Facile synthesis of ultrathin magnetic iron oxide nanoplates by Schikorr reaction
© Ma et al.; licensee Springer. 2013
Received: 12 October 2012
Accepted: 14 December 2012
Published: 7 January 2013
In this work, a very facile one-pot hydrothermal synthesis approach has been developed for the preparation of ultrathin magnetite nanoplates. The hydrothermal procedure was performed by aging ferrous hydroxide under anaerobic conditions, which is known as Schikorr reaction. Ethylene glycol (EG), which was introduced to the reaction as another solvent, played a critical role in the formation process of these nanoplates. Typically, hexagonal Fe3O4 nanoplates with a thickness of 10 to 15 nm and a side length of 150 to 200 nm have been synthesized with EG/H2O = 1:1 in experiments. Our data suggest that the thickness of Fe3O4 nanoplates decreases, and the shape of the nanoplate becomes more irregular when the concentration of EG increases. The as-prepared Fe3O4 nanoplates were highly crystallized single crystals and exhibited large coercivity and specific absorption rate coefficient.
KeywordsMagnetite nanoplates Schikorr reaction Ethylene glycol Ferrous hydroxide
Magnetite (Fe3O4) is an attractive material for essential applications such as magnetic storage, ferrofluids, catalysts, chemical sensor, biological assays, and hyperthermia because of its magnetic features combined with nanosize and surface effects[1–9]. To date, a number of nanosized magnetite crystals with a variety of morphologies, such as nanoparticles, nanospheres, hollow spheres, nanorods, nanowires, nanotubes, nanorings, nanopyramids, nano-octahedra, and flowerlike nanostructures, have been prepared by a variety of chemistry-based processing routes, including coprecipitation, thermal decomposition, microemulsion, electrochemical synthesis, and solvothermal or hydrothermal synthesis[10–15]. However, to the best of our knowledge, there are only limited reports concerning the synthesis of ultrathin magnetite nanoplate and its interesting properties. Chen's group synthesized γ-Fe2O3 nanoplates by a solvothermal process using ethanol as solvent and poly(vinylpyrrolidone) (PVP) as stabilizer, followed by a reduction process to generate Fe3O4 nanoplates. Xu and coworkers prepared triangular Fe3O4 nanoplates between two carbon films by pyrolyzing ferrocene and sodium oxalate at 600°C.
The Schikorr reaction usually occurs in the process of anaerobic corrosion of iron and carbon steel in various conditions[21, 22]. Herein, this reaction was used to prepare magnetite nanoplates. In addition, ethylene glycol (EG) was introduced to this reaction as another solvent besides H2O to adjust the morphology and thickness of the products. In a typical procedure, a FeSO4 water solution was added to a H2O-EG mixture containing NaOH at a constant rate and under stirring after nitrogen was bubbled through the two solutions for 2 h. When the precipitation was completed, the system was undisturbed and heated to 90°C for 24 h.
All chemicals used in our experiments were purchased and used as received without further purification. Iron(II) sulfate heptahydrate (FeSO4·7H2O, 99+%), ethylene glycol (C2H6O2, 99%), and sodium hydroxide (NaOH, 98%) were purchased from Alfa Aesar (Ward Hill, MA, USA). Sulfuric acid (H2SO4, >92%) was purchased from Shanghai Ling-Feng Chemical Reagent Co., Ltd. (Changshu City, China).
In the typical synthetic procedure of the Fe3O4 nanoplates, nitrogen is bubbled through two solutions independently: (a) 54 ml of water-EG mixture containing NaOH to obtain the final concentration of 0.22 M NaOH and (b) 6 ml of FeSO4·7H2O dissolved in 10−2 M H2SO4 to obtain the final concentration of 2. 4 × 10−2 M. After 2 h, the iron(II) sulfate solution was added to the basic solution at a constant rate and under stirring. When the precipitation was completed, nitrogen was allowed to pass for another 3 min, and the system was undisturbed and heated to 90°C for 24 h in a Teflon autoclave. Aging time was fixed at 24 h in order to reach conditions near equilibrium. At this point, the solution was cooled at room temperature with an ice bath, and the solid was separated by magnetic decantation and washed several times with distilled water.
