Abstract
The thermal decomposition of organometallic precursors in the presence of surfactants and a long-chain alcohol is a valuable method to synthesize magnetic nanoparticles (MNPs) because it provides good control of the final morphology and crystallinity of the magnetic material. These parameters, and consequently the magnetic properties, depend on several details of the experimental procedure of chemical synthesis. We have studied the role of the pre-decomposition step, heating the system to 373–393 K in inert gas flux, on the final composition and morphology of the system. By adding this intermediate step, we were able to produce MNPs with a Fe1-yO/Fe3O4 core–shell structure and sizes of 20–25 nm. When the same synthesis protocol was used skipping the pre-decomposition stage, monophasic MNPs of 11 nm with ferrite structure were obtained. These differences in the composition have a major effect on the resulting magnetic properties of MNPs, and are related to some by-reactions in the synthesis solution during the preparation procedure.
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References
Bronstein LM, Atkinson JE, Malyutin AG, Kidwai F, Stein BD, Morgan DG, Perry JM, Karty JA (2011) Nanoparticles by decomposition of long chain iron carboxylates: from spheres to stars and cubes. Langmuir 27:3044–3050
Chen R, Christiansen MG, Sourakov A, Mohr A, Matsumoto Y, Okada S, Jasanoff A, Anikeeva P (2016) High-performance ferrite nanoparticles through nonaqueous redox phase tuning. Nano Lett 16:1345–1351
Cornell RM, Schwertmann U (2003) The iron oxides: structure, properties, reactions, occurrences and uses, 2a edn. Wiley & VCH Verlag, Weinhein
El Medilli Y, Bardeau J-F, Randrianantoandro N, Grasset F, Greneche J-M (2012) Insights into the mechanism related to the phase transition from γ-Fe2O3 to α-Fe2O3 nanoparticles induced by thermal treatment and laser irradiation. J Phys Chem C 116:23785–23792
Escoda-Torroella M, Moya C, Fraile Rodríguez A, Batlle Z, Labarta A (2021) Selective control over the morphology and the oxidation state of iron oxide nanoparticles. Langmuir 37:35–45
Gao X, Liu H, Hidajat K, Kawi S (2015) Anti-coking Ni/SiO2 catalyst for dry reforming of methane: role of oleylamine/oleic acid organic pair. ChemCatChem 7:4188–4196
Hai HT, Yang HT, Kura H, Hasegawa D, Ogata Y, Takahashi M, Ogawa T (2010) Size control and characterization of wustite (core)/spinel (shell) nanocubes obtained by decomposition of iron oleate complex. J Colloid Interface Sci 346:37–42
Harris RA, Shumbula PM, van der Walt H (2015) Analysis of the interaction of surfactants oleic acid and oleylamine with iron oxide nanoparticles through molecular mechanics modeling. Langmuir 31:3934–3943
Hou Y, Xu Z, Sun S (2007) Controlled synthesis and chemical conversions of FeO nanoparticles. Angew Chem Int Ed 119:6329–6332
Hufschmid R, Arami H, Ferguson RM, Gonzales M, Teeman E, Brush LN, Browning ND, Krishnan KM (2015) Synthesis of phase-pure and monodisperse iron oxide nanoparticles by thermal decomposition. Nanoscale 7:11142–11154
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 123:12798–12801
Kemp SJ, Ferguson RM, Khandhar AP, Krishnan KM (2016) Monodisperse magnetite nanoparticles with nearly ideal saturation magnetization. RSC Adv 6:77452–77464
Khurshid H, Li W, Chandra S, Phan M-H, Hadjipanayis GC, Mukherjee P, Srikanth H (2013) Mechanism and controlled growth of shape and size variant core/shell FeO/Fe3O4 nanoparticles. Nanoscale 5:7942–7952
Kwon SG, Piao Y, Park J, Angappane S, Jo Y, Hwang N-M, Park J-G, Hyeon T (2007) Kinetics of monodisperse iron oxide nanocrystal formation by “heating-up” process. J Am Chem Soc 129:12571–12584
Lavorato GC, Lima E Jr, Troiani HE, Zysler RD, Winkler EL (2017) Tuning the coercivity and exchange bias by controlling the interface coupling in bimagnetic core/shell nanoparticles. Nanoscale 9:10240–10247
Lohr J, Almeida AA, Moreno MS, Troiani H, Goya GF, Torres TE, Fernandez-Pacheco R, Winkler EL, Vasquez Mansilla M, Cohen R, Nagamine LCCM, Rodríguez LM, Fregenal DE, Zysler RD, Lima E Jr (2019) Effects of Zn substitution in the magnetic and morphological properties of Fe-oxide-based core–shell nanoparticles produced in a single chemical synthesis. J Phys Chem C 123:1444–1453
Lucena IL, Saboya RMA, Oliveira JFG, Rodrigues ML, Torres AEB, Cavalcante CL Jr, Parente EJS Jr, Silva GF, Fernandes FAN (2011) Oleic acid esterification with ethanol under continuous water removal conditions. Fuel 90:902–904
