THAI NGUYEN UNIVERSITY UNIVERSITYOF AGRICULTURAL AND FORESTRY GIANG NAM KHÁNH TOPIC TITLE:USE CARBON NANOTUBES AND GRAPHENE OXIDE ABSORBED COPPER ION BACHELOR THESIS Study Mode : Full-time Major : Environmental Science And Management Faculty : International Training and Development Center Batch : 2010 - 2015 Thai Nguyen, 21/01/2015 ACKNOWLEDGMENT First of all, I would like to express sincere thanks to the school board Thai Nguyen University of Agriculture and Forestry, Faculty of International Training and Development; advanced program, thank the teachers who has imparted to me the knowledge and valuable experience during the process of learning and researching here In the process of implementing and completing thesis, I have received the enthusiastic help of the teachers of National Tsing Hua University I would like to express my special thanks to Prof Ruey An Doong who has spent a lot of time, created favorable conditions, enthusiastic to guide me to complete this thesis I sincerely thank my friends in the laboratory facilitated, and provided the information and data necessary for my implementation process and helped me finish this thesis In the process of implementing the project, due to time, financial and research levels of myself is limited so this project is inevitable shortcomings So, I would like to receive the attention and feedback from teachers and friends to this thesis is more complete I sincerely thank you! Taiwan, 2014 Students perform Giang Nam Khanh Table of Contents Abstract 1 INTRODUCTION 1.1 Rationale of study 1.2 Aim of the study 1.3 Research questions 1.4 Scope of the study LITERATURE REVIEW 2.1 Carbon nanotube (CNTs) 2.1.1 Structure of Carbon nanotubes Single-walled Multi-walled 2.1.2 Properties adsorption of Carbon Nanotubes (CNTs) 10 2.1.3 Applications of Carbon Nanotubes 13 2.2 Graphene oxide (GO) 15 2.2.1 Structure of Graphene oxide (GO) 15 2.2.2 Properties adsorption of Graphene oxide (GO) 19 2.2.3 Applications of Graphene oxide 21 2.3 Atomic Absorption Spectrometric machine (AAS) 23 MATERIALS AND METHODOLOGY 26 3.1 MATERIALS 26 3.1.1 Carbon nanotubes (CNTs) 26 3.1.2 Graphene oxide (GO) 27 3.1.3 Solution Cu2+ 29 3.2 METHODOLOGY 30 3.2.1 Carbon nanotubes (CNTs) 30 3.2.2 Graphene oxide (GO) 30 RESULTS AND DISCUSSION 32 4.1 RESULTS 32 4.1.1 Results of solution Cu2+ 32 4.1.2 Carbon nanotubes (CNTs) 33 4.1.3 Graphene oxide (GO) 36 4.2 Discussion 39 4.2.1 Carbon nanotubes (CNTs) 39 4.2.2 Graphene oxide (GO) 40 CONCLUSION 42 REFERENCES 43 LIST OF ABBREVIATIONS AAS Atomic Absorption Spectrometric AFM Atomic force microscopy CNTs Carbon nanotubes DSC Differential scanning calorimetry DWNTs Double-walled carbon nanotubes F-AAS Flame atomic absorption spectrometry FT-IR Infrared spectroscopy GO Graphene oxide MWNTs Multi-walled carbon nanotubes PZC Point of zero charge SWNTs Single-walled carbon nanotubes XRD X-ray diffraction XPS X-ray photoelectron spectroscopy RSD Relative standard deviation LIST OF TABLES Table 3.1 Stock solution……………… ……………………………………………… 30 Table 4.1 The volume of the stock solution based on the concentration of the final volume……………………………………………………………………………………32 Table 4.2 Concentration before add CNTs and GO………………………….……….…33 Table 4.3 The concentration after use Atomic Absorption Spectrometric of CNTs… …34 Table 4.4 The adsorption capacity q (mg/g CNTs) of CNTs ………………….……… 35 Table 4.5 The concentration after use Atomic Absorption Spectrometric of GO … …36 Table 4.6 The adsorption capacity q (mg/g CNTs) of GO… ………………….….