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Centro de Investigacion en Ciencias Fsico Matematicas (CICFiM)/Facultad de Ciencias Fsico Matematicas (FCFM) and Facultad
de Ingeniera Mecanica y Electrica (FIME), Universidad Autonoma de Nuevo Leon (UANL), Avda. Universidad S/N, San Nicolas de
los Garza, Nuevo Leon 66450, Mexico
Centro de Fsica de Materiales (CFM-CSIC), P Manuel de Lardizabal 5, 20018 San Sebastian, Spain
Departamento de Fsica, Facultad de Ciencias, Universidad de Oviedo, Calvo Sotelo S/N, 33007 Oviedo, Spain
Departamento Fsica de Materiales, Facultad de Qu mica, Universidad del Pais Vasco (UPV/EHU), Paseo Manuel de Lardizabal 3,
20018 San Sebastian, Spain
ABSTRACT: The magnetic properties of low dimensional materials of several
iron oxyhydroxide phases, such as akaganeite (-FeOOH) or lepidocrocite (FeO(OH)), remain poorly explored, probably due to their specic preparation as
single crystalline phase requires special conditions owing to their structural
instability. In the present work, ultrane akaganeite nanoparticles were prepared
by the hydrolysis of FeCl3 solutions at room temperature induced by the presence
of NaOH. The resulting product was characterized by several analytical
techniques. Structural investigations using X-ray diraction (XRD), highresolution transmission electron microscopy (HRTEM), and selected area
electron diraction (SAED) revealed that the sample was mainly constituted by
rather-equiaxial akaganeite nanocrystals with mean diameter of 3.3 0.5 nm. In
addition, a small amount of rodlike akaganeite particles with 23 5 nm in length
and 5 1 nm in width was also detected. The study of the respective
dependences of the dc magnetization and the ac susceptibility on temperature and exciting magnetic eld revealed complex
magnetic relaxation processes, high coercivity values at low temperature, and exchange bias eect. These results have been
tentatively explained considering size distribution eects and the presence of superparamagnetic and spin glass-like contributions
arising from the frustration of the antiferromagnetic order owing to surface eects and an insucient lling of the akaganeite
channels with Cl anions.
1. INTRODUCTION
The materials that constitute the iron oxide family (which,
according to the tradition, includes iron hydroxides and iron
oxyhydroxides1) are of key importance due to their extensive
presence in nature and their functional properties.1 Particularly,
the wide variety of their magnetic responses, including
ferrimagnetic, antiferromagnetic, weak ferromagnetic, superparamagnetic, or speromagnetic behaviors,1 which are closely
correlated with the size, morphology, and crystallochemical
features of these materials, has attracted enormous attention for
several decades. Moreover, some of the iron oxides exhibit
interesting rst-order magnetic phase transitions, such as the
Morin transition found in hematite2,3 and the Verwey transition
discovered in magnetite.46 However, it is remarkable that the
research in iron oxides still remains a subject of intense study
and controversy, and the interpretation of some experimental
results demands better renements. In fact, the crystallographic
properties and magnetic behaviors of some iron oxyhydroxides
are the subject of debate. One clear example of this is
2014 American Chemical Society
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2. EXPERIMENTAL SECTION
Chemicals. Anhydrous iron(III) chloride (FeCl3, 97%,
Sigma-Aldrich), sodium hydroxide (NaOH, 98%, J. T. Baker),
and absolute ethanol (Sigma-Aldrich) were used with the as
received purity. The water added in all experiments was doubly
distilled.
Preparation of Akaganeite Nanoparticles. Nanosized
akaganeite particles were prepared by the hydrolysis of aqueous
iron(III) chloride solution at room temperature. This one-step
preparation of an akaganeite colloid consisted in the simple
following procedure based on the results of previous works.26
Briey, 25 mL of 2 M aqueous solution of FeCl3 was rapidly
added to 30 mL of 5 M aqueous sodium hydroxide solution
under vigorous and continuous stirring using a stirring plate at
room temperature. Immediately, the solution changed its color,
and it acquired a yellowish-brown color, suggesting the
formation of an iron oxyhydroxide colloidal suspension. After
10 min, the resulting suspension was diluted with absolute
ethanol and centrifuged. The supernatant solution was
removed, and the precipitated powder was washed several
times with doubly distilled water, absolute ethanol, and
centrifugation. Finally, the so-prepared powders were dried at
50 C for 5 h. The obtained particles were not subjected to
posterior aging process at temperatures close to 100 C as in
previous works.26
Characterization Techniques. The crystalline phase of
the sample was identied by powder X-ray diraction (XRD),
using a Panalytical Empyrean diractometer. This diractometer is equipped with a graphite monochromator on the
diraction bean and a X Celerator linear detector. The
difractometer was calibrated with a silicon standard sample.