The morphology and microstructure were characterized using a transmission electron microscope (TEM; JEM-2100, JEOL, Tokyo, Japan) with an accelerating voltage of 200 kV and a Zeiss Ultra Plus field emission scanning electron microscope (SEM; Zeiss, Oberkochen, Germany) with in-lens capabilities, using nitrogen gas and ultrahigh-resolution BSE imaging. X-ray diffraction (XRD) patterns were collected on a Rigaku D/Max 2200PC diffractometer (Rigaku Corp., Tokyo, Japan) with a graphite monochromator and CuKR radiation. X-ray photoelectron spectra (XPS) were recorded on a PHI-5300 ESCA spectrometer (Perkin-Elmer, Waltham, MA, USA). The infrared spectra were recorded on a Thermo Nicolet-5700 Fourier transform infrared spectrometer (FTIR; Thermo Scientific, Logan, UT, USA). The micro-Raman analyses were performed on a Renishaw Invis Reflex (Renishaw, Gloucestershire, UK) system equipment with Peltier-cooled charge-coupled device and a Leica confocal microscope (Leica, Solms, Germany). The magnetic properties were measured at room temperature using a vibration sample magnetometer (7404, LakeShore, Westerville, OH, USA). To investigate the specific absorption rate (SAR) coefficient of the nanoplates, the calorimetric measurements were performed on an alternating current (AC) magnetic field generator (model SPG-10-I, Shenzhen Shuangping, Guangdong, China; 10 kW, 100 to 300 kHz).
Results and discussion
In summary, ultrathin single-crystalline Fe3O4 nanoplates can be synthesized facilely on a large scale by a hydrothermal route of Schikorr reaction. The experimental results showed that the concentration of EG played a key role in the information and adjustment of the thickness of the nanoplates. The as-prepared Fe3O4 nanoplates are highly crystallized single crystals. Also, Fe3O4 nanoplates are ferromagnetic at room temperature and exhibit large coercivity and specific absorption rate coefficient under external alternating magnetic field.
This research was supported by the National Important Science Research Program of China (no. 2011CB933503), National Natural Science Foundation of China (no. 30970787, 31170959, and 61127002), and the Basic Research Program of Jiangsu Province (Natural Science Foundation, no. BK2011036, BK2009013).
- Yang C, Wu J, Hou Y: Fe3O4nanostructures: synthesis, growth mechanism, properties and applications. Chem Commun 2011, 47: 5130. 10.1039/c0cc05862aView ArticleGoogle Scholar
- Fried T, Shemer G, Markovich G: Ordered two-dimensional arrays of ferrite nanoparticles. Adv Mater 2001, 13: 1158–1161. 10.1002/1521-4095(200108)13:15<1158::AID-ADMA1158>3.0.CO;2-6View ArticleGoogle Scholar
- Ding N, Yan N, Ren CL, Chen XG: Colorimetric determination of melamine in dairy products by Fe3O4magnetic nanoparticles H2O2ABTS detection system. Anal Chem 2010, 82: 5897–5899. 10.1021/ac100597sView ArticleGoogle Scholar
- Todorovic M, Schultz S, Wong J, Scherer A: Writing and reading of single magnetic domain per bit perpendicular patterned media. Appl Phys Lett 1999, 74: 2516–2518. 10.1063/1.123885View ArticleGoogle Scholar
- Zeng H, Sun S: Syntheses, properties, and potential applications of multicomponent magnetic nanoparticles. Adv Funct Mater 2008, 18: 391. 10.1002/adfm.200701211View ArticleGoogle Scholar
- Laurent S, Forge D, Port M, Roch A, Robic C, Elst LV, Muller RN: Magnetic iron oxide nanoparticles: synthesis, stabilization, vectorization, physicochemical characterizations, and biological applications. Chem Rev 2064, 2008: 108.Google Scholar
- Wang Y, Teng X, Wang J, Yang H: Solvent-free atom transfer radical polymerization in the synthesis of Fe2O3@Polystyrene core−shell nanoparticles. Nano Lett 2003, 3: 789–793. 10.1021/nl034211oView ArticleGoogle Scholar
- Hyeon T: Chemical synthesis of magnetic nanoparticles. Chem Commun 2003, 8: 927.View ArticleGoogle Scholar