…….38 LIST OF FIGURES Figure 2.1 The (n,m) nanotube naming scheme can be thought of as a vector (Ch) in an infinite graphene sheet that describes how to "roll up" the graphene sheet to make the nanotube T denotes the tube axis, and a1 and a2 are the unit vectors of graphene in real space ……………………………………………………………………… ……………8 Figure 2.2 Structure of the GO…………………………………………….…………….19 Figure 2.3 Diagram systems AAS Atomic Absorption………………………………….24 Figure 3.1 Heat to appropriate temperature (35oc) for 10 hour………………………….27 Figure 3.2 Rotary – Vacuum – Evaporate……………………………….………………28 Figure 4.1 Concentration adsorption of CNTs…………………… …………….…… 34 Figure 4.2 Adsorption capacity of CNTs.……………………………… ……… …… 36 Figure 4.3 Concentration adsorption of GO…………………………………… ….……37 Figure 4.4 Adsorption capacity of GO………………………………………… ……….38 ABSTRACT Thai Nguyen University of Agriculture and Forestry Degree Program Bachelor of Environmental Science and Management Student name Giang Nam Khanh Student ID DTN 1053180062 Thesis Title Adsorption of copper ions by carbon nanotubes and graphene oxides Supervisor (s) Prof Ruey An Doong Assoc.Prof Dam Xuan Van Abstract: Copper is an element with atomic number of 29 and is heavy metal ion in the water which is not only harmful to the environment but also human health The study using carbon nanotubes and graphene oxide nanomaterial to absorb copper oxide ion in water is absolutely necessary Prepare a quantity carbon nanotubes and graphene oxide required like in the calculation and clean them with as required of the experiment (pH, drying, and ensure it is unique) Prepare a solution containing Cu 2+ by means of synthetic compounds Cu(NO3)2 + H2O in tubes test at concentrations of was calculated from the previous To absorb Cu2+, we used direct absorption from the nanomaterials already used for solution into tubes test containing Cu2+ ion solution with different concentrations Then, apply the appropriate conditions for the best absorption After the appropriate time hour, hour, hour, we will absorb the sample to measure the concentration of Cu 2+ in solution by Atomic Absorption Spectrometric machine The last result of the absorption of the formula we use to calculate the adsorption capacity of the carbon nanotubes and graphene oxide Concluded: volume, solution concentration, time, conditions similar in laboratory, we identified graphene oxide Cu2+ ion absorption better than carbon nanotubes Keywords: Absorb, Atomic Absorption Spectrometric, Carbon nanotubes, Graphene oxide, Copper(II) Number of pages: 47 Date of Submision : INTRODUCTION 1.1 Rationale of study The 21st century is the reign of nanotechnology Nanotechnology has brought to the world many astonishing applications for life Scientists, industrialists and manufacturers always pay attention to every detail of the development of this technology, also the nature, characteristics and applications of it The new properties of nanotechnology are results of the reducing in the size of materials to nanometers; this changes the mechanism of quantum interference People often call this phenomenon is the size effect or the confinement effect As a result, nano-materials are used a lot in practice, becoming super hard, super durable, and superconductivity products Heavy metals in water have been a major preoccupation for many years because of their toxicity towards aquatic-life, human beings and the environment As they not degrade biologically like organic pollutants, their presence in drinking water or industrial effluents is a public health problem due to their