journal article·2012-09

A facile synthetic route toward air-stable magnetic nanoalloys with Fe–Ni/Fe–Co core and iron oxide shell

Alexios P. Douvalis, Radek Zboril, Athanasios B. Bourlinos, Jiri Tucek, Stavroula Spyridi, Thomas Bakas

Journal of Nanoparticle Research· Volume 14· Issue 9
Publisher page

Abstract

Air-stable bimetallic spherically shaped Fe–Ni and Fe–Co magnetic nanoparticles (MNPs), having an average size of 15 nm and core–shell structure, were synthesized by a simple wet chemical method under ambient conditions. For the first time, sodium borohydride reduction method, commonly applied for the syntheses of metal nanoparticles, was used for the preparation of well-defined Fe–Ni and Fe–Co nanoalloys, avoiding exploitation of any organic solvent. This approach allows a large scale production of nanoparticles specifically stabilized by an iron oxyhydroxide shell without a need of secondary functionalization. Transmission electron microscopy, X-ray powder diffraction, X-ray fluorescence, magnetization, and Mossbauer data demonstrate a core–shell nature of the as-synthesized nanoparticles. The nanoparticle core is of metallic origin and is inhomogeneous at the atomic level, consisting of iron-rich and iron-poor alloy phases. The composition of the shell is close to the ferrihydrite and its role lies in prevention of oxidation-induced degradation of nanoparticle properties. The core is ferromagnetic at and below room temperature, experiencing superparamagnetic relaxation effects due to a reduced size of nanoparticles, whereas the shell is completely superparamagnetic at 300 K and magnetically orders below ~25 K. Both developed types of magnetic nanoalloys exhibit a strong magnetic response under applied magnetic fields with a high magnetization values achievable at relatively low applied magnetic fields. Beside this, the highly biocompatible chemical composition of the nanoparticle shell and ability of its chemical modification by substitution or addition of other ions or molecules further empower the application potential of these MNPs, especially in the field of biomedicine.
Source: openaire · Quality: candidate unverified · Source record ↗

Research context

OpenAlex topics: Magnetic Properties and Synthesis of Ferrites · Iron oxide chemistry and applications · Magnetic properties of thin films

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

References (56)

