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Article history: The aim of this work was to create a biocomposite which coupled the reducing capability of iron nanopar-
Received 7 June 2011 ticles with the adsorption capacity of cellulose to effectively remove hexavalent chromium from industrial
Received in revised form 2 August 2011 wastewater. The iron nanoparticles were synthesized on the orange peel pith using a simple redox precip-
Accepted 4 August 2011
itation reaction to ensure the biocomposite was inexpensive and easy to produce. The nanoparticles were
characterized for size, composition, oxidation state, and distribution before and after the Cr(VI) expo-
Keywords:
sure. The nanoparticles were mostly 20 × 80 nm tubular shapes, but there were also some octahedral
Iron oxide nanoparticles
crystals around 20–40 nm. The biocomposite with the nanoparticles exhibited twice the Cr(VI) removal
Orange peel
Chromium removal
of the unmodified orange peel pith and also possesses over twice the adsorption capacity −5.37 mg/g vs.
1.90 mg/g.
© 2011 Published by Elsevier B.V.
precipitation reaction. In addition to characterizing the adsorption capacity. The mixtures were filtered and the supernatant analyzed
behavior compared to unmodified orange peel, the biocomposite for Cr(VI) concentration.
and the embedded nanoparticles before and after the sorption were
characterized for particle size, composition, and chemical oxidation 2.5. Chromium adsorption kinetics and adsorption isotherms
state.
Batch studies were performed to determine the adsorption
2. Materials and methods kinetics and the sorbent adsorption isotherms in a series of test
tubes with 25 mg of sorbent (biomass or biocomposite) and 5 mL
2.1. Preparation of biomass of chromium solution, according to the results obtained from the
effect of pH studies an optimum pH of 1 was selected, since at that
Orange peel samples of about 5 mm × 5 mm squares were pH the maximum adsorption capacity was obtained. The mixtures
treated for 3 h with 5% ethanol to remove the color, then triple were filtered and the supernatant analyzed for Cr(VI) concentra-
rinsed with deionized water. Afterwards, they were dried under tion. In the kinetics experiments, both sorbents were evaluated
vacuum in a desiccator for 24 h at room temperature (25 ◦ C), then in 10 and 20 mg/L Cr(VI) solutions in 5–10 min increments. In the
milled and sieved through a no. 40 mesh (420–600 m). The pow- adsorption isotherms studies, each sorbent was mixed with Cr(VI)
der was stored under vacuum until use. solutions varying between 10 and 50 mg/L in 10 mg/L increments
at pH 1 for 1 h.
2.2. Preparation of biocomposite
2.6. Chromium detection in aqueous solution
A mixture of 0.6 g orange peel powder and 15 mL of 1 × 10−2 M
iron(II) acetate was stirred while 1 × 10−2 M sodium borohydride The colorimetric method according to the NMX-AA-044-SCFI-
was added dropwise. Afterwards, the mixture was stirred for an 2001 test method was used to measure the concentration of Cr(VI).
additional 20 min, filtered, washed five times in ethanol, and dried A solution of 1–5 diphenylcarbazide in acid forms a pink complex
at room temperature for 48 h in a homemade desiccator. with Cr(VI), which was spectrophotometrically analyzed at 540 nm
in a single wavelength HACH DR/4000U spectrophotometer.
2.3. Effect of pH
2.7. Scanning electronic microscopy
In order to evaluate the effect of pH on the adsorption capacity of
the biomass and the biocomposite, batch studies were performed Images were obtained in a JEOL JSM 6510LV at 15 KV and 10 mm
on each at 7 pH values between 1 and 7. This pH selection was WD, using both secondary and backscattered electron signals. Sam-
selected because a redox reaction between iron and Cr(VI) species ples were sputtered with about 20 nm of gold using a Denton
was expected and is favored at low values of pH [26]. For each Vacuum DESK IV.
material, 25 mg of sorbent was added to 7 test tubes with 5 mL
of a 20 mg/L Cr(VI) solution which had been adjusted to pH values
between 1 and 7 with dilutions of concentrated sulfuric acid or 5 M 2.8. Energy dispersive X-ray spectroscopy
sodium hydroxide.
EDS analysis was performed with an Oxford PentaFetx5 probe
attached to the microscope detailed above, the probe was calibrated
2.4. Effect of concentration on adsorption effectiveness
prior to the analysis with a copper standard.
Batch studies were performed to determine the effectiveness
of the biomass and the biocomposite at five different initial con- 2.9. Transmission electronic microscopy
centrations of Cr(VI) solutions (10, 20, 30, 40, and 50 mg/L). For
each concentration, 25 mg of sorbent was added to 3 test tubes Images were obtained in a JEOL JEM-2100 at 200 KV. Samples of
with 5 mL of Cr(VI) solution, the pH used was 1 according to the the nanoparticles were isolated by ultrasonically treating the sor-
results obtained from the effect of pH studies, then left for a con- bent in acetone and drying the residual solvent on formvar-coated
tact time of 60 min in order to obtain the maximum adsorption copper TEM grids.
Fig. 1. Kinetics of the Cr(VI) removal at initial concentration Cr(VI) of (a) 10 mg/L, (b) 20 mg/L. pH 1, T = 25 ◦ C, biocomposite and orange peel quantities of 25 mg each and
after 60 min of equilibrium time.
