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production of the weaker radical (i.e. SO5c) for BPA degradation and Fe2+ quenching of SO4c at higher
DOI: 10.1039/c5ta06563a
the BPA degradation rate was also investigated. The CuFe2O4Fe2O3 catalyst exhibited excellent stability
and can be reused several times without signicant deterioration in performance.
catalyst loading. The inuence of water matrix species (i.e. Cl, NO3, HCO3, PO43 and humic acid) on
www.rsc.org/MaterialsA
1. Introduction
Advanced oxidation processes utilizing redox changes in transition metals are extensively used for the catalytic oxidation of
organic pollutants. Oxidation of organic pollutants by using
sulfate radicals generated from the redox reaction between
commercially available oxidants and transition metals is being
increasingly adopted as an eco-friendly and ecient method for
removing recalcitrant pollutants from water. Sulfate radicals
have a relatively high oxidation potential (Eo 2.7 V) and they
are selective for electron transfer reactions.1 A sulfate radical
has a longer half-life compared to a hydroxyl radical thus
allowing better diusion of the generated reactive sulfate
c
School of Materials Science and Engineering, Nanyang Technological University, 50
Nanyang Avenue, Singapore 639798, Singapore
Electronic supplementary
10.1039/c5ta06563a
information
(ESI)
available.
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DOI:
J. Mater. Chem. A
2.
2.1
Experimental
Chemicals
All the chemicals used in this study are of analytical grade. The
chemicals used are as follows: Cu(NO3)2$3H2O (Qr
eC),
Co(NO3)2$6H2O (Alfa Aesar), Mn(NO3)2$4H2O (Sigma-Aldrich),
Fe(NO3)3$9H2O
(Merck), Bi(NO3)3$5H2O
(Alfa Aesar),
Al(NO3)3$9H2O (Sigma-Aldrich), NaOH (Alfa Aesar), HCl (Merck),
acetonitrile (Merck), citric acid (Merck), ammonia (Hach), KI
(Fisons), PMS (in the form of Oxone, 2KHSO5$KHSO4$K2SO4,
Alfa Aesar), NaCl (Qr
ec), NaNO3 (Sigma-Aldrich), humic acid
(HA, Aldrich), NaHCO3 (Sigma-Aldrich), polyethylene glycol
(Sigma-Aldrich), sodium acetate (Sigma-Aldrich), bisphenol A
(Merck) and methanol (Merck). All the experiments were conducted using deionized (DI) water (18.2 MU cm).
2.2
Synthesis of catalysts
The CuFe2O4Fe2O3 catalyst was prepared using a facile coprecipitation method at low temperature. In a typical synthesis
procedure, metal precursors consisting of 5 mmol of
Cu(NO3)2$3H2O and 10 mmol of Fe(NO3)3$9H2O were dissolved
in 50 mL of DI water and the pH of the solution mixture was
adjusted to pH 1011 using 6 M NaOH under rapid magnetic
stirring. Then, the resultant solution was heated under vigorous
stirring at 95 C for 24 h to promote hydrolysis and the
formation of the CuFe2O4Fe2O3 catalyst. The resultant
brownish product was separated from the solution by using a
simple magnetic separation procedure and freeze-dried for 24
J. Mater. Chem. A
Paper
2.3
Characterization technique
The crystallographic and mineralogical information of the asprepared catalysts was obtained using a X-ray diractometer
(Bruker AXS D8 Advance) operating at 40 kV and 40 mA with a
X-ray source. The surface morphology and
Cu-Ka (l 1.5418 A)
EDX elemental distribution were studied by obtaining the
electron micrographs and elemental mappings using a eld
emission scanning electron microscope (FESEM, JEOL JSM7600F) equipped with an energy dispersive X-ray spectrometer
(EDX, Oxford Xmax80 LN2 Free). The Fourier transform infrared
(FTIR) spectra were obtained using a FTIR spectrometer (Perkin
Elmer Spectrum GX). The BrunauerEmmettTeller (BET)
specic surface area of the catalysts was calculated from the N2
adsorptiondesorption isotherm analysis at 77 K (Quantachrome Autosorb-1 Analyzer).
