Size- and phase-controlled synthesis of cobalt nanoparticles for potential biomedical

applications
C. Osorio-Cantillo, A. N. Santiago-Miranda, O. Perales-Perez, and Y. Xin

Citation: Journal of Applied Physics 111, 07B324 (2012); doi: 10.1063/1.3676620

View online: http://dx.doi.org/10.1063/1.3676620
View Table of Contents: http://scitation.aip.org/content/aip/journal/jap/111/7?ver=pdfcov
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 JOURNAL OF APPLIED PHYSICS 111, 07B324 (2012)

Size- and phase-controlled synthesis of cobalt nanoparticles for potential

biomedical applications
C. Osorio-Cantillo,1,a) A. N. Santiago-Miranda,2 O. Perales-Perez,1,3 and Y. Xin4
1
Department of Chemistry, University of Puerto Rico - Mayagüez, Puerto Rico 00681-9000, USA
2
Department of Chemical Engineering, University of Puerto Rico, Mayagüez, Puerto Rico 00681-9044, USA
3
Department of Engineering Science and Materials, University of Puerto Rico, Mayagüez,
Puerto Rico 00681-9044, USA
4
National High Magnetic Field Laboratory, Tallahassee, Florida 32310, USA
(Presented 2 November 2011; received 11 October 2011; accepted 14 November 2011; published
online 7 March 2012)
The present work addresses the synthesis and characterization of crystalline cobalt nanoparticles
produced through a modified polyol-process conducive to the controlled formation of magnetic
soft-Co structures with potential for applications in biomedicine. XRD characterization evidenced the
influence of oleate and acetate species on the formation and crystal growth-inhibition of crystalline
fcc-Co with controlled average crystallite sizes in the 8–10nm range. Magnetic measurements
confirmed the strong influence of synthesis conditions on crystal structure and hence, on magnetic
properties. As-synthesized nanoparticles exhibited coercivity values below 100 Oe and magnetization
as high as 155 emu/g at room temperature. These values agreed with the soft magnetic nature of the
fcc-Co phase. VC 2012 American Institute of Physics. [doi:10.1063/1.3676620]

I. INTRODUCTION through a modified polyol process in presence of oleate and ace-

Actual and potential applications of metallic cobalt nano-
particles are based on the corresponding magnetic properties.1
Metallic cobalt exhibits three well-known allotropes: anisotropic
high-coercivity hcp-Co, pseudo-cubic e-Co, and symmetric low-
coercivity fcc-Co; it is the last one that can be used in soft mag-
netic applications involving power electronics and biomedicine.2
Superparamagnetic Fe oxide nanoparticles (Fe3O4 and c-Fe2O3)
are among the most widely used materials in the biomedical
arena;3 however, their relatively low magnetization value starts
to become a concern when the size of the particles becomes
very small, making their magnetic manipulation a challenging
task. A better alternative would be the use of particles exhibiting
high-magnetic moment and high-initial magnetic susceptibility
even at the nanoscale. Accordingly, particles of magnetically
soft fcc-Co phase exhibiting nanometric size, high saturation
magnetization and reasonably low coercivity promise to be a
good candidate for either medical diagnostic or therapy applica-
tions. Various synthesis routes have been developed to produce
nanocrystalline cobalt with a suitable control of the particle mor-
phology, surface stability, and magnetic properties.4 Regarding
the control on particle size and prevention of nanocrystals aggre-
gation, the use of surfactants and stabilizing agents have been
suggested.5 Our earlier works reported the use of oleate and ace-
tate species to control the phase stability conditions of crystal-
line and sub-micrometric Co synthesized in trimethylene glycol
and tetraethylene glycol;6 however, the proper control of size
monodispersity and magnetic moment at the nanoscale is still a
challenging task. Based on these considerations, the present
work addresses the determination of the most suitable conditions
leading to the formation of magnetically soft Co nanoparticles
a)
Author to whom correspondence should be addressed. Electronic mail:
celiaosorio@yahoo.com.
tate species that will act as surfactants to prevent particles from
growth and aggregation as well as surface modifiers.
II. EXPERIMENTAL
A. Materials
Ethylene glycol, EG (99%, Alfa Aesar), was used as the
solvent and the reducing medium. Co(II)-acetate tetrahydrate
(98%, Alfa Aesar) was the metal precursor, whereas sodium
hydroxide, NaOH (98%, Alfa Aesar), was selected as the
reaction catalyst. Sodium oleate (95%, TCI) and sodium ace-
tate (99.0–100.5%, Alfa Aesar) were used as surfactants.
B. Synthesis and characterization of nanocrystalline
cobalt
Cobalt particles were synthesized by refluxing a 0.01 M
cobalt acetate solution in ethylene glycol containing sodium ole-
ate or sodium acetate at specific molar ratios with respect to Co.
All synthesis experiments were carried out at a fixed OH/Co
mole ratio of 50. The alkaline condition provided by the excess
of OH ions leads to an acceleration of the reduction reaction
due to the improvement in the solubility of the intermediate.6
The resulting solution was then refluxed at 195–198  C for 2
hours to facilitate the precursor dissolution and final formation
of metallic Co. Resulting powders were recovered by centrifu-
gation, washed three times with acetone and ethanol, and then
stored in ethanol to prevent oxidation. The structural characteri-
zation of recovered Co nanocrystals was carried out in a Sie-
mens D500 X-Ray diffractometer using the Cu-Ka radiation,
and the average crystallite size was estimated by using the
Scherrer’s equation. For morphology and size analyses a Trans-
mission Electron Microscopy TEM (JEOL 2011) was used;

