- Nano Commentary
- Open Access
Shape and Size-Dependent Magnetic Properties of Fe3O4 Nanoparticles Synthesized Using Piperidine
© The Author(s). 2017
- Received: 15 February 2017
- Accepted: 29 March 2017
- Published: 26 April 2017
In this article, we proposed a facile one-step synthesis of Fe3O4 nanoparticles of different shapes and sizes by co-precipitation of FeCl2 with piperidine. A careful investigation of TEM micrographs shows that the shape and size of nanoparticles can be tuned by varying the molarity of piperidine. XRD patterns match the standard phase of the spinal structure of Fe3O4 which confirms the formation of Fe3O4 nanoparticles. Transmission electron microscopy reveals that molar concentration of FeCl2 solution plays a significant role in determining the shape and size of Fe3O4 nanoparticles. Changes in the shape and sizes of Fe3O4 nanoparticles which are influenced by the molar concentration of FeCl2 can easily be explained with the help of surface free energy minimization principle. Further, to study the magnetic behavior of synthesized Fe3O4 nanoparticles, magnetization vs. magnetic field (M-H) and magnetization vs. temperature (M-T) measurements were carried out by using Physical Property Measurement System (PPMS). These results show systematic changes in various magnetic parameters like remanent magnetization (Mr), saturation magnetization (Ms), coercivity (Hc), and blocking temperature (T B) with shapes and sizes of Fe3O4. These variations of magnetic properties of different shaped Fe3O4 nanoparticles can be explained with surface effect and finite size effect.
- Fe3O4 Nanoparticles
Nano-sized materials on account of their surface and quantum size effect not only are known to possess better physical and chemical properties but also have enhanced biocompatibility and bioefficacy [1, 2]. In this context, magnetic nanoparticles for their unique magnetic behavior have gained much attention in recent years, whereby they are known to have promising potential for various medical applications such as targeted drug delivery systems, MRI, diagnostics, radiofrequency hyperthermia, and cancer therapy [3–7]. Besides, magnetic nanoparticles are also being utilized as a key material for magnetic ferrofluid , catalysis , data storage , and environmental remediation . Fe3O4, a magnetic nanoparticle, has the cubic inverse spinal structure (two Fe3+ with one Fe2+) in which oxygen forms an fcc closed-pack structure . It is an important class of half-metallic materials, as electrons hop between Fe2+ and Fe3+. However, their utilization for practical application still requires rectification of several parameters, broadly categorized into two main class: (a) their tendency to get aggregate in order to reduce their surface energy and (b) their ability to get oxidize easily. The aforementioned parameters can hamper their interfacial area, thereby hindering their magnetism and dispersibility. Henceforth, it becomes essentially important to overcome such parameters which possibly can be achieved by developing potential synthesis methods which overrule such problems. With the advent of several wet chemical methods for the synthesis of nanoparticles in the recent past, the magnetic nanoparticles have been synthesized by different methods such as solvothermal , sol-gel , co-precipitation , thermal decomposition , and sonochemical reaction . Here in this work, we have designed a new and facile one-step synthesis of Fe3O4 nanoparticles by using a new chemical piperidine (C5H11N) by hydrolysis method. Amongst several chemicals such as ether (CH3OCH3) and formaldehyde (HCHO), piperidine was found most effective for the synthesis of Fe3O4 nanoparticles.
Chemicals: FeCl2·4H2O (anhydrous) was procured from Sigma-Aldrich, while piperidine (C6H5N) was procured from Merck. All chemicals were used as received. Double-distilled water was used in reaction as a medium.
Synthesis of Fe3O4 nanoparticles was made in four different sets (by varying the molarity of FeCl2 solution) to study the influence of the reaction parameters on the size and shape of Fe3O4 nanoparticles. A solution of piperidine (50 ml, 0.25 M) was prepared by mixing 1.24 ml piperidine (C5H11N) homogeneously into 50 ml double-distilled water. This was used as stock solution throughout the experiments. The solutions of FeCl2 (10 ml) with varying molarity (0.025, 0.05, 0.075, and 0.1 M) was prepared by dissolving 0.0497, 0.0994, 0.1491, and 0.1988 g FeCl2 in double-distilled water, respectively. These samples were designated as S1, S2, S3, and S4, respectively. Now, 5 ml of prepared piperidine solution was mixed with FeCl2 solution of different molarities as in above, under stirring. An instant change in color indicated the formation of Fe3O4 nanoparticles. The reaction mixture was then centrifuged at 10,000 rpm for 10 min. Particles were collected and resuspended in 5 ml double-distilled water for further characterizations.