Show source-provided references
1. Berry CC, Curtis ASG (2003) Functionalisation of magnetic nanoparticles for applications in biomedicine. J Phys D 36:R198–R206. doi: 10.1088/0022-3727/36/13/20310.1088/0022-3727/36/13/203 ↗
2. Bertotti G (1998) Hysteresis in magnetism. Academic Press, San Diego
3. Bourlinos AB, Panagiotopoulos I, Niarchos D, Petridis D (2004) Hydrophilic Co–Pt alloy nanoparticles: synthesis, characterization, and perspectives. J Mater Res 19:1227–1233. doi: 10.1557/JMR.2004.015910.1557/JMR.2004.0159 ↗
4. Bourlinos AB, Bakandritsos A, Petridis D (2005) One-pot borohydride synthesis of magnetically modified lepidocrocite. Chem Lett 34:666–667. doi: 10.1246/cl.2005.66610.1246/cl.2005.666 ↗
5. Chen YZ, Luo XH, Yue GH, Luo XT, Peng DL (2009) Synthesis of iron–nickel nanoparticles via a nonaqueous organometallic route. Mater Chem Phys 113:412–416. doi: 10.1016/j.matchemphys.2008.07.11810.1016/j.matchemphys.2008.07.118 ↗
6. Chu SY, Kline C, Huang MQ, MacHenry ME, Cross J, Harris VG (1999) Preparation, characterization and magnetic properties of an ordered FeCo single crystal. J Appl Phys 85:6031–6033. doi: 10.1063/1.36907210.1063/1.369072 ↗
7. Cornell RM, Schwertmann U (1996) The iron oxides: structure, properties, reactions, occurrences and uses. Wiley-VCH, Weinheim
8. Cullity BD (1956) Elements of X-ray diffraction. Addison-Wesley, Massachusetts
9. Cullity BD, Graham CD (2009) Introduction to magnetic materials. Wiley, New Jersey
10. Djekoun A, Boudinar N, Chebli A, Otmani A, Benabdeslem M, Bouzabata B, Greneche JM (2009) Characterization of Fe and Fe50Ni50 ultrafine nanoparticles synthesized by inert gas-condensation method. Physica B 404:3824–3829. doi: 10.1016/j.physb.2009.07.07410.1016/j.physb.2009.07.074 ↗
11. Dong XL, Zhang ZD, Zhao XG, Chuang YC, Jin SR, Sun WM (1999) The preparation and characterization of ultrafine Fe–Ni particles. J Mater Res 14:398–406. doi: 10.1557/JMR.1999.005810.1557/JMR.1999.0058 ↗
12. Douvalis AP, Polymeros A, Bakas T (2010) IMSG09: a 57Fe–119Sn Mossbauer spectra computer fitting program with novel interactive user interface. J Phys: Conf Ser 217:012014. doi: 10.1088/1742-6596/217/1/01201410.1088/1742-6596/217/1/012014 ↗
13. Fiorani D (2005) Surface effects in magnetic nanoparticles. Springer, New York10.1007/b136494 ↗
14. Ford GC, Harrison PM, Rice DW, Smith JM, Treffry A, White JL, Yariv J (1984) Ferritin: design and formation of an iron-storage molecule. Philos Trans R Soc B 304:551–565. doi: 10.1098/rstb.1984.004610.1098/rstb.1984.0046 ↗
15. Greenwood NN, Gibb TC (1971) Mössbauer spectroscopy. Chapman and Hall Ltd., London10.1007/978-94-009-5697-1 ↗
16. Gubin SP (2009) Magnetic nanoparticles. Wiley-VCH, Weinheim10.1002/9783527627561 ↗
17. Habib AH, Ondeck CL, Chaudhary P, Bockstaller MR, McHenry ME (2008) Evaluation of iron–cobalt/ferrite core–shell nanoparticles for cancer thermotherapy. J Appl Phys 103:07A307. doi: 10.1063/1.283097510.1063/1.2830975 ↗
18. He H, Heist RH, McIntyre BL, Blanton TN (1997) Ultrafine nickel particles generated by laser-induced gas phase photonucleation. Nanostruct Mater 8:879–888. doi: 10.1016/S0965-9773(98)00016-610.1016/S0965-9773(98)00016-6 ↗
19. Hoinville J, Bewick A, Gleeson D, Jones R, Kasyutich O, Mayes E, Nartowski A, Warne B, Wiggins J, Wong K (2003) High density magnetic recording on protein-derived nanoparticles. J Appl Phys 93:7187–7189. doi: 10.1063/1.155589610.1063/1.1555896 ↗
20. Jang HD, Hwang DW, Kim DP, Kim HC, Lee BY, Jeong IB (2004) Preparation of cobalt nanoparticles by hydrogen reduction of cobalt chloride in the gas phase. Mater Res Bull 39:63–70. doi: 10.1016/j.materresbull.2003.09.02310.1016/j.materresbull.2003.09.023 ↗
21. Johnson CE, Ridout MS, Cranshaw TE, Madsen PE (1961) Hyperfine field and atomic moment of iron in ferromagnetic alloys. Phys Rev Lett 6:450–451. doi: 10.1103/PhysRevLett.6.45010.1103/PhysRevLett.6.450 ↗