0021-8979/2012/111(7)/07B324/3/$30.00 111, 07B324-1 C 2012 American Institute of Physics

V

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 07B324-2 Osorio-Cantillo et al.
FIG. 1. XRD patterns for powders synthesized in EG at a mole ratio OH/
Co of 50 and different oleate/Co and acetate/Co mole ratios: (a) nor oleate
or acetate; (b) oleate/Co mole ratio 5; (c) oleate/Co mole ratio 10; and (d)
oleate/Co and acetate/Co mole ratios of 5 and 40, respectively. The reaction
time was 2 h in all experiments.
Fourier Transform Infrared spectroscopy (Shimadzu IRAffinity-
1) allowed study the chemical structure characterization of sur-
face species. The magnetic properties of the nanocrystalline par-
ticles were measured at room temperature (RT) using a
vibrating sample magnetometer (VSM, Lakeshore 7400 Series)
at a maximum applied field of 22 kOe. The corresponding
magnetization and coercivity values were determined for the
powders compacted in the VSM holder. Magnetization was
reported per unit weight of dried sample.
III. RESULTS AND DISCUSSION
A. XRD analyses
Figure 1 shows the XRD patterns for the solids synthe-
sized in EG after 2 h of reaction. The pattern of Figure 1(a) evi-
denced the co-existence of e-Co, fcc- and hcp-Co phases when
the synthesis reaction took place at a OH/Co mole ratio of
50. The progressive inhibition of the e-Co and hcp-Co phases
FIG. 2. TEM image of Cobalt particles synthesized in EG and mole ratios
of oleate/Co ¼ 5 and acetate/Co ¼ 40. The inset corresponds to the size dis-
tribution histogram.
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J. Appl. Phys. 111, 07B324 (2012)
FIG. 3. FT-IR spectra of cobalt nanoparticles synthesized at different ole-
ate/Co and acetate/Co mole ratios in EG: (a) oleate/Co ¼ 5 and acetate/
Co ¼ 40; (b) oleate/Co ¼ 10; (c) oleate/Co ¼ 5; (d) oleate/Co ¼ acetate/
Co ¼ 0. The FT-IR spectra for pure sodium oleate and sodium acetate [(e),
(f)] are shown here for comparison purposes.
at expenses of the exclusive development of the fcc-Co phase
became evident when oleate/Co mole ratios of 5 and 10 were
selected (Figures 1(b), 1(c)); oleate groups should have been
adsorbed onto specific crystal planes, inhibiting the further
growth of the e- and hcp-phases while promoting the develop-
ment of the fcc structure. As Figure 1(d) evidences, Co-fcc
was the only phase when the particles were synthesized when
oleate and acetate species co-existed at different molar ratios
in reacting solutions (oleate/Co ¼ 5, acetate/Co ¼ 40). Acetate
species should have reinforced the specific adsorption effect
of oleate species involved with the inhibition of the Co-
phases other than fcc. The average crystallite size of fcc-Co
particles and the lattice parameter were estimated at
9.2 6 1.1 nm and 0.3544 6 0.0002 nm, respectively. The lat-
tice parameter was in good agreement with the value for the
bulk (0.35447 nm, Powder diffraction file N 00-015-0806).
B. Electron microscopy analyses
FCC-cobalt particles synthesized in presence of oleate
and acetate species, consisted of rather monodisperse
FIG. 4. M-H loops at 300 K for cobalt particles synthesized at different ole-
ate/Co and acetate/Co mole ratios. The inset corresponds to details about the
origin of curve.
 07B324-3 Osorio-Cantillo et al.
spherical particles with an average crystal size of
5.13 6 0.65 nm as shown in the TEM image and the corre-
sponding size distribution histogram of Figure 2. The dis-
crepancy between the TEM size (5.13 6 0.65 nm) and the
average crystallite size estimated by (9.2 6 1.1 nm) can be
attributed to the lack of precision in the determination of the
full-width-half-maximum (FWHM) value in broad diffrac-
tion patterns typical of nanocrystalline samples. TEM analy-
ses evidenced the critical role of oleate and acetate species
not only on the development of specific Co structures but
also on limiting crystal growth through probable steric repul-
sive inter-particle interactions.
C. FT-IR measurements
The FT-IR spectra of Co powders produced in the pres-
ence of oleate and acetate species at different synthesis condi-
tions are shown in Figure 3. Spectra 3-e and 3-f correspond to
pure sodium oleate and sodium acetate salts and are shown for
comparison purposes only. These spectra show two signature
