Chemosphere 234 (2019) 302e309

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Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

NO oxidation over Fe-based catalysts supported on montmorillonite

K10, g-alumina and ZSM-5 with gas-phase H2O2
Rongji Cui, Suxia Ma*, Jie Wang, Shujun Sun
College of Electrical and Power Engineering, Taiyuan University of Technology, 79 Yingze West Street, Taiyuan 030024, PR China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Lower electron cloud density of Fe3þ

in Fe/K10 favors the generation of
·
OH.

Fe2O3 is more active than Fe3O4 in
catalytic gas-phase H2O2 oxidation of
NO.

Both Fe and Brønsted acid sites in Fe/
ZSM-5 provide the catalytic
functionality.

a r t i c l e i n f o a b s t r a c t

Article history: The catalytic gas-phase H2O2 oxidation of NO was achieved over Fe-based catalysts supported on
Received 22 March 2019 montmorillonite K10, g-alumina and ZSM-5. ESR tests illustrate that the three catalysts can catalyze
Received in revised form decomposition of H2O2 yielding highly reactive hydroxyl radicals, of which Fe/K10 has the fastest rate,
16 May 2019
followed by Fe/g-alumina. Fe3þ in Fe/K10 and Fe/g-alumina show lower density of electron cloud due to a
Accepted 4 June 2019
Available online 4 June 2019
strong interaction between Fe3þ and the support, which benefits the electron transfer from the H2O2 to
Fe3þ, thus favoring the production of hydroxyl radicals. Fe species exist on the surface of Fe/K10 mainly in
Handling Editor: Jun Huang the form of Fe2O3, whereas Fe species of Fe/g-alumina and Fe/ZSM-5 exist mainly in the form of Fe3O4,
and it is found that Fe2O3 is more active than Fe3O4 in catalytic gas-phase H2O2 oxidation of NO.
Keywords: Interestingly, Fe/ZSM-5 has the lowest efficiency in generating hydroxyl radicals, its NO removal effi-
NO oxidation ciency is 90%, which is much higher than 47.5% for Fe/g-alumina and 62.3% for Fe/K10. In-situ IR results
Gas-phase H2O2 suggested that Fe/ZSM-5 are dual functional in oxidation of NO, that is, whether both Fe ion sites and
Fe-based catalysts Brønsted acid sites collectively provide the catalytic functionality. In the meantime, a possible reaction
Supports
mechanism on catalytic gas-phase H2O2 oxidation of NO over Brønsted acid sites is proposed.
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction rain, photochemical smog, secondary particulate matter and res-

SO2 and NO, mainly emitted from coal-fired power plants,
deteriorate the environment and human health by causing the acid
* Corresponding author.
E-mail addresses: 13643665215@163.com (R. Cui), masuxia@tyut.edu.cn (S. Ma),
wj18535461229@163.com (J. Wang), sunshujun687194@163.com (S. Sun).
piratory diseases (Wu et al., 2011; Zhang et al., 2015; Liu et al.,
2016). At present, in coal-fired power plants, the desulfurization
and denitrification of coal-fired flue gas are generally removed by
wet flue-gas desulfurization technology (WFGD) and selective
catalytic reduction (SCR) with NH3. However, the separate removal
of SO2 and NO results in serious dust deposition on the air-
preheater, large and complex systems, high investment and

https://doi.org/10.1016/j.chemosphere.2019.06.029
0045-6535/© 2019 Elsevier Ltd. All rights reserved.
 R. Cui et al. / Chemosphere 234 (2019) 302e309
operating costs, which is widely considered not economically
viable (Bokare and Choi, 2014). Accordingly, developing an inte-
grated multiple pollutants removal system concerning the simul-
taneous removal of NO and SO2 has become one of the most
attractive topics in the field (Ye et al., 2014). In these simultaneously
removal processes, oxidation-absorption process has prospects in
applications because of the simple system and low cost, in which
the key is to rapidly oxidize NO because NO is a stable radical
species with a low ionization energy of 9.26 eV.
Many reports have been published on the oxidation of NO using
Advanced Oxidation Processes (AOPs), Selective Catalytic Oxidation
(SCO) and strong oxidant oxidation (Chen et al., 2013; Ding et al.,
2014b; Zhao et al., 2017). Oxidation of NO by strong oxidants like
NaClO2, ClO2, O3 and KMnO4 is likely to cause high costs and sec-
ondary pollution problems. SCO always suffers from catalyst
poisoning and unsatisfied