absorption and therefore possible accumulation in organ-isms Several processes have been used and developed over the years to remove metal ions, such as chemical precipitation, reverse osmosis, electrolytic recovery, ion exchange or adsorption The latter has been studied for both mineral and organic materials (Bailey et al, 1999; Ricordel et al, 2001) Moreover, one of the important properties of solid matrices explored is related to the adsorption of trace elements taking preconcentration or separation into account, where from a complex mixture, a single concentrations in the sample analyzed Using methods Atomic Absorption Spectrometric we have concentration before as shown in Table 4.2 Table 4.2 Concentration before add CNTs and GO Tubes test Concentration before (mg/l) C1 0.359 C2 0.405 C3 0.488 C4 0.660 C5 0.972 4.1.2 Carbon nanotubes (CNTs) Using methods Atomic Absorption Spectrometric we have concentration after as shown in Table 4.3: 33 Table 4.3 The concentration after use Atomic Absorption Spectrometric of CNTs After(mg/l) Concentration Tubes test Before (mg/l) (mg/l) 120’ 240’ 360’ C1 0.359 0.315 0.291 0.285 C2 0.405 0.342 0.323 0.313 C3 0.488 0.406 0.389 0.386 C4 16 0.660 0.534 0.507 0.502 C5 32 0.972 0.763 0.733 0.722 From the data of Table 4.3 we charting software origin then we have Figure 4.1 concentration adsorption of CNTs: Figure 4.1 Concentration adsorption of CNTs 34 The adsorption capacity q (mg/g CNTs) were obtained as follows: q =[(Co −Cf)V/m]; where Co and Cf are the initial and final concentrations (mg/L)of metal ion in the aqueous solution, respectively V the volumeof metal ion solution m is the weight of CNTs What can be gained by using formulas adsorption capacity at q (mg / g CNTs) is shown in the Table 4.4: Table 4.4 The adsorption capacity q (mg/g CNTs) of CNTs q(mg/g CNTs) Tubes test 120’ 240’ 360’ C1 0.022 0.034 0.037 C2 0.0315 0.041 0.046 C3 0.041 0.0495 0.051 C4 0.063 0.0765 0.079 C5 0.1045 0.1195 0.125 From the data of Table 4.4 we charting software origin then we have Figure 4.2 adsorption capacity of CNTs: 35 Figure 4.2 Adsorption capacity of CNTs 4.1.3 Graphene oxide (GO) Using methods Atomic Absorption Spectrometric we have concentration after as shown in Table 4.5: Table 4.5 The concentration after use Atomic Absorption Spectrometric of GO Concentration After(mg/L) Before(mg/L) Tube test (mg/L) 120’ 240’ 360’ C1 0.359 0.295 0.276 0.262 C2 0.405 0.296 0.276 0.264 C3 0.488 0.300 0.290 0.289 C4 16 0.660 0.305 0.296 0.275 C5 32 0.972 0.306 0.296 0.275 36 From the data of Table 4.5 we charting software origin then we have Figure 4.3 concentration adsorption of GO: Figure 4.3 Concentration adsorption of GO The adsorption capacity q (mg/g GO) were obtained as follows: q =[(Co −Cf)V/m]; where Co and Cf are the initial and final concentrations (mg/l)of metal ion in the aqueous solution, respectively V the volumeof metal ion solution m is the weight of GO What can be gained by using formulas adsorption capacity at q (mg/g GO) is shown in the Table 4.6: 37 Table 4.6 The adsorption capacity q (mg/g CNTs) of GO q(mg/g SGO) Tube test 120’ 240’ 360’ C1 0.032 0.0415 0.0485 C2 0.0545 0.0645 0.0705 C3 0.094 0.099 0.0995 C4 0.1775 0.182 0.1925 C5 0.333 0.338 0.3385 From the data of Table 4.6 we charting software origin then we have Figure 4.4 adsorption capacity of GO: Figure 4.4 Adsorption capacity of GO 38 4.2 Discussion The adsorption capacity is an important factor because it determines how much sorbent is required for quantitative enrichment of the analyte from a given