Effect of solvothermal synthesis parameters on the crystallite size and atomic structure of cobalt iron oxide nanoparticles

Aalling-Frederiksen, Olivia; Pittkowski, Rebecca K.; Anker, Andy S.; Quinson, Jonathan; Klemeyer, Lars; Frandsen, Benjamin A.; Koziej, Dorota; Jensen, Kirsten M. Ø.

doi:10.1039/D4NA00590B

Effect of solvothermal synthesis parameters on the crystallite size and atomic structure of cobalt iron oxide nanoparticles

Journal Article · Mon Sep 16 00:00:00 EDT 2024 · Nanoscale Advances

DOI:https://doi.org/10.1039/D4NA00590B· OSTI ID:2568403

Aalling-Frederiksen, Olivia ^[1]; ^[1]; ^[1]; ^[2]; ^[3]; Frandsen, Benjamin A. ^[4]; Koziej, Dorota ^[3]; ^[1]

University of Copenhagen (Denmark)
University of Copenhagen (Denmark); Aarhus University (Denmark)
University of Hamburg (Germany)
Brigham Young University, Provo, UT (United States)

We here investigate how the synthesis method affects the crystallite size and atomic structure of cobalt iron oxide nanoparticles. By using a simple solvothermal method, we first synthesized cobalt ferrite nanoparticles of ca. 2 and 7 nm, characterized by Transmission Electron Microscopy (TEM), Small Angle X-ray scattering (SAXS), X-ray and neutron total scattering. The smallest particle size corresponds to only a few spinel unit cells. Nevertheless, Pair Distribution Function (PDF) analysis of X-ray and neutron total scattering data shows that the atomic structure, even in the smallest nanoparticles, is well described by the spinel structure, although with significant disorder and a contraction of the unit cell parameter. These effects can be explained by the surface oxidation of the small nanoparticles, which is confirmed by X-ray near edge absorption spectroscopy (XANES). Neutron total scattering data and PDF analysis reveal a higher degree of inversion in the spinel structure of the smallest nanoparticles. Neutron total scattering data also allow magnetic PDF (mPDF) analysis, which shows that the ferrimagnetic domains correspond to ca. 80% of the crystallite size in the larger particles. A similar but less well-defined magnetic ordering was observed for the smallest nanoparticles. Finally, we used a co-precipitation synthesis method at room temperature to synthesize ferrite nanoparticles similar in size to the smallest crystallites synthesized by the solvothermal method. Structural analysis with PDF demonstrates that the ferrite nanoparticles synthesized via this method exhibit a significantly more defective structure compared to those synthesized via a solvothermal method.

View Accepted Manuscript (DOE)

Research Organization:: Brigham Young University, Provo, UT (United States)

Sponsoring Organization:: Villum Fonden; Danish National Research Foundation Center; Carlsberg Foundation; Deutsche Forschungsgemeinschaft (DFG); European Research Council; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0021134

OSTI ID:: 2568403

Journal Information:: Nanoscale Advances, Journal Name: Nanoscale Advances Journal Issue: 23 Vol. 6; ISSN 2516-0230

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (56)

