SYNTHESIS, CHARACTERIZATION, AND APPLICATION OF ZIRCONIA AND SULFATED ZIRCONIA DERIVED FROM SINGLE SOURCE PRECURSORS By MOHAMMED H. AL-HAZMI Bachelor of Science King Saud University Riyadh, Saudi Arabia 1995 Master of Science King Saud University Riyadh, Saudi Arabia 1999 Submitted to the Faculty of the Graduate College of the Oklahoma State University In partial fulfilment of The requirements for The Degree of DOCTOR OF PHILOSOPHY May, 2005 SYNTHESIS, CHARACTERIZATION, AND APPLICATION OF ZIRCONIA AND SULFATED ZIRCONIA DERIVED FROM SINGLE SOURCE PRECURSORS Thesis Approved: _______________Dr. Allen Apblett_____________ Thesis Adviser ___________________________________________ ______________Dr. K. Darrell Berlin___________ _____________Dr. LeGrand Slaughter__________ _______________Dr. Gary Foutch______________ _____________Dr. A. Gordon Emslie___________ Dean of the Graduate College ii ACKNOWLEDGMENTS The words are inadequate to express my truthful and profound thanks to my phenomenal advisor Dr. Allen W. Apblett for his advice and guidance, continued support, tremendous help, encouragements, and insight and sharp criticism. Since the time that he offered and accepted me to work in this intriguing project, and during the last four and half years, I have learned lots of things from his way of thinking and his research methodology. When encountering some problems and difficulties in different research issues, he simply gives the guidance and the strength to embellish an acceptable idea into a great one. I can honestly say that this Ph.D. dissertation work would not be accomplished without his outstanding supervision, scientific knowledge and experience, and his magnanimous and warm personality of research. My committee members, Dr. Berlin, Dr. Slaughter, and Dr. Foutch are deeply appreciated for their assistance, reading, editing, and invaluable discussion and comments. I would like to express my sincere acknowledge to my colleagues, all Dr. Apblett’s group members, faculty and staff at the Department of Chemistry of Oklahoma State University for their support, kindness and indispensable help during my research period. Furthermore, I extend my warm thanks to Dr. Resasco and his group members at the Department of the Chemical Engineering, University of Oklahoma for performing the X-ray photoelectron spectroscopy analysis. iii I would also like to express many thanks to Dr. Margaret Eastman for her effort in performing solid state NMR experiments and Mrs. Phoebe Doss from the electron microscopy laboratory for doing some SEM morphological images. My utmost sincerest gratitude need to be directed also to Dr. Khalid Karim, Dr. Esam Jami, and Mr. Irhsad Zahir at SABIC R&T, Saudi Arabia, for performing some elemental analysis and pore volume measurements. I am also grateful to SABIC management for their financial support during my study. Deep appreciations and enormous grateful tribute to my wife (Wafaa AL-Hazmi), my children and my parents for their love, patience, care, sacrifice and trust during my study. Without that, I would never be succeeding in my life. Thank you so much for continuous assistance no matter what the need was. Finally and humbly, I would like to express my sincere thanks and appreciation to God for giving me the strength and dedication to achieve and complete this degree. THANK YOU ALL iv TABLE OF CONTENTS CHAPTER 1: GENERAL INTRODUCTION ...............................................................1 BACKGROUND AND AIM OF RESEARCH...................................................... 1 AQUEOUS CHEMISTRY AND STRUCTURE OF ZIRCONIUM (IV).............. 2 HYDROUS ZIRCONIUM OXIDE ........................................................................ 4 ZIRCONIUM OXIDE ............................................................................................ 6 CRYSTAL STRUCTURE OF ZIRCONIUM OXIDE........................................... 7 PHASE TRANSFORMATION............................................................................ 10 SULFATED ZIRCONIA, A STRONG ACID MATERIAL................................ 13 NATURE OF THE ACTIVE SITES ON SULFATED ZIRCONIA.................... 15 ACIDIC PROPERTIES OF SULFATED ZIRCONIA: ....................................... 19 MODIFIED SULFATED ZIRCONIA ................................................................. 24 CONCLUSIONS AND REMARKS..................................................................... 26 REFERENCES CITED......................................................................................... 28 CHAPTER 2: SYNTHESIS OF ZIRCONIA DERIVED FROM SINGLE SOURCE ZIRCONIUM CARBOXYLATE PRECURSORES ........33 INTRODUCTION: ............................................................................................... 33 EXPERIMENTAL:............................................................................................... 37 Chemicals:..................................................................................................37 Preparation of the zirconium carboxylate precursor:.................................38 Characterizations: ......................................................................................47 RESULTS AND DISCUSSION:.......................................................................... 49 Zirconium carboxylate precursors: ............................................................49 v Zirconium oxide form zirconium carboxylates: ........................................65 CONCLUSIONS AND REMARKS: ....................................................................79 REFERENCES CITED:.........................................................................................80 CHAPTER 3: SYNTHESIS OF SULFATED ZIRCONIA POWDERS DERIVED FROM SINGLE SOURCE ZIRCONIUM SULFONATE PRECURSORS ......................................................................................82 INTRODUCTION: ............................................................................................... 82 EXPERIMENTAL:............................................................................................... 84 Chemicals:..................................................................................................84 Synthesis of the zirconium sulfonate precursors: ......................................85 Precursor from the reaction of zirconium salts with other sulfonate reagents: .....................................................................................89 Characterization:........................................................................................95 Acidity measurements:...............................................................................96 Acidity measurements using cyclohexylamine probe: ..............................96 Acid strength using Hammett indicators: ..................................................97 Acidity Evaluation via acetonylacetone conversion reaction:.................100 RESULTS AND DISCUSSIONS....................................................................... 101 Precursors obtained from the reaction of zirconium salts with ethanesulfonic acid and its corresponding oxides:...................................101 Other synthesized zirconium sulfonate precursors and their corresponding oxides: ..............................................................................120 Surface acidity: ........................................................................................129 Thermal decomposition of the sulfated zirconia precursors:...................135 CONCLUSIONS AND REMARKS: ................................................................. 140 vi CHAPTER 4: SYNTHESIS AND CHARACTERIZATION OF SUPPORTED SULFATED ZIRCONIA OVER MESOPOROUS MOBIL CRYSTALLINE MATERIALS (MSM-41) ......................................144 INTRODUCTION: ............................................................................................. 144 EXPERIMENTS:................................................................................................ 148 Chemicals:................................................................................................148 Synthesis: .................................................................................................149 Characterization:......................................................................................150 RESULTS AND DISCUSSION:........................................................................ 151 Thermogravimetric Analysis and Infrared Spectroscopy:.......................151 X-ray Diffraction (XRD): ........................................................................153 Elemental analysis and pore volume: ......................................................157 XPS Analysis: ..........................................................................................158 Scanning Electron Microscopy:...............................................................160 Surface Acidity of the Supported Sulfated Zirconia:...............................161 CONCLUSIONS AND REMARKS: ................................................................. 166 REFERENCES CITED:...................................................................................... 167 CHAPTER 5: ALKYLATION OF BENZENE OVER SULFATED ZIRCONIA USING ETHERS AS ALKYLATING AGENTS .............................169 INTRODUCTION: ............................................................................................. 169 EXPERIMENTAL:............................................................................................. 170 Chemicals:................................................................................................170