bands at 1600 cm1 and 1400 cm1, which can be assigned to
the vs(C¼O) and va(C¼O) stretching modes in the oleate and
acetate structures. The presence of these bands (Figures
3(a)–3(c)), would indicate the adsorption of oleate species
onto the metal surface. It has been suggested that the interac-
tions between the Co atoms and the surfactants functional
group involve the coordinating bonding between the COOH-
group, of either oleate or acetate, and the metal atom on the
surface through the donation of lone-pair electrons from oxy-
gen to cobalt charging negatively its surface.7 This fact could
have helped the observed inhibition in crystal growth. Addi-
tionally, the spectrum for the sample synthesized in absence
of oleate or acetate species, Figure 3(d), also shows the above
mentioned carboxylic surface groups belonging to the oxi-
dized polyol. The presence of the identified functional groups
adsorbed onto Cobalt surface will also be of importance for
envisioned applications in nanomedicine.8
D. Room-temperature M-H measurements
The room temperature M-H measurements for cobalt par-
ticles synthesized in presence of oleate and acetate species con-
firmed the phase-dependence of their magnetic properties
(Figure 4). The coercivity decreased from 425 Oe to 83 Oe when
mole ratios of oleate/Co ¼ 5 and acetate/Co ¼ 40 were used. The
remarkable decrease in coercivity can be explained by the con-
version of the magnetically hard hcp-Co phase contained in the
mixture of crystalline phases obtained in the absence of surfac-
tants into the magnetically soft fcc-Co nanoparticles in the region
of single domain (below 10 nm for fcc-Co).9 The corresponding
saturation magnetization values were increased from 121 emu/g
(mixture of Co-phases produced in absence of surfactants) to
155 emu/g and 147 emu/g for the samples synthesized in the
presence of oleate, and oleate þ acetate, respectively. These satu-
ration magnetization values are very high when compared with
magnetite (92 emu/g and 69 emu/g for bulk and 7 nm-sized
particles) (Ref. 10) and comparable to the bulk value
166 emu/g.
The attained high saturation values and the low but no-
ticeable coercivity, unexpected for fcc-cobalt nanoparticles
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J. Appl. Phys. 111, 07B324 (2012)
of around 5 nm in diameter, could be attributed to interpar-
ticle magnetic interactions11 promoted by some extent of
agglomeration in the sample. The ferromagnetic behavior of
fcc-Co nanoparticles with a diameter below 6 nm has also
been observed by Gajbhiye et al, and others.12
In general, the detected drop in magnetization in the
samples corresponding to fcc-Co can be associated to the ex-
istence of a magnetically dead layer onto the particles sur-
face, presence of surface canted spins, or spin-glass-like
behavior of the surface spins.13 Other works have also sug-
gested that the reduction of the magnetic moment in colloi-
dal cobalt particles stabilized with organic ligands should be
a consequence of the quenching of the surface magnetic
moments due to surface-bonded ligands.7 In our case, the de-
velopment of a non-magnetic layer of organic species
adsorbed onto the surface of the metallic particles, as sug-
gested by FT-IR analyses, can also be involved with the
observed lowering in magnetization values compared with
bulk of cobalt. The present results suggests the feasibility in
controlling the exclusive formation of magnetically soft fcc-
Co nanoparticles exhibiting high saturation magnetization,
rather monodisperse nanometric size and a surface viable for
subsequent bio-functionalization as required by the envi-
sioned biomedical applications.
IV. CONCLUSIONS
Nanocrystalline fcc-Co particles have been successfully
synthesized by a modified polyol method. Characterization
results evidenced the influence of oleate and acetate species,
promoting the stability of the magnetically soft fcc structure
and high-magnetization, as well as favoring the size reduc-
tion and surface functionalization.
ACKNOWLEDGMENTS
This work is supported by the National Science Founda-
tion under Grant No. (CREST-HRD 0833112), and NSF-
EPSCoR Institute for Functional Nanomaterials (IFN).
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