Inorganic Nanoparticles for MRI Contrast Agents Na, Hyon Bin; Song, In Chan; Hyeon, Taeghwan Advanced Materials, Vol. 21, Issue 21, p. 2133-2148 https://doi.org/10.1002/adma.200802366	journal	June 2009
Magnetic Nanoparticles: Synthesis, Protection, Functionalization, and Application Lu, An-Hui; Salabas, E. L.; Schüth, Ferdi Angewandte Chemie International Edition, Vol. 46, Issue 8 https://doi.org/10.1002/anie.200602866	journal	February 2007
Critical Enhancements of MRI Contrast and Hyperthermic Effects by Dopant-Controlled Magnetic Nanoparticles Jang, Jung-tak; Nah, Hyunsoo; Lee, Jae-Hyun Angewandte Chemie International Edition, Vol. 48, Issue 7 https://doi.org/10.1002/anie.200805149	journal	January 2009
Role of Composition and Size of Cobalt Ferrite Nanocrystals in the Oxygen Evolution Reaction Chakrapani, Kalapu; Bendt, Georg; Hajiyani, Hamidreza ChemCatChem, Vol. 9, Issue 15 https://doi.org/10.1002/cctc.201700376	journal	June 2017
First-Row Transition Metal Based Catalysts for the Oxygen Evolution Reaction under Alkaline Conditions: Basic Principles and Recent Advances Lu, Fei; Zhou, Min; Zhou, Yuxue Small, Vol. 13, Issue 45 https://doi.org/10.1002/smll.201701931	journal	September 2017
Amorphous Catalysts and Electrochemical Water Splitting: An Untold Story of Harmony Anantharaj, Sengeni; Noda, Suguru Small, Vol. 16, Issue 2 https://doi.org/10.1002/smll.201905779	journal	December 2019
Recent advances in magnetic structure determination by neutron powder diffraction Rodríguez-Carvajal, Juan Physica B: Condensed Matter, Vol. 192, Issue 1-2 https://doi.org/10.1016/0921-4526(93)90108-I	journal	October 1993
A powder neutron diffraction investigation of vacancy ordering and covalence in γ-Fe2O3 Greaves, C. Journal of Solid State Chemistry, Vol. 49, Issue 3 https://doi.org/10.1016/S0022-4596(83)80010-3	journal	October 1983
Spinel ferrite magnetic adsorbents: Alternative future materials for water purification? Reddy, D. Harikishore Kumar; Yun, Yeoung-Sang Coordination Chemistry Reviews, Vol. 315 https://doi.org/10.1016/j.ccr.2016.01.012	journal	May 2016
Toward a comprehensive understanding of effect of cation distribution and M2+ constituent in spinel ferrite nanocrystals MFe2O4 (M = Co, Mn, and Ni) on the electrochemical response in sensitive detection of chloramphenicol Ong, Van Hoang; Pham, Tuyet Nhung; Tien, Van Manh Journal of Alloys and Compounds, Vol. 949 https://doi.org/10.1016/j.jallcom.2023.169880	journal	July 2023
A simple solvothermal synthesis of MFe2O4 (M=Mn, Co and Ni) nanoparticles Yáñez-Vilar, S.; Sánchez-Andújar, M.; Gómez-Aguirre, C. Journal of Solid State Chemistry, Vol. 182, Issue 10 https://doi.org/10.1016/j.jssc.2009.07.028	journal	October 2009
One-pot solvothermal synthesis and performance of mesoporous magnetic ferrite MFe2O4 nanospheres Reddy, M. Penchal; Mohamed, A. M. A. Microporous and Mesoporous Materials, Vol. 215 https://doi.org/10.1016/j.micromeso.2015.05.024	journal	October 2015
Application of spinel ferrite nanoparticles in water and wastewater treatment: A review Kefeni, Kebede K.; Mamba, Bhekie B.; Msagati, Titus A. M. Separation and Purification Technology, Vol. 188 https://doi.org/10.1016/j.seppur.2017.07.015	journal	November 2017
Correlating Size and Composition-Dependent Effects with Magnetic, Mössbauer, and Pair Distribution Function Measurements in a Family of Catalytically Active Ferrite Nanoparticles Tiano, Amanda L.; Papaefthymiou, Georgia C.; Lewis, Crystal S. Chemistry of Materials, Vol. 27, Issue 10 https://doi.org/10.1021/acs.chemmater.5b00767	journal	May 2015
