Water bath synthesis and enhanced photocatalytic performances of

urchin-like micro/nanostructured a-FeOOH

Shenghong Kang, Guozhong Wang, Ming Fang, Huiming Wang, Xianbiao Wang, and Weiping Caia)
Key Laboratory of Materials Physics, Centre for Environmental and Energy Nanomaterials, Anhui Key Laboratory
of Nanomaterials and Nanotechnology, Institute of Solid State Physics, Chinese Academy of Sciences, Hefei
230031, People’s Republic of China

(Received 10 December 2014; accepted 30 March 2015)

Micro/nanostructured goethite (a-FeOOH) was synthesized by a low-temperature water bath

method based on the reaction of urea and FeSO4d7H2O at 95 °C. It has been shown that the
as-prepared a-FeOOH consists of nearly spherical particles with about 0.5–1 lm in diameter.
The microsized a-FeOOH particles are urchin-like in morphology and composed of nanosized
leaf-like objects, with about 150–200 nm in length and about 30–50 nm in width, in radial
arrangement, showing high specific surface area (;118 m2/g). The formation of such urchin-like
a-FeOOH could be described by a two-step process, or formation of spherical particles, and
ethylene glycol-adsorption induced preferential growth of nanoleaves on the preformed spherical
particles. Importantly, such micro/nanostructured a-FeOOH has exhibited much higher
photocatalytic activity to the organic pollutants, such as Rhodamine 6G, and better re-usable
performances than the goethite nanorod powders, exhibiting the good application potential in
the environmental treatment. This study could provide a useful material for environmental
pollution treatment.

I. INTRODUCTION (
OH) and surface iron complex (e.g., surface Fe(III)

It is well known that the textile, painting, leather,
printing, and photography industries would release some
organic pollutants, which could seriously contaminate the
water environment.1,2 The removal of the pollutants
based on photocatalysis, before they are released to water
system, has attracted extensive concerns over the last few
decades.3–5 TiO2, a popular semiconductor-based photo-
catalyst, has been extensively investigated for the degra-
dation of dyes in aqueous solution.6 Due to the broad
band gap of 3.0–3.3 eV, however, TiO2 can only work
under the ultraviolet (UV) light irradiation. The UV light
only occupies about 5% in the normal sunlight. There-
fore, utilization and development of photocatalysts’
working in the visible light range are of great interest.
Goethite (a-FeOOH), an important member of limonite
with a narrow band gap of 2.1 eV, is one of the most
common and reactive crystalline iron oxide phases found
in the soils and sediments. It is environment friendly and
acts as natural regulators of nutrients or pollutants.7–9
Recently, a-FeOOH has been reported as a visible light
photocatalyst owing to its nontoxicity, low cost, and
relatively good stability.10–13 Under UV–visible (UV–vis)
irradiation, a-FeOOH easily produces hydroxyl radical
Contributing Editor: Akira Nakajima
a)
Address all correspondence to this author.
e-mail: wpcai@issp.ac.cn
DOI: 10.1557/jmr.2015.103
species). The
OH is a nonspecific oxidant which can
react with most of organic contaminants.14–16 The highly
oxidized and unstable surface iron complex could also
react with water to form
OH.17 So, these characteristics
of a-FeOOH make it a promising photocatalyst in
the heterogeneous system. 6,18,19 To date, various
nanostructured a-FeOOH have been fabricated in-
cluding nanowires,9,10 nanobelts,12 etc. For instance,
Krýsa et al. synthesized a-FeOOH nanorods by a
solution method and showed that the photocatalytic
degradation of salicylate and oxalate was about 20 h
under Philips HPW 125 W lamps.12 Zhou et al.
fabricated a-FeOOH nanobelts by an assembly
method within ferritin and demonstrated that photo-
catalytic degradation to Rhodamine B is about 70 min
with H2O2 additive under a 300 W xenon lamp.13
However, thermodynamically, the powders consisting
of such nanoobjects are easily tending to aggregate if
they are not chemically surface-modified, which
would decrease reusability and weaken the photocatalytic
performances. The micro/nanostructured photocatalysts,
which consist of microsized objects with nanostructures,
could provide an effective way to solve this problem, due
to their high activity of nanostructure and stability of the
bulk.12,13,16 There are some reports about fabrication of
micro/nanostructured a-FeOOH by a hydrothermal
route.8,9,15,19 For instance, Wang et al. synthesized
a-FeOOH hollow spheres with hierarchical structures
by glycerol-assisted one-pot reaction at 120 °C8 and

