THAI NGUYEN UNIVERSITY UNIVERSITY OF AGRICULTURE AND FORESTRY NGUYEN THUY TRANG APPLICATION OF TITANATE NANOTUBES-SILICON DIOXIDE (TNT@SiO2) NANOCOMPOSITE FOR THE ADSORPTION HEAVY METAL (COPPER (II) ION) IN AQUEOUS SOLUTION BACHELOR THESIS Study Mode: Full-time Major: Environmental Science and Management Faculty: International Training and Development Center Batch: 2012-2016 Thai Nguyen, 20/07/2016 Thai Nguyen University of Agriculture and Forestry Degree Program Bachelor of Environmental Science and Management Student name Nguyen Thuy Trang Student ID DTN1253060015 Thesis Title Application of Titanate nanotubes-Silicon dioxide (TNT@SiO2) nanocomposite for the adsorption heavy metal (Copper (II) ion) in aqueous solution Supervisor(s) Prof Dr Ruey- an Doong- National Tsing Hua University, Taiwan Assoc Prof Dr Tran Thi Thu Ha- Thai Nguyen University of Agriculture and Forestry, Vietnam Abstract: The objective of this study was to fabricate TNT@SiO2 nanocomposite material with specific surface areas, pore structure for the adsorption heavy metal- Cu(II) ion in aqueous solution With a large amount of SiO2 was contained in waste display panel glass combined with TiO2 have the unique morphology, strong oxidative properties, low cost, non-toxicity, chemical and thermal stability through a hydrothermal method The morphology changed when mixing SiO2 with TiO2 and then the TNT surface area improved, -O-Ti-O-Si- linkage is formed In addition, TNT@SiO2 nanocomposite is an effective adsorbent heavy metal in aqueous solution The results demonstrated that 100% Cu(II) ion is absorbed by TNT@SiO2 nanocomposite and separated out of aqueous solution within 30 minutes reaction Results obtained in this study clearly show TNT@SiO2 nanocomposite is successful i for the adsorption heavy metals ion in solution Keywords TNT@SiO2 nanocomposite , hydrothermal method, adsorption, heavy metal, Cu(II) ion Number of pages 56 Date of submission 30th August, 2016 Supervisor’s signature ii ACKNOWLEAGEMENT Firstly, I would like to say thanks to the cooperation between Thai Nguyen University of Agriculture and Forestry and National Tsing Hua University for providing me an amazing opportunity to internship in Taiwan It brings me great pleasure to work and submit my thesis for graduation I would like to express my deeply gratitude to Prof Dr Ruey- an Doong whose guidance, encouragement, suggestion and very constructive criticism have contributed immensely to the evolution of my ideas during the project Without his guidance, I may not have this thesis I sincerely thanks to Assoc Prof Dr Tran Thi Thu Ha for her advices, assistance, sharing experiences before and after I went to Taiwan, helping me to understand and complete proposal and thesis I am also thankful to Mr Nguyen Thanh Binh (PhD) and Ms Khuat Thi Thanh Huyen for teaching me the synthesis of nanotubes and various other techniques and methods used in environmental field They were very helpful in providing me constructive feedback and suggestions on my project and helping me to successful complete several of my experiments and report Without them help and devotion, I would not be able to reach this stage I am really fortunate to be in Prof Dr Ruey- an Doong’s lab Thanks to all the members in Professor Doong’s laboratory who hearty help me a lot when I work in there iii I also thank to my family for providing me emotional, unceasing encouragement and physical and financial support At last, I would like to thank all those other persons who helped me in completing this report Because of my lack knowledge, the mistake is inevitable, I am very grateful if I receive the comments and opinions from teachers and others to contribute my report Sincerely, Nguyen Thuy Trang iv TABLE OF CONTENT LIST OF FIGURES LIST OF TABLES LIST OF ABBREVIATIONS PART I INTRODUCTION 1.1 Research rationale: 1.2 Research’s objectives 1.3 Research questions 1.4 Limitations PART II LITERATURE REVIEW 2.1 Heavy metals 