Ultrafast and continuous synthesis of crystalline ferrite nanoparticles in supercritical ethanol.

Magnetic nanoparticles (NPs) are of increasing interest in various industrially relevant products. For these, the development of greener and faster approaches facilitating scaling-up production is of paramount importance. Here, we report a novel, green and potentially scalable approach for the continuous and ultrafast (90 s) synthesis of superparamagnetic ferrite NPs (MnFe(2)O(4), Fe(3)O(4)) in supercritical ethanol (scEtOH) at a fairly moderate temperature (260 °C). ScEtOH exhibits numerous advantages such as its production from bio-resources, its lack of toxicity and its relatively low supercritical coordinates (p(c) = 6.39 MPa and T(c) = 243 °C), being therefore appropriate for the development of sustainable technologies. The present study is completed by the investigation of both in situ and ex situ NP surface functionalization. The as-obtained nanoparticles present good crystallinity, sizes below 8 nm, superparamagnetic behavior at room temperature and high saturation magnetization. Moreover, depending on the capping strategy, the ferrite NPs present extended (for in situ coated NPs) or short-term (for ex situ coated NPs) colloidal stability.

[1]  Bambang Veriansyah,et al.  Continuous synthesis of surface-modified zinc oxide nanoparticles in supercritical methanol , 2010 .

[2]  C. Xu,et al.  Supercritical water synthesis and deposition of iron oxide (α-Fe2O3) nanoparticles in activated carbon , 2006 .

[3]  Yong Ding,et al.  Tuning the Thermal Stability of Molecular Precursors for the Nonhydrolytic Synthesis of Magnetic MnFe2O4 Spinel Nanocrystals , 2007 .

[4]  Bambang Veriansyah,et al.  Characterization of surface-modified ceria oxide nanoparticles synthesized continuously in supercritical methanol , 2009 .

[5]  Xiaolian Sun,et al.  Magnetic Nanoparticles for Magnetoresistance-Based Biodetection , 2012, IEEE Transactions on NanoBioscience.

[6]  Cyril Aymonier,et al.  Synthesis of exciton luminescent ZnO nanocrystals using continuous supercritical microfluidics. , 2011, Angewandte Chemie.

[7]  P. Charpentier,et al.  Synthesis of metal oxide nanostructures by direct sol-gel chemistry in supercritical fluids. , 2012, Chemical reviews.

[8]  Christian Binek,et al.  Magnetic nanoparticles: recent advances in synthesis, self-assembly and applications , 2011 .

[9]  Lijun Zhao,et al.  Synthesis and Characterization of Single-Crystalline MnFe2O4 Ferrite Nanocrystals and Their Possible Application in Water Treatment , 2011 .

[10]  A. Roig,et al.  Surface Reactivity of Iron Oxide Nanoparticles by Microwave- Assisted Synthesis; Comparison with the Thermal Decomposition Route , 2012 .

[11]  C. Aymonier,et al.  Preparation of functional hybrid palladium nanoparticles using supercritical fluids: a novel approach to detach the growth and functionalization steps. , 2008, Chemical communications.

[12]  Cyril Aymonier,et al.  Design of functional nanostructured materials using supercritical fluids , 2009 .

[13]  J. S. Pedersen,et al.  Critical size of crystalline ZrO(2) nanoparticles synthesized in near- and supercritical water and supercritical isopropyl alcohol. , 2008, ACS nano.

[14]  S. Marre,et al.  Design at the nanometre scale of multifunctional materials using supercritical fluid chemical deposition , 2006, Nanotechnology.

[15]  Bambang Veriansyah,et al.  Metal nanoparticle synthesis using supercritical alcohol , 2009 .

[16]  Cyril Aymonier,et al.  Review of supercritical fluids in inorganic materials science , 2006 .

[17]  Mary Elizabeth Williams,et al.  The use of magnetic nanoparticles in analytical chemistry. , 2011, Annual review of analytical chemistry.

[18]  Motonobu Goto,et al.  Green materials synthesis with supercritical water , 2011 .

[19]  S. Marre,et al.  Near- and supercritical alcohols as solvents and surface modifiers for the continuous synthesis of cerium oxide nanoparticles. , 2012, Langmuir : the ACS journal of surfaces and colloids.