J. Mater. Res., Vol. 30, No. 10, May 28, 2015 Ó Materials Research Society 2015 1629
 S. Kang et al.: Water bath synthesis and enhanced photocatalytic performances of urchin-like micro/nanostructured a-FeOOH
one-pot hydrothermal treatment of Fe2(SO4)3 aqueous
solution at 160 °C.9
Herein, we present a facile route to fabricate the micro/
nanostructured a-FeOOH via a low-temperature water
bath treatment of the precursor containing urea and
ethanediol, in addition to FeSO4d7H2O, at 95 °C. The
obtained a-FeOOH consists of the microsized particles
with nanostructure, which are urchin-like in morphology
and of high specific surface area (;118 m2/g). Impor-
tantly, such micro/nanostructured a-FeOOH has shown
much higher photocatalytic activity to the organic pollu-
tants, such as Rhodamine 6G (R6G), and better re-usable
performances than the nanostructured goethite, exhibiting
the good material for the environmental treatment.
II. EXPERIMENTAL
All the used chemical reagents, such as ferrous sulfate
(FeSO4d7H2O), ethanol (C2H5OH), urea (CO(NH2)2),
glycol (C2H6O2), and hydrogen peroxide solution
(H2O2), were of analytical grade and obtained from
National Medicines Co. Ltd. of China. These reagents
were used as-received without further purification.
A. Preparation
The micro/nanostructured a-FeOOH (or MNF for
short) was prepared based on a low-temperature water
bath treatment at 95 °C. In a typical procedure, the ferrous
sulfate solution was first prepared in a three-neck flask by
dissolution of FeSO4d7H2O (7 mmol) in 45 mL deionized
water and mixing with 45 mL C2H6O2. Subsequently, the
urea solution was prepared in a 50 mL conical flask in
nitrogen atmosphere by mixing CO(NH2)2 (25 mmol),
15 mL deionized water, and 15 mL C2H6O2. The three-
neck flask with the ferrous sulfate solution was put into
a thermostatic water tank with the constant temperature at
95 °C and mechanically stirred for 15 min in nitrogen
atmosphere. The urea solution in the conical flask was
then added into the three-neck flask with a flow rate of
1 mL min1 by a peristaltic pump in nitrogen atmosphere.
After that, the atmosphere was imported into the mixed
solution with a flow rate of 3 mL min1 by the peristaltic
pump. After 3 h, the solution was taken out from the water
bath and naturally cooled in air. Finally, the powder
products were obtained by filtering, washing with distilled
water and ethanol several times, and then drying in the
vacuum chamber at 55 °C for 6 h.
For reference, the a-FeOOH nanorods were also pre-
pared via a chemical route, as previously described.20
Briefly, a mixture of FeSO4d7H2O (0.5 mmol) and anhy-
drous CH3COONa (1 mmol) was dissolved in 20 mL of
distilled water in a beaker, followed by stirring vigorously
for about 20 min. A yellow suspension was thus obtained,
and then transferred into a Teflon-lined autoclave up to 80%
of the total volume, sealed, and heated at 100 °C for 8 h,
1630 J. Mater. Res., Vol. 30, No. 10, May 28, 2015
before cooling to room temperature naturally. The final
yellow solid products were collected by centrifuging,
washing with distilled water and absolute ethanol, and then
drying at 40 °C under a vacuum for 4 h.
B. Characterization
Phase structure of the products was characterized by x-ray
diffraction (XRD, Philips X’Pert Pro MPD) with Cu Ka
radiation (1.5406 Å). The morphological observation and
microstructural examination were conducted on a field
emission scanning electron microscope (FESEM; FEI
Sirion-200) and a transmission electron microscope (TEM;
JEOL JEM-2010, 200 kV). Thermal gravimetric (TG)
analysis and differential thermal analysis (DTA) were carried
out on a Pyris 1 thermal analyzer at a heating rate of
10 °C/min from room temperature to 500 °C under the
nitrogen environment. The spectral measurements were
performed by Fourier transform infrared spectroscopy
(FTIR, Nexus). The diffuse reflectance spectra were mea-
sured on an UV–visible–near infrared spectrophotometer
(Shimadzu, UV3600). The N2 isothermal sorption was
measured on a sorption apparatus (Omnisorp 100 CX,
Coulter).
C. Evaluation of the photocatalytic activity
The photocatalytic activity of the as-prepared products
was evaluated by measuring the optical absorbance of the
UV–vis irradiated pollutant-contained solution. Rhoda-
mine 6G (R6G, Alfa Aesar) aqueous solution was
selected as a model contamination. Prior to irradiation,
30 mg photocatalyst was mixed with R6G solution
(30 mL, 1  105 mol L1) in a 100 mL sample bottle
and stirred for 5 min in the dark. Subsequently, 100 lL of
hydrogen peroxide solution (H2O2, 30 wt%) was added to
the mixed solution (the H2O2 concentration in the mixed
solution was 33 mmol L1). The pH value of the mixed
solution was adjusted to 7 by hydrochloric acid or sodium
hydroxide. Then, the solution was exposed to a 300 W
xenon lamp at the distance of 15 cm with stirring. The
irradiated solution was sampled in each interval of 8 min
for optical absorbance measurement. The photocatalytic
degradation conversion was calculated by the formula:
A0  At
g¼ ; ð1Þ
A0
where g is the degradation ratio of R6G, A0 and At are the
absorbances at 525 nm for the R6G solution before and
after irradiation for time t, respectively.
