QUEENSLAND UNIVERSITY OF TECHNOLOGY SCHOOL OF PHYSICAL AND CHEMICAL SCIENCES THE MORPHOLOGY AND STRUCTURE OF INTERCALATED AND PILLARED CLAYS Submitted by Loc Van Duong to the school of Physical and Chemical Sciences, Queensland University of Technology, in partial fulfilment of the requirements of the degree of Doctor of Philosophy. i This thesis is dedicated to my wife Bach-Yen Thi Nguyen and children Tien-Nam Nguyen Duong, Thuy-Tien Nguyen Duong and Dang-Khoa Nguyen Duong ii Acknowledgements I would like to take the opportunity to express my sincere thanks to people who have contributed greatly to my research: My principal supervisor, Dr. Theo Kloprogge, for his support, advice and guidance throughout my program of study. My co-supervisors Professor Ray Frost and Dr. Thor Bostrom for their invaluable advice, encouragement and discussions. Other people who involved in helping me with techniques and applications include: • Dr Barry Wood, University of Queensland for his advice and assistance on the XPS equipment and techniques. • Dr Gregory Watson, Griffith University for assistance and comments on the Scanning Probe microscope work. • Dr Marek Zbik, Ian Wak Research Centre, South Australia for discussion on the application of Atomic Force Microscope for clay minerals. • Dr Wayde Martens for discussion and comments on vibrational spectroscopy work on clay minerals. • Professor H. Zhu and Professor HongPing He for the comments on organoclay and pillared clay application. Gratefully acknowledgements go to the X- Ray Analytical Facility, Mr Tony Raftery and Mr Lambert Bekessy The Queensland University of Technology (QUT) Faculty of Science is acknowledged for providing time off and funding for me to complete my research. iii Finally I would like to thank my wife Bach-Yen and my children Tien-Nam, Thuy- Tien and Dang- Khoa for their understanding, patience, assistance and supporting me during the time of study. iv The work contained in this thesis has not been previously submitted for a degree or diploma at any other tertiary educational institution. To the best of my knowledge and belief, the thesis contains no material previously published or written by another person except where due reference is made. __________________________Signed ________________Date v Abstract This thesis is submitted in a format of published papers by the candidate. Advanced methods of electron microscopy and X-ray spectroscopy have been used to study the relationship between the pillars and the silicate structure ranging from Al13 and Ga13 complexes to the final products Al- and Ga-pillared clays. The Al13 and Ga13 pillared montmorillonites have been prepared by conventional and ultrasonic methods. The ultrasonic method has been proven to be effective and showed very good catalytically activity. Transmission electron microscopy combined with elemental mapping by EDS showed the distribution of the Ga and Al pillars in the clay structure. The use of gallium allowed the independent observation of the Ga pillar distribution from the Al distribution in the clay structure. XPS spectra of the Ga13 pillared montmorillonites showed that the pillars has been changed from the original Keggin structure with a 7+ charge to something more stable with a lower charge upon intercalation. No direct evidence of the inverted silicon tetrahedron structure bonding to the pillar structure, as suggested by Plee in his original thesis, was observed. For comparative reasons the major aluminium hydroxide minerals in bauxite (gibbsite, bayerite and (pseudo-) boehmite) were studied. Detailed information about the Al13 structure was obtained by studying the basic sulphate and nitrate salts with XPS. The XPS results of a set of starting clays in comparison to the pillared clays indicated that small changes in the binding energy could explain the changes in the pillar structure and the formation of chemical bonds to the clay tetrahedral sheets during the calcination leading to the final products. vi LIST OF PUBLICATIONS DERIVED FROM THIS RESEARCH 1. Duong, L.V., Wood, B.J. and Kloprogge, J.T. (2005). XPS study of basic aluminium sulphate and basic aluminium nitrate. Materials Letters, 59 (14/15), 1932-1936. 2. Duong, L., Bostrom, T., Kloprogge, T. and Frost, R., (2005). The distribution of Ga in Ga- pillared montmorillonites: a transmission electron microscopy and microanalysis study. Microporous and Mesoporous Materials, 82, 165-172. 3. Duong, L.V., Kloprogge, J.T., Frost, R.L. and van Veen, J.A.R. (2007) An improved route for the synthesis of Al13-pillared montmorillonite catalysts. Journal of Porous Materials 14(1), 71-79 4. Kloprogge, J.T., Duong, L.V., Wood, B.J. and Frost, R.L. (2005) X-ray photoelectron spectroscopic study of the major minerals in bauxite: gibbsite, bayerite and (pseudo-) boehmite. Journal of Colloid and Interface Science, 296, 572-576. 