solution 4.2.1 Carbon nanotubes (CNTs) Results shows the adsorption isotherm of Cu2+ and at their initial concentration range of 0.359 - 0.972mg/l with oxidized CNTs Copper ions are more favorably adsorbed on CNTs and the adsorption capacity of Cu2+ attained 0.022 mg/g in tube test C1, 0.0315 mg/g in tube test C2, 0.041 mg/g in tube test C3, 0.063 mg/g in tube test C4 0.1045mg/g in tube test C5 at a equilibrium concentration after hour After hour, results shows the adsorption isotherm of Cu2+ and initial concentration copper ions are more slowly adsorbed on CNTs and the adsorption capacity of Cu2+ attained 0.034 mg/g in tube test C1, 0.041 mg/g in tube test C2, 0.0495 mg/g in tube test C3, 0.0765 mg/g in tube test C4, 0.1195 mg/g in tube test C5 at a equilibrium concentration after hour And after hour, results shows the adsorption isotherm of Cu2+ and initial concentration copper ions are more slowly adsorbed on CNTs and the adsorption capacity of Cu2+ attained 0.037 mg/g in tube test C1, 0.046 mg/g in tube test C2, 0.051 mg/g in tube test C3, 0.079 mg/g in tube test C4, 0.125 mg/g in tube test C5 at a equilibrium concentration after hour The experimental data for copper ion adsorption onto CNTs were analyzed using the Freundlich adsorption isotherm mode which is applicable to highly heterogeneous surfaces From the adsorption capacity we can know adsorption capacity the best after hour and adsorption capacity at more slowly after hour and hour 39 However, the performance of CNT is limited by its relatively low density of surface functional groups In addition, the high cost of CNT restricts its large-scale applications for wastewater treatment 4.2.2 Graphene oxide (GO) The results showed that the adsorption isotherm of Cu2+ and about their initial concentration of 0.359 - 0.972 mg/l with oxidized GO Copper ions are more favorable adsorption on GO and Cu2+ adsorption capacity reached 0032 mg/g in tube test C1, 0.0545 mg/g in tube test C2, 0094 mg/g in tube test C3, 0.1775 mg/g in tube test C4, 0333 mg/g C5 in tube test by equilibrium concentration after hours After hours, the results showed that the adsorption isotherm and Cu2+ ion concentration of the original contract did not change significantly adsorbed on GO and Cu2+ adsorption capacity reached 0.0415 mg/g in tube test C1, 0.0645 mg/g in tube test C2, 0099 mg/g in tube test C3, 0182 mg/g in tube test C4, 0338 mg/g in tube test C5 equilibrium concentration after hours And after hours, the results showed that the adsorption isotherm and Cu2+ ion concentration of the original contract did not change significantly adsorbed on GO and Cu2+ adsorption capacity reached 0.0485 mg/g in tube test C1, 0.0705 mg/g in tube test C2, 0.0995 mg/g in tube test C3, 0.1925 mg/g in tube test C4, 0.3385 mg/g in tube test C5 equilibrium concentration after hours The experimental data for copper ion adsorption onto GO were analyzed using the Freundlich adsorption isotherm mode which is applicable to highly heterogeneous surfaces From the adsorption capacity at we can know adsorption 40 capacity GO the good and almost no change when it was adsorbed to the equilibrium concentration 41 CONCLUSION Neutralized graphene oxide, GO, is as effective as GO in cation adsorption The maximum adsorption capacity of GO for copper ion was calculated using the adsorption model and was shown to be a function of equilibrium pH With an adsorption capacity of 0.0485 mg/g in tube test C1, 0.0705 mg/g in tube test C2, 0.0995 mg/g in tube test C3, 0.1925 mg/g in tube test C4, 0.3385 mg/g