Abstract
We have investigated the crystal structure of nanosized iron-oxide by X-ray diffraction (XRD), extended X-ray absorption fine structure measurements at the iron K-edge as well as by transmission electron microscopy (TEM). Iron-oxide nanoparticles were produced by thermal treatment of horse spleen ferritin molecules. The structure of these particles was compared to α-Fe2O3 and γ-Fe2O3 nanopowder references. The thermal treatment of a submonolayer film of ferritin molecules results in pure γ-Fe2O3 nanoparticles, while for films above a certain thickness α-Fe2O3 and γ-Fe2O3 coexist, exhibiting two different crystallite sizes. TEM shows a characteristic particle diameter of ~7 nm for γ-Fe2O3 resulting from thermal treatment of monolayers, consistent with the crystallite size of the γ-phase as obtained from XRD measurements on multi-layered samples. XRD shows the α-Fe2O3 phase to be characterized by a crystallite size of ~34 nm.
Similar content being viewed by others
Notes
To produce nanosized iron oxide particles we made use of the ability of ferritin to self-assemble and construct a core, which shows a structure similar to that of the mineral ferrihydrite (5Fe2O3·9H2O). Ferritin is the major cellular iron-storage protein. It is able to store iron as hydrated iron oxide in the internal cavity which is composed of 24 polypeptide subunits. The inner and outer diameters of the protein shell are about 8 and 12.5 nm, respectively. Hydrophilic and hydrophobic channels penetrate the protein shell and provide the means by which iron ions can be accumulated within or removed from the molecules. (Cornell and Schwertmann 2003; Massover 1993; Mann et al. 1989).
References
Banfield JF, Welch SA, Zhang H, Thomson Ebert T, Penn RL (2000) Aggregation-based crystal growth and microstructure development in natural iron oxyhydroxide biomineralization products. Science 289:751–754
Barbier A, Belkhou R, Ohresser P, Gautier-Soyer M, Bezencenet O, Mulazzi M, Guittet M-J, Moussy J-B (2005) Electronic and crystalline structure, morphology, and magnetism of nanometric Fe2O3 layers deposited on Pt(111) by atomic-oxygen-assisted molecular beam epitaxy. Phys Rev B 72:245423
Belin T, Millot N, Bovet N, Gailhanou M (2007) In situ and time resolved study of the γ/α-Fe2O3 transition in nanometric particles. J Sol State Chem 180:2377–2385
Bermejo E, Becue T, Lacour C, Quarton M (1997) Synthesis of nanoscaled iron particles from freeze-dried precursors. Powder Technol 94:29–34
Chirita M, Grozescu I (2009) Fe2O3—nanoparticles, physical properties and their photochemical and photoelectrochemical applications. Chem Bull POLITEHNICA Univ. (Timişoara) 54:1–8
Cornell RM, Schwertmann U (2003) The iron oxides: structure, properties, reactions, occurence and uses, 2nd edn. VCH, Weinheim
Fang C, Zhang M (2009) Multifunctional magnetic nanoparticles for medical imaging applications. J Mater Chem 19:6258–6266
Furuno T, Sasabe H, Ulmer KM (1989) Binding of ferritin molecules to a charged polypeptide layer of poly-1-benzyl-l-histidine. Thin Solid Films 180:23–30
Jacob J, Khadar MA (2010) VSM and Mössbauer study of nanostructured hematite. J Magn Magn Mater 322:614–621
Janzen C, Roth P, Rellinghaus B (1999) Characteristics of Fe2O3 nanoparticles from doped low-pressure H2/O2/Ar flames. J Nanopart Res 1:163–167
Janzen C, Knipping J, Rellinghaus B, Roth P (2003) Formation of silica-embedded iron-oxide nanoparticles in low-pressure flames. J Nanopart Res 5:589–596
Johnson CA, Yuan Y, Lenhoff AM (2000) Adsorbed layers of ferritin at solid and fluid interfaces studied by atomic force microscopy. J Colloid Interface Sci 223:261–272
Li P, Miser DE, Rabiei S, Yadav RT, Hajaligol MR (2003) The removal of carbon monoxide by iron oxide nanoparticles. Appl Catal B 43:151–162
Mann S, Webb J, Williams RJP (1989) Biomineralization: chemical and biochemical perspectives. VCH, Weinheim