Cu K1 X-ray radiation ( =1.540 598 0 ) was generated from
a Cu anode and was set up on 45 kV and 40 mA. Data were
collected at room temperature in the 2 range between 19.996
and 90.000, with a scan step size of 0.017. The mean
coherence lengths (MCL) perpendicular to some crystallographic planes of the sample were calculated from the full width
at half-maximum of the corresponding XRD peak using the
Scherrer equation:27
MCL =
0.9
cos B
HC =
HC+ HC
,
2
HEB =
(HC+ + HC)
2
(2)
(1)
(3)
Article
Figure 2. (a) TEM micrograph of the akaganeite nanoparticles at low magnication. The inset shows the SAED pattern of the large-area showed in
panel a. The presence of rod-like shape nanoparticles is highlighted by arrows. (b) HRTEM image. The upper inset is a magnication of the image,
and the lower inset is the FFT pattern of the area highlighted by square. (c, d) Histograms of the eective particle diameter of the equiaxial particles
and nanorods observed in the TEM micrographs.
The in-phase component (i.e., the real part, ) and the out-ofphase component (i.e., the imaginary part, ) of the ac
susceptibility were both simultaneously measured at 21
dierent frequencies, , in the range of 10010 000 Hz and
at the temperature range of 5100 K in absence of dc elds
using a PPMS (physical property measurement system), model
6000 (Quantum Design). The data were recorded following the
next procedure. First, the sample was cooled from room
temperature to 5 K in the absence of exciting magnetic elds.
Then a probing ac magnetic eld of amplitude 2 Oe was
applied with frequencies varied from 10 up to 10 000 Hz.
Afterward, the same measurements were carried out at higher
temperatures up to 101 K in steps of 2 K. The cusp
temperatures of the vs T and vs T curves were accurately
determined as the temperature at which the corresponding rstderivative curve changes of sign.
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T
C
(4)
Article
(5)
(6)
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Figure 7. (a) Thermoremanent magnetization (MTRM) curve measured at 100 Oe (inset) and its temperature derivative, dMTRM/dT. (bf)
Thermal dependence of the derivative of the dierence MFC MZFC with respect to temperature obtained at dierent magnetic elds. The green
curve is the best curve t to the sum of two log-normal distributions (curves in blue and red, named 1 and 2, respectively).
(7)
H (1 Tp/Tg)3/2
(8)
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Ed d = 0 MS2dm 3
(9)
24
TCr =
gkB 2HAHE
2kB
(10)
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Figure 10. Thermal dependence of the (a) real and (b) imaginary
parts of the ac susceptibility of the akaganeite nanoparticles obtained at
dierent frequencies of the exciting magnetic eld.
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T
HC(T ) = HC(0)1
TB
(11)
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AUTHOR INFORMATION
Corresponding Author
ACKNOWLEDGMENTS
The authors acknowledge the division Unidad de Medidas
Magneticas PPMS de los Servicios Generales de Investigacion
SGIker from The University of the Basque Country for having
allowed us to use the PPMS. Financial support from the
Mexican Council of Science and Technology (CONACYT)
and Universidad Autonoma de Nuevo Leon under research
projects CB12-179486 and PAICYT-CE793-11, respectively, is
acknowledged. Spanish funding under the MINECO research
project MAT2010-20798-C05-04 and FEDER is also acknowledged.
REFERENCES
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Transition in Hematite Nanocrystals Self-Assembled Into ThreeDimensional Structures. J. Nanosci. Nanotechnol. 2012, 12, 75717576.
(4) Verwey, E. J. W. Electronic Conduction of Magnetite (Fe3O4)
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4. CONCLUSIONS
The hydrolysis of FeCl3 solutions at room temperature induced
by the presence of NaOH, and without further thermal
treatments, yields the formation of ultrane akaganeite
particles. Such nanoscale system is mainly constituted by
rather-equiaxial -FeOOH nanocrystals with diameters around
3.3 nm and by a small fraction of rod-like particles with 23 5
nm in length and 5 1 nm in width. These particles exhibit an
interesting magnetic phenomenology that includes superparamagnetic-like behaviors, anomalous eld dependences of
Tp and Tirr, magnetic hysteresis at low temperatures with small
jumps of the magnetization at low eld values, and exchange
bias. This complex phenomenology has been explained
considering the presence of two particle populations (rather
equiaxial and rod-like particles) and the coexistence of
antiferromagnetically coupled spins and uncompensated spins
in a freezing magnetic state at low temperatures. The partial
breakdown of the antiferromagnetic order is produced by two
sources of frustration of antiferromagnetic interactions and
magnetic disorder: (i) the geometrical frustration of the
antiferromagnetic coupling produced by the reduced coordination number and structural disorder at the particle surface,
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