III. RESULTS AND DISCUSSION
A. The morphology and structure
Figure 1 shows the XRD pattern of the as-prepared
products. All the diffraction peaks can be indexed to the
 S. Kang et al.: Water bath synthesis and enhanced photocatalytic performances of urchin-like micro/nanostructured a-FeOOH
pure orthorhombic structure of a-FeOOH with lattice
constants of a 5 4.6188 Å, b 5 9.9528 Å, and c 5
3.0236 Å (JCPDS No. 81-0462). The reference sample
shows the same structure, as similarly seen in Fig. 1. The
corresponding FESEM observation has revealed that the
as-prepared products or the a-FeOOH powders consist
of nearly spherical particles with about 0.5–1 lm in
diameter [Fig. 2(a)]. The high magnification image has
shown that the microsized a-FeOOH particles are urchin-
like in morphology and composed of nanosized leaf-like
building blocks in radial arrangement, as clearly seen in
Figs. 2(b)–2(d). The reference sample consists of rod-like
particles which are 30–50 nm in diameter and
130–220 nm in length, as shown in Figs. 2(e)–2(f).
Further, TEM examination was performed to reveal the
microstructure of the urchin-like a-FeOOH objects.
Figure 3(a) gives the TEM image of a single urchin-like
particle. We can see that the particle is built of nanoscaled
leaves with about 150–200 nm in length and about
30–50 nm in width. The high resolution TEM has
revealed that there is a distinct lattice fringe observed
in the nanoleaves, corresponding to the (101) plane of
a-FeOOH, as illustrated in Fig. 3(b). The growth of the
nanoleaves was preferentially along the direction [101].
The energy-dispersive x-ray (EDX) spectroscopic analy-
sis has confirmed that the products are only comprised of
Fe and O elements (the hydrogen could not be observed
due to the light element), as demonstrated in Fig. 3(c).
The atomic ratio of Fe to O elements is approximately
1:2, which is in good agreement with the elemental ratio
in FeOOH. The signals of Cu and C should come from
the Cu grid. No impurity such as sulfur was observed in
the sample.
The FTIR spectral measurements were carried out for
the urchin-like a-FeOOH, as shown in Fig. 4. The
absorption bands, centered at 1346, 979, and 619 cm1,
correspond to the Fe–O vibrational modes.21 The bands
at 899 and 797 cm1 are assigned to the characteristic
Fe–O–OH bending vibration modes in a-FeOOH,21,22
FIG. 1. XRD pattern of the as-prepared products. The line spectrum is
the standard diffraction pattern of a-FeOOH powders.
J. Mater. Res., Vol. 30, No. 10, May 28, 2015
indicating that the surfaces of the urchin-like a-FeOOH
particles were hydroxylated. The hydroxylated surface
could adsorb water molecules, which has been confirmed
due to the existence of the bands at 3395 and 1636 cm1,
in the spectrum, corresponding to the H2O stretching and
bending modes, respectively.23
Furthermore, the nitrogen sorption isotherms of the as-
prepared urchin-like micro/nanostructured a-FeOOH
were measured, as illustrated in Figure S1. The specific
surface area was thus estimated to be about 118 m2/g,
much larger than that of the reference sample or the
a-FeOOH nanorods (only 52 m2/g). The TG and DTA
results show that there are two main weight loss pro-
cesses in the temperature ranges from 30 to 200 °C and
from 200 to 380 °C, respectively, as illustrated in Fig. 5(a).
The weight loss (;6.0%) from 30 to 200 °C should be
attributed to the desorption of physically adsorbed water,
whereas that in the range of 200–380 °C (;10%) could
be ascribed to the decomposition of a-FeOOH due to the
reaction:
2a-FeOOH ! Fe2 O3 þ H2 O : ð2Þ
No significant weight loss occurred when the temper-
ature is higher than 380 °C. According to Eq. (2), the
weight loss induced by decomposition of a-FeOOH can
be estimated to be 10.1%, which is consistent with the
experimental measurement. As a consequence, the stable
residue could reasonably be ascribed to a-Fe2O3. For
further confirmation, a-FeOOH was calcined at 500 °C
for 5 h in air before XRD measurement. Figure 5(b)
shows the corresponding result and indicates the forma-
tion of a-Fe2O3.
B. Morphological evolution with reaction time
To understand the formation of such urchin-like micro/
nanostructured a-FeOOH, evolution of the products’
morphology with reaction time was examined, as shown
in Fig. 6. When the reaction was for a short time (say,
about 6 min), only spherical a-FeOOH nanoparticles with
about 30–50 nm in size were observed [Fig. 6(a)]. If the
reaction time was prolonged to 30 min, the larger
a-FeOOH particles of about 200–300 nm in size were
formed with large number of nanoleaves on the particle
surface, as illustrated in Fig. 6(b). Finally, when the
reaction was long enough (about 3 h or longer), the
urchin-like micro/nanostructured a-FeOOH objects were
obtained, as shown in Fig. 2.
C. Formation of the urchin-like a-FeOOH
On basis of the morphological evolution with reaction
time shown in Fig. 6, the formation process of the urchin-
like a-FeOOH could be proposed, involving two steps
during the water bath synthesis, or Step I: formation of
1631
 S. Kang et al.: Water bath synthesis and enhanced photocatalytic performances of urchin-like micro/nanostructured a-FeOOH