Massover WH (1993) Ultrastructure of ferritin and apoferritin: a review. Micron 24:389–437
McHale JM, Auroux A, Perrotta AJ, Navrotsky A (1997) Surface energies and thermodynamic phase stability in nanocrystalline aluminas. Science 277:788–791
Navrotsky A, Mazeina L, Majzlan J (2008) Size-driven structural and thermodynamic complexity in iron oxides. Science 319:1635–1638
Newville M (2001) IFEFFIT: interactive XAFS analysis and FEFF fitting. J Synchrotron Rad 8:322–324
Newville M, Līviņš P, Yacoby Y, Rehr JJ, Stern EA (1993) Near-edge X-ray-absorption fine structure of Pb: a comparison of theory and experiment. Phys Rev B 47:14126–14131
Nickels JE, Fineman MA, Wallace WE (1949) X-ray diffraction studies of sodium chloride–sodium bromide solid solutions. J Phys Chem 53:625–628
Preisinger M, Krispin M, Rudolf T, Horn S, Strongin DR (2005) Electronic structure of nanoscale iron oxide particles measured by scanning tunneling and photoelectron spectroscopies. Phys Rev B 71:165409
Rasmussen SE, Jørgensen JE, Lundtoft B (1996) Structures and Phase Transitions of Na2SO4. J Appl Cryst 29:42–47
Ravel B, Newville M (2005) ATHENA, ARTEMIS, HEPHAESTUS: data analysis for X-ray absorption spectroscopy using IFEFFIT. J Synchrotron Rad 12:537–541
Rodríguez-Carvajal J (1993) Recent advances in magnetic structure determination by neutron powder diffraction. Physica B 192:55–69
Sadeghi M, Sarabadani P, Karami H (2010) Synthesis of maghemite nano-particles and its application as radionuclidic adsorbant to purify 109Cd radionuclide. J Radioanal Nucl Chem 283:297–303
Sawada H (1996) An electron density residual study of α-ferric oxide. Mater Res Bull 31:141–146
Scherrer P (1918) Bestimmung der Größe und der inneren Struktur von Kolloidteilchen mittels Röntgenstrahlen. Göttinger Nachrichten 2:98–100
Schimanke G, Martin M (2000) In situ XRD study of the phase transition of nanocrystalline maghemite (γ-Fe2O3) to hematite (α-Fe2O3). Solid State Ionics 136–137:1235–1240
Schwertmann U, Fechter H (1984) The influence of aluminum on iron oxides: XI. Aluminum-substituted Maghemite in soils and its formation. Soil Sci Soc Am J 48:1462–1463
Shmakov AN, Kryukova GN, Tsybulya SV, Chuvilin AL, Solovyeva LP (1995) Vacancy ordering in γ-Fe2O3: synchrotron X-ray powder diffraction and high-resolution electron microscopy studies. J Appl Cryst 28:141–145
Stanjek H, Weidler PG (1992) The effect of dry heating on the chemistry, surface are and oxalate solubility of synthetic 2-line and 6-line ferrihydrites. Clay Minerals 27:397–412
Stokes AR, Wilson AJC (1942) A method of calculating the integral breadths of Debye–Scherrer lines. Math Proc Camb Phil Soc 38:313–322
Tamura H, Goto K, Nagayama M (1976) Effect of anions on the oxygenation of ferrous ion in neutral solutions. J Inorg Nucl Chem 38:113–117
Tronc E, Jolivet JP (1986) Surface effects on magnetically coupled iron oxide “γ-Fe2O3” colloids. Hyperfine Interact 28:525–528
Ye X, Lin D, Jiao Z, Zhang L (1998) The thermal stability of nanocrystalline maghemite Fe2O3. J Phys D Appl Phys 31:2739–2744
Acknowledgments
We acknowledge the ANKA Angstroemquelle Karlsruhe for the provision of beamtime and we would like to thank S. Mangold and S. Doyle for their valuable assistance using beamline ANKA-XAS and ANKA-PDIFF. We thank M. Klemm and P.S. Riseborough for fruitful discussion. This work was supported by the Deutsche Forschungsgemeinschaft in context of SFB 484 and PROALMEX Mexico-Germany binational collaboration project.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Krispin, M., Ullrich, A. & Horn, S. Crystal structure of iron-oxide nanoparticles synthesized from ferritin. J Nanopart Res 14, 669 (2012). https://doi.org/10.1007/s11051-011-0669-4
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s11051-011-0669-4