22. Johnson CE, Ridout MS, Cranshaw TE (1963) The Mössbauer effect in iron alloys. Proc Phys Soc 81:1079–1090. doi: 10.1088/0370-1328/81/6/31310.1088/0370-1328/81/6/313 ↗
23. Kim SS, Kim ST, Ahn JM, Kim KH (2004) Magnetic and microwave absorbing properties of Co–Fe thin films plated on hollow ceramic microspheres of low density. J Magn Magn Mater 271:39–45. doi: 10.1016/j.jmmm.2003.09.01210.1016/j.jmmm.2003.09.012 ↗
24. Klabunde KL, Stark JV, Koper O, Mohs C, Khaleel A, Glavee G, Zhang D, Sorensen CM, Hadjipanayis GC (1994) Chemical synthesis of nanophase materials. In: Hadjipanayis GC, Siegel RW (eds) Nanophase materials: synthesis–properties–applications. NATO Advanced Science Institutes Series, Series E, Applied Science, vol 260. Kluwer, Dordrecht, pp 1–19
25. Kodama RH (1999) Magnetic nanoparticles. J Magn Magn Mater 200:359–372. doi: 10.1016/S0304-8853(99)00347-910.1016/S0304-8853(99)00347-9 ↗
26. Krishnan KM, Pakhomov AB, Bao Y, Blomqvist P, Chun Y, Gonzales M, Griffin K, Ji X, Roberts BK (2006) Nanomagnetism and spin electronics: materials, microstructure and novel properties. J Mater Sci 41:793–815. doi: 10.1007/s10853-006-6564-110.1007/s10853-006-6564-1 ↗
27. Li XG, Murai T, Saito T, Takahashi S (1998) Thermal stability, oxidation behavior and magnetic properties of Fe–Co ultrafine particles prepared by hydrogen plasma-metal reaction. J Magn Magn Mater 190:277–288. doi: 10.1016/S0304-8853(98)00314-X10.1016/S0304-8853(98)00314-X ↗
28. Li XG, Takahashi S, Watanabe K, Kikuchi Y, Koishi M (2001) Hybridization and characteristics of Fe and Fe–Co nanoparticles with polymer particles. Nano Lett 1:475–480. doi: 10.1021/nl010007u10.1021/nl010007u ↗
29. Li QL, Li HL, Pol VG, Bruckental I, Koltypin Y, Calderon-Moreno J, Nowik I, Gedanken A (2003) Sonochemical synthesis, structural and magnetic properties of air-stable Fe/Co alloy nanoparticles. New J Chem 27:1194–1199. doi: 10.1039/b302136j10.1039/b302136j ↗
30. Liu LJ, Guan JG, Shi WD, Sun ZG, Zhao JS (2010) Facile synthesis and growth mechanism of flowerlike Ni–Fe alloy nanostructures. J Phys Chem C 114:13565–13570. doi: 10.1021/jp104212v10.1021/jp104212v ↗
31. Madsen MB, Mørup S (1986) Magnetic properties of ferrihydrite. Hyperfine Interact 27:329–332. doi: 10.1007/BF0235477310.1007/BF02354773 ↗
32. Majetich S, Jin Y (1999) Magnetization directions of individual nanoparticles. Science 284:470–473. doi: 10.1126/science.284.5413.47010.1126/science.284.5413.470 ↗
33. Mazaleyrat F, Ammar M, LoBue M, Bonnet JP, Audebert P, Wang GY, Champion Y, Hytch M, Snoeck E (2009) Silica coated nanoparticles: synthesis, magnetic properties and spin structure. J Alloy Compd 483:473–478. doi: 10.1016/j.jallcom.2008.08.12110.1016/j.jallcom.2008.08.121 ↗
34. Mørup S, Hansen MF (2007) Superparamagnetic particles. In: Kronmüller H, Parkin S (eds) Handbook of magnetism and advanced magnetic materials. Wiley-VCH, Weinheim
35. Naik SH, Carroll KJ, Carpenter EE (2011) Characterization of oxidation resistant Fe@M (M = Cr, Ni) core@shell nanoparticles prepared by a modified reverse micelle reaction. J Appl Phys 109:07B519. doi: 10.1063/1.354882810.1063/1.3548828 ↗
36. Nie Y, He HH, Gong RZ, Zhang XC (2007) The electromagnetic characteristics and design of mechanically alloyed Fe–Co particles for electromagnetic-wave absorber. J Magn Magn Mater 310:13–16. doi: 10.1016/j.jmmm.2006.07.02110.1016/j.jmmm.2006.07.021 ↗
37. Nogues J, Sort J, Langlais V, Skumryev V, Surinach S, Munoz JS, Baro MD (2005) Exchange bias in nanostructures. Phys Rep Rev Sec Phys Lett 422:65–117. doi: 10.1016/j.physrep.2005.08.004
38. Otsuka K, Yamamoto H, Yosizawa A (1984) Preparation of Fe, Co., and Ni ultrafine particles by hydrogen reduction of chloride vapors. Jpn J Chem 6:869–878
