Fabrication and Characterization of Novel Iron Oxide/ Alumina Nanomaterials for Environmental Applications
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FABRICATION AND CHARACTERIZATION OF NOVEL IRON OXIDE/ ALUMINA NANOMATERIALS FOR ENVIRONMENTAL APPLICATIONS Thesis submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy By Abhipsa Mahapatra Under the guidance of Dr. Garudadhwaj Hota & Dr. Braja Gopal Mishra DEPARTMENT OF CHEMISTRY NATIONAL INSTITUTE OF TECHNOLOGY, ROURKELA ROURKELA-769008, ODISHA, INDIA July 2013 i CERTIFICATE This is to certify that the thesis entitled “Fabrication and Characterization of Novel Iron Oxide/ Alumina Nanomaterials for Environmental Applications” being submitted by Abhipsa Mahapatra to the National Institute of Technology, Rourkela, India, for the award of the degree of Doctor of Philosophy is a record of bonafide research work carried out by her under my supervision and guidance. I am satisfied that the thesis has reached the standard fulfilling the requirements of the regulations relating to the nature of the degree. To the best of my knowledge, the matter embodied in the thesis has not been submitted to any other University / Institute for the award of any Degree or Diploma. Supervisor Place: Rourkela Dr. Garudadhawaj Hota, Date: Department of Chemistry, National Institute of Technology, Rourkela-769008 Co-Supervisor Dr. Braja Gopal Mishra Department of Chemistry National Institute of Technology Rourkela- 769008 ii Acknowledgement I take this opportunity to express my deep sense of gratitude and indebtedness to my research mentor Prof Garudadhawaj Hota, for providing his excellent guidance, support, encouragement, and inspiration throughout my doctoral work. It has been a great opportunity to work with him with his vast scientific knowledge and analytical approach. Many discussions I had with him have made me to think logically and have helped me to improve my knowledge. I greatly feel fortunate enough for his patience to assist me, which he devoted from his busy schedule. Without his expertise and guidance, this work would not have been accomplished. I am also very much thankful to his family members for their hospitality, love and encouragement during my stay. I would also like to acknowledge Prof. B.G. Mishra, my co-supervisor for providing his excellent technical support and valuable time, which helped me making this research work a success. I am thankful to all my Doctoral Scrutiny Committee members Prof. R. K. Patel, (Chairman DSC), Prof. M. Kundu, Prof. S. Mahapatra and Prof. A. Mondal for their valuable suggestions throughout my research career. I would also like to express my deep sense of gratitude to Head of the Chemistry Department, NIT Rourkela for allowing me to avail the facilities of the department. I wish to express my sincere thanks to Dr. K. M. Purohit (Ex-HOD), Prof S. Patel and Prof U. Subbudhi, Department of Chemistry, NIT, Rourkela for good suggestions and useful discussions during my research work. I am also very much thankful to Prof B. P. Nayak, Department of Biotechnology and Medical Engineering, NIT Rourkela, for carrying out the related biological work with the help of Nidhi Garg, his M.Tech student. I would like to thank all the faculty members and staff members, Department of Chemistry, NIT Rourkela for their constructive suggestions and inspirations. I convey my heartfelt thanks to Dr. S. K. Swain, BIT Mesra, for his support in characterization of samples. I am also grateful to Department of Chemical, Ceramic and iii Metallurgical Engineering, NIT Rourkela, for acquiring various characterization techniques presented in this thesis. I wish to thank my labmates Jyoti Prakash, Shabna, Tapaswini, Priyadarshini didi and Saswati Madam for their immense help, timeless effort and cooperation throughout my work in laboratory. My special thanks to T. Deepthi, Subhraseema and Nagachaitanya for their companionship, emotional support and entertainment, which helped me a lot to get through the difficult times during my work. My earnest thanks to my dear juniors and friends Prakash, Smruti Snigdha, Smruti Ranjan, Sandip, Vijayalaxmi, Sagarika didi and Biswajit Bhai for their unconditional love, affection and care during my stay. No words can convey my gratitude to my parents, for their constant inspiration and mental support, without which it would have never been possible for me to complete my thesis. My husband, Subodh K. Panigrahi, was a gem in the ring for being more friend than family and providing absolutely necessary inputs in every little bit of time. I must thank my elder sisters, Archana nani and Amrita nani who have