in tube test C5, after hour, GO surpasses the maximum adsorption capacity oxidized multi-walled carbon nanotubes 0.037 mg/g in tube test C1, 0.046 mg/g in tube test C2, 0.051 mg/g in tube test C3, 0.079 mg/g in tube test C4, 0.125 mg/g in tube test C5, after hour The results provided in this study support further investigation into the chemistry, the geometry and the application of GO for cation adsorption 42 REFERENCES Apalkov V.M and Chakraborty T (2006)., “ Fractional Quantum Hall States of Dirac Electrons in Graphene ” Bailey, S.E Olin, T.J Bricka , R.M Adrian, D.D (1999) A review of potentially low-cost sorbents for heavy metals Bolotin, K.I Ghahari, F Shulman, M.D Stormer, H.L Kim, P (2009) Graphene: Synthesis, Properties, and Phenomena , pp.462 Camel, V (2003) Review Solid phase extraction of trace elements, pp 1177–1233 Cassel, A.M Raymakers, J.A Kong, J Dai, H (1999) Large scale CVD synthesis of single-walled carbon nanotubes, pp 6484–6492 Chambers, A Park, C Baker, R.T.K Rodriguez, N (1998) Hydrogen storage in graphite nanofiber, pp 4253–4256 D.L Miller , K.D Kubista , G.M Rutter , M Ruan , W.A de Heer , P.N First , J.A (2009) Observing the Quantization of Zero Mass Carriers in Graphene Dai, H Rinzler, A.G Nikolaev, P Thess, A Col-bert, D.T Smalley, R.E (1996) Single-wall nanotubes produced by metal-catalysed disproportionation of carbon monoxide, pp.471–475 Dalton, Trans (2013) Adsorption of divalent metal ions from aqueous solutions using graphene oxide, pp.42 10 Du, X Skachko, I Duerr, F Luican, A Andrei, E.Y (2009) Raman Spectroscopy of Carbon Nanostructures in Strong Magnetic Field, pp.462 43 11 Farmer, D.B Chiu, H.Y Lin, Y.M Jenkins, K.A Xia, F Avouris, P (2009) Utilization of a buffered dielectric to achieve high field-effect carrier mobility in graphene transistors 12 Fujiwara, A Ishii, K Suematsu, H Kataura, H Maniwa, Y Suzuki, S Achiba, Y (2001) Gas adsorption in the inside and outside of single-walled carbon nanotubes, pp.205–211 13 Giraudet, J Dubois, M Claves, D Pinheiro, J.P Schouler, M.C Gadelle,P Hamwi, A (2003) Modifying the electronic properties of multi-wall carbon nanotubes via charge transfer, by chemical doping with some inorganic fluorides, pp 306–314 14 Gusynin, V.P Sharapov, S.G (2005) Condensed matter physics 15 Heer, W.A de Châtelain, A Ugarte, D (1995) A carbon nanotube field-emission electron source, pp.1179–1180 16 Heersche, H.B Jarillo-Herrero, P Oostinga, J.B L Vandersypen, M.K Morpurgo, A.F (2007) Bipolar supercurrent in graphene, pp.56 17 Hilding, J Grulke, E.A Sinnott, S.B Qian, D An-drews, R Jagtoyen, M (2001) Sorption of butane on carbon multiwall nanotubes at room temperature, pp.7540– 7544 18 Jiang, J Sandler , S.I (2003) Nitrogen adsorption on carbon nanotubes bundles: Role of the external surface, pp.68 44 19 Kitiyanan, B Alvarez, W.E Harwell, J.H Resasco, D.E (2000) Controlled production of single-wall carbon nanotubes by catalytic decomposition of CO on bimetallic Co-Mo catalysts, pp.497–503 20 Lei, Y Chen, F Luo, Y Zhang, L (2013) Synthesis of three -dimensional graphene oxide foam for the removal of heavy metal ions 21 Levendorf, M.P Ruiz-Vargas, C.S Garg, S Park, J (2009) Transfer-free batch fabrication of single layer graphene transistors 22 Li, D Müller, M B Gilje, S Kaner, R B Wallace, G G (2008) Processable aqueous dispersions of graphene nanosheets, Nature Nanotechnology, pp 3, 101 23 Li, Y.H, Wang, H Luan, S Ding, X Xu, J Wu C Wu, D (2003) Effect of Carboxylic Functional Group Functionalized on Carbon Nanotubes Surface on the Removal of Lead from Water Carbon 41, pp.1057–1062 24 Lin, Y.M Dimitrakopoulos, C Jenkins, K.A Farmer, D.B Chiu, H.Y Grill, Avouris, A.P (2010) 100-GHz transistors from wafer-scale epitaxial grapheme Science 2010, 327, 662 25 Lin, Y.M Jenkins, K.A Valdes-Garcia, A Small, J.P Farmer, D.B Avouris, P (2009) Operation of Graphene Transistors at Gigahertz Frequencies Nano Lett 2009, pp.422-426 26 Lu, X Chen, Z Schleyer, P (2005) Are Stone–Wales defect sites always smore reactive than perfect sites in the side walls of single-wall carbon nanotubes?, pp 20–21 27 Marjorie, R.W (2012) Metal removal by sodium graphene oxide 45 28 Masenelli-Varlot, K McRae, E Dupont-Pavlosky , N (2002): Comparative adsorption of simple molecules on carbon nanotubes Dependence of the adsorption properties on the nanotube morphology, pp 209–215 29 Miller, D.L Kubista, K.D Rutter , G.M Ruan, M Heer, W.A.de First, P.N Stroscio, J.A (2009) Observing the Quantization of Zero Mass Carriers in Graphene Science 2009,324, 924 30 Novoselov, K.S Geim, A.K Morozov, S Zhang, V.Y Dubonos, S.V Grigorieva, I.V Firsov, A.A (2004) Reports Electric Field Effect in Atomically Thin Carbon Films, pp.306 31 Peng, X Li, Y Luan, Z Di, Z Wang, H Tian, B Jia, Z (2003) Treatment of Micropollutants in Water and Wastewater, Chem Phys Lett 376, pp.154–158 32 Peres, N M Guinea ,R.F Neto, A.H.C, Tính chất điện tử rối loạn carbon hai chiều Physical Review 2006, 73, 125411 33 Pyrzynska, K Trojanowicz, M (1999) Study on the solid phase extraction and spectrophotometric determination of cobalt with 5-(2-benzothiazolylazo)-8hydroxyquinolene Crit Rev Anal Chem 29, pp 313–321 34 Ricordel, S Taba, Cisse, I Dorange, G (2001) Adsorption of Lead(II) and Cadmium(II) ions from aqueous solutions by adsorption on activated carbon prepared from cashew nut shells Sep Purif Technol 24, pp 389 35 Seol, J.H Jo, I Moore, A.L Lindsay, L Aitken, Z.H Pettes, M.T Li, X Yao, Z Huang, R Broido, D Mingo, N Ruoff, R S Shi, L (2010) Thermal Properties Of Graphene: Fundamentals and applications, pp.213 46 36 Talyzin, A.V Szabó, T.S DéKáNy, I Langenhorst, F Sokolov, P.S Solozhenko, V.L (2009) "Nanocarbons by High-Temperature Decomposition of Graphite Oxide at Various Pressures" 37 Toke, C Jain, J.K (2007) Numerical studies of the Pfaffian model of the nu=5/2 fractional quantum Hall effect,pp.75 38 Yang, C.M Kanoh, H Kaneko, K Yudasaka, M Iijima, S (2002) Adsorption behaviors of HiPco single-walled carbon nanotubes aggregates for alcohol vapors, pp 8994–8999 39 You, S Luzan, S.M Szabó, T.S Talyzin, A.V (2013) "Effect of synthesis method on solvation and exfoliation of graphite oxide" 40 Zavalniuk, V Marchenko, S (2011) "Theoretical analysis of telescopic oscillations in multi-walled carbon nanotubes" 41 Zhou, S.Y Gweon, G.H Fedorov, A.V First, P.N Heer, W.A.de Lee, D.H Guinea, F Neto, A.H.C Lanzara, A (2007) Broadband electromagnetic response and ultrafast dynamics of few-layer epitaxial graphene, pp.770 47 ... The study using carbon nanotubes and graphene oxide nanomaterial to absorb copper oxide ion in water is absolutely necessary Prepare a quantity carbon nanotubes and graphene oxide required like... find out which one has better ion copper absorbance 1.3 Research questions What are the efficiency of carbon nanotubes and graphene oxide in absorption of ion copper? And which one is better in... which is bulky and subject to complexation with hydroxide and carbonate anions in aqueous solution, graphene oxide has exhibited an adsorption capacity surpassing any known natural and engineering