FIG. 2. (a–d) FESEM images of the as-prepared products and (e–f ) reference sample.

spherical a-FeOOH nanoparticles, and Step II: growth of

nanoleaves on the spherical nanoparticles, as schemati- Fe2þ þ OH ! FeðOHÞ2 ; ð5Þ
cally illustrated in Fig. 7.
During preparation of the precursor solution and sub- 4FeðOHÞ2 þ O2 ! 4FeOOH þ 2H2 O : ð6Þ
sequent reaction at 95 °C, the following reactions would
take place. At the initial stage, the urea was slowly decomposed
during heating and ammonia would be released over
COðNH2 Þ2 þ H2 O ! CO2 þ 2NH3 ; ð3Þ 70–80 °C according to reaction (3).24 The ammonia was
then hydrolyzed, forming hydroxyl ions, through reaction
NH3 þ H2 O ! NH4 þ þOH ; ð4Þ (4). The hydroxyl ions reacted with Fe21 to form Fe(OH)2
in nitrogen atmosphere [reaction (5)]. Finally, the Fe(OH)2
reacted with O2, under the ambient conditions, to form

1632 J. Mater. Res., Vol. 30, No. 10, May 28, 2015
 S. Kang et al.: Water bath synthesis and enhanced photocatalytic performances of urchin-like micro/nanostructured a-FeOOH
FIG. 3. Microstructure and composition of urchin-like a-FeOOH particles. (a) TEM image of a single a-FeOOH particle. (b) High resolution TEM
image of the segment of a single leaf. The arrow is along the axial direction of the leaf or [101]. (c) EDX spectrum.
FIG. 4. FTIR spectrum of the as-prepared a-FeOOH.
FeOOH according to reaction (6). Here, the Fe21 ions
are easily oxidized to Fe31, as previously reported.19
When the concentration of FeOOH in solution was high
enough, the nucleation and fast growth of a-FeOOH can
lead to the spherical morphology, which is a kinetic
crystallization process as clarified by the chemical
bonding theory of single crystal growth25,26 [see Fig. 6(a)
or Step I in Fig. 7].
As mentioned above, there exist hydroxy groups on
a-FeOOH nanoparticles’ surface (Fig. 4). After the
formation of a-FeOOH nanoparticles, their surface hy-
droxy groups could adsorb ethylene glycol in the
solution. Such adsorption would hinder the further
spherical or isotropic growth of the nanoparticles. In this
case, preferential growth could take place on some
special sites on the nanoparticles’ surface, where no
ethylene glycol was adsorbed, forming the spokewise
nanoleaves on the a-FeOOH nanoparticles, as shown in
Fig. 6(b) or Step II of Fig. 7. Finally, the urchin-like
micro/nanostructured particles were thus obtained after
enough long reaction.
D. Photocatalytic performances
1. Measurements
The optical absorption spectrum of the urchin-like
a-FeOOH, from the diffuse reflectance spectral measurement,
J. Mater. Res., Vol. 30, No. 10, May 28, 2015
is shown in Fig. 8(a). The absorption edge is at about
550 nm, indicating that a-FeOOH could be used as the
potential visible light high efficient photocatalyst. The
catalytic activity of the as-prepared a-FeOOH was
evaluated by photodegradation of R6G under xenon lamp
illumination. Figure 8(b) shows the optical absorption
spectral evolution of the R6G solution with irradiation
time, in the presence of the as-prepared urchin-like
a-FeOOH and H2O2. The strong absorbance band in
the visible region around 525 nm is attributed to the
monomer and dimmer of R6G in the solution.27,28 The
absorbance band decreases with increasing irradiation
time. It was suggested that both chromophores and
aromatic rings of R6G have been destroyed.29 After
irradiation for 56 min, the R6G was fully degraded and
the solution turned into transparency. The absorption
peak around 525 nm completely disappeared. For the
reference sample or the a-FeOOH nanorods, the R6G
was completely degraded in 80 min under the same
conditions (see Fig. S2). The catalytic activity of the
urchin-like a-FeOOH is higher than that of the rod-like
a-FeOOH nanoparticles, as clearly shown in Fig. 8(c).
The photocatalytic activity of the urchin-like a-FeOOH is
more than three times as high as that of the flower-like
nanostructured TiO2 for degradation of R6G,30 and very
close to that of P-25 under the same conditions
(see Fig. S4). For the R6G solution with hydrogen
peroxide but without catalysts, the R6G degradation ratio
was only 19% in 80 min in our experiment [Fig. 8(c)].
Further, under the dark conditions, the R6G concentra-
tion was only decreased by 23% in 60 min after addition
of the a-FeOOH catalyst in the R6G solution with
hydrogen peroxide, as shown in Fig. S3. This should
be attributed to the adsorption of R6G on a-FeOOH.
We also studied the effect of initial pH values. The
corresponding results are presented in Fig. 9(a). The initial
pH values have only insignificant effect on the photo-
degradation in the range of 3.0–9.0. The removal rates
of the R6G in the solution within the pH range of 3.0–9.0
were above 99% after irradiation for about 60 min.
1633
 S. Kang et al.: Water bath synthesis and enhanced photocatalytic performances of urchin-like micro/nanostructured a-FeOOH

FIG. 5. (a) TG and DTA curves of the as-prepared a-FeOOH. (b) The XRD pattern of the a-FeOOH after calcination at 500 °C. The line spectrum
is the standard diffraction of a-Fe2O3.