The XRD analyses of resulting samples were carried out with an X-Pert Pro X-ray diffractometer (PAN analyst BV the Netherlands with a build in graphite monochromator meter) with Cu Kα radiation (λ = 1.54056 A°). Sample preparation for XRD was done by placing one drop of the reaction mixture on a circular disk (5 mm diameter) and allowing it to dry. Transmission electron microscopic (TEM) studies were done by employing TECHNI 20 G2 microscope at an accelerating voltage 200 KeV. Samples for TEM were prepared by suspending powder in double-distilled water and ultrasonicated it for 1 h. The suspension obtained was placed on a formvar-coated Cu grid. Magnetic measurements were performed on 14 T Physical Properties Measurement System, Cryogenics Limited, USA.
The XRD pattern can be matched to the series of Bragg reflections corresponding to the standard phase of the spinal structure of Fe3O4 with a lattice constant of a = 8.41A° (ICSD82-1533). Six peaks at 30.16°, 35.49°, 43.01°, 53.78°, 57.21°, and 62.73° can be indexed as (220), (311), (400), (422), (511), and (440) of the cubic structure (Fd3m space group) of Fe3O4 nanoparticles.
Magnetic Properties of Nano-sized Fe3O4
Some useful parameters of M-T and M-H measurements
Mr (emu/g) at 300 K
Ms (emu/g) at 300 K
Hc (Oe) at 300 K
Mr (emu/g) at 5 K
Ms (emu/g) at 5 K
Hc (Oe) at 5 K
T B (K)
Mechanism of Formation of Fe3O4 Nanoparticles
Fe3O4 nanoparticles are indeed synthesized using piperidine, which is confirmed by XRD characterization of as-synthesized samples.
TEM images give some useful information related to the shape and sizes of the particles. Our investigation shows that shape and size of the particles can be changed from rods to spheres by varying the molar concentration of FeCl2 solutions (from 0.025 to 0.1 M).
Measurement of magnetic properties found after deep analysis shows that these magnetic parameters like Ms, Mr, Hc, and T B have shown improved values than reported earlier.
These synthesized Fe3O4 nanoparticles of different shapes and sizes will further be used for their applications like EMI shielding. Some primitive experiments are going on and very soon will be followed by respective publications.
Authors are thankful to AIRF for the various measurements. AKS is especially thankful to UGC for the DSK PDF and UPE-II which have provided the financial support for the research. Further support from DST-FIST is gratefully acknowledged.
This study was funded by UPE-II/(172) and UGC/(BSR/14-15/0078).
AKS performed the experiments and characterizations. KS has done the magnetic measurements and its explanetion. ONS has drafted the paper. All authors read and approved the final manuscript.
The authors declare that they have no competing interests.
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Open AccessThis article is distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made.
- Brust M, Kiely CJ (2002) Some recent advances in nanostructure preparation from gold and silver: a short topical review. Colloids Surf A Physicochem Eng Asp 202:175–186View ArticleGoogle Scholar
- Alivisatos AP (1996) Semiconductor clusters, nanocrystals, and quantum dots. Science 271:933–937View ArticleGoogle Scholar
- Cengelli F, Grzyb JA, Montoro A, Hofmann H, Hanessian S, Juillerat-Jeanneret L (2009) Surface-functionalized ultrasmall superparamagnetic nanoparticles as magnetic delivery vectors for camptothecin. ChemMedChem 4:988–997View ArticleGoogle Scholar
- Chen B, Lai B, Cheng J, Xia G, Gao F, Xu WJ, Gao C, Sun X, Xu C, Chen W, Chen N, Liu L, Li X, Wang X (2009) Daunorubicin-loaded magnetic nanoparticles of Fe3O4 overcome multidrug resistance and induce apoptosis of K562-n/VCR cells in vivo. Int J Nanomed 4:201–208View ArticleGoogle Scholar
- Howes P, Green M, Bowers A, Parker D, Varma G, Kallumadil M, Hughes M, Warley A, Brain A, Botnar R (2010) Magnetic conjugated polymer nanoparticles as bimodal imaging agents. J Am Chem Soc 132:9833–9842View ArticleGoogle Scholar