[20]  J. Bocquet,et al.  Barium titanate powders synthesis from solvothermal reaction and supercritical treatment , 1999 .

[21]  C. López,et al.  Magnetophotonic response of three-dimensional opals. , 2011, ACS nano.

[22]  Rafael Luque,et al.  Magnetically recoverable nanocatalysts. , 2011, Chemical reviews.

[23]  K. Matsuyama,et al.  Preparation of Hollow ZnO Microspheres Using Poly(methyl methacrylate) as a Template with Supercritical CO2-Ethanol Solution , 2010 .

[24]  A. Panda,et al.  Synthesis of monodispersed nanocrystalline materials in supercritical ethanol: a generalized approach , 2011 .

[25]  N. Foster,et al.  Processing of Iron Oxide Nanoparticles by Supercritical Fluids , 2008 .

[26]  C. López,et al.  Ultrathin conformal coating for complex magneto-photonic structures. , 2011, Nanoscale.

[27]  Bambang Veriansyah,et al.  Continuous synthesis of magnetite nanoparticles in supercritical methanol , 2010 .

[28]  Min Sun,et al.  Synthesis and characterization of magnetic β-cyclodextrin-chitosan nanoparticles as nano-adsorbents for removal of methyl blue. , 2012, International journal of biological macromolecules.

[29]  M. Morris,et al.  Supercritical fluid synthesis of magnetic hexagonal nanoplatelets of magnetite. , 2010, Journal of the American Chemical Society.

[30]  Taeghwan Hyeon,et al.  Designed synthesis of uniformly sized iron oxide nanoparticles for efficient magnetic resonance imaging contrast agents. , 2012, Chemical Society reviews.

[31]  B. Iversen,et al.  Time-resolved in situ synchrotron X-ray study and large-scale production of magnetite nanoparticles in supercritical water. , 2009, Angewandte Chemie.

[32]  Hao Zeng,et al.  Monodisperse MFe2O4 (M = Fe, Co, Mn) nanoparticles. , 2004, Journal of the American Chemical Society.

[33]  Ernesto Reverchon,et al.  Nanomaterials and supercritical fluids , 2006 .

[34]  H. Reveron,et al.  Single-step synthesis of well-crystallized and pure barium titanate nanoparticles in supercritical fluids , 2005 .

[35]  Anna Roig,et al.  Relaxometric and magnetic characterization of ultrasmall iron oxide nanoparticles with high magnetization. Evaluation as potential T1 magnetic resonance imaging contrast agents for molecular imaging. , 2007, Langmuir : the ACS journal of surfaces and colloids.

[36]  K. Arai,et al.  Hydrothermal Synthesis of Metal Oxide Nanoparticles at Supercritical Conditions , 2000 .

[37]  J. S. Pedersen,et al.  Supercritical Propanol–Water Synthesis and Comprehensive Size Characterisation of Highly Crystalline anatase TiO2 Nanoparticles , 2006 .

[38]  P. Tomasik,et al.  Thermal properties of complexes of amaranthus starch with selected metal salts , 2003 .

[39]  K. Wieczorek-Ciurowa,et al.  The Thermal Decomposition of Fe(NO3)3·9H2O , 1999 .

[40]  T. Kudo,et al.  Rapid one-pot synthesis of LiMPO4 (M = Fe, Mn) colloidal nanocrystals by supercritical ethanol process. , 2010, Chemical communications.

[41]  R. Weissleder,et al.  Supercritical‐Fluid‐Assisted One‐Pot Synthesis of Biocompatible Core(γ‐Fe2O3)/Shell(SiO2) Nanoparticles as High Relaxivity T2‐Contrast Agents for Magnetic Resonance Imaging , 2009 .

[42]  L. Love,et al.  Large-scale production of magnetic nanoparticles using bacterial fermentation , 2010, Journal of Industrial Microbiology & Biotechnology.

[43]  E. Han,et al.  Study on supercritical hydrothermal synthesis of CoFe2O4 nanoparticles , 2007 .

[44]  Klavs F. Jensen,et al.  Supercritical Continuous‐Microflow Synthesis of Narrow Size Distribution Quantum Dots , 2008 .