Environ. Sci. Technol.
2008, 42, 6955–6960
Efficient Removal of Cr(VI) from
Aqueous Solution with Fe@Fe2O3
Core-Shell Nanowires
Z H I H U I A I , †,‡ Y I N G C H E N G , †
L I Z H I Z H A N G , †,* A N D J I A N R O N G Q I U ‡
Key Laboratory of Pesticide & Chemical Biology of Ministry of
Education, College of Chemistry, Central China Normal
University, Wuhan 430079, People’s Republic of China, and
National Coal Combustion Laboratory,
Huazhong University of Science and Technology,
Wuhan 430074, People’s Republic of China
Received April 7, 2008. Revised manuscript received July 8,
2008. Accepted July 10, 2008.
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The batch removal of Cr(VI) from simulated wastewater with
Publication Date (Web): August 14, 2008 | doi: 10.1021/es800962m
Fe@Fe2O3 core-shell nanowires (FCSNs) was investigated in
this study. It was found that each gram of the FCSNs could remove
7.78 mg of Cr(VI) from simulated wastewater containing 8.0
mg L-1 of Cr(VI) with an initial pH of 6.5 at room temperature.
The Freundlich adsorption isotherm was applicable to
describe the removal processes. Kinetics of the Cr(VI) removal
was found to follow pseudo-second-order rate equation.
Furthermore, the as-prepared and Cr(VI)-adsorbed FCSNs were
carefully examined by scanning electron microscopy (SEM),
energy dispersive X-ray analysis (EDX), Fourier transform infrared
spectroscopy (FT-IR), and X-ray photoelectron spectroscopic
analysis (XPS). The characterization results suggested that the
adsorbed Cr(VI) was partially reduced to Cr(III) in Cr2O3/
Cr(OH)3 on the FCSNs. The possible mechanism of removal
of Cr(VI) on FCSNs was proposed, which involved the dominant
Cr(VI) adsorption, followed by the partial reduction of Cr(VI)
to Cr(III) (chromium(III) oxyhydroides) on the surface of FCSNs.
These Fe@Fe2O3 core-shell nanowires with high specific
surface area and strong magnetic property are very attractive
for the removal of Cr(VI) from wastewater.
Introduction
In the environment, chromium is widely distributed and exists
in two common oxidation states, Cr(III) and Cr(VI) (1). Usually
Cr(III) occurs naturally, while Cr(VI) is generally produced
from industrial processes, such as electroplating, metal
finishing, pigment manufacture, tannery facilities, and
chromium mining. Cr(VI), existing in most aquatic environ-
ments as water soluble oxy-anions, HCrO4- or CrO42-, is highly
toxic and environmentally harmful once introduced into the
environment (2). For example, exposure to Cr(VI) in drinking
water increases risk of bladder, liver, kidney, and skin cancers
(1-15). Therefore, the development of technologies to
prevent further chromium discharge and remediate Cr(VI)
contamination are of great importance (14).
The removal of Cr(VI) from aqueous environment has
been widely studied and reported in the literature (3-8, 16-24).
* Corresponding author e-mail: zhanglz@mail.ccnu.edu.cn; phone/
fax: +86-27-6786 7535.
†
Central China Normal University.
‡
Huazhong University of Science and Technology.
10.1021/es800962m CCC: $40.75  2008 American Chemical Society
Published on Web 08/14/2008
The conventional methods to remove Cr(VI) from wastewater
are chemical redox, followed by precipitation, ion exchange,
adsorption, solvent extraction, membrane separation, con-
centration, evaporation, reverse osmosis, biosorption, and
emulsion pertraction technology (2, 11, 13, 18, 21-24). A
major drawback of precipitation is sludge production. Ion
exchange and reverse osmosis are not economically attrac-
tive because of their high operating costs (15). Among the
above-mentioned methods, adsorption is highly efficient and
economical, and therefore, it is a promising technique for
the removal of Cr(VI) from wastewater.
Various adsorbents have been used to remove Cr(VI) from
wastewater. They include activated carbons, coconut husk
carbon, MnO2 coated sand, basic yttrium carbonate, activated
alumina, carbon from fly ash, granular titanium dioxide,
hybrid polymeric adsorbent, etc. (6, 9, 12, 17, 21, 25, 26).