FIG. 6. (a) FESEM images of the products after reaction for 6 min and (b) 30 min, respectively.

FIG. 7. Schematic illustration of formation process for the urchin-like a-FeOOH particles. (a) The reaction solution. (b) The spherical particles.
(c) The particles with initially growing nanoleaves. (d) The urchin-like a-FeOOH particles. Step I: formation of spherical a-FeOOH particles; Step II:
growth of nanoleaves on the spherical particles.

In addition, it should be mentioned that the presence of

H2O2 in the solution is important for the catalysts to
degrade R6G in the solution under photoirradiation, as
shown in Fig. 9(b). Without addition of H2O2, the
degradation ratio of R6G was only about 13%. The photo-
catalytic degradation ratio of R6G increased with rising in
H2O2 concentration, and when H2O2 is up to 33 mmol L1,
the degradation ratio could reach 100% within 60 min.
2. Structurally enhanced mechanism of
photocatalytic activity
When the catalyst a-FeOOH was added into the R6G
aqueous solution with H2O2 under photoirradiation, the reaction
a-FeOOH ! a-FeOOHðe ; hþ Þ ; ð7Þ
would take place. At this time, there are two electron
transfer pathways. On one hand, the photogenerated
electrons are trapped by H2O2 on the surface of
a-FeOOH photocatalysts to form
OH radicals, or
H2 O2 þ e ! OH þ
OH : ð8Þ
On the other hand, the electrons can be trapped by
the Fe31 on the surface of a-FeOOH particles to form
Fe21, or

1634 J. Mater. Res., Vol. 30, No. 10, May 28, 2015
 S. Kang et al.: Water bath synthesis and enhanced photocatalytic performances of urchin-like micro/nanostructured a-FeOOH
FIG. 8. (a) Optical absorption spectrum of the urchin-like a-FeOOH.
(b) Time-dependent optical absorbance spectra of the R6G solution
(the starting concentration: 1  105 M, 30 mL) containing H2O2
(33 mmol L1) and the urchin-like a-FeOOH (30 mg) after its exposure
to the xenon lamp for different durations. (c) Degradation ratio of R6G
as a function of time for different catalysts.
Fe3þ þ e ! Fe2þ : ð9Þ
The reduced Fe21 ions would react with H2O2 to form

OH radicals in addition to (Fe31 1 OH), or
Fe2þ þ H2 O2 ! Fe3þ þ OH þ
OH : ð10Þ
The formed radicals would lead to degradation of the
R6G, according to the reaction31–33
J. Mater. Res., Vol. 30, No. 10, May 28, 2015
FIG. 9. (a) Influence of pH values and (b) H2O2 amount in the R6G
aqueous solution on photocatalytic performances.
C28 H32 N2 O3 þ
OH ! CO2 þ H2 O þ HNO3
ðor small moleculesÞ : ð11Þ
The radicals
OH are the nonselective strong oxidant,
which can oxidize some organic compounds into CO2
and H2O.34
The high photocatalytic activity of the urchin-like
a-FeOOH particles could be easily understood. It can
be attributed to their special structure. The urchin-like
a-FeOOH possesses a much higher specific surface area,
due to the micro/nanostructure, than the reference sample.
Furthermore, the urchin-like micro/nanostructure would
effectively prevent aggregation and keep a high active
surface area, which is favorable for highly efficient
photocatalytic degradation of organic pollutants in waste-
water.35 Comparatively, for the nanoparticles’ or nanorods’
powders, the undesired aggregation during the photo-
catalytic reaction usually induces a significant decrease in
the active surface area and hence the photocatalytic
performance. Additionally, the nanoscaled thickness of
the leaves on the urchin-like a-FeOOH particles is close
to the region where the quantum size effect is prominent.
The nanoleaves’ band gap broadening, induced by the
quantum size effect, would not only bring higher redox
potentials, but also promote electrons’ transferring
from the conductive bands of nanoleaves with high
1635
 S. Kang et al.: Water bath synthesis and enhanced photocatalytic performances of urchin-like micro/nanostructured a-FeOOH