Cation Distribution in Spinel Ferrite Nanocrystals: Characterization, Impact on their Physical Properties, and Opportunities for Synthetic Control Sanchez-Lievanos, Karla R.; Stair, James L.; Knowles, Kathryn E. Inorganic Chemistry, Vol. 60, Issue 7 https://doi.org/10.1021/acs.inorgchem.1c00040	journal	March 2021
Amorphous versus Crystalline in Water Oxidation Catalysis: A Case Study of NiFe Alloy Cai, Weizheng; Chen, Rong; Yang, Hongbin Nano Letters, Vol. 20, Issue 6 https://doi.org/10.1021/acs.nanolett.0c00840	journal	May 2020
Amorphous Cobalt Vanadium Oxide as a Highly Active Electrocatalyst for Oxygen Evolution Liardet, Laurent; Hu, Xile ACS Catalysis, Vol. 8, Issue 1 https://doi.org/10.1021/acscatal.7b03198	journal	December 2017
Size Induced Structural Changes in Molybdenum Oxide Nanoparticles Christiansen, Troels Lindahl; Bøjesen, Espen D.; Juelsholt, Mikkel ACS Nano, Vol. 13, Issue 8 https://doi.org/10.1021/acsnano.9b01367	journal	July 2019
Evolution of Atomic-Level Structure in Sub-10 Nanometer Iron Oxide Nanocrystals: Influence on Cation Occupancy and Growth Rates Cooper, Susan R.; Candler, Randall O.; Cosby, Alexia G. ACS Nano, Vol. 14, Issue 5 https://doi.org/10.1021/acsnano.9b09551	journal	April 2020
Superparamagnetic MFe ₂ O ₄ (M = Fe, Co, Mn) Nanoparticles: Tuning the Particle Size and Magnetic Properties through a Novel One-Step Coprecipitation Route Pereira, Clara; Pereira, André M.; Fernandes, Carlos Chemistry of Materials, Vol. 24, Issue 8 https://doi.org/10.1021/cm300301c	journal	April 2012
Water Oxidation Catalysis: Electrocatalytic Response to Metal Stoichiometry in Amorphous Metal Oxide Films Containing Iron, Cobalt, and Nickel Smith, Rodney D. L.; Prévot, Mathieu S.; Fagan, Randal D. Journal of the American Chemical Society, Vol. 135, Issue 31 https://doi.org/10.1021/ja403102j	journal	July 2013
Unification of Catalytic Water Oxidation and Oxygen Reduction Reactions: Amorphous Beat Crystalline Cobalt Iron Oxides Indra, Arindam; Menezes, Prashanth W.; Sahraie, Nastaran Ranjbar Journal of the American Chemical Society, Vol. 136, Issue 50 https://doi.org/10.1021/ja509348t	journal	December 2014
Tuning the Size, the Shape, and the Magnetic Properties of Iron Oxide Nanoparticles Guardia, Pablo; Labarta, Amilcar; Batlle, Xavier The Journal of Physical Chemistry C, Vol. 115, Issue 2 https://doi.org/10.1021/jp1084982	journal	December 2010
Enhanced Adsorption of Arsenic onto Maghemites Nanoparticles: As(III) as a Probe of the Surface Structure and Heterogeneity Auffan, Mélanie; Rose, Jérôme; Proux, Olivier Langmuir, Vol. 24, Issue 7 https://doi.org/10.1021/la702998x	journal	April 2008
Mechanisms for Iron Oxide Formation under Hydrothermal Conditions: An in Situ Total Scattering Study Jensen, Kirsten M. Ø.; Andersen, Henrik L.; Tyrsted, Christoffer ACS Nano, Vol. 8, Issue 10 https://doi.org/10.1021/nn5044096	journal	October 2014
Artificially engineered magnetic nanoparticles for ultra-sensitive molecular imaging Lee, Jae-Hyun; Huh, Yong-Min; Jun, Young-wook Nature Medicine, Vol. 13, Issue 1, p. 95-99 https://doi.org/10.1038/nm1467	journal	December 2006
Fiji: an open-source platform for biological-image analysis Schindelin, Johannes; Arganda-Carreras, Ignacio; Frise, Erwin Nature Methods, Vol. 9, Issue 7 https://doi.org/10.1038/nmeth.2019	journal	June 2012
Cu(Ir1 − xCrx)2S4: a model system for studying nanoscale phase coexistence at the metal-insulator transition Božin, E. S.; Knox, K. R.; Juhás, P. Scientific Reports, Vol. 4, Issue 1 https://doi.org/10.1038/srep04081	journal	February 2014
In situ powder X-ray diffraction study of magnetic CoFe ₂ O ₄ nanocrystallite synthesis Andersen, Henrik L.; Christensen, Mogens Nanoscale, Vol. 7, Issue 8 https://doi.org/10.1039/C4NR06937D	journal	January 2015