Among these adsorbents, activated carbon has been studied
extensively (12-14, 18, 27, 28). However, its application is
restricted by the subsequent difficult solid-liquid separation.
Because of the affinity of chromium toward iron and the
magnetic properties of the iron-based materials, various types
of iron-based materials have been used as adsorbents for
the removal of Cr(VI) from the aqueous environment
(15, 16, 25, 29). For example, Lu et al. found that clinopy-
rrhotite is effective for removal of Cr(III) and Cr(VI) (8). Ludwig
and co-workers reported on the in situ chemical reduction
of Cr(VI) in groundwater using a combination of ferrous
sulfate and sodium dithionite (16). Hu and co-workers
reported that surface-modified jacobsite (MnFe2O4) was an
effective adsorbent for hexavalent chromium from synthetic
wastewater. More interestingly, the MnFe2O4 adsorbent can
be easily separated from the solution by a simple magnetic
process after the Cr(VI) adsorption (15).
We have synthesized Fe@Fe2O3 core-shell nanowires
(FCSNs) by reduction of Fe3+ ions with sodium borohydride
in aqueous solution at ambient atmosphere in gram quantity
(30). These FCSNs were able to efficiently degrade azo dye
pollutants and pentachlorophenol in different Fenton sys-
tems (31-34). Meanwhile, these FCSNs were found to possess
a high saturation magnetization (30), suggesting their easy
separation under magnetic field.
In the present work, we study the ability of FCSNs to
remove Cr(VI) from simulated wastewater to clarify the
possible removal mechanism and widen the application of
FCSNs in the field of remediation of Cr(VI) contaminated
groundwater and industrial wastewater with low Cr(VI)
concentration.
Experimental Section
Chemicals. FeCl3 · 6H2O, NaBH4, C2H5OH, K2Cr2O7, NaOH,
and H2SO4 were obtained from National Medicines Corpo-
ration Ltd. of China. All the chemicals were of analytical
grade and were used as received without further purification.
Deionized water was used throughout the experiments.
Core-shell Fe@Fe2O3 nanowires were synthesized as de-
scribed in our previous report (30).
Removal Procedure. The stock solution containing 1000
mg L-1 of Cr(VI) was prepared by dissolving 1.4114 g of
K2Cr2O7 in 500 mL of deionized water. Simulated wastewaters
with different Cr(VI) concentrations (1.0-8.0 mg L-1) were
prepared by dilution of the stock K2Cr2O7 standard solution
with deionized water. pH values were measured with an Orion
model 920A pH/ISE meter with a Beckman combination
electrode. All the experiments were carried out in a 100 mL
beaker containing 50 mL of simulated wastewater at room
temperature (25 °C). The initial pH of Cr(VI) solution was
VOL. 42, NO. 18, 2008 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 6955
 6.36 without pH adjustment. In some cases, the initial pH
values of the Cr(VI) solution were adjusted to 3 and 9 by
addition of 0.1 M H2SO4 and 0.1 M NaOH, respectively. Batch
removal studies were carried out at the desired contact time
and adsorbent dosage levels, where the concentrations of
FCSNs adsorbent range from 1 to 8 g L-1. After the adsorption
processes, the samples were filtered through a 0.45 µm
membrane, and the filtrates were analyzed by atom absorp-
tion spectrometry (WFX-1F2, China). All the adsorption
experiments were carried out in duplicate. The reproducibility
and relative deviation are on the order of (5.0%. The amount
of Cr(VI) adsorbed per unit mass of the adsorbent was
evaluated by using the mass balance equation (eq 1)

(C0 - Ct)V
qt ) (1)
W

where qt (mg g-1) is the amount adsorbed per gram of

adsorbent at time t (min), C0 is the initial concentration of
Cr(VI) in the solution (mg L-1), Ct is the concentration
of Cr(VI) at time t of adsorption (mg L-1), W is the mass of
the adsorbent used (g), and V is the volume of the solution
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FIGURE 1. Time profile of Cr(VI) removal with FCSNs. The
concentration of FCSNs adsorbent was 1.0 g L-1; the initial
Cr(VI) concentrations ranged from 1.0 to 8.0 mg L-1.