2.1.1.Definition and sources of heavy metals: 2.1.2.Characteristics of heavy metals: 2.1.3.Heavy metals pollution in the world and Vietnam 2.1.3.1 Heavy metals pollution in the soil 2.1.3.2 Heavy metals pollution in coastal, marine environment 2.1.4.Effecting of heavy metals to environment and human’s health 10 2.1.5.The characteristics and health effects of Copper 12 2.1.6.Method for treament heavy metals in aqueous solutions 13 2.2 Nanomaterials: 13 2.2.1.Titanate nanotubes ( TNT) : 15 2.2.1.1 Overview of Titanium dioxide: 15 2.2.1.1.1.Titanium oxidation structures and properties: 15 2.2.1.1.2.Titanate nanotubes(TNT) 16 2.2.2.Overview of SiO2: 17 2.2.3.Overview of nanocomposite 18 2.2.3.1 Definition and characteristics of nanocomposite 18 2.2.3.2 SiO2@TNT nanocomposite 19 PART III MATERIALS AND METHODS 20 3.1 Materials 20 3.2 Methods: 22 3.2.1.The synthesis of TNT: 22 3.2.2.The synthesis of TNT@SiO2 nanocomposite 23 3.2.3.Adsorption experiment: 23 v 3.2.4.The methods for determining the characteristics of materials 24 3.2.4.1 X-ray Diffraction ( XRD) 25 3.2.4.2 Scanning Electron Microscopy ( SEM) 26 3.2.4.3 Transmission Electron Microscopy ( TEM) 28 3.2.4.4 Fourier transform infrared spectroscopy ( FTIR) 29 3.2.4.5 Zeta potential (ZP) 30 3.2.4.6 Atomic absorption spectroscopy 32 PART IV RESULTS 33 4.1 The X-ray diffraction of TNT, SiO2 and SiO2@TNT composite 33 4.2 Morphology of TNT, SiO2 and TNT@SiO2 composite 34 4.3 Fourier transform infrared (FTIR) spectrum of SiO2, the synthesis TNT and TNT@SiO2 37 4.4 Zeta potential 38 4.5 Application of TNT@SiO2 for the adsorption Cu(II) ion 39 PART V DISCUSSION AND CONCLUSION 41 5.1 Discussion 41 5.2 Conclusion 42 REFERENCES 43 vi LIST OF FIGURES Figure 2.2.1.1.1: Crystal structure of the three forms of titanium dioxide 15 Figure 2.2.2 : Crystal structure of SiO2 17 Figure 3.1.2: Some instruments used for this study 21 Figure 3.2.1: Schematic of the synthesis TNT 22 Figure 3.2.2: Schematic of the synthesis TNT@SiO2 23 Figure 3.2.3 : The samples of Cu(II) ion (10mg/L) and TNT@SiO2 of the adsorption experiment at pH=5 in the different times 24 Figure 3.2.4.1: Schematics of X-ray diffractometer technique used for crystal structure analysis 26 Figure 3.2.4.2: Schematic diagram of SEM 28 Figure 3.2.4.3: Schematic diagram of TEM 29 Figure 3.2.4.5: The effect of pH on Zeta potential 31 Figure 3.2.4.6: Schematic of an atomic-absorption experiment 32 Figure 4.1: XRD patterns of TNT, SiO2 and SiO2@TNT composite 33 Figure 4.2 A: SEM images of the synthesis TNT(a) and TNT@SiO2 composite (b) 34 Figure 4.2 B: TEM images of SiO2, the synthesis TNT and TNT@SiO2 composite 36 Figure 4.3: FTIR spectrum of SiO2, the synthesis TNT and TNT@SiO2 37 Figure 4.4: The effect of pH to zeta potential of SiO2@TNT 38 Figure 4.5: The adsorption Cu (II) ion (10mg/L) by TNT@ SiO2 at pH=5 in aqueous solution at room temperature 39 LIST OF TABLES Table 3.1.1: Sources of chemical materials 20 LIST OF ABBREVIATIONS TNT TiO2/ Titanate nanotubes SiO2@TNT or SiO2 + TiO2 nano composite TNT@SiO2 TiO2 + SiO2 nano composite XRD X-Ray Diffraction SEM Scanning Electron Microscopy TEM Transmission Electron Microscopy FTIR Fourier transform infrared spectroscopy ZP Zeta Potential AAS Atomic absorption spectroscopy PART IV RESULTS 4.1 The X-ray diffraction of TNT, SiO2 and SiO2@TNT composite The XRD results for the crystal structures of TNT, SiO2 and SiO2@TNT composite were shown in Figure 4.1 as below SiO2@TNT SiO2 Intensity (a.u.) TNT 20 40 60 80 2θ (degree) Figure 4.1: XRD patterns of TNT, SiO2 and SiO2@TNT composite Figure 12 shows the XRD pattern of the TNT, SiO2 and SiO2@TNT nanocomposite obtained by the hydrothermal method It reveals that as-synthesized SiO2@TNT nanocomposite has crystalline anatase phase mixed with amorphous silica matrix The XDR pattern of SiO2@TNT nanocomposite showed the diffraction peaks indicating crystalline phase over the amorphous background The crystalline phase was indexed