2.4
Performance evaluation
Batch experiments were conducted to investigate the performance of the catalyst for BPA treatment via PMS activation. In
a typical experimental procedure, a known amount of PMS
was introduced into the reaction vessels containing 100 mL of
5 mg L1 of BPA at 25 C. The pH of the solution was immediately adjusted to the desired pH (pH 4.5, 7.0 or 9.5). Then, a
known amount of the catalyst was added into the solution to
commence the catalytic reaction. At various time intervals,
2 mL aliquots were sampled from the reaction vessel to
determine the BPA concentration. The collected aliquots were
ltered using a cellulose acetate membrane lter and the
catalytic reaction was quenched using methanol. The BPA
concentration was then determined by using high performance liquid chromatography (HPLC). At the end of the
reaction time, the pH change of the solution at pH 4.5 was
insignicant while for pH 7.0 and 9.5, the nal pH was 6.1 and
8.1, respectively, due to their unbuered condition and the
formation of acidic BPA intermediates such as organic acids.13
The experimental parameters studied were the PMS dosage
(0.18, 0.27 and 0.36 g L1), catalyst loading (0.05, 0.10 and
0.20 g L1) and initial pH (4.5, 7.0 and 9.5). The mole ratio of
PMS to pollutant used in this study was comparable to that of
another study.19 At the end of the reaction time, the total
organic carbon and Cu leaching were also determined for the
selected conditions. For the TOC determination, the samples
were ltered and analyzed immediately without quenching
with methanol. Investigation of the changes in PMS concentration over time was also conducted.
Paper
2.5
Analytical methods
3.
3.1
Fig. 1 XRD patterns (a) and FTIR spectra (b) of the as-prepared catalysts. * Fe2O3, # Cu and CuO.
rate.22,23 The distinctive peak at 600 cm1 in all the FTIR spectra
was attributed to the characteristic MeO bond.
The FESEM micrograph (Fig. 2d) of the CuFe2O4Fe2O3
catalyst consists of a quasi-cubic morphology with a mean size
of 100200 nm. The EDX elemental mapping (Fig. 2e) shows
that Cu and Fe were homogeneously distributed on the surface
at a ratio of 1 Cu to 5.5 Fe which is close to the theoretical ratio
of 1 Cu to5 Fe. This indicates the coexistence of CuFe2O4 and
Fe2O3 phases in the cubic nanostructure. The BET result indicates that it has a specic surface area of 63 m2 g1. As the
synthesis of spinel CuFe2O4 was carried out at a relatively lower
synthesis temperature than those reported in the literature, the
elapsed-aging time was crucial for obtaining the desired
morphology and crystallographic phase.6,7,24 To obtain insights
into the formation of CuFe2O4Fe2O3, time-dependent FESEM
micrographs and XRD patterns of CuFe2O4Fe2O3 were
obtained (Fig. 2). Although the catalysts prepared at t 3 and 5
h have magnetic properties, the FESEM micrograph and XRD
pattern indicate that they consist of relatively amorphous
nanoparticles. With further increase in the reaction time, the
crystallinity of the nanoparticles improved and the nanoparticles began to self-assemble forming a quasi-cubic structure
via Ostwald ripening as indicated in Fig. 2c. The increase in the
synthesis time for the low temperature synthesis has also been
reported to increase the crystallinity of a material.25 The
proposed schematic illustration of the CuFe2O4Fe2O3 formation mechanism is shown in Fig. 3.
All the other catalysts were of quasi-spherical morphologies
(Fig. S1ae) except for CuAl2O4 which consists of irregular
microparticles (Fig. S1f). The solvothermal synthesis protocol
involving the use of surfactants resulted in materials with a
relatively higher specic surface area than the low temperature
co-precipitation method due to a signicant reduction in the
agglomeration of the materials prepared with a surfactant.26
However, this occurs at the expense of possible environmental
pollution due to surfactant leaching during the application (if
the surfactant is not removed) and a higher production cost.
J. Mater. Chem. A
Paper
3.2
Performance evaluation
Fig. 2
(1)
(2)
(3)
BPA degradation curves for dierent catalysts. Initial conditions: [pH] 7.0 0.2, [PMS] 0.36 g L1, [catalyst] 0.2 g L1, and
[BPA] 5 mg L1.
