Magnetite (Fe3O4) nanoparticles with controllable size and shape were synthesized by the thermal decomposition method. In contrast to previously reported thermal decomposition methods, our synthesis method had utilized a much cheaper and less toxic iron precursor, iron acetylacetonate (Fe(acac)3), and environmentally benign and non-toxic polyethylene oxide (PEO) was being used as the solvent and surfactant simultaneously. Fe3O4 nanoparticles of controllable size and shape were prepared by manipulating the synthesis parameters such as precursor concentrations, reaction durations and surfactants

Chin, SF

Pang, SC

Tan, CH

Journal of Materials and Environmental Sciences

English

Spiral - Imperial College Digital Repository

J. Mater. Environ. Sci. 2 (3) (2011) 299-302                                                                        Chin et al. ISSN: 2028-2508   299  Green Synthesis of Magnetite Nanoparticles (via Thermal Decomposition Method) with Controllable Size and Shape  Suk Fun Chin*, Suh Cem Pang, Ching Hong Tan  Department of Chemistry, Faculty of Resource Science and Technology, Universiti Malaysia Sarawak, 94300 Kota Samarahan, Sarawak, Malaysia   Received in 26 Apr 2011, Revised 18 June 2011, Accepted 18 June 2011. *Corresponding author, E-mail: Email address: sukfunchin@gmail.com; sfchin@frst.unimas.my, Tel No: +6082 582999; Fax No: +6082 583160;  Abstract Magnetite (Fe3O4) nanoparticles with controllable size and shape were synthesized by the thermal decomposition method. In contrast to previously repo ted thermal decomposition methods, our synthesis method had utilized a much cheaper and less toxic iron precursor, iron acetylacetonate (Fe(acac)3), and environmentally benign and non-toxic polyethylene oxide (PEO) was being used as the solvent and surfactant simultaneously. Fe3O4 nanoparticles of controllable size and shape were prepared by manipulating the synthesis parameters such as precursor concentratios, reaction durations and surfactants.   Keywords: magnetic nanoparticles, magnetite, thermal decomposition, green synthesis  1.  Introduction  Iron-based magnetic nanoparticles such as magnetite (Fe3O4) have received numerous attentions due to their unique properties and potential applications in biomedical applications[1-4]. Fe3O4 nanoparticles can potentially be used as magnetic targeted drug delivery carriers and magnetic resonance imaging (MRI) contrast agents due to their high saturation magneitzation, low toxicity, and biocompatibility. Magnetic properties of magnetic nanoparticles can be tailored by their particle sizes and size distributions. The particle sizes and size distributions of magnetic nanoparticles are in turn, affected by the synthesis route. For these reasons, various synthesis approaches have been developed to produce Fe3O4 nanoparticles in order to obtain desired properties.  Synthesis methods of Fe3O4 nanoparticles that have been developed include co-precipitation [5-7] thermal decomposition [8,9] microemulsion route [10] hydrothermal synthesis [11] and continuous flow technique [12].  However, success in precise particles size control of Fe3O4 nanoparticle has only been achieved through thermal decomposition using large quantities of toxic and expensive precursors and surfactants in organic solvent. Laborious purification steps are required before the end product can be used in biomedical applications. Thermal decomposition of iron pentacarbonyl [Fe(CO)5] has been used for the preparation of monodisperse γ-Fe2O3 nanoparticles with average diameters from 4 to 16 nm by careful control of the molar ratio of metal precursor to surfactant, [Fe(CO)5] and oleic acid respectively[13]. Since Fe(CO)5 is very expensive and toxic, some attempts have been made  to replace Fe(CO)5 with iron acetylacetonate [Fe(acac)3]. Fe3O4 nanoparticles of narrow size distribution have been synthesized by thermal decomposition of Fe(acac)3 in phenyl ether in the presence of stearyl alcohol, oleic acid and oleylamine [14].  