- Gao L, Zhuang J, Nie L, Zhang J, Zhang Y, Gu N, Wang TH, Feng J, Yang D, Perrett S, Yan X: Intrinsic peroxidase-like activity of ferromagnetic nanoparticles. Nat Nanotechnol 2007, 2: 577–583.View ArticleGoogle Scholar
- Vergés A, Costo R, Roca AG, Marco JF, Goya GF, Serna CJ: Uniform and water stable magnetite nanoparticles with diameters around the monodomain–multidomain limit. J Phys D: Appl Phys 2008, 41: 134003. 10.1088/0022-3727/41/13/134003View ArticleGoogle Scholar
- Yang HT, Ogawa T, Hasegawa D, Takahashi M: Synthesis and magnetic properties of monodisperse magnetite nanocubes. J Appl Phys 2008, 103: 07d526. 10.1063/1.2833820Google Scholar
- Sun S, Zeng H: Size-controlled synthesis of magnetite nanoparticles. J Am Chem Soc 2002, 124: 8204–8205. 10.1021/ja026501xView ArticleGoogle Scholar
- Sun Z, Li Y, Zhang J, Li Y, Zhao Z, Zhang K, Zhang G, Guo J, Yang B: A universal approach to fabricate various nanoring arrays based on a colloidal-crystal-assisted-lithography strategy. Adv Funct Mater 2008, 18: 4036–4042. 10.1002/adfm.200801103View ArticleGoogle Scholar
- Fan H, Yi J, Yang Y, Kho K, Tan H, Shen Z, Ding J, Sun X, Olivo MC, Feng Y: Single-crystalline MFe2O4nanotubes/nanorings synthesized by thermal transformation process for biological applications. ACS Nano 2009, 3: 2798–2808. 10.1021/nn9006797View ArticleGoogle Scholar
- Li X, Zhang D, Chen J: Synthesis of amphiphilic superparamagnetic ferrite/block copolymer hollow submicrospheres. J Am Chem Soc 2006, 128: 8382. 10.1021/ja061460gView ArticleGoogle Scholar
- Lu J, Jiao X, Chen D, Li W: Solvothermal synthesis and characterization of Fe3O4and γ-Fe2O3nanoplates. J Phys Chem C 2009, 113: 4012–4017. 10.1021/jp810583eView ArticleGoogle Scholar
- Fan N, Ma X, Liu X, Xu L, Qian Y: The formation of a layer of Fe3O4nanoplates between two carbon films. Carbon 2007, 45: 1839–1846. 10.1016/j.carbon.2007.04.029View ArticleGoogle Scholar
- Rihan RO, Nešić S: Erosion–corrosion of mild steel in hot caustic. Part I: NaOH solution. Corros Sci 2006, 48: 2633–2659.Google Scholar
- Booy M, Swaddle TW: Hydrothermal preparation of magnetite from iron chelates. Can J Chem 1978, 56: 402. 10.1139/v78-064View ArticleGoogle Scholar
- Schikorr G: Über die Reaktionen zwischen Eisen, seinen Hydroxyden und Wasser. Z Elektrochem 1929, 35: 65–70.Google Scholar
- Joshi PS, Venkateswaran G, Venkateswarlu KS, Rao KA: Stimulated decomposition of Fe(OH)2in the presence of AVT chemicals and metallic surfaces—relevance to low-temperature feedwater line corrosion. Corrosion 1993, 49: 300–309. 10.5006/1.3316053View ArticleGoogle Scholar
- Reardon EJ: Zerovalent irons: styles of corrosion and inorganic control on hydrogen pressure buildup. Environ Sci Technol 2005, 39: 7311–7317. 10.1021/es050507fView ArticleGoogle Scholar
- Goya GF, Berquo TS, Fonseca FC: Static and dynamic magnetic properties of spherical magnetite nanoparticles. J Appl Phys 2003, 94: 3520. 10.1063/1.1599959View ArticleGoogle Scholar
- Teng X, Black D, Watkins N, Gao Y, Yang H: Platinum-maghemite core-shell nanoparticles using a sequential synthesis. Nano Lett 2003, 3: 261–264. 10.1021/nl025918yView ArticleGoogle Scholar
- Daou TJ, Grenèche JM, Pourroy G, Buathong S, Derory A, Ulhaq-Bouillet C, Donnio B, Guillon D, Begin-Colin S: Coupling agent effect on magnetic properties of functionalized magnetite-based nanoparticles. Chem Mater 2008, 20: 5869–5875. 10.1021/cm801405nView ArticleGoogle Scholar
- Du N, Xu Y, Zhang H, Zhai C, Yang D: Selective synthesis of Fe2O3and Fe3O4nanowires via a single precursor: a general method for metal oxide nanowires. Nanoscale Res Lett 2010, 5: 1295–1300. 10.1007/s11671-010-9641-yView ArticleGoogle Scholar
- Dunn DS, Bogart MB, Brossia CS, Cragnolino GA: Corrosion of iron under alternating wet and dry conditions. Corrosion 2000, 56: 470–481. 10.5006/1.3280551View ArticleGoogle Scholar
- Balasubramaniam R, Ramesh Kumar AV, Dillmann P: Characterization of rust on ancient Indian iron. Curr Sci 2003, 85: 1546–1555.Google Scholar
