15-based polyamidoamine dendrimer tethered Wilkinson’s rhodium complex for hydroformylation of styrene”, Journal of Catalysis, (In press, 2008) [5] Li P. and S. Kawi. “MCM-41 based polyamidoamine supported Wilkinson’s catalyst for hydroformylation of styrene”, Journal of Molecular Catalysis A-Chemical, (Submitted, 2008) [6] Li P., T. Warintorn and S. Kawi. “Highly active and selective nano-alumina supported Wilkinson’s catalysts for the hydroformylation of styrene”, Industrial & Engineering Chemistry Research, (Submitted, 2008) 187 [...]... supported Wilkinson’s catalysts Hydroformylation of styrene using nano-alumina and SBA-15 supported Wilkinson’s catalysts Regio-selctivity of hydroformylation of styrene using nanoalumina and SBA-15 supported Wilkinson’s catalysts Activity of hydroformylation of styrene using nano-alumina supported Wilkinson’s catalysts of PAMAM Dendrimer Generation 0 to 3 Selectivity of hydroformylation of styrene using nano-alumina... 7.2 Hydroformylation of styrene using nano-alumina and αalumina supported Wilkinson’s catalysts 143 Selectivity of hydroformylation of styrene using nano-alumina and Fig 7.3 Fig 7.4 Fig 7.5 Fig 7.6 Fig 7.7 Fig 7.8 Fig 7.9 α-alumina supported Wilkinson’s catalysts Hydroformylation of styrene using nano-alumina and αalumina supported Wilkinson’s catalysts Regio-selctivity of hydroformylation of styrene. .. CO (3b) Fig 2.1 Generally accepted mechanism for rhodium- catalyzed hydroformylation Figure 2.1 illustrates the generally accepted mechanism of rhodium- catalyzed hydroformylation reaction [33] The elemental steps are as follows: (a) The rhodium precursor break up and forms rhodium hydride tricarbonyl species (1) under the hydroformylation conditions; (b) The formed hydride coordinates the vinyl substrate... as-synthesized catalysts The substrate we choose for this project is styrene which is a model substrate studied extensively and can give us informative implications for synthesis of intermediates for pharmaceuticals The hydroformylation reaction is shown in Scheme 1.1 shown below: 5 Chapter 1 Introduction CHO O CO/H2 + Rh Styrene 3-phenylpropionaldehyde 2-phenylpropionaldehde Scheme 1.1 Hydroformylation of Styrene. .. Fig 5.8a Fig 5.8b Fig 5.9a Fig 5.9b Fig 5.10 Fig 5.11 Fig 5.12 Fig 6.1 Generally accepted mechanism for rhodium- catalyzed hydroformylation Associative pathway for the rhodium- triphenylphosphine-catalyzed hydroformylation of olefins Dissociative pathway for the rhodium- triphenylphosphinecatalyzed hydroformylation of olefins Three different configurations of surface hydroxyl groups PAMAM (generation 3)... (g) used WPM0 Hydroformylation of styrene using homogeneous Wilkinson’s catalyst; passivated MCM-41 based heterogenized Wilkinson’s catalysts, WPM0-WPM2 and non-passivated MCM-41 based heterogenized Wilkinson’s catalysts, WM0-WM2 Activity of hydroformylation of styrene using homogeneous PAMAM dendrimer with homogeneous RhCl(PPh3)3 118 119 119 122 125 127 129 Fig 6.6a Hydroformylation of styrene using... species catalyzed hydroformylation reactions [18, 19] 8 Chapter 2 Literature Review On the way of seeking more active and selective catalysts, various metals have been tested [20] And the accepted order of hydroformylation activity on the basis of unmodified monometallic catalysts is: Rh >> Co > Ir, Ru > Os > Pt > Pd > Fe > Ni Rhodium becomes the focus of the second generation hydroformylation catalysts, ... industry nowadays The rhodium- phosphine-catalyzed hydroformylation, first reported by Wilkinson and coworkers in the late 1960s, which operated at lower pressure and temperature than earlier cobalt-based catalysts provided a better choice of transition metal for hydroformylation And the rhodium- based catalysts were commercialized by Union Carbide in 1970s So far, homogeneous hydroformylation process... to hydroformylation, MCM-41, SBA-15, nanoparticle and dendrimers Chapter 3 demonstrates the experimental steps in detail for synthesis of materials, heterogenized catalysts and instruments applied for reactions and characterizations Chapters 4, 5, 6 and 7 describe in details the results and discussion sections for each topic covering the using of SBA-15, MCM-41 and nano-alumina as supports for hydroformylation. .. that the main goal in rhodium- catalyzed hydroformylation of olefins, concerns the control of regioselectivity It is obvious that some steps in the hydroformylation cycle are crucial in deciding the final regioselectivity For example, step c controls the ratio between branch and linear alkyl rhodium intermediates and if these alkyl rhodium intermediates go forward in the cycle will form branch and linear . FUNCTIONALISED NANOSTRUCTURED DENDRITIC RHODIUM CATALYSTS FOR STYRENE HYDROFORMYLATION REACTIONS LI PENG (B. Eng., Tianjin University) A THESIS SUBMITTED FOR. mechanism for rhodium- catalyzed hydroformylation 11 Fig. 2.2 Associative pathway for the rhodium- triphenylphosphine-catalyzed hydroformylation of olefins 13 Fig 2.3 Dissociative pathway for. are stable during the hydroformylation reactions. The synthesized nano-Al 2 O 3 catalysts are highly active, selective and stable. Keywords: Hydroformylation, styrene, rhodium, Wilkinson’s