in the light of available XRD data for TiO2 crystal structure and the diffraction peaks of XRD could be assigned to anatase structure of TiO2 at about the 2θ = 25.4 and 48.50 The presence amorphous silica appeared in the XRD pattern as a 33 large band at around 20-300 The crystalline nature became prominent with increase the content of TiO2 in the SiO2@TNT composite From the XRD investigations, we could confirm that nano composite of SiO2 and TiO2 is formed 4.2 Morphology of TNT, SiO2 and TNT@SiO2 composite Figure 4.2 A, 4.2 B were shown the SEM and TEM images of SiO2,TNT and TNT@SiO2 composite The SEM image of TNT was presented in figure 4.2 A ( a) which clearly titanate nanotubes are formed, the nanotube is found to be predominant in the sample After the successful fabrication of TNT nanomaterials, the synthesized of TNT@SiO2 through an alkaline hydrothermal treatment have been illustrated the morphology in figure 4.2 A (b) Further observation indicates that silica nanoparticles presented on the surface of the titanate nanotubes It also seen that the average diameter of the tubes increases The distribution of the tubes become less uniform due to the mixing between silica particles and titanate nanotubes made TNT@SiO2 composite has a rough surface a b Figure 4.2 A : SEM images of the synthesis TNT (a) and TNT@SiO2 composite (b) 34 The TEM micrographs of TNT, SiO2, TNT@SiO2 composite are shown in figure 4.2 B (a,b,c,d,e) TEM images Figure 4.2 B (a,b), reveals the presence of silica nanoparticles and titanate nanotubes, respectively And the characteristics of TNT@SiO2 composite were further examined and showed in figure 4.2 B (c,d,e) It was observed that silica nanoparticles were distributed in wide area on titanate nanotubes, in where the silica interacted with the nanotube via oxygen atoms, and formed -Ti-O-Si-O- linkage to enhance the pore structure and surface area of nanomaterial The TEM images illustrate the good dispersion of silica nanoparticles on the nanotubes As shown in the TEM images, the nanostructure is confirmed 35 SiO2 TNT a b TNT@SiO2 TNT@SiO2 c d TNT@SiO2 e Figure 4.2 B: TEM images of SiO2, the synthesis TNT and TNT@SiO2 composite 36 4.3 Fourier transform infrared (FTIR) spectrum of SiO2, the synthesis TNT and TNT@SiO2 Figure 4.3: FTIR spectrum of SiO2, the synthesis TNT and TNT@SiO2 Fourier transform infrared (FTIR) spectrum of as-synthesized TiO2 nanotubes is shown in Figure 4.3 It was absorbed that the strong band in the range of 950–500 cm−1 is associated with the characteristic vibrational modes of TiO2 This confirms that the TiO2 phase has been formed The IR spectrum of SiO2 depicted in this figure 4.3 shows the characteristic adsorption bands of silicon dioxide, the Si–O–Si asymmetric and symmetric stretching vibration at 1,100 and almost 800 cm−1, respectively, and the O–Si–O symmetric bending vibration at about 500 cm−1 The absorption bands at 3,420 and 1,400 cm−1 were due to the presence of O–H stretching and bending vibrations, respectively 37 Fourier transform infrared (FTIR) spectrum of as-synthesized of TNT@SiO2 nanocomposite is also shown in this figure 4.3 The band observed at 923 cm−1 is associated with Si–O–Ti vibration The two strong bands at 1,100 and 800 cm−1 observed are associated with asymmetric and symmetric Si–O–Si stretching vibration, respectively The strong bands in the range 950–500 cm−1 are associated with vibrational modes of TiO2 The absorption bands at around 3,500 and 1,400 cm−1 were due to the presence of O–H stretching and bending vibrations, respectively 4.4 Zeta potential 40 30 SiO2@TNT Zeta potential (mV) 20 10 -10 -20 -30 -40 10 pH Figure 4.4: The effect of pH to zeta potential of SiO2@TNT It can be seen that if the zeta potential is possitive from about 33mV to mV belong to pH 1-5 However if the pH of the system has pH between and 10, the zeta potential is negative from to -28mV The zeta potential is about mV, pH reach to 38 around pH ~5 (the