(L).
An adsorption experiment of Cr(VI) with a high initial
Adsorption Isotherm and Adsorption Kinetics. The
concentration (20 mg L-1) was also performed (Figure S2,
adsorption isotherm of Cr(VI) on FCSNs was conducted with
Supporting Information), the adsorption capacity of FCSNs
Publication Date (Web): August 14, 2008 | doi: 10.1021/es800962m

various initial Cr(VI) concentrations (1.0-8.0 mg L-1) at room

temperature. Two adsorption isotherms, namely, Langmuir
(35) and Freundlich (36), were used to analyze the adsorption
data. The kinetics of the adsorption describing the rate of
the removal of Cr(VI) on FCSNs is one of the important
characteristics that define the efficiency of removal. The
pseudo-first-order (37) and pseudo-second-order (38) models
were used to interpret the experimental data (Supporting
Information).
Characterizations of the As-Prepared and Cr(VI)-Ad-
sorbed FCSNs. FCSNs were separated from the solution
through a 0.45 µm membrane and then air-dried for about
1 h prior to their characterizations. Scanning electron
microscopy and energy dispersive X-ray (EDX) analysis were
performed on a LEO 1450VP scanning electron microscope.
X-ray photoemission spectroscopy was recorded on a Kratos
ASIS-HS X-ray photoelectron spectroscope equipped with a
standard and monochromatic source (Al KR) operated at
150 W (15 KV, 10 mA). FT-IR spectra were recorded on a
Nicolet Nexus spectrometer with the standard KBr pellet
method. The magnetization curves and hysteresis loop of
the nanocomposite were characterized with a Lake model
7300 vibrating sample magnetometer (VSM). The nitrogen
adsorption and desorption isotherms at 77 K were measured
using a Micrometritics ASAP2010 system after samples were
vacuum-dried at 473 K overnight. The BET surface area of
the as-prepared FCSNs was found to be 31.1 m2/g (Figure S1,
Supporting Information).
Results and Discussion
Removal of Cr(VI). Figure 1 shows the time profile of Cr(VI)
removal with 1.0 g L-1 of FCSNs at different initial Cr(VI)
concentrations at 25 °C. From Figure 1, two important
conclusions could be drawn. First, the adsorption process
almost finished within 120 min, and no significant change
was observed from 120 to 300 min, suggesting that the
adsorption rates were quite fast under all the concentrations.
Second, the total amount of Cr(VI) adsorbed increased with
the increasing initial Cr(VI) concentrations. This is because
more Cr(VI) is available at higher initial concentrations of
Cr(VI), and higher initial adsorbate concentration provides
higher driving force for the ions from the solution to the
FCSNs, resulting in more collisions between Cr(VI) ions and
active sites on the FCSNs (3). Similar phenomena were
observed in the literature (4, 7, 19, 22).
was found to be 10.06 mg/g at the initial Cr(VI) concentration
of 20 mg L-1. In addition, the magnetic properties of FCSNs
were measured (Figure S3, Supporting Information). The
room-temperature magnetization curve of the FCSNs shows
a large magnetic hysteresis loop with a saturation magne-
tization (Ms) of 900 emu/g and a coercivity (Hc) of about 0.62
kOe, implying a strong magnetic response to a magnetic
field. This provides an easy and efficient way to separate the
FCSNs from aqueous solutions. We found that the FCSNs
with adsorbed Cr(VI) could be easily separated by a magnetic
field, resulting in clean water (Figure S4, Supporting Infor-
mation).
We studied the pH value changes during the adsorption
process when the initial pH was 6.36 and found that the
initial pH increased from 6.36 to 7.91 after 60 min adsorption,
then decreased slowly, and finally kept constant at around
pH 7.1 (Figure S5, Supporting Information). This is because
Cr(VI) reduction would produce hydroxyl ions to consume
H+ during the removal process (Cr2O72- + 3Fe0 + 8H+ )
2Cr(OH)3 + 3Fe2+ + H2O), resulting in the pH increase.