Fig. 4
Paper
Table 1 Synthesis method, BET specic surface area, TOC removal eciency, Cu leaching and pseudo rst-order rate constant (kapp) values of
various catalystsa
Catalyst
Synthesis method
Specic surface
area (m2 g1)
kapp
CuFe2O4Fe2O3
CuFe2O4
CuBi2O4
CuAl2O4
MnFe2O4
CoFe2O4
Fe2O3
Low-temperature co-precipitation
Solvothermal
Low temperature co-precipitation
Solgel
Solvothermal
Solvothermal
Low-temperature co-precipitation
63
101
9
39
151
139
188
24 (52)*
23
15
13
12
32
11
0.9 (<0.1%)
0.7 (<0.1%)
0.6 (<0.1%)
0.2 (<0.1%)
0.62 0.04
0.52 0.02
0.08 0.01
0.07 0.00
0.04 0.00
0.38 0.01
0.05 0.00
J. Mater. Chem. A
Paper
Fig. 6
SO2OOH + H /
+
OH+2]
SO2OOH2+
(4)
(5)
where [Cat OH] and [Cat OH2+] are the densities of active
and deactivated catalytic sites, respectively. The catalyst surface
contains many surface hydroxyl moieties which are important
for PMS activation, and surface protonation inuences the
density of surface hydroxyl moieties. The eect was particularly
more pronounced at lower catalyst loading and PMS dosage.
J. Mater. Chem. A
Fig. 7
(6)
(7)
where CBPA and CPMS are the concentrations of BPA and PMS,
respectively, and ki is the intrinsic reaction rate constant.
Considering that the changes of the CPMS follows the rst-order
kinetics (Fig. S3) and by incorporating eqn (6) into (7), the
kinetic model can be further simplied as follows:
dCBPA
Cat OHo
CBPA CPMSo ekPMS t
ki
dt
Keq H 1
(8)
Paper
Table 2
0.27
0.36
pH 7.0
0.18
0.27
0.36
pH 9.0
0.18
0.27
0.36
kapp
0.05
0.10
0.20
0.05
0.10
0.20
0.05
0.10
0.20
0.031
0.046
0.13
0.043
0.062
0.17
0.067
0.083
0.23
0.002
0.001
0.01
0.003
0.001
0.01
0.001
0.003
0.02
0.19
0.21
0.95
0.47
0.49
0.83
0.49
0.59
0.90
6.07
4.85
2.15
3.85
3.27
2.13
4.59
2.71
1.98
1.25
0.50
0.15
0.07
0.18
0.08
0.06
0.06
0.04
0.22
0.23
0.050
0.15
0.19
0.07
0.15
0.15
0.06
0.04
0.03
0.003
0.01
0.01
0.01
0.00
0.01
0.02
0.996
0.991
0.999
0.998
0.985
0.999
0.997
0.995
0.996
0.05
0.10
0.20
0.05
0.10
0.20
0.05
0.10
0.20
0.11
0.16
0.46
0.14
0.24
0.53
0.14
0.28
0.62
0.01
0.01
0.04
0.01
0.01
0.07
0.01
0.04
0.04
0.99
0.99
0.98
0.96
0.98
0.91
0.90
0.96
0.99
4.98
4.68
4.13
4.18
4.03
5.43
4.16
3.98
4.00
0.41
0.29
0.18
0.10
0.02
0.10
0.20
0.33
0.00
0.02
0.04
0.004
0.016
0.03
0.11
0.043
0.05
0.002
0.01
0.01
0.002
0.002
0.01
0.02
0.001
0.01
0.001
0.996
0.999
0.999
0.999
0.999
0.999
0.999
0.999
0.999
0.05
0.10
0.20
0.05
0.10
0.20
0.05
0.10
0.20
0.33
0.56
0.69
0.75
0.90
1.66
0.90
1.23
1.41
0.01
0.01
0.02
0.12
0.08
0.41
0.08
0.04
0.11
0.97
0.88
0.91
0.98
0.97
0.99
0.93
0.98
0.99
17.05
16.70
12.88
24.77
16.52
13.14
32.88
16.54
13.71
0.37
0.62
1.11
0.60
1.64
2.07
1.32
1.38
1.07
0.02
0.09
0.24
0.11
0.18
0.17
0.30
0.19
0.76
0.01
0.01
0.03
0.07
0.13
0.08
0.08
0.05
0.01
0.999
0.999
0.999
0.999
0.999
0.999
0.999
0.999
0.999
kt
kapp Keq H 1
Cat OHo PMSo
R2
where kPMS is the rst-order rate constant for PMS consumption. Eqn (8) can be solved analytically to become eqn (9) by
integrating with respect to t under the following boundary
conditions: at t 0, CBPA CBPAo.