39. Pankhurst QA, Pollard RJ (1992) Structural and magnetic properties of ferrihydrite. Clay Clay Min 40:268–272. doi: 10.1346/CCMN.1992.040030310.1346/CCMN.1992.0400303 ↗
40. Pankhurst QA, Connolly J, Jones SK, Dobson J (2003) Applications of magnetic nanoparticles in biomedicine. J Phys D 36:R167–R181. doi: 10.1088/0022-3727/36/13/20110.1088/0022-3727/36/13/201 ↗
41. Pardoe H, Chua-anusorn W, St. Pierre TG, Dobson J (2003) Detection limits for ferrimagnetic particle concentrations using magnetic resonance imaging based proton transverse relaxation rate measurements. Phys Med Biol 48:N89–N95. doi: 10.1088/0031-9155/48/6/40110.1088/0031-9155/48/6/401 ↗
42. Poddar P, Wilson JL, Srikanth H, Ravi BG, Wachsmuth J, Sudarshan TS (2004) Grain size influence on soft ferromagnetic properties in Fe–Co nanoparticles. Mater Sci Eng B 106:95–100. doi: 10.1016/j.mseb.2003.09.01110.1016/j.mseb.2003.09.011 ↗
43. Rheinlander T, Kotitz R, Weitschies W, Semmler W (2000) Magnetic fractionation of magnetic fluids. J Magn Magn Mater 219:219–228. doi: 10.1016/S0304-8853(00)00439-X10.1016/S0304-8853(00)00439-X ↗
44. Shafi KVPM, Gedanken A, Goldfarb RB, Felner I (1997) Sonochemical preparation of nanosized amorphous Fe–Ni alloys. J Appl Phys 81:6901–6905. doi: 10.1063/1.36525010.1063/1.365250 ↗
45. Shen XQ, Guo LP, Liu MQ, Song FZ, Zhu YW (2011) A simple process for magnetic nanocrystalline porous Co–Fe alloy hollow microfibers. Mater Lett 65:17–18. doi: 10.1016/j.matlet.2011.05.08210.1016/j.matlet.2010.09.048 ↗
46. Sinfelt JH (1983) Bimetallic catalysts—discoveries, concepts, and applications. Wiley, New York
47. Skumryev V, Stoyanov S, Zhang Y, Hadjipanayis G, Givord D, Nogues J (2003) Beating the superparamagnetic limit with exchange bias. Nature 423:850–853. doi: 10.1038/nature0168710.1038/nature01687 ↗
48. Sugimoto M (1999) The past, present, and future of ferrites. J Am Ceram Soc 82:269–280. doi: 10.1111/j.1551-2916.1999.tb20058.x10.1111/j.1551-2916.1999.tb20058.x ↗
49. Suh YJ, Jang HD, Chang H, Kim WB, Kim HC (2006) Size-controlled synthesis of Fe–Ni alloy nanoparticles by hydrogen reduction of metal chlorides. Powder Technol 161:196–201. doi: 10.1016/j.powtec.2005.11.00210.1016/j.powtec.2005.11.002 ↗
50. Sun SH, Murray CB, Weller D, Folks L, Moser A (2000) Monodisperse FePt nanoparticles and ferromagnetic FePt nanocrystal superlattices. Science 287:1989–1992. doi: 10.1126/science.287.5460.198910.1126/science.287.5460.1989 ↗
51. Suresh G, Saravanan P, Babu DR (2011) Synthesis of Fe–Co nanobars using sodium sulfite assisted polyol process and their structural and magnetic studies. J Nano Res 15:21–28. doi: 10.4028/www.scientific.net/JNanoR.15.2110.4028/www.scientific.net/JNanoR.15.21 ↗
52. Wang J, Zeng XC (2009) Core–shell magnetic nanoclusters. In: Liu JP, Fullerton E, Gutfleisch O, Sellmyer DJ (eds) Nanoscale magnetic materials and applications. Springer, Dordrecht, pp 35–6610.1007/978-0-387-85600-1_2 ↗
53. Webb J, Macey DJ, Chua-anusorn W, St. Pierre TG, Brooker L, Rahman RI, Noller B (1999) Iron biominerals in medicine and the environment. Coord Chem Rev 190–192:1199–1215. doi: 10.1016/S0010-8545(99)00176-910.1016/S0010-8545(99)00176-9 ↗
54. Wertheim GK, Jaccarino V, Wernick JH, Buchanan DNE (1964) Range of the exchange interaction in iron alloys. Phys Rev Lett 12:24–27. doi: 10.1103/PhysRevLett.12.2410.1103/PhysRevLett.12.24 ↗
55. Wu Z, Zhang M, Yu K, Zhang S, Xie Y (2008) Self-assembled double-shelled ferrihydrite hollow spheres with a tunable aperture. Chem Eur J 14:5346–5352. doi: 10.1002/chem.20070194510.1002/chem.200701945 ↗
56. Xu HM, Zhong W, Qi XS, Au CT, Deng Y, Du YW (2010) Highly stable Fe–Ni alloy nanoparticles encapsulated in carbon nanotubes: synthesis, structure and magnetic properties. J Alloy Compd 495:200–204. doi: 10.1016/j.jallcom.2010.01.12110.1016/j.jallcom.2010.01.121 ↗