However, the Fe2+ produced by Cr(VI) reduction as well as
Fe2+ and Fe3+ produced by the slow leaching of FCSNs would
further react with hydroxide groups to give ferrous hydroxide
(Fe(OH)2) and ferric hydroxide (Fe(OH)3) at a basic pH value
of 7.91 (Fe2+ + 2OH- ) Fe(OH)2; Fe3+ + 3OH- ) Fe(OH)3).
The later step would cause the pH decrease. The influence
of the initial pH on the removal efficiency of Cr(VI) by the
FCSNs was investigated (Figure S6, Supporting Information).
The adsorption capacity at pH 3 was close to that at neutral
pH (pH 6.36). We found that a higher pH value (pH 9)
disfavored the adsorption of Cr(VI). This may be attributed
to that the precipitation of mixed chromium (III)/iron(III)
oxides may block access to Cr(VI) reduction and the
abundance of OH- ions could hinder the diffusion of
dichromate ions at pH 9 (39, 40).
Adsorption Isotherms. The adsorption isotherms of Cr(VI)
on FCSNs were measured under various initial Cr(VI)
concentrations in the presence of 1.0 g L-1 of the FCSNs at
25 °C. All the removal efficiencies were found to be higher
than 96%. For example, the maximum Cr(VI) adsorption
capacity of the FCSNs was found to be 7.78 mg g-1 when the
initial Cr(VI) concentration was 8.0 mg L-1. This suggests the
high efficiency of the FCSNs for the removal of Cr(VI) ions
in aqueous environment and industrial wastewater with low
Cr(VI) concentration. In addition, the adsorption capacity of

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FIGURE 2. Representative Freundlich isotherm of Cr(VI) adsorp-
tion. The initial Cr(VI) concentrations were from 1.0 to 8.0 mg
L-1; the FCSNs adsorbent dose was 1.0 g L-1, and the the
contact time was 5 h.
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Publication Date (Web): August 14, 2008 | doi: 10.1021/es800962m
FIGURE 3. Removal kinetics of 1.0 mg L-1 of Cr(VI) in the
presence of FCSNs ranging from 1.0 to 8.0 g L-1. The contact
time was 5 h.
Cr(VI) removal on the FCSNs was comparable with other
common adsorbents such as coal, paper mill sludge, sago-
waste activated carbon, and oxidized activated carbon
(41, 42). Figure 2 shows the representative Freundlich
adsorption isotherm of Cr(VI) on the FCSNs. It was observed
that the adsorption data fitted well to this isotherm model
with a calculated R2 value of 0.98. In addition, the Langmuir
model was also used for the adsorption data, but the fitting
result was not as good as that of Freundlich model (Figure
S7, Supporting Information). The better fitting of the Fre-
undlich isotherm model may be attributed to the hetero-
geneous distribution of active sites on the FCSNs surface
(25).
Kinetics Study. The kinetics of Cr(VI) removal on FCSNs
was further investigated by changing the FCSNs dosage in
the simulated wastewater with 1.0 mg L-1 of Cr(VI). The
pseudo-second-order rate constants, k2 and qe, were calcu-
lated from the slope and intercept of the plots of t/qt versus
t according to eq S7 (Supporting Information). The kinetics
of the removal process was shown in Figure 3. Table 1
summarizes the theoretical and calculated qe values (the
amount of Cr(VI) adsorbed at equilibrium), pseudo-second-
order rate constants k2, and correlation coefficient values
(R2). The calculated qe is calculated from the slope and
intercept of the plots of t/qt versus t according to eq S7 [(t/qt
) 1/k2qe2 +1/qe)t]. Because the plot of log(qe - qt) versus t
gives a linear relationship, qe can be determined from the
TABLE 1. Theoretical and Calculated qe Values, Pseudo-Sec-
ond-Order Rate Constants, k2, and Correlation Coefficient
Values (R2)a
theoretical qe calculated qe k2 (g/mg-1
R2
(mg g-1) (mg g-1) min-1)
1.0 0.98 0.136 0.998
2.0 1.90 0.041 0.998
4.0 3.85 0.017 0.997
8.0 7.78 0.005 0.998
a
The dosage of FCSNs adsorbent was 1.0 g L-1.
intercept of the plot. The theoretical qe values are the
equilibrium concentrations of Cr(VI) in the adsorbed FCSNs
assuming 100% of Cr(VI) is removed. The calculated qe values
are in agreement with the theoretical ones, and the plots
show quite good linearity with R2 above 0.99. Therefore, the
adsorption kinetics follows the pseudo-second-order model,
suggesting a chemisorption process (11).
