SYNTHESIS OF PURE AND TRANSITION METALS (TM=Mn, Co) DOPED ZnO NANOPARTICLES AND THEIR PHOTOCATALYTIC, ANTIBACTERIAL AND ETHANOL SENSING APPLICATIONS

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1 SYNTHESIS OF PURE AND TRANSITION METALS (TM=Mn, Co) DOPED ZnO NANOPARTICLES AND THEIR PHOTOCATALYTIC, ANTIBACTERIAL AND ETHANOL SENSING APPLICATIONS A thesis submitted to the Bharathiar University Coimbatore in partial fulfillment of the requirements for the award of the Degree of DOCTOR OF PHILOSOPHY IN PHYSICS Submitted by M.NIRMALA M.Sc.,M.Phil. Under the Guidance of Dr.A.ANU KALIANI M.Sc.,MPhil.,Ph.D. DEPARTMENT OF PHYSICS KONGUNADU ARTS AND SCIENCE COLLEGE COIMBATORE, TAMILNADU INDIA OCTOBER 2011

2 ACKNOWLEDGEMENT This project itself is an acknowledgement to the inspiration, drive and assistance contributed to it by many individuals. This project would have never seen the light of this day without the help and guidance I received. I am indebted greatly to many personalities for successful completion of this work. I specially want to thank my guide Dr. A.Anu Kaliani, M.Sc., M.Phil., Ph.D., Assistant Professor in Physics, Kongunadu Arts and Science College, Coimbatore for her constant encouragement, inspiration and valuable suggestions in accomplishing this work. In addition, she was always accessible and willing to help her students with their research. Her wide knowledge and her logical way of thinking have been of great value for me. Her understanding, encouraging and personal guidance have provided a good basis for the present thesis. As a result, research life became smooth and rewarding for me. One simply could not wish for a better or friendlier supervisor. I am extremely thankful to Dr. R.Sathyamoorthy, M.Sc., M.Phil., Ph.D., Associate Professor & Head of the Department of Physics, Kongunadu Arts and Science College, for providing all facilities and encouragement throughout the project. I am extremely thankful to Dr. A. Subbarayan, M.Sc., M.Phil., Ph.D., Dip. Ed., Former Head of the Department of Physics, Kongunadu Arts and Science College, for providing all facilities and encouragement throughout the project. I submit my earnest thanks to our Secretary and Director Dr. M. Aruchami, M.Sc., BT, Ph.D., FAZ., FRESc (Lond.) and our Principal, Dr.R.Devi, M.Sc., M.Phil Ph.D., Kongunadu Arts and Science College, Coimbatore for providing all facilities for the present investigation. I would like to thank Dr. S. Ravisankar, M.Sc., Ph.D.,

3 DipPO, RBA in ABI, Dean, R&D, Kongunadu Arts and Science College, Coimbatore for his care and support. I would like to thank with pleasure all the Teaching and Non-Teaching Staff members of Physics Department, Kongunadu Arts and Science College, Coimbatore for their care and support. My special thanks to Dr. K. Muthukumar, MA,Ph.D, Laboratory Assistant, Kongunadu Arts and Science College, Coimbatore for his timely assistance in the laboratory works to complete this project successfully. For the generous assistance in the research, I would like to acknowledge the Iron Arc Private Ltd., Coimbatore, who provided facilities for preparing samples by DC thermal plasma method. I am greatly thankful to Dr. Sushil Kumar Kansal, Reader, University Institute of Chemical Engg. & Technology (Formerly Department of Chemical Engg. & Technology) Punjab University, Chandigarh , India, for doing photocatalytic analysis. I transmit my intense thanks and sincere gratitude to Prof. S.K. Samdarshi, Head Dept of Energy, Tezpur University, Assam, for volunteering his time in analyzing the photocatalytic study. I am extremely thankful to Dr. R. Kalaiselvan, Assistant professor, Bharathiar University, Coimbatore for doing pellets of my samples. I wish to express my profound thanks to Dr.C. Sanjeeviraja, Professor & Head, Department of Physics, Alagappa University, Karaikudi for helping me to carry out the sensor measurement. I also like to acknowledge my indebtedness to Dr.K. Saravanakumar M.Sc., Ph.D., Assistant Professor in Physics, Kongunadu Arts and Science College, Coimbatore, for the valuable suggestions. I wish to express my profound thanks to Mr.S.Rajendran, Laboratory Assistant, Poultech Agro Research Centre, Namakkal, for his valuable help to carry out the antimicrobial study.