482 G. López-Téllez et al. / Chemical Engineering Journal 173 (2011) 480–485
The XPS wide and narrow spectra were aquired using a JEOL
JPS-9200, equipped with a Mg X-ray source (1253.6 eV) at 200 W,
over an analysis area of 1 mm2 , under vacuum on the order of
10−8 Torr for all samples. The spectra was analyzed using the
specsurfTM software included with the instrument and all spec-
tra were charge corrected by means of the adventitious carbon
signal (C1s) at 284.5 eV. The Shirley method was used for the back-
ground substraction, whereas the curve fitting was done with the
Gauss-Lorentz method.
Fig. 3. (a) SEM image of the biocomposite formed with orange peel, iron(II) acetate and sodium borohydride. (b) EDS qualitative results of the biocomposite formed with
orange peel, iron(II) acetate and sodium borohydride. (c) SEM image of biocomposite after contact with a Cr(VI) solution, (d) EDS spectra of biocomposite after contact with
a Cr(VI) solution.
G. López-Téllez et al. / Chemical Engineering Journal 173 (2011) 480–485 483
Fig. 4. (a)TEM image of a tube shaped iron oxide nanoparticle, (b) TEM image of an octahedral shaped iron oxide nanoparticle.
Table 1 binding to or near the iron nanoparticles, since both metals appear
Comparison of Cr(VI) removal between orange peel and biocomposite, pH 1,
bright in the image.
T = 25 ◦ C, biocomposite and orange peel quantities of 25 mg each and after 60 min of
equilibrium time.
3.6. TEM analysis
Cr(VI) concentration (mg/L) Orange peel Biocomposite
10 34.3% 71% TEM was used to determine the size and shape of the nanopar-
20 23.7% 43.4%
ticles. As shown in Fig. 4, two different iron oxide nanoparticles
30 19.4% 32.2%
40 17.2% 28%
50 13.8% 25%
(1.90 mg/g). Since the substrate (orange peel) is the same in both
materials, the iron nanoparticles in the biocomposite must play a
strong role in the process.
Table 2
Langmuir parameters obtained for the orange peel and biocomposite, pH 1, T = 25 ◦ C,
biocomposite and orange peel quantities of 25 mg each and after 60 min of equilib-
rium time.
H
Cr6+ H
O
O H
Fe
O
Cr6+
Fe
O H
O H
Fe Cr6+
O H
Step 1
6Fe2++Cr2O72-+14H+ 6Fe3++2Cr3++7H2O
Step 2
H H H
H H H H
O O O O O O O
Step 3
were found. The majority of the nanoparticles were tubular struc- which is attributed to the reaction of iron with H2 SO4 present from
tures of about 20 nm in diameter and 80 nm in length. However, acidification of the solution.
there were also some octahedral nanoparticles varying in size from The XPS spectrum of the biocomposite after Cr(VI) contact in
20 to 40 nm. Both shapes are consistent with expected structures the chromium binding energy range exhibits a peak that can be
of iron oxides. Since both structures have dimensions well below separated into two components (Fig. 5c). The two components are
100 nm the synthesis process was successful in forming iron oxide chromium (III) oxide (56.7%) and chromium (III) hydroxide (43.3%).
nanoparticles. It is interesting to note that there is no chromium(VI) sig-
nal in the spectra. Both signals correspond to chromium(III) with
3.7. XPS analysis chromium(III) oxide in a slightly higher ratio than the hydrox-
ide [29,30]. The results show that the redox reaction between
XPS analysis was performed in order to corroborate the presence chromium and iron oxide nanoparticles, proceeds practically to
of iron and chromium on the biocomposite surface and to identify completion, and that it occurs mainly on the surface of the bio-
their chemical state. The XPS spectrum corresponding to the Fe composite (Fig. 6), this is in good agreement with the assumption
2p3/2 narrow scan region of the biocomposite before contact with that there is a binding of metal ions to the surface via the functional
the chromium solution is shown in Fig. 5a. The deconvolution of the groups [31–34].
Fe 2p3/2 signal separates into 3 components, each corresponding
to the following chemical states of iron: Fe metallic (28.4%), FeO
(25.3%) and Fe2 O3 (46.3%).
The iron oxides are expected due to the high reactivity of metal- 4. Conclusions
lic iron [27,28]. Since one of the possible chromium(VI) removal
mechanisms is the reduction to Cr(III), the metallic and Fe(II) com- The biocomposite of iron/iron oxide nanoparticles embedded
ponents are very important reducing agents. in a porous orange peel pith matrix demonstrates effectiveness in
The XPS analysis of the biocomposite after contact with a Cr(VI) adsorbing and reducing Cr(VI) in solution, making it a promising
solution is shown in Fig. 5b, the curve fitting results are as fol- material for heavy metal bearing industrial wastewater. The bio-
lows: FeO (25.5%), Fe2 O3 (65.6%) and FeSO4 (8.8%). After contact composite adsorbs up to 71% of Cr(VI) from a 10 mg/L solution and
with chromium solution, the metallic Fe signal is no longer present has a capacity of 5.37 mg/g. This is an improvement over unmod-
due to its high reactivity, the ratio of iron(III) oxide increases as ified orange peel pith, which only removes 34% of Cr(VI) from a
a result of the redox reaction with chromium(VI) since iron is oxi- 10 mg/L solution with a capacity of 1.90 mg/g. The adsorption pro-
dized in reducing Cr(VI) to Cr(III). To corroborate this, the chromium cess appears to involve two processes: reduction of Cr(VI) to Cr(III)
region was also analyzed. Finally there is a signal related to FeSO4 by Fe or Fe(II) and adsorption of the Cr(III).
G. López-Téllez et al. / Chemical Engineering Journal 173 (2011) 480–485 485
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