- Li Calzi S, Kent DL, Chang KH, Padgett KR, Afzal A, Chandra SB, Caballero S, English D, Garlington W, Hiscott PS, Sheridan CM, Grant MB, Forder JR (2009) Labeling of stem cells with monocrystalline iron oxide for tracking and localization by magnetic resonance imaging. Microvasc Res 78:132–139View ArticleGoogle Scholar
- Balivada S, Rachakatla RS, Wang H, Samarakoon TN, Dani RK, Pyle M, Kroh FO, Walker B, Leaym X, Koper OB, Tamura M, Chikan V, Bossmann SH, Troyer DL (2010) A/C magnetic hyperthermia of melanoma mediated by iron (0)/iron oxide core/shell magnetic nanoparticles: a mouse study. BMC Cancer 10:119–127View ArticleGoogle Scholar
- Parekh K, Upadhyay RV, Mehta RV (2005) Magnetic and rheological characterization of Fe3O4 ferrofluid. Hyperfine Interact 160:211–217View ArticleGoogle Scholar
- Bautista FM, Campelo JM, Luna D, Marinas JM, Quiros RA, Romero AA (2007) Screening of amorphous metal–phosphate catalysts for the oxidative dehydrogenation of ethylbenzene to styrene. Appl Catal B 70:611–620.Google Scholar
- Fried T, Shemer G, Markovich G (2001) Ordered two-dimensional arrays of ferrite nanoparticles. Adv Mater 13:1158–1161View ArticleGoogle Scholar
- Zhu J, Wei S, Chen M, Gu H, Rapole SB, Pallavkar S, Ho TC, Hopper J, Guo Z (2013) Magnetic nanocomposites for environmental remediation. Adv Powder Technol 24:459–467View ArticleGoogle Scholar
- Yang T, Wen X, Ren J, Li Y, Wang J, Huo C (2010) Surface structures of Fe 3 O 4 (111), (110), and (001): a density functional theory study. J Fuel Chem Technol 38:121–128View ArticleGoogle Scholar
- Gupta AK, Gupta M (2005) Synthesis and surface engineering of iron oxide nanoparticles for biomedical applications. Biomaterials 26:3995–4021View ArticleGoogle Scholar
- Wanga X, Zhangb Y, Wu Z (2010) Magnetic and optical properties of multiferroic bismuth ferrite nanoparticles by tartaric acid-assisted sol–gel strategy. Mater Lett 64:486–488View ArticleGoogle Scholar
- Dacoata GM, Degrave E, Debakker PMA, Vandenberghe RE (1994) Synthesis and characterization of some iron oxides by sol-gel method. J Solid State Chem 113:405–412View ArticleGoogle Scholar
- Hyeon T, Lee SS, Park J, Chung Y, Na HB (2001) Synthesis of highly crystalline and monodisperse maghemite nanocrystallites without a size-selection process. J Am Chem Soc 123:12798–12801View ArticleGoogle Scholar
- Abu Mukh-Qasem R, Gedanken A (2005) Sonochemical synthesis of stable hydrosol of Fe3O4 nanoparticles. J Colloid Interface Sci 284:489–494View ArticleGoogle Scholar
- Wang ZL (2000) Transmission electron microscopy of shape-controlled nanocrystals and their assemblies. J Phys Chem B 104:1153–1175View ArticleGoogle Scholar
- Sun YG, Xia YN (2002) Shape-controlled synthesis of gold and silver nanoparticles. Science 298:2176–2179View ArticleGoogle Scholar
- Xiong Y, Xia Y (2007) Shape-controlled synthesis of metal nanostructures: the case of palladium. Adv Mater 19:3385–3391View ArticleGoogle Scholar
- Sun S, Zeng H, Robinson DB, Raoux S, Rice PM, Wang SX, Li G (2004) Monodisperse MFe2O4 (M = Fe, Co, Mn) nanoparticles. J Am Chem Soc 126:273–279View ArticleGoogle Scholar
- He X, Zhong W, Chak-Tong A, Du Y (2013) Size dependence of the magnetic properties of Ni nanoparticles prepared by thermal decomposition method. Nanoscale Res Lett 8:446–450View ArticleGoogle Scholar
- Rondinone AJ, Samia ACS, Zhang ZJJ (1999) Superparamagnetic relaxation and magnetic anisotropy energy distribution in CoFe2O4 spinel ferrite nanocrystallites. Phys Chem B 103:6876–6880View ArticleGoogle Scholar
- Cao H, Liang R, Qian D, Shao J, Qu M (2011) L-Serine assisted synthesis of superparamagnetic Fe3O4 nanocubes for lithuim ion batteries. J Phys Chem C 115:24688–24695View ArticleGoogle Scholar
- Yang T, Shen C, Li Z, Zhang H, Xiao C, Chen S, Xu Z, Shi D, Li J, Gao H (2005) Highly ordered self-assembly with large area of Fe3O4 nanoparticles and the magnetic properties. J Phys Chem B 109:23233–23236View ArticleGoogle Scholar