Electrocatalysis for the oxygen evolution reaction: recent development and future perspectives Suen, Nian-Tzu; Hung, Sung-Fu; Quan, Quan Chemical Society Reviews, Vol. 46, Issue 2 https://doi.org/10.1039/C6CS00328A	journal	January 2017
Recent advances in nanostructured Nb-based oxides for electrochemical energy storage Yan, Litao; Rui, Xianhong; Chen, Gen Nanoscale, Vol. 8, Issue 16 https://doi.org/10.1039/C6NR01340F	journal	January 2016
Crystalline and magnetic structure–property relationship in spinel ferrite nanoparticles Andersen, Henrik Lyder; Saura-Múzquiz, Matilde; Granados-Miralles, Cecilia Nanoscale, Vol. 10, Issue 31 https://doi.org/10.1039/C8NR01534A	journal	January 2018
Enhanced intrinsic saturation magnetization of Zn _x Co _1−x Fe ₂ O ₄ nanocrystallites with metastable spinel inversion Andersen, Henrik Lyder; Granados-Miralles, Cecilia; Saura-Múzquiz, Matilde Materials Chemistry Frontiers, Vol. 3, Issue 4 https://doi.org/10.1039/C9QM00012G	journal	January 2019
Nanostructured spinel cobalt ferrites: Fe and Co chemical state, cation distribution and size effects by X-ray photoelectron spectroscopy Fantauzzi, Marzia; Secci, Fausto; Sanna Angotzi, Marco RSC Advances, Vol. 9, Issue 33 https://doi.org/10.1039/C9RA03488A	journal	January 2019
Water electrolysis: from textbook knowledge to the latest scientific strategies and industrial developments Chatenet, Marian; Pollet, Bruno G.; Dekel, Dario R. Chemical Society Reviews, Vol. 51, Issue 11 https://doi.org/10.1039/D0CS01079K	journal	January 2022
There's no place like real-space: elucidating size-dependent atomic structure of nanomaterials using pair distribution function analysis Christiansen, Troels Lindahl; Cooper, Susan R.; Jensen, Kirsten M. Ø. Nanoscale Advances, Vol. 2, Issue 6 https://doi.org/10.1039/D0NA00120A	journal	January 2020
Exploring the direct synthesis of exchange-spring nanocomposites by reduction of CoFe₂O₄ spinel nanoparticles using in situ neutron diffraction Ahlburg, Jakob Voldum; Granados-Miralles, Cecilia; Gjørup, Frederik Holm Nanoscale, Vol. 12, Issue 17 https://doi.org/10.1039/D0NR00912A	journal	January 2020
Size-induced amorphous structure in tungsten oxide nanoparticles Juelsholt, Mikkel; Anker, Andy S.; Christiansen, Troels Lindahl Nanoscale, Vol. 13, Issue 47 https://doi.org/10.1039/D1NR05991B	journal	January 2021
Tuning of cationic distribution in “partially inversed” cobalt ferrite spinel nanocubes via a nitrogen-doped graphene oxide support for enhanced bifunctional oxygen electrocatalysis Jha, Shwetambara; Jain, Priya; Palkovits, Regina Journal of Materials Chemistry A, Vol. 11, Issue 42 https://doi.org/10.1039/D3TA03486K	journal	January 2023
Cation distribution: a descriptor for hydrogen evolution electrocatalysis on transition-metal spinels Gomaa, Aya K.; Zonkol, Maram G.; Khedr, Ghada E. EES Catalysis, Vol. 2, Issue 6 https://doi.org/10.1039/D4EY00121D	journal	January 2024
Applications of magnetic nanoparticles in biomedicine Pankhurst, Q. A.; Connolly, J.; Jones, S. K. Journal of Physics D: Applied Physics, Vol. 36, Issue 13 https://doi.org/10.1088/0022-3727/36/13/201	journal	June 2003
Rapid-acquisition pair distribution function (RA-PDF) analysis Chupas, Peter J.; Qiu, Xiangyun; Hanson, Jonathan C. Journal of Applied Crystallography, Vol. 36, Issue 6, p. 1342-1347 https://doi.org/10.1107/S0021889803017564	journal	November 2003
PDFgetX3 : a rapid and highly automatable program for processing powder diffraction data into total scattering pair distribution functions Juhás, P.; Davis, T.; Farrow, C. L. Journal of Applied Crystallography, Vol. 46, Issue 2 https://doi.org/10.1107/S0021889813005190	journal	March 2013
The structure of cobalt oxide, Co ₃ O ₄ Smith, W. L.; Hobson, A. D. Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 29, Issue 2 https://doi.org/10.1107/S0567740873002505	journal	February 1973