electric-potential to those of the core-part micropar-

ticles with low electric-potential. It is well known that
band positions would move and higher redox potentials
of the free electrons and holes will be achieved
accordingly in this region, which reduces the proba-
bility of the photogenerated electron/hole pair recom-
bination and in turn enhances the charge-transfer rates
in the materials.36,37 On basis of all these above, the
urchin-like a-FeOOH particles would promote forma-
tion of the more radicals
OH [see reactions (7–10)]
and thus induce an enhanced photocatalytic perfor-
mance.
From reaction (11), the existence of radicals in the
solution is crucial to R6G’s degradation. For further
confirmation, irradiation-induced
OH radicals were
measured based on the photoluminescence (PL) technique
using terephthalic acid (TA) as the probe molecules,
which would readily react with
OH to produce highly
fluorescent product 2-hydroxyterephthalic acid.22 The PL
intensity of 2-hydroxyterephthalic acid at 425 nm is
proportional to the amount of
OH produced on the
surface of the photocatalyst. The measurement details
are described as previously reported.38 Briefly, 30 mg
of a-FeOOH powder sample was dispersed in a 30 mL
5  10 4 mol L 1 TA aqueous solution with 1 mL
2  10 3 mol L 1 NaOH in a 50 ml quartz tube.
Subsequently, 100 lL of hydrogen peroxide solution
(H2O2, 30 wt%) was added to the mixed solution and
FIG. 10. (a) PL spectral evolution with the irradiation time for the TA
stirred for about 5 min in the dark. The experiment was solution (5  104 M) in the presence of the urchin-like a-FeOOH (the
carried out under irradiation using a 300 W xenon lamp. details are seen in the text). (b) Plot of PL intensity at 425 nm versus
PL spectra of the generated 2-hydroxyterephthalic acid irradiation time [data from (a)].
were thus recorded with excitation by 320 nm light, as
illustrated in Fig. 10(a). The PL peak at 425 nm R6G could occur effectively just as in an acidic condition
corresponds to 2-hydroxyterephthalic acid.22 The PL under irradiation.
intensity at about 425 nm increases linearly with the
irradiation time, as shown in Fig. 10(b). However, such
PL peak was not observed without irradiation or in the 3. Reusability
absence of a-FeOOH powders under irradiation within The recycling photocatalytic efficiency of the urchin-
60 min. This indicates that the PL peak is from the like a-FeOOH particles was also tested. Experiments were
chemical reaction between TA and
OH occurred at the carried out (the reaction time is for 56 min at pH of 7.0).
interface of H2O2/a-FeOOH. The increasing trend of
OH The solid powders were carefully separated from the
radicals is consistent with the decreasing trend of R6G treated solution and rinsed with water and nonaqueous
concentration in Fig. 8. The
OH radicals produced on the ether 3 times respectively to remove any possible rem-
urchin-like a-FeOOH particles should be much more than nants on surface of the catalyst before next cycle. The
those on the reference sample. corresponding results are shown in Fig. 11(a) or Fig. S5.
As for insignificant effect of the initial pH value in the The R6G degradation was higher than 95% in the first
solution on the photodegradation processes, shown in three runs, showing high structural stability of the urchin-
Fig. 9(a), it should be ascribed to the acid-alkaline like a-FeOOH particles. In the fourth and fifth runs, the
buffering capacities of the catalyst caused by Fe-poly- efficiency of the catalyst decreased to 86 and 80%,
cations [Fen(OH)m(H2O)x](3nm)1,39 which were interme- respectively, which could be attributed to unavoidable
diate derivatives between the primary hydrolyzed leaching of iron and possible effect of contaminant
products and the insoluble FeOOH due to the intrinsic adsorption on reactive sites on the catalyst surface.
features of Fe-cations in the solution.40,41 Under the Nevertheless, when the reaction time was prolonged to
alkaline condition, most bases would be consumed by 80 min, the R6G degradation was above 95% for five
the Fe-polycations, and as a result, the degradation of cycles, as shown in Fig. 11(b) or Fig. S5.