In this study, we have attempted to synthesize Fe3O4 nanoparticles by the thermal decomposition method without using toxic organic J. Mater. Environ. Sci. 2 (3) (2011) 299-302                                                                        Chin et al. ISSN: 2028-2508   300 surfactants and solvents. Poly(ethylene glycol), PEO was being used  as both solvent and surfactant simultaneously to synthesize Fe3O4 nanoparticles of controllable particle size and narrow size distribution.  PEO has been widely used as a green solvent for various organic syntheses due to its low toxicity and high boiling point [15-17].   2. Experimental  2.1 Synthesis of Fe3O4 nanoparticles In a typical synthesis, Fe(acac)3 was added to 20 mL of PEO and heated to reflux for 1 hour   under a flow of nitrogen gas until a stable black suspension was obtained. The concentrations of Fe(acac)3 and volumes of PEO were varied in order to study their effects on the particles size of Fe3O4 nanoparticles formed.   2.2 Characterization of Fe3O4 nanoparticles The size and morphology of the Fe3O4 nanoparticles were determined using a Transmission Electron Microscope (TEM) (Model JEM-1230).  Size distributions were determined based on the average of particle diameters from at least 50 particle measurements per sample.   3. Results and discussion  3.1 Effect of concentration Fig. 1 shows TEM images of Fe3O4 nanoparticles synthesized using various concentrations of Fe(acac)3 precursor. The mean size of Fe3O4 nanoparticles was observed to increase with increased concentrations of Fe(acac)3 precursor, which varied between 2 nm to 7 nm as the concentration of Fe(acac)3 was increased from 0.1 mmol to 8 mmol. Table 1 shows the summary of mean particles sizes synthesized at various concentrations of Fe(acac)3 precursor. At higher Fe(acac)3 precursor concentrations, Ostwald ripening of smaller particles have resulted in the formation of larger particles. Besides, the shape of the Fe3O4 nanoparticles was observed to be irregular and not spherical.  Figure 1(f) shows the TEM micrograph of Fe3O4 nanoparticles prepared with fixed amount of Fe(acac)3 at 8 mmol and varying volumes of PEO. The mean size of Fe3O4 nanoparticles was observed to reduce from 9 nm to 7 nm as the volume of PEO used as solvent was increased from 10 mL to 20 mL. Increasing the volume of PEO would result in decreasing the concentration of Fe(acac)3 precursor, which in turn led to the production of Fe3O4 nanoparticles of smaller mean sizes.  Table 1: Summary of particle size of Fe3O4 nanoparticles synthesized at various concentration of Fe(acac)3 precursor:  Concentrationof Fe(acac)3, mmol Particle sizes (nm) 0.1 2 1 4 2 5 4 6 8 7  3.2 Effects of reaction duration The reaction duration was increased from 1 hour to 2 hours to investigate the effect of reaction duration on the mean particle size. Figure 2 (a) shows welldispersed Fe3O4 nanoparticles of mean size of 4 nm prepared at reaction duration of 1 hour. As shown in Figure 2(b), agglomerated Fe3O4 nanoparticles of 6 nm in mean size were prepared at the reaction duration of 2 hours. The larger and more agglomerated nanoparticles obtained at longer reaction duration could be attributed to the Ostwald ripening of smaller particles which agglomerated and grew into larger particles.  3.3 Effects of surfactant Although PEO had successfully served as a surfactant to prevent agglomeration of Fe3O4 nanoparticles through steric stabilization, the shape of Fe3O4 nanoparticles were observed to be less spherical. This could be due to the weak interaction of Fe(acac)3 with PEO polymer chains as PEO does not have any carboxylic acid (-COOH) functional group for binding to Fe(acac)3 precursor convalently. Thus, oleic acid (CH3(CH2)7CH=CH(CH2)7COOH) was added during the synthesis in order to study its effect on the size and shape of Fe3O4 nanoparticles.  