The structure of magnetite Fleet, M. E. Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 37, Issue 4 https://doi.org/10.1107/S0567740881004597	journal	April 1981
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT Ravel, B.; Newville, M. Journal of Synchrotron Radiation, Vol. 12, Issue 4 https://doi.org/10.1107/S0909049505012719	journal	June 2005
Neutron and X-ray diffraction study of ferrite nanocrystals obtained by microwave-assisted growth. A structural comparison with the thermal synthetic route Solano, Eduardo; Frontera, Carlos; Puig, Teresa Journal of Applied Crystallography, Vol. 47, Issue 1 https://doi.org/10.1107/S1600576713032895	journal	January 2014
PDFgetN3 : atomic pair distribution functions from neutron powder diffraction data using ad hoc corrections Juhás, Pavol; Louwen, Jaap N.; van Eijck, Lambert Journal of Applied Crystallography, Vol. 51, Issue 5 https://doi.org/10.1107/S1600576718010002	journal	August 2018
diffpy.mpdf: open-source software for magnetic pair distribution function analysis Frandsen, Benjamin A.; Hamilton, Parker K.; Christensen, Jacob A. Journal of Applied Crystallography, Vol. 55, Issue 5 https://doi.org/10.1107/S1600576722007257	journal	August 2022
Local and long-range atomic/magnetic structure of non-stoichiometric spinel iron oxide nanocrystallites Andersen, Henrik L.; Frandsen, Benjamin A.; Gunnlaugsson, Haraldur P. IUCrJ, Vol. 8, Issue 1 https://doi.org/10.1107/S2052252520013585	journal	January 2021
Magnetic pair distribution function analysis of local magnetic correlations Frandsen, Benjamin A.; Yang, Xiaohao; Billinge, Simon J. L. Acta Crystallographica Section A Foundations and Advances, Vol. 70, Issue 1, p. 3-11 https://doi.org/10.1107/S2053273313033081	journal	December 2013
Magnetic structure determination from the magnetic pair distribution function (mPDF): ground state of MnO Frandsen, Benjamin A.; Billinge, Simon J. L. Acta Crystallographica Section A Foundations and Advances, Vol. 71, Issue 3, p. 325-334 https://doi.org/10.1107/S205327331500306X	journal	April 2015
Nanoparticles: Strained and Stiff Gilbert, B. Science, Vol. 305, Issue 5684 https://doi.org/10.1126/science.1098454	journal	July 2004
Photochemical Route for Accessing Amorphous Metal Oxide Materials for Water Oxidation Catalysis Smith, Rodney D. L.; Prévot, Mathieu S.; Fagan, Randal D. Science, Vol. 340, Issue 6128 https://doi.org/10.1126/science.1233638	journal	March 2013
Synthesis of magnetic spinel ferrite CoFe2O4 nanoparticles from ferric salt and characterization of the size-dependent superparamagnetic properties Liu, Chao; Rondinone, Adam J.; Zhang, Z. John Pure and Applied Chemistry, Vol. 72, Issue 1-2 https://doi.org/10.1351/pac200072010037	journal	January 2000
Influence of change in cation distribution on the magnetic and catalytic properties via thermal annealing of spinel-type CoFe₂O₄ Roongtao, Rachanusorn; Ruttanapun, Chesta Japanese Journal of Applied Physics, Vol. 58, Issue 10 https://doi.org/10.7567/1347-4065/ab3bef	journal	September 2019

Similar Records

Local and long-range atomic/magnetic structure of non-stoichiometric spinel iron oxide nanocrystallites

Journal Article · Thu Dec 31 23:00:00 EST 2020 · IUCrJ · OSTI ID:1712508

Preparation of submicrometer-sized copper and silver crystallites by a facile solvothermal complexation-reduction route

Journal Article · Sun May 15 00:00:00 EDT 2005 · Journal of Solid State Chemistry · OSTI ID:20725941

Related Subjects

77 NANOSCIENCE AND NANOTECHNOLOGY

Effect of solvothermal synthesis parameters on the crystallite size and atomic structure of cobalt iron oxide nanoparticles

Citation Formats

References (56)

Similar Records

Related Subjects