4 I would also like to thank my colleagues in my research group, Mr. S. Inbakumar, Mr.T.Abdul kareem, Dr.P.Anuradha, Mrs.R.Ramalakshmi, for the useful discussions and assistance throughout my work. I owe an incalculable debt to Manjula G.Nair, K.Rekha, P.Smitha, M.Phil Research Scholars, Department of Physics, Kongunadu Arts and Science College for their valuable and timely help to complete this project successfully. I sincerely thank Mr.P.Matheswaran, Mrs. B. Kavitha, Mrs. L.Kungumadevi, R.Saravanakumar, B.Maheswari, K.M.Abirami, B.Gokul, S.Sathish, K.Maheswari, Research Scholars, Department of Physics, Kongunadu Arts and Science College, Coimbatore for their support to bring out this project a successful one. I record my deep sense of gratitude to my friends and well wishers for their everlasting love, wishes, blessings and care towards me in each and every moment of all steps of my life. Finally, I would like to thank my beloved parents for their love, undying support and encouragement which have always been the bedrock upon which every worthwhile achievement in my life has been built. Through every hardship or triumph they have been behind me in every step of the way and this work is a direct result. Last but not least, thanks be to God for my life through all tests in the past three years. May your name be exalted, honored and glorified. M.Nirmala

5 LIST OF PUBLICATIONS Significant publication Top 25 Hottest Articles - Physica B: Condensed Matter K.Rekha, M.Nirmala, Manjula G.Nair, A.Anu kaliani, Structural, Optical, Photo catalytic and antibacterial activity of zinc oxide and manganese doped zinc oxide nanoparticles Physica B, 405(2010) July to September rd position in the Top 25 hottest articles January to March th position in the Top 25 hottest articles International Journals 1. K. Rekha, M.Nirmala, Manjula G.Nair, A.Anu kaliani, Structural, Optical, Photo catalytic and antibacterial activity of zinc oxide and manganese doped zinc oxide nanoparticles Physica B, 405(2010) M.Nirmala and A. Anu kaliani, Characterization of undoped and Co doped ZnO nano particles synthesized by DC thermal plasma method, Physica B, 406(2011) M.Nirmala and A.Anu kaliani, Structural and optical properties of Co doped and undoped ZnO nano crystalline thin films, Suranaree Journal of Science and Technology, 18(1) (2011) M.Nirmala and A.Anu kaliani, Structural and optical properties of undoped and Mn doped ZnO nano crystalline thin film, Photonics letters of Poland, Vol 2(4) (2010)

6 5. M. Nirmala, Manjula G Nair, K. Rekha, A. Anukaliani, S.K. Samdarshi, Ranjith G Nair, Photo catalytic activity of ZnO nanopowders synthesized by DC thermal plasma, African Journal of Basic and Applied Sciences 2(5-6) (2010) Manjula G Nair, M. Nirmala, K. Rekha, A.Anukaliani, Structural, optical, photo catalytic and antibacterial activity of ZnO and Co doped ZnO nanoparticles, Materials letters, 65(2011) M.Nirmala and A.Anu kaliani, Synthesis and characterization of undoped and Tm (Co, Mn) doped ZnO nanoparticles. Materials letters 65(2011) M.Nirmala, P.Smitha, A.Anu kaliani, Optical and electrical properties of undoped and (Mn, Co) co-doped ZnO nanoparticles synthesized by DC thermal plasma method, Superlattices and Microstructures, 50(2011) Articles communicated 1. M.Nirmala and A.Anu kaliani, Structural and optical properties of transition metals (Mn, Co) doped and Undoped ZnO nano crystalline thin films, Songklanakarin Journal of Science and Technology, M.Nirmala and A.Anu kaliani, Characterization of undoped and Mn doped ZnO nanoparticles synthesized by DC thermal plasma method, Arabian Journal of Chemistry M.Nirmala, Manjula G.Nair, K.Rekha, A.Anu kaliani, Structural, Optical, Photo catalytic and antibacterial activity of pure and transition metals doped zinc oxide nanoparticles. Journal of Molecular Catalysis A: Chemical, 2011.

7 4. M.Nirmala and A.Anu kaliani, Annealing effects on undoped and Co doped ZnO pellets synthesized by DC thermal plasma method, Current Applied Physics, M.Nirmala and A.Anu kaliani, Antibacterial activity of pure and Transition metals (TM=Mn, Co) doped ZnO nanoparticles synthesized by chemical and plasma assisted methods, Applied Surface Science, M.Nirmala, A.Anu kaliani, C.Sanjeeviraja, Fabrication of ethanol sensor based on pure and (Mn, Co) co-doped ZnO nanoparticles synthesized by DC thermal plasma method, Sensors and Actuators B, 2011.

8 ABSTRACT In the present work, pure ZnO nanoparticles were prepared by co-precipitation and dc thermal plasma methods. Dopants such as Mn and Co were doped separately and doped ZnO nanoparticles were prepared by both co-precipitation and dc thermal plasma methods and their characterizations are studied. Dopants Mn and Co together were doped and co-doped ZnO nanoparticles were prepared by using both co-precipitation and dc thermal plasma methods and their characterizations are also studied. Additionally photo catalytic, antibacterial activity and ethanol sensing applications of pure and TM (Mn,Co) doped ZnO nanoparticles were investigated. From the above studies it was concluded that TM (Co, Mn) doped ZnO nanoparticles prepared by co-precipitation method and dc thermal plasma methods may be used as promising material for biomedical, UV blocking agent, waste water treatment and ethanol sensing applications.