- Genin JM, Bauer P, Olowe AA, Rezel D: Mössbauer study of the kinetics of simulated corrosion process of iron in chlorinated aqueous solution around room temperature: the hyperfine structure of ferrous hydroxides and Green Rust I. Hyperfine Interactions 1986, 29: 1355–1360. 10.1007/BF02399485View ArticleGoogle Scholar
- Sun Y, Xia Y: Shape-controlled synthesis of gold and silver nanoparticles. Science 2002, 298: 2176–2179. 10.1126/science.1077229View ArticleGoogle Scholar
- Sun Y, Mayers B, Herricks T, Xia Y: Polyol synthesis of uniform silver nanowires: a plausible growth mechanism and the supporting evidence. Nano Lett 2003, 3(7):955–960. 10.1021/nl034312mView ArticleGoogle Scholar
- Hu X, Gong J, Zhang L, Yu JC: Continuous size tuning of monodisperse ZnO colloidal nanocrystal clusters by a microwave-polyol process and their application for humidity sensing. Adv Mater 2008, 20: 4845–4850. 10.1002/adma.200801433View ArticleGoogle Scholar
- Deng H, Li X, Peng Q, Wang X, Chen J, Li Y: Monodisperse magnetic single-crystal ferrite microspheres. Angew Chem Int Ed 2005, 44: 2782–2785. 10.1002/anie.200462551View ArticleGoogle Scholar
- Zhu L, Xiao H, Zhang W, Yang G, Fu S: One-pot template-free synthesis of monodisperse and single-crystal magnetite hollow spheres by a simple solvothermal route. Crystal Growth & Design 2008, 8: 957–963. 10.1021/cg700861aView ArticleGoogle Scholar
- Refait P, Génin JMR: The oxidation of ferrous hydroxide in chloride-containing aqueous media and Pourbaix diagrams of green rust one. Corros Sci 1993, 34: 797–819. 10.1016/0010-938X(93)90101-LView ArticleGoogle Scholar
- Refait P, Abdelmoula M, Génin JMR: Mechanisms of formation and structure of green rust one in aqueous corrosion of iron in the presence of chloride ions. Corros Sci 1998, 40: 1547–1560. 10.1016/S0010-938X(98)00066-3View ArticleGoogle Scholar
- McGill IR, McEnaney B, Smith DC: Crystal structure of green rust formed by corrosion of cast iron. Nature 1976, 259: 200–201. 10.1038/259200a0View ArticleGoogle Scholar
- Smit J, Wijn HPJ: Ferrites: Physical Properties of Ferrimagnetic Oxides in Relation to Their Technical Applications. New York: Wiley; 1959.Google Scholar
- Daou TJ, Grenéche JM, Pourroy G, Buathong S, Derory A, Ulhaq-Bouillet C, Donnio B, Guillon D, Begin-Colin S: Coupling agent effect on magnetic properties of functionalized magnetite-based nanoparticles. Chem Mater 2008, 20: 5869–5875. 10.1021/cm801405nView ArticleGoogle Scholar
- Serna CJ, Bødker F, Mørup S, Morales MP, Sandiumenge F, Veintemillas-Verdaguer S: Spin frustration in maghemite nanoparticles. Solid State Commun 2001, 118: 437–440. 10.1016/S0038-1098(01)00150-8View ArticleGoogle Scholar
- Morales MP, Serna CJ, Bødker F, Mørup S: Spin canting due to structural disorder in maghemite. J Phys Condens Matter 1997, 9: 5461–5467. 10.1088/0953-8984/9/25/013View ArticleGoogle Scholar
- Horng L, Chern G, Chen MC, Kang PC, Lee DS: Magnetic anisotropic properties in Fe3O4and CoFe2O4ferrite epitaxy thin films. J Magn Magn Mater 2004, 270: 389–396. 10.1016/j.jmmm.2003.09.005View ArticleGoogle Scholar
- Ma M, Wu Y, Zhou J, Sun Y, Zhang Y, Gu N: Size dependence of specific power absorption of Fe3O4particles in AC magnetic field. J Magn Magn Mater 2004, 268: 33–39. 10.1016/S0304-8853(03)00426-8View ArticleGoogle Scholar
- Hayashi K, Moriya M, Sakamoto W, Yogo T: Chemoselective synthesis of folic acid-functionalized magnetite nanoparticles via click chemistry for magnetic hyperthermia. Chem Mater 2009, 21: 1318–1325. 10.1021/cm803113eView ArticleGoogle Scholar
- Rashad MM, El-Sayed HM, Rasly M, Nasr MI: Induction heating studies of magnetite nanospheres synthesized at room temperature for magnetic hyperthermia. J Magn Magn Mater 2012, 324: 4019–4023. 10.1016/j.jmmm.2012.07.010View ArticleGoogle Scholar
This article is published under license to BioMed Central Ltd. This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.