As shown in Figures 3 (a) and (b), the Fe3O4 nanoparticles synthesized in the presence of oleic acid were more spherical in shape. Oleic acid contains –COOH functional group which can bind covalently to iron atoms, resulting in the observed more spherical particle shape. However, the mean size of Fe3O4 nanoparticles synthesized with various concentrations of oleic acid remained at 6 nm, which indicated that the concentration of oleic acid had no effect on the mean size of Fe3O4 nanoparticles formed. J. Mater. Environ. Sci. 2 (3) (2011) 299-302                                                                        Chin et al. ISSN: 2028-2508   301  (a) (b)(c) (d)(e) (f)50nm50nm50nm50nm50nm50nm  Figure 1. TEM images of Fe3O4 nanoparticles prepared from (a) 0.1 mmol; (b) 1 mmol; (c) 2 mmol; (d) 4 mmol; (e) 8 mmol of  Fe(acac)3 in 20 ml of PEO and (f)  8 mmol of  Fe(acac)3 in 10 ml of PEO   50 nm 50 nm(a) (b)  Figure 2. Fe3O4 nanoparticles prepared from 1 mmol of Fe(acac)3 in 20 mL of PEO and refluxed  for (a) 1 hour and (b) 2 hours.  J. Mater. Environ. Sci. 2 (3) (2011) 299-302                                                                        Chin et al. ISSN: 2028-2508   300      Figure 3  Fe3O4 nanoparticles prepared in the presence of (a) 1 mL and (b) 2 mL of oleic acid   Conclusion  In conclusion, Fe3O4 nanoparticles of various mean sizes were successfully synthesized by the thermal decomposition method. Our synthesis approach employed an environmental friendly solvent, PEO, as an alternative to organic solvent. PEO serves both as a solvent and a surfactant which prevents the agglomeration of Fe3O4 nanoparticles formed during synthesis. The size and shape of the Fe3O4 nanoparticles could be controlled by judicious choie of synthesis parameters such as precursor concentrations, reaction durations and surfactants.    Acknowledgement This work was funded by Universiti Malaysia Sarawak (UNIMAS) Small Grant Scheme No: 01(S53)/718/2010(04).   References  1. Chin, S.F., Iyer, K.S., Saunders, M., Pierre, Tim G.St., Buckley, C., Paskevicius, M., Raston, C.L. Chem. Eur. J. 15 (2009) 5661. 2. Liu, G., Wang, Z, Lu J, Xia, C., Gao, F., Gong, Q., Song, Bin, Zhao, Xuna., Shuai, X., Chen,  X., Ai, H., Gu, Z. Biomaterials. 32 (2011) 528. 3. Dandamudi, S., Campbell, R.B. iomaterials. 28 (2007) 4673. 4. Pan, B.F., Gao, F., Gu H.C. J. Colloid Interface Sci. 284 (2005) 1. 5. Chin, S.F., Makha, M., Raston, C.L., Saunders M. Chem. Commun. (2007) 1948. 6. Pang, S.C., Khoh, W.H., Chin, S.F. J. Mater. Sci.45 (2010) 5598. 7. Pang, S.C., Chin, S.F., Anderson, M.A. J. Colloid Interface Sci. (2007) 31, 94. 8. Yu, W.W., Falkner, J.C., Yavuz, C.T., Colvin, V.L. Chem. Commun. (2004) 2306. 9. Li, Z., Sun, Q., Gao, M. Angew. Chem. Int. Ed. 44 (2005) 123. 10. Liu, Z. L., Wang, X., Yao, K.L., Du, G.H., Lu, Q.H., Ding, Z.H. Tao, J., Ning, Q., Luo, X. P., Tian, D.Y., Xi, D. J. Mater. Sci. 39 (2004) 2633 11. Xuan, S., Hao, L., Jiang, W., Gong, X., Hu, Y., Chen, Z. J. Magn. Magn. Mater. 308 (2007) 210. 12. Chin, S.F., Iyer, K.S., Raston, C.L., Saunders, M. Adv. Funct. Mater. 18 (2008) 922 13. Park, J., Lee, E., Hwang, N.M., Kang, M., Kim, S.C., Hwang, Y., Park, J.G., Noh, H.J., Kim, J.Y., Park, J.H., Hyeon, T. Angew. Chem. Int. Ed. 44 (2005) 2872. 14. Sun, S., Zeng, H. J. Am. Chem. Soc. 124 (2002) 8204.  15. Smith, B., Raston, C. L., Sobolev A.N., Green Chem. 7, (2005) 650 16. Kidwai, M.,  Bhatnagar, D., Mishra, N.K. Green Chem. 3 (2010) 55 17.  Smith, N.M., Raston, C.L. Smith, C.B., Sobolev, A.N.  Green Chem. 9 (2007) 1185    (2011) http://www.jmaterenvironsci.com  

