Published on Web 02/02/2007

Sonochemical Synthesis of Nanosized Hollow Hematite

Jin Ho Bang and Kenneth S. Suslick*
School of Chemical Sciences, UniVersity of Illinois at Urbana-Champaign, 600 South Mathews AVenue,
Urbana, Illinois 61801
Received October 26, 2006; E-mail: [email protected]

Hollow inorganic materials are of great interest, in part because

of their diverse applications for drug delivery, catalysis, photonic
crystals, etc.1 Various preparation methods have been developed
to fabricate hollow inorganic materials2,3 and even hollow single
crystals;4 most commonly these synthetic methods exploit the use
of silica nanospheres as a sacrificial template material. While silica
colloids are commercially available in various sizes, silica template
removal is time-consuming, and the use of the highly aggressive
and toxic hydrofluoric acid is unavoidable. Here, we report a
sonochemical fabrication of crystalline hollow hematite (R-Fe2O3)
using carbon nanoparticles as a spontaneously removable template
for nanosized hollow core formation. Figure 1. (a) Bright-field TEM image and (b) dark-field TEM image
Ultrasound has found an important niche in the preparation of (inset: SAED pattern) of nanosized hollow iron oxide.
inorganic materials, including amorphous metals and metal oxides,
nanostructured layered materials with high catalytic activity, and Figure 2 parts a and b show powder X-ray diffraction (XRD)
semiconductor quantum dots.4,5 During the irradiation of liquids pattern and Raman spectrum of the nanosized hollow iron oxide.
with ultrasound, the extreme but transient local conditions caused The resolved diffraction peaks match the standard R-Fe2O3 sample
by acoustic cavitation (∼5000 K, ∼500 bar)6 can not only perfectly (JCPDS 33-0664), and no characteristic peaks of impurities
decompose organometallic precursors to generate metal atoms but were observed. The Raman spectrum of the hollow iron oxide also
can also facilitate the uniform deposition of the nanosized inorganic matches that of typical hematite (R-Fe2O3),9 including the unusual
particles onto another surface or template.4,7 two-magnon scattering (i.e., a collective spin transition) at 1320
Nanosized hollow iron oxide was prepared by irradiating a cm-1. Mössbauer spectra (Figure S7 in SI) confirm the presence
mixture of carbon nanoparticles (0.1 g) and iron pentacarbonyl (0.5 of hematite as the only iron species.
mL) in 40 mL of hexadecane with a high-intensity ultrasound horn The as-produced hollow hematite was annealed at 450 °C for 2
(Sonics & Materials, model VCX-750, 1 cm2 Ti horn at 20 kHz h under air to completely remove any organic residues. TEM
and 50 W/cm2 at 20 °C for 3 h under argon flow) (Figure S1 in observation and EDS analysis reveal that the hollow hematite still
Supporting Information (SI)). Spherical carbon nanoparticles (4- maintains its morphology and composition after the heat-treatment.
12 nm diameter, Figures S2 and S3 in SI) were prepared from the The SAED pattern indicates improved crystallinity of the hollow
carbonization of polypyrrole nanoparticles as previously reported hematite after annealing. Consistent with the improved crystallinity,
with some modification.8 The initial product of Fe/carbon composite the XRD pattern and Raman spectrum are more sharply defined
was quickly washed with pentane and filtered under air to remove (Figure 2c,d).
hexadecane and unreacted Fe(CO)5. As soon as the Fe/carbon As a control experiment, we sonicated iron pentacarbonyl in
composite was dried, the composite rapidly oxidized with release hexadecane without the carbon nanoparticles under the same
of heat, turning color from black to red. (CAUTION: On larger reaction conditions. A TEM examination of the as-prepared product
scale, this autoignition might prove hazardous.) After a few minutes, (Figure S8 in SI) shows agglomerated nanoparticles of ∼6 nm, as
the resulting red-colored product was thoroughly washed again with noted before.5b In contrast to the hollow iron oxide synthesized in
pentane. the presence of the carbon template, XRD analysis reveals that the
The as-obtained product was investigated by transmission product is amorphous iron oxide, and Raman spectrum of the
electron microscopy (TEM). The TEM image (Figure 1a) shows amorphous iron oxide is featureless, consistent with the XRD
iron oxide with nanosized hollow cores. The hollow structure is analysis (Figure S9 in SI).
more clearly visible with a dark-field image as shown in Figure Hematite, which has relevance to corrosion, pigments, catalysis,
1b, and selected-area electron diffraction (SAED) pattern reveals and even sensors, is the most thermodynamically stable phase of
the crystalline nature of the hollow iron oxide (Figures S3 and S4 iron oxide.10 In addition, hematite has been investigated as a
in SI). Energy dispersive X-ray spectroscopy (EDS) analysis and photoanode for water splitting because of its ability to absorb a
electron energy loss spectroscopy (EELS) performed in nanoprobe large part of the solar spectrum with its band gap of 2.2 eV.11 Bulk
mode confirm the formation of hollow iron oxide (Figure S5 in hematite is weakly ferromagnetic at 298 K with a Néel temperature
SI). The hollow iron oxide was also examined by scanning of 950 K and undergoes a “spin-flop” (Morin) transition at 263 K,
transmission electron microscopy (STEM) with EDS line analysis in which the magnetic moments change orientation.12 Nanoparticles,
across a single hollow iron oxide sphere. The Fe K line decreases however, often exhibit unusual magnetic behaviors different from
from the outer wall in toward the center of a particle, confirming that of bulk samples, owing to finite size effects.13 Figure 3 shows
the presence of the inner hollow core (Figure S6 in SI). magnetization curves of the hollow hematite measured at 5 and
2242 9 J. AM. CHEM. SOC. 2007, 129, 2242-2243 10.1021/ja0676657 CCC: $37.00 © 2007 American Chemical Society
 COMMUNICATIONS

ticles as a template has been demonstrated. The hollow iron oxide

is the thermodynamically stable crystalline hematite (R-Fe2O3) and
shows weak ferromagnetism down to 5 K. Without the use of
carbon template, only agglomerated amorphous iron oxide was
obtained, demonstrating the dual roles of the carbon nanopar-
ticles: template and fuel for combustion. We believe that this
procedure will be easily extended to prepare other hollow inorganic
materials.
Acknowledgment. We gratefully acknowledge K.-W. Kwon
and Prof. M. Shim (Raman spectra), Dr. Jian-Guo Wen and
Changhui Lei (EELS and STEM), and Profs. J. W. Stucki and B.
A. Goodman (Mössbauer). This work was supported by the DOE
(Grant DEFG02-91-ER45439) and the Center for Microanalysis of
Materials and the Frederick Seitz Materials Research Laboratory,
with salary support from NSF (Grant CHE-03-15494).
Supporting Information Available: Further characterization of
nanosized hollow hematite and characterization of amorphous iron oxide
synthesized without carbon template. This material is available free of
charge via the Internet at http://pubs.acs.org.
Figure 2. XRD patterns and Raman spectra of nanosized hollow iron oxide,
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preparation of nanosized hollow iron oxide using carbon nanopar- JA0676657

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