SEM Images and EDX Analysis of the Cr(VI)-Adsorbed
FCSNs. The morphology of the Cr(VI)-adsorbed FCSNs was
examined by SEM (Figure 4). Different from the as-prepared
FCSNs (Figure S8, Supporting Information), the Cr(VI)-
adsorbed FCSNs possessed much rougher surfaces. This may
be attributed to two main reasons. One is the oxidation and
corrosion of zero-valent iron to produce Fe(III) oxide/
hydroxide on the surface of the FCSNs (30-32, 41). The other
is the possible reaction of Cr(VI) with the FCSNs in the
aqueous solution, resulting in the deposition of the chromium
oxide or chromium hydroxide on the surface of the FCSNs
(43). The energy-dispersive X-ray analysis (EDX) reveals that
carbon, iron, chromium, and oxygen elements coexist in the
Cr(VI)-adsorbed FCSNs (inset of Figure 4), where carbon
comes from the surface adventitious carbon from atmosphere
and the conductive adhesive tape for SEM measurements,
confirming the deposition of chromium compounds on the
surface of FCSNs.
XPS Spectra of the Cr(VI)-Adsorbed FCSNs. X-ray pho-
toelectron spectroscopy was further used to study the surface
chemical compositions of the Cr(VI)-adsorbed FCSNs (Figure
5). As shown from the survey spectra in Figure 5a, element
Cr existed in the Cr(VI)-adsorbed FCSNs, which was different
from the as-prepared FCSNs (30). The high resolution XPS
spectrum of the Cr 2p region are shown in Figure 5b; Cr 2p1/2
and Cr 2p3/2 line peaks are located at 586.9 and 577.2 eV,
respectively (29). The broad peak of Cr 2p3/2 could be fitted
to two peaks at binding energies of 578.1 and 576.3 eV, which
are the characteristics of Cr(VI) and Cr(III), respectively. This
suggests that both Cr(VI) and Cr(III) coexist on the surface
of Cr(VI)-adsorbed FCSNs. It is most likely that the zero-
valent iron in FCSNs favors the Cr(VI) reduction to Cr(III).
This is consistent with Fang’s observation (14). Furthermore,
the splitting of Cr 2p3/2 line peak into two peaks indicated
that Cr2O3 or Cr(OH)3 precipitates were formed during the
adsorption (29). The reduction of Cr(VI) to Cr(III) by FCSNs
is believed to follow the adsorption process. Figure 5c shows
the Fe 2p peaks at binding energies of 710.1 and 724.1 eV,
with a shakeup satellite at 719.0 eV. The dominant peak at
710.1 eV and the satellite signal at 719.0 eV can be attributed
to Fe in Fe2O3 (43, 44). The shoulder peak at 724.1 eV can be
assigned to Fe in Fe2O3 (45). Meanwhile, O 1s spectrum of
the Cr(VI)-adsorbed FCSNs was also recorded (Figure 5d).
The broad peak of O 1s can be fitted by two peaks at binding
energies of 530.4 and 531.9 eV, respectively. The dominant
peak at 530.4 eV is characteristics of oxygen in metal oxide,
and the other peak at around 531.9 eV suggests the presence
of -OH oxygen in metal hydroxides, such as Cr(OH)3, on the
surface of FCSNs (46).
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FIGURE 4. SEM image of the Cr(VI)-adsorbed FCSNs. The inset is the EDX pattern of the Cr(VI)-adsorbed FCSNs.
Publication Date (Web): August 14, 2008 | doi: 10.1021/es800962m

FIGURE 5. XPS spectra of the Cr(VI)-adsorbed FCSNs: (a) survey, (b) Cr 2p, (c) Fe 2p, and (d) O 1s.

Infrared Spectra of the As-Prepared and Cr(VI)-Ad-
sorbed FCSNs. Fourier transform infrared (FT-IR) analysis
was also performed to reveal the nature of the FCSNs surface.