McCammon CA (1992) Magnetic properties of FexO (x > 0.95): variation of Neel temperature. J Magn Magn Mater 104–107:1937–1938
Mourdikoudis S, Liz-Marzán LM (2013) Oleylamine in nanoparticle synthesis. Chem Mater 25:1465–1476
Omidghane M, Jenab E, Chae M, Bressler DC (2017) Production of renewable hydrocarbons by thermal cracking of oleic acid in the presence of water. Energy Fuels 31:9446–9454
Palchoudhury S, An W, Xu Y, Qin Y, Zhang Z, Chopra N, Holler RA, Turner CH, Bao Y (2011) Synthesis and Growth Mechanism of Iron Oxide Nanowhiskers. Nano Lett 11:1141–1146
Park J, An K, Hwang Y, Park J-G, Noh H-J, Kim J-Y, Park J-H, Hwang N-M, Hyeon T (2004) Ultra-large-scale syntheses of monodisperse nanocrystals. Nat Mater 3:891–895
Parker FS (1971) Applications of infrared spectroscopy in biochemistry, biology, and medicine. Plenum Press, New York (Chapter 8)
Quiao L, Fu Z, Li J, Ghosen J, Zeng M, Stebbins J, Prasad PN, Swihart MT (2017) Standardizing size- and shape-controlled synthesis of monodisperse magnetite (Fe3O4) nanocrystals by identifying and exploiting effects of organic impurities. ACS Nano 11:6370–6381
Salazar-Alvarez G, Sort J, Suriñach S, Baró MD, Nogués J (2007) Synthesis and size-dependent exchange bias in inverted core−shell MnO/Mn3O4 nanoparticles. J Am Chem Soc 129:9102–9108
Smith BC (2018) The C=O bond, part VI: esters and the rule of three. Spectroscopy Online 33:20–23
Sun S, Zeng H (2002) Size-controlled synthesis of magnetite nanoparticles. J Am Chem Soc 124:8204–8205
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 126:273–279
Sun X, Huls NF, Sigdel A, Sun S (2012) Tuning exchange bias in core/shell FeO/Fe3O4 nanoparticles. Nano Lett 12:246–251
Unni M, Uhl AM, Savliwala S, Savitzky BH, Dhavalikar R, Garraud N, Arnold DP, Kourkoutis LF, Andrew JS, Rinaldi C (2017) Thermal decomposition synthesis of iron oxide nanoparticles with diminished magnetic dead layer by controlled addition of oxygen. ACS Nano 11:2284–2303
Vargas JM, Zysler RD (2005) Tailoring the size in colloidal iron oxide magnetic nanoparticles. Nanotechnol 16:1474–1476
Lavorato GC, Lima Jr. E, Tobia D, Fiorani D, Troiani HE, Zysler RD, Winkler EL (2014) Size effects in bimagnetic CoO/CoFe2O4 core/shell nanoparticles. Nanotechnol. 25:355704
Kavich DW, Dickerson JH, Mahajan SV, Hasan SA, Park J-H (2008) Exchange bias of singly inverted FeO/Fe3O4 core-shell nanocrystals. Phys Rev B 78:174414.
Cotin G, Kiefer C, Perton F, Ihiawakrim D, Blanco Andujar C, Moldovan S, Lefevre C, Ersen O, Pichon B, Mertz D, Begin-Colin S (2018) Unravelling the thermal decomposition parameters for the synthesis of anisotropic iron oxide nanoparticles. Nanomaterials 8:881
Krispin M, Ullrich A, Horn S (2012) Crystal structure of iron-oxide nanoparticles synthesized from ferritin. J. Nanopart. Res. 14:669
Scopel E, Conti PP, Stroppa DG, Dalmaschio CJ (2019) Synthesis of functionalized magnetite nanoparticles using only oleic acid and iron (III) acetylacetonate. SN Appl Sci 1:147
Song L, Yan C, Zhang W, Wu H, Jia Z, Ma M, Xie J, Gu N, Zhang Y (2016) Influence of reaction solvent on crystallinity and magnetic properties of MnFe2O4 nanoparticles synthesized by thermal decomposition. J Nanomater 2016:4878935
Wallace WE (direc.) (2020) Infrared spectra in NIST chemistry WebBook. In: Linstrom PJ, Mallard WG. NIST standard reference database number 69. National Institute of Standards and Technology, Gaithersburg MD, 20899
Funding
The authors acknowledge the financial support of the Argentinian Agencia Nacional de Promoción de Ciencia y Tecnológica (ANPCyT) through the project nos. PICT-2016–0288 and PICT-2018–02565. The authors also thank the Universidad Nacional de Cuyo (UNCuyo) by the financial support through the project nos. 06/C527 and 06/C528. The authors also acknowledge the support of the EU commission under the grant H2020-MSCA-RISE-2016, SPICOLOST project no. 734187. GFG thanks the Spanish Ministerio de Ciencia, Innovación y Universidades by the partial financial support through project PID2019-106947RB-C21.
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Lohr, J., Vasquez Mansilla, M., Gerbaldo, M.V. et al. Dependence of the composition, morphology and magnetic properties with the water and air exposure during the Fe1-yO/Fe3O4 core–shell nanoparticles synthesis. J Nanopart Res 23, 140 (2021). https://doi.org/10.1007/s11051-021-05275-5
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DOI: https://doi.org/10.1007/s11051-021-05275-5