isoelectric point- IEP) in the pH range from to 11 At pH values less than 3, there is significant positive charge present In addition, at pH values greater than 8, there is significant negative charge present 4.5 Application of TNT@SiO2 for the adsorption Cu (II) ion The adsorption capacity Copper ion by TNT@SiO2 nano composite was examined 1.0 0.8 C/Co 0.6 0.4 0.2 0.0 20 40 60 Time (min) Figure 4.5: The adsorption Cu (II) ion (10mg/L) by TNT@ SiO2 at pH=5 in aqueous solution at room temperature There was a significant increase in the adsorption capacity Cu(II) ion by TNT@SiO2 nano composite at pH=5 in the different times The results presented in figure 4.5 above In the concentration 10ppm, at the beginning, 100% Cu(II) ion was contained in an aqueous solution In the first 15 minutes, the separation efficiency Cu(II) ion out of aqueous solution increased dramatically and reached to 90% But 15 39 minutes later, 100% Cu(II) ion was adsorbed by TNT@SiO2 nanocomposite in aqueous solution and did not show changes in the remaining 30 minutes It is clearly demonstrated that the synthesized TNT@SiO2 composite with high pore structure volume and high surface area, as well as surface functionality, that are very good for the adsorption capacity of heavy metal in aqueous solution 40 PART V DISCUSSION AND CONCLUSION 5.1 Discussion The study has developed TNT@SiO2 nano composite for the adsorption heavy metals-Cu(II) ion in aqueous solution A large amount of SiO2 was collected in waste display panel glass combined with TiO2 have the unique morphology, strong oxidative properties, low cost, non-toxicity, chemical and thermal stability The main advantages of this adsorption procedure include simplicity, cost effectiveness, rapidity, and higher separation efficiency heavy metals of TNT@SiO2 composite In the study, TNT and TNT@SiO2 were synthesized through an alkaline hydrothermal treatment, and their adsorption capacity was evaluated The characteristics of TNT, TNT@SiO2 nanocomposite were determined by XRD, TEM, SEM, FTIR, and AAS The variation of morphology of silica nano particles, titanate nanotubes and formation of – O-Ti-OSi- function group were thus determined with SEM, TEM and FTIR The presence of anatase phases in the TNT@SiO2 composite and the structural properties were confirmed by XRD The effect of pH on the zeta potential is investigated in TNT@SiO2 composite at pH~5 (IEP) The results demonstrated that TNT@SiO2 composite is an effective adsorbent heavy metal in aqueous solution 100% Cu(II) ion is absorbed by TNT@SiO2 nanocomposite and separated out of aqueous solution after 30 minutes reaction The synthesized TNT@SiO2 have an effective adsorption heavy metal with contributing of the pore structure and high surface area Thus, TNT@SiO2 is promising adsorption in the successful treatment other metals ion in aqueous solution The outstanding physicochemical properties of the TNT@SiO2 41 nanocomposite will play a very important role in environmental pollution management in the future 5.2 Conclusion In conclusion, nano composites have gained much interest recently Significant efforts are underway to control the nano structures via innovative synthetic approaches The successful combination of waste display panel glass which contains a large of SiO2 with TiO2 which has confirmed by the characteristics of nanotubes, the pore structure, the specific surface area and TNT@SiO2 nano composite was formed The synthesized TNT@SiO2 nanocomposite by hydrothermal method was 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Considering all aspects and issues mentioned above, I propose research: Application of Titanate nanotubes-Silicon dioxide (TNT@SiO2) nanocomposite for the adsorption heavy metal ( Copper (II) ion) in. .. dried in air drying oven at 50oC for 12 h 22 3.2.2 The synthesis of TNT@SiO2 nanocomposite Figure 3.2.2: Schematic of the synthesis TNT@SiO2 According to the synthesis of TNT, the TNT@SiO2 nanocomposite