Figure 6 presents the spectra of the as-prepared and Cr(VI)-
adsorbed FCSNs, respectively. The spectra display broad
bands at 3410 cm-1, which are believed to be associated with
the stretching vibrations of hydrogen-bonded surface water
molecules and hydroxyl groups. The weak adsorption at 1631
cm-1 is assigned to the bending mode of water. In addition,
the bands at 1227 and 1162 cm-1, implying the existence of
large numbers of residual hydroxyl groups, only appear in
the IR spectra of the Cr(VI)-adsorbed FCSNs. It seems that
the adsorption can increase the amount of surface hydroxyl
groups, which may arise from the formation of Cr(OH)3
precipitate on the FCSNs surface. This agrees with the SEM
and XPS results. Generally, the bands in the low-frequency

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FIGURE 6. Infrared spectra of (a) the as-prepared and (b)
Cr(VI)-adsorbed FCSNs.
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400-1000 cm-1 region of the spectrum are attributed to
metal-oxygen and metal-hydroxy vibration modes. The
peak at 594 cm-1 is attributed to the Fe-O bond vibration
Publication Date (Web): August 14, 2008 | doi: 10.1021/es800962m
(47). Comparing the two spectra, we found that the peak at
594 cm-1 characterizing the Fe-O transverse vibration
disappeared, but a new peak at 510 cm-1 was found in the
IR spectrum of the Cr(VI)-adsorbed FCSNs. This could be
assigned to the Cr-O bond vibration, confirming Cr(VI) in
simulated wastewater was adsorbed and transferred to
chromium oxide (Cr2O3/Cr(OH)3) precipitates on the surface
of the FCSNs during this removal process.
Possible Adsorption and Reduction Mechanism of Cr(VI)
with FCSNs. The characterization results revealed the
presence of Cr2O3/Cr(OH)3 precipitates because of the
reductive reaction of the FCSNs. On the basis of the above
results, we proposed a possible mechanism for the removal
of Cr(VI) with the FCSNs. This removal process may involve
three steps: (1) mass transfer of Cr(VI) from the bulk solution
to the FCSNs surface, (2) physical/chemical adsorption of
Cr(VI) on the FCSNs surface, and (3) reduction of Cr(VI) to
Cr(III) with the FCSNs to deposit precipitation of Cr(III) in
oxide or hydroxide nature on the FCSNs surface. We have
mentioned that the structure of oxide shell allowed the
dissolved oxygen in the solution and water to reach the inner
iron core (32); as soon as the inner iron core contacted water
and oxygen, they would further react with Cr(VI) to form
chromium oxide precipitates such as Cr(OH)3 and Cr2O3 on
the surface of the FCSNs. Because no chromium was detected
in the solution after the absorption process, most of the Cr(VI)
and Cr(III) species are believed to be adsorbed on the surface
of the FCSNs. This phenomenon is in agreement with the
literature reported recently (16, 29, 41). For instance, Man-
ning’s research suggested that the product of Cr(VI)-treated
zero-valent iron was either a poorly ordered Cr(OH)3
precipitate or possible a mixed -phase CrxFe1-x(OH)3 product
(29).
Acknowledgments
This work was supported by National Science Foundation of
China (Grants 20503009, 20673041, and 20777026), National
Basic Research Program of China (973 Program) (Grant
2007CB613301), Program for New Century Excellent Talents
in University (Grant NCET-07-0352), the Key Project of
Ministry of Education of China (Grant 108097), Outstanding
Young Research Award of National Natural Science Founda-
tion of China (Grant 50525619), and Postdoctors Foundation
of China (Grant 20070410935).
Supporting Information Available
The Langmuir and the Freundlich adsorption isotherms, the
pseudo-first-order and pseudo-second-order models, N2
adsorption-desorption isotherms of the prepared FCSNs,
adsorption experiment of Cr(VI) with a high initial concen-
tration, magnetic property of the FCSNs, separation experi-
ment by a magnetic field, the pH value changes during the
adsorption process, the influence of the initial pH on the
removal efficiency, the Langmuir isotherm of Cr(VI) at room
temperature, SEM images of the as-prepared FCSNs, and
the recovery procedure of adsorbed Cr(VI). This material is
available free of charge via the Internet at http://pubs.acs.org.
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