1636 J. Mater. Res., Vol. 30, No. 10, May 28, 2015
 S. Kang et al.: Water bath synthesis and enhanced photocatalytic performances of urchin-like micro/nanostructured a-FeOOH
FIG. 11. The recycling photocatalytic efficiency of the urchin-like
a-FeOOH particles (the details are seen in the text). (a) After reaction
time for 56 min for each cycle. (b) After reaction time for 80 min for
each cycle.
IV. CONCLUSIONS
In summary, the urchin-like a-FeOOH with micro/
nanostructure has been fabricated by a simple low-
temperature water bath method based on the reaction of
urea and ferric sulfate aqueous solution at 95 °C. The
obtained a-FeOOH particles are microsized and composed
of nanosized leaf-like objects in radial arrangement, showing
high specific surface area (;118 m2/g). The formation of
urchin-like morphology could be attributed to the ethylene
glycol-adsorption induced preferential growth of nanoleaves
on the preformed spherical particles. Importantly, due to its
unique structure, such urchin-like a-FeOOH has shown
much higher photocatalytic activity to the R6G, under the
existence of H2O2, than the goethite nanorod powders,
exhibiting significant structural enhancement of the photo-
catalytic performance. Also, because of its high structural
stability, this material has good recycling photocatalytic
performances. Since the a-FeOOH is a mineral substance in
natural word and its disturbance to the environment is
comparatively small, this work could thus provide a useful
candidate of environmental materials for pollution treatment.
J. Mater. Res., Vol. 30, No. 10, May 28, 2015
ACKNOWLEDGMENTS
This work was financially supported by the National
Key Basic Research Program of China (Grant No.
2013CB934303), the China Postdoctoral Science Foun-
dation (2013T60632), and the CAS/SAFEA International
Partnership Program for Creative Research Teams.
REFERENCES
1. J.R. Domínguez, J. Beltrán, and O. Rodríguez: Vis and UV
photocatalytic detoxification methods (using TiO2, TiO2/H2O2,
TiO2/O3, TiO2/S2O82, O3, H2O2, S2O82, Fe31/H2O2 and
Fe31/H2O2/C2O42) for dyes treatment. Catal. Today 101, 389–
396 (2005).
2. L.D. Zhang and M. Fang: Nanomaterials in pollution trace detection
and environmental improvement. Nano Today 5, 128–142 (2010).
3. T. Inoue, A. Fujishima, S. Konishi, and K. Honda: Photoelec-
trocatalytic reduction of carbon-dioxide in aqueous suspensions of
semiconductor powder. Nature 277, 637–638 (1979).
4. M.R. Hoffmann, S.T. Martin, W. Choi, and D.W. Bahnemann:
Environmental applications of semiconductor photocatalysis.
Chem. Rev. 95, 69–96 (1995).
5. M.L. Chen, J.S. Bae, and W.C. Oh: Characterization of AC/TiO2
composite prepared with pitch binder and their photocatalytic
activity. Bull. Korean Chem. Soc. 27, 1423–1428 (2006).
6. A. Panniello, M.L. Curri, D. Diso, A. Licciulli, V. Locaputo,
A. Agostiano, R. Comparelli, and G. Mascolo: Nanocrystalline
TiO2 based films onto fibers for photocatalytic degradation of organic
dye in aqueous solution. Appl. Catal., B 121, 190–197 (2012).
7. B.A. Manning, J.R. Kiser, H. Kwon, and S.R. Kanel: Spectro-
scopic investigation of Cr31 and Cr61 treated nanoscale zerovalent
iron. Environ. Sci. Technol. 41, 586–592 (2007).
8. B. Wang, H.B. Wu, L. Yu, R. Xu, T. Lim, and X.W. Lou:
Template-free formation of uniform urchin-like a-FeOOH hollow
spheres with superior capability for water treatment. Adv. Mater.
24, 1111–1116 (2012).
9. Y. Wang, J. Ma, and K. Chen: Adsorptive removal of Cr(VI) from
wastewater by a-FeOOH hierarchical structure: Kinetics, equilib-
rium and thermodynamics. Phys. Chem. Chem. Phys. 15, 19415–
19421 (2013).
10. K. Amstaetter, T. Borch, P. Larese-Casanova, and A. Kappler:
Redox transformation of arsenic by Fe(II)-activated goethite
(a-FeOOH). Environ. Sci. Technol. 44, 102–108 (2010).
11. A. Iglesias, R. López, D. Gondar, J. Antelo, S. Fiol, and
A. Florencio: Adsorption of paraquat on goethite and humic
acid-coated goethite. J. Hazard. Mater. 183, 664–668 (2010).
12. J. Krýsa, J. Jirkovský, O. Bajt, and G. Mailhot: Competitive
adsorption and photodegradation of salicylate and oxalate on
goethite. Catal. Today 161, 221–227 (2011).
13. X. Zhou, H. Yang, C. Wang, X. Mao, Y. Wang, and G. Liu:
Visible-light induced photocatalytic degradation of rhodamine B
on one-dimensional iron oxide particles. J. Phys. Chem. C 114,
17051–17061 (2010).
14. L.J. Xu and J.L. Wang: A heterogeneous Fenton-like system with
nanoparticulate zero-valent iron for removal of 4-chloro-3-methyl
phenol. J. Hazard. Mater. 186, 256–264 (2011).
15. M. Hojamberdiev, G.Q. Zhu, A. Eminov, and K. Okada: Template-
free hydrothermal synthesis of hollow a-FeOOH urchin-like
spheres and their conversion to a-Fe2O3 under low-temperature
thermal treatment in air. J. Cluster Sci. 24, 97–106 (2013).
16. W.P. Kwan and B.M. Voelker: Rates of hydroxyl radical gener-
ation and organic compound oxidation in mineralcatalyzed
Fenton-like systems. Environ. Sci. Technol. 37, 1150–1158