stood beside me in every trajectory of my life and made it pretty exciting and lovely. My immense thanks are due to the members of my in-laws’ family for their love, blessing and good wishes. I would like to add a special note of thanks for my grandfather Dr B. Mahapatra for his motivation in carrying out the research work. July 2013 Abhipsa Mahapatra iv CONTENT CERTIFICATE ii ACKNOWLEDGEMENTS iii CONTENTS v LIST OF TABLES xi LIST OF FIGURES xvi ABBREVIATIONS xvii NOTATIONS xviii ABSTRACT xix CHAPTER 1- INTRODUCTION 01 1. Introduction to nanomaterials 01 1.1 Nanofibers/nanowires 02 1.2 Composite nanomaterials 04 1.3 Methods of preparation of nanomaterials 04 1.3.1 Physical methods 04 1.3.1.1 Laser ablation method 04 1.3.1.2 Inert gas condensation 05 1.3.1.3 High energy ball milling 05 1.3.1.4 Chemical vapour deposition 06 1.3.1.5 Electro-deposition method 06 1.3.2 Chemical methods 07 1.3.2.1 Hydrothermal method 07 v 1.3.2.2 Sol-gel method 08 1.3.2.3 Sonochemical method 09 1.3.2.4 Co-precipitation method 09 1.3.2.5 Electrospinning method 10 1.4 Importance of alumina and iron oxide nanomaterials 11 1.4.1 Alumina 11 1.4.2 Iron oxide 12 1.5 Application of nanomaterials 13 1.5.1 Chemical applications 14 1.5.2 Optical and Electronic applications 15 1.5.3 Magnetic applications 15 1.5.4 Metal and Ceramics applications 16 1.5.5 Biological applications 17 1.5.6 Environmental applications 18 1.6 Objective of this study 20 1.7 Organization of the thesis 20 CHAPTER 2 LITERATURE REVIEW 21 2.1. Sol-gel method 21 2.1.1 Iron oxide nanomaterial by sol gel method 22 2.1.2 Alumina nanomaterial by sol-gel method 23 2.1.3 Mixed metal oxide nanocomposite by sol gel method 26 2.2. Hydrothermal method 29 2.2.1 Iron oxide nanomaterials by hydrothermal method 29 2.2.2 Alumina nanomaterials by hydrothermal method 34 2.2.3 Mixed metal oxide nanocomposite by hydrothermal method 45 2.3. Electrospinning method 46 2.3.1 Iron oxide nanomaterial by electrospinning method 48 vi 2.3.2 Alumina nanomaterial by electrospinning method 52 2.3.3 Mixed metal oxide nanocomposite by electrospinning method 55 2.4. Characterization techniques 58 2.4.1 UV-Vis spectroscopy 58 2.4.2 Fourier transforms infrared spectroscopy 59 2.4.3 X-Ray Diffraction 59 2.4.4 Scanning electron microscope 61 2.4.5 Transmission electron microscopy 61 2.4.6 Brunauer, Emmett Teller (BET) 62 2.4.7 Thermogravimetric analysis (TGA-DTA) 63 2.4.8 Atomic absorption spectrometry (AAS) 65 2.5. Concluding remarks 66 CHAPTER 3 SOL-GEL MEDIATED SYNTHESIS OF BOEHMITE (ALOOH) 67 NANOMATERIALS FOR REMOVAL OF CONGO RED DYE FROM AQUEOUS SOLUTIONS 3.1 Introduction 67 3.2 Experimental section 69 3.2.1 Materials and methods 69 3.2.2 Characterizations techniques 69 3.2.3 Adsorption experiments 69 3.3 Results and discussion 70 3.3.1 Structural properties 70 3.3.2 Morphology 71 3.4 Adsorption studies 72 3.4.1 Effect of pH on adsorption of Congo red 72 3.4.2 Effect of contact time on adsorption of Congo red 73 3.4.3 Effect of adsorbent dosage on adsorption of Congo red 75 3.4.4 Effect of change in initial concentration on adsorption of Congo red dye 76 3.4.5 Adsorption isotherms 77 vii 3.4.6 Adsorption kinetics 79 3.5 Conclusions 80 CHAPTER 4 STUDIES ON ELECTROSPUN ALUMINA NANOFIBERS FOR 81 REMOVAL OF Cr (VI) & F- TOXIC IONS FROM AQUEOUS SYSTEM 4.1 Introduction 81 4.2 Experimental procedure 85 4.2.1 Materials 85 4.2.2 Fabrication of Alumina nanofibers 86 4.2.3 Adsorbent characterization techniques 86 4.2.4 Adsorption experiments 87 4.3 Results and discussion 88 4.4 Adsorption studies 94 4.4.1 Effect of pH on adsorption of Cr (VI) and fluoride ions 94 4.4.2 Effect of contact time on adsorption of Cr (VI) and fluoride ions 96 4.4.3 Adsorption kinetics study 96 4.4.4 Effect of initial concentration on adsorption of Cr (VI) and fluoride ions 98 4.4.5 Adsorption Isotherm study 99 4.4.6 Effect of adsorbent dosage on adsorption of Cr (VI) and fluoride ions 100 4.5 Conclusions 101 CHAPTER 5 SYNTHESIS OF MIXED Fe2O3-Al2O3 NANOCOMPOSITES 103 FOR ADSORPTIVE REMOVAL OF CONGO RED DYE 5.1 Introduction 103 5.2 Experimental procedure 105 5.2.1 Materials 105 5.2.2 Synthesis of Fe2O3 –Al2O3 nanocomposites 106 5.2.3 Characterization techniques 106 viii 5.2.4 Adsorption experiments for Congo red dye by batch process 106 5.3 Results and discussion 107 5.3.1 Structural properties 107 5.3.2 UV-Vis adsorption spectroscopy analysis 109 5.4 Adsorption study of Congo red by mixed nanocomposites 111 5.4.1 Effect of pH on adsorption of Congo red dye 112 5.4.2. Effect of contact time on adsorption study on Congo red dye 113 5.4.3. Effect of initial concentration on adsorption study of Congo red dye 114 5.4.4.