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).
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