(2003).
1637
 S. Kang et al.: Water bath synthesis and enhanced photocatalytic performances of urchin-like micro/nanostructured a-FeOOH
17. J. He, W. Ma, J. He, J. Zhao, and J.C. Yu: Photooxidation of azo
dye in aqueous dispersions of H2O2/a-FeOOH. Appl. Catal., B 39,
211–220 (2002).
18. N. Murakami, T. Matsuo, T. Tsubota, and T. Ohno: Photocatalytic
reaction over iron hydroxides: A novel visible-light responsive
photocatalyst. Catal. Commun. 12, 341–344 (2011).
19. G. Tong, J. Guan, and Q. Zhang: Goethite hierarchical nano-
structures: Glucose-assisted synthesis, chemical conversion into
hematite with excellent photocatalytic properties. Mater. Chem.
Phys. 127, 371–378 (2011).
20. B. Tang, G.L. Wang, L.H. Zhuo, J.H. Ge, and L.J. Cui: Facile
route to a-FeOOH and a-Fe2O3 nanorods and magnetic property
of a-Fe2O3 nanorods. Inorg. Chem. 45, 5196–5200 (2006).
21. D.M. Cwiertny, G.J. Hunter, J.M. Pettibone, M.M. Scherer, and
V.H. Grassian: Surface chemistry and dissolution of a-FeOOH
nanorods and microrods: Environmental implications of size-
dependent interactions with oxalate. J. Phys. Chem. C 113,
2175–2186 (2009).
22. S. Musi, S. Krehula, and S. Popovi: Effect of HCl additions on
forced hydrolysis of FeCl3 solutions. Mater. Lett. 58, 2640–2645
(2004).
23. C. Morterra, A. Chiorlno, and E. Borello: An IR spectroscopic
characterization of a-FeOOH (goethite). Mater. Chem. Phys. 10,
119–138 (1984).
24. X.B. Wang, W.P. Cai, Y.X. Lin, G.Z. Wang, and C.H. Liang:
Mass production of micro/nanostructured porous ZnO plates and
their strong structurally enhanced and selective adsorption perfor-
mance for environmental remediation. J. Mater. Chem. 20, 8582–
8590 (2010).
25. C.T. Sun and D.F. Xue: Tailoring anisotropic morphology at the
nanoregime: Surface bonding motif determines the morphology
transformation of ZnO nanostructures source. J. Phys. Chem. C
117, 5505–5511 (2013).
26. C.T. Sun and D.F. Xue: Chemical bonding theory of single crystal
growth and its application to phi 3. CrystEngComm 16, 2129–
2135 (2014).
27. K. Igarashi, M. Maeda, T. Takao, Y. Oki, and H. Kusama:
Dominant factors of preventing rhodamine 6G from dimer
formation in aqueous solutions. Bull. Chem. Soc. Jpn. 72, 1197–
1202 (1999).
28. F.L. Arbeloa, M.J. Tapia Estévez, T.L. Arbeloa, and I.L. Arbeloa:
Spectroscopic study of the adsorption of rhodamine 6G on clay
minerals in aqueous suspensions. Clay Miner. 32, 97 (1997).
Supplementary Material
To view supplementary material for this article, please visit http://dx.doi.org/jmr.2015.103.
1638 J. Mater. Res., Vol. 30, No. 10, May 28, 2015
29. X. Li and N. Kikugawa: A comparison study of rhodamine B
photodegradation over nitrogen-doped lamellar niobic acid and
titanic acid under visible-light irradiation. Chem. - Eur. J. 15,
3538–3545 (2009).
30. L. Zhang, Q.Q. Ding, and Y. Zhou: Hydrothermal synthesis of
anatase flower-like nanostructures for photocatalytic degradation
of dye. Cryst. Res. Technol. 46, 1202–1206 (2011).
31. J.G. Yu, X.X. Yu, B.B. Huang, X.Y. Zhang, and Y. Dai:
Hydrothermal synthesis and visible-light photocatalytic activity
of novel cage-like ferric oxide hollow spheres. Cryst. Growth Des.
9, 1474–1480 (2009).
32. H. Xie, Y.Z. Li, S.F. Jin, J.J. Han, and X.J. Zhao: Facile
fabrication of 3D-Ordered macroporous nanocrystalline iron oxide
films with highly efficient visible light induced photocatalytic
activity. J. Phys. Chem. C 114, 9706–9712 (2010).
33. X.H. Li, G.Y. Chen, L.B. Yang, Z. Jin, and H. Liu: Multifunc-
tional Au-coated TiO2 nanotube arrays as recyclable SERS
substrates for multifold organic pollutants detection. Adv. Funct.
Mater. 20, 2815–2824 (2010).
34. Y. Jiang, P. Zhang, Z.W. Liu, and F. Xu: The preparation of
porous nano-TiO2 with high activity and the discussion of the
cooperation photocatalysis mechanism. Mater. Chem. Phys. 99,
498–504 (2006).
35. F. Lu, W.P. Cai, and Y.G. Zhang: ZnO hierarchical micro/
nanoarchitectures: Solvothermal synthesis and structurally en-
hanced photocatalytic performance. Adv. Funct. Mater. 18,
1047–1056 (2008).
36. C.H. Ye, Y. Bando, G.Z. Shen, and D. Golberg: Thickness-
dependent photocatalytic performance of ZnO nanoplatelets.
J. Phys. Chem. B 110, 15146–15151 (2006).
37. X.B. Chen, S.H. Shen, L.J. Guo, and S.S. Mao: Semiconductor-
based photocatalytic hydrogen generation. Chem. Rev. 110, 6503–
6570 (2010).
38. Q. Xiao, Z.C. Si, J. Zhang, C. Xiao, and X.K. Tan: Photoinduced
hydroxyl radical and photocatalytic activity of samarium-doped
TiO2 nanocrystalline. J. Hazard. Mater. 150, 62–67 (2008).
39. J. Chen and L. Zhu: J. Photochem. Photobiol., A 188, 56 (2007).
40. K.Y. Li, M. Li, and D.F. Xue: Solution-phase electronegativity
scale: Insight into the chemical behaviors of metal ions in solution.
J. Phys. Chem. A 116, 4192 (2012).
41. X. Chen, K.F. Chen, H. Wang, S.Y. Song, and D.F. Xue:
Crystallization of Fe31 in an alkaline aqueous pseudocapacitor
system. CrystEngComm 16, 6707–6715 (2014).