5. He, H., Zhou, Q., Frost, R.L., Wood, B.J., Duong, L.V., and Kloprogge, J.T. (2007) A X- ray photoelectron spectroscopy study of HDTMAB distribution in organoclays. Spectrochimica Acta A, 66, 1180-1188. 6. Kloprogge, J.T., Duong, L.V. and Frost, R.L. (2005). A review of the synthesis and characterization of pillared clays and related porous materials for cracking of vegetable oil to produce biofuels. Environmental Geology, 47(7), 967-981 7. Kloprogge, J.T., Xi, Y., Duong, L.V. and Frost, R.L. (2005) High-resolution X-ray photoelectron spectroscopy of alkyl ammonium intercalated montmorillonites. 13th International Clay Conference, Tokyo, Japan, August 21-27, 113. 8. Kloprogge, J.T., Duong, L.V. and Frost, R.L. (2005). High-resolution XPS of boehmite: What is the difference between boehmite and pseudoboehmite? 13th International Clay Conference, Tokyo, Japan, August 21-27, 93. 9. Duong, L.V., Kloprogge, J.T., Frost, R.L. and Wood, B.J. (2005) The structure of Al13 and th Ga13 pillars in pillared montmorillonites. 13 International Clay Conference, Tokyo, Japan, August 21-27, 77. vii LIST OF PUBLICATIONS RELATED TO THIS RESEARCH 1. Frost, R. L., W. N. Martens, Duong, L., Kloprogge, J. T. (2002). Evidence for molecular assembly in hydrotalcites. Journal of Materials Science Letters 21(16): 1237-1239. 2. He, H., R. L. Frost, Bostrom, T.,Yuan P., Duong L.,Yang .D., Xi Y. Kloprogge T. (2006). Changes in the morphology of organoclays with HDTMA+ surfactant loading. Applied Clay Science 31(3-4): 262-271. 3. Kloprogge, J.T., Duong, L.V., Frost, R.L. and Wood, B.J. (2008) Baseline studies of the Clay Minerals Society Source Clays: X-ray photoelectron spectroscopy. Clays and Clay Minerals, submitted. 4. Kloprogge, J.T., Duong, L.V., Martens, W.N., van der Eerden, A.J.M. and Frost, R.L. (2007) Mid- and Near-Infrared transmittance spectroscopy of hydrothermally synthesised 2:1 phyllosilicates in the system Na2O-Al2O3-SiO2-H2O. In Progress in Solid State Chemistry Research (ed. Buckley R.W.), Chapter 7, 285-300. 5. Kloprogge, T., Duong L., Frost, R., Bostrom, T. (2005). Environmental SEM: Application Of Low Voltage Sem, Heating Stage Sem And Variable Relative Humidity Sem To Study Uncoated Minerals. Microscopy and Analysis(July):17-17. 17. 6. Kloprogge, J.T., Broekmans, M., Duong, L.V., Martens, W.N., Hickey, L. and Frost, R.L. (2006) Low temperature synthesis and characterisation of lecontite, (NH4)Na(SO4).2H2O. Journal of Materials Science, 41, 3535- 3529. 7. Ruan, H. D., R. L. Frost, Kloprogge, J. T., Duong, L., Schulze, D. G. (2001). Photo acoustic spectroscopy of kaolinite and gibbsite surfaces. 12th ICC, 22-28July 2001, Bahia Blanca. Argentina. 171. 8. Ruan, H. D., R. L. Frost, Kloprogge, J. T., Schulze, D. G., Duong, L. (2001). FT-Raman spectroscopy and SEM of gibbsite, bayerite, boehmite and diaspore in relation to the characterization of bauxite. The 12th International Clay Conference, 22-28 July 2001, Bahia Blanca, Argentina. 184. 9. Ruan, H. D., R. L. Frost, Kloprogge, J. T., Duong, L. (2002). Infrared spectroscopy of goethite dehydroxylation: III. FT-IR microscopy of in situ study of the thermal transformation of goethite to hematite. Spectrochimica Acta, Part A:Molecular and Biomolecular Spectroscopy 58(5): 967-981. 10. Ruan, H. D., R. L. Frost, Kloprogge, J. T., Duong L. (2002). Far Infared Spectroscopy of Alumina phases. Spectrochim. Acta, Part A 58A (1): 265-272. viii 11. Ruan, H. D., R. L. Frost, Kloprogge,T., Duong, L (2002). Infrared spectroscopy of goethite dehydroxylation. II Effect of aluminium substitution on the behaviour of hydroxyl units. Spectrochimica Acta 58: 479-491. ix TABLE OF CONTENTS Acknowledgments ………………………………………...……………………………..iv Abstract ………………………..………………………………………...…….…………vi List of publication derived from this research …………………….………….................vii List of publication related to this research ……………………………………...………viii Table of contents ……………………………………………….………………………....x List of tables ………………………………………………………………..…………....xv List of figures ……………………………………………………………...……......….xvii CHAPTER 1 .................................................................................................................. 1 LITERATURE REVIEW ON CLAY MINERALOGY, PILLARED CLAY AND TECHNIQUES USED FOR STUDYING PILLARED CLAYS 1.1 Introduction ...................................................................................................... 1 1.2 Clay Mineralogy .............................................................................................. .2 1.2.1 The basic structure of clay minerals ..................................................... 2 1.2.1.1 The tetrahedral sheet ……………………....……………. .3 1.2.1.2