ki
CBPA CBPAo e
CatOHo
kPMS Keq H 1
CPMSo e
k2 t
1
(9)
Eqn (9) will be explicitly validated by tting with the experimentally obtained BPA degradation results using Matlab and
the kinetic parameters can be calculated by optimization using
the nonlinear least squares method. Preliminary ttings indicated that all Keq have a value close to 1.0. The Keq 1 indicates
that neither the [Cat OH2+] nor the [Cat OH] are favoured
species and the equilibrium is dependent on pH (i.e.: when [H+]
is higher at acidic pH, the [Cat OH2+]/[Cat OH] is higher).
Therefore, Keq was used as a constant for the subsequent kinetic
modelling studies.
Table 2 also shows the calculated kinetic parameters consisting of ki and kPMS with their respective R2. When the PMS is
readily available for activation without signicant inuence by
the pH (rst-order), the relationship between kapp and ki can be
established by using the following equation:
ki
R2
kPMS
(10)
A relatively good t was observed for all cases (R2 > 0.99)
indicating that the kinetic model is able to account for the eect
of dierent reaction pH values. In general, the trend of ki value
decreases linearly with increasing catalyst loading suggesting
that the BPA oxidation reaction per unit catalyst proceeds
slower at higher catalyst loading. It should be noted that ki has
been normalized with respect to the catalyst loading and PMS
dosage. This was also observed previously for the ki values
calculated from eqn (10) in other heterogeneous PMS systems
employing pseudo-rst-order kinetics to model the pollutant
degradation rate.14,27 This observation could be due to the fact
that PMS activation by using CuFe2O3Fe2O3 is a multi-step
activation process generating both SO4c and SO5c for BPA
degradation (eqn (11)(14)):2,22
Cu2+ + HSO5 / Cu+ + SO5c + H+
(11)
(12)
(13)
J. Mater. Chem. A
Paper
(14)
(15)
(16)
(17)
SO42
+ O2 + H3O
(18)
(19)
J. Mater. Chem. A
Fig. 8
kCl
Cl Clc/Cl2 c
1 1
9
s
Clc 8 10 M
(20)
(21)
(22)
(23)
(24)
Paper
Acknowledgements
The nancial support from Academic Research Fund RG76/12 is
gratefully acknowledged. The authors would also like to thank
the interdisciplinary graduate school (IGS) and Nanyang Environment and Water Research Institute (NEWRI) for the award of
PhD research Scholarship. The kind assistance from all the
technical sta in the Environmental Laboratories is deeply
appreciated.
Fig. 9 Reusability of the CuFe2O3Fe2O3 catalyst. Initial conditions:
pH 7.0 0.2, [PMS] 0.18 g L1, [catalyst] 0.05 g L1, and [BPA]
5 mg L1.
c
HCO3 OHc/CO3 2 O
kHCO3 OHc 8:5 106 M1 s1
3.3
(25)
4. Conclusions
The CuFe2O3Fe2O3 catalyst was successfully synthesized via an
eco-friendly co-precipitation protocol at low temperature to
generate sulfate radicals from PMS for BPA removal. The
mechanism of the formation of CuFe2O3Fe2O3 at low temperature is proposed. The CuFe2O3Fe2O3 catalyst performed
signicantly better than other catalysts, namely ferrospinels
(YFe2O4, Y Cu, Co and Mn), Cu-based spinels (CuX2O4, X Bi
and Al) and Fe2O3, due to its preparation method without the
use of organic precursors and ecient synergistic redox
coupling between Cu2+ and Fe3+. A kinetic model was developed
based on the mechanistic consideration of the inuences of
various operating parameters, namely pH, PMS dosage and
catalyst loading. The proposed mechanistic kinetic model tted
relatively better than the pseudo-rst order kinetics, which did
not take into consideration the pH-dependent surface-charge
eect. The relationship between the pseudo rst-order rate
constant (kapp) and the intrinsic rate constant (ki) was
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