Green Synthesis of Magnetite Nanoparticles (via Thermal Decomposition Method) with Controllable Size and Shape

Chin, S.F.

Pang, S.C.

Tan, Ching Hong

Unimas Institutional Repository

J. Mater. Environ. Sci. 2 (3) (2011) 299-302                                                                        Chin et al. ISSN: 2028-2508   299  Green Synthesis of Magnetite Nanoparticles (via Thermal Decomposition Method) with Controllable Size and Shape  Suk Fun Chin*, Suh Cem Pang, Ching Hong Tan  Department of Chemistry, Faculty of Resource Science and Technology, Universiti Malaysia Sarawak, 94300 Kota Samarahan, Sarawak, Malaysia   Received in 26 Apr 2011, Revised 18 June 2011, Accepted 18 June 2011. *Corresponding author, E-mail: Email address: sukfunchin@gmail.com; sfchin@frst.unimas.my, Tel No: +6082 582999; Fax No: +6082 583160;  Abstract Magnetite (Fe3O4) nanoparticles with controllable size and shape were synthesized by the thermal decomposition method. In contrast to previously repo ted thermal decomposition methods, our synthesis method had utilized a much cheaper and less toxic iron precursor, iron acetylacetonate (Fe(acac)3), and environmentally benign and non-toxic polyethylene oxide (PEO) was being used as the solvent and surfactant simultaneously. Fe3O4 nanoparticles of controllable size and shape were prepared by manipulating the synthesis parameters such as precursor concentratios, reaction durations and surfactants.   Keywords: magnetic nanoparticles, magnetite, thermal decomposition, green synthesis  1.  Introduction  Iron-based magnetic nanoparticles such as magnetite (Fe3O4) have received numerous attentions due to their unique properties and potential applications in biomedical applications[1-4]. Fe3O4 nanoparticles can potentially be used as magnetic targeted drug delivery carriers and magnetic resonance imaging (MRI) contrast agents due to their high saturation magneitzation, low toxicity, and biocompatibility. Magnetic properties of magnetic nanoparticles can be tailored by their particle sizes and size distributions. The particle sizes and size distributions of magnetic nanoparticles are in turn, affected by the synthesis route. For these reasons, various synthesis approaches have been developed to produce Fe3O4 nanoparticles in order to obtain desired properties.  Synthesis methods of Fe3O4 nanoparticles that have been developed include co-precipitation [5-7] thermal decomposition [8,9] microemulsion route [10] hydrothermal synthesis [11] and continuous flow technique [12].  However, success in precise particles size control of Fe3O4 nanoparticle has only been achieved through thermal decomposition using large quantities of toxic and expensive precursors and surfactants in organic solvent. Laborious purification steps are required before the end product can be used in biomedical applications. Thermal decomposition of iron pentacarbonyl [Fe(CO)5] has been used for the preparation of monodisperse γ-Fe2O3 nanoparticles with average diameters from 4 to 16 nm by careful control of the molar ratio of metal precursor to surfactant, [Fe(CO)5] and oleic acid respectively[13]. Since Fe(CO)5 is very expensive and toxic, some attempts have been made  to replace Fe(CO)5 with iron acetylacetonate [Fe(acac)3]. Fe3O4 nanoparticles of narrow size distribution have been synthesized by thermal decomposition of Fe(acac)3 in phenyl ether in the presence of stearyl alcohol, oleic acid and oleylamine [14].  In this study, we have attempted to synthesize Fe3O4 nanoparticles by the thermal decomposition method without using toxic organic 

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Green Synthesis of Magnetite Nanoparticles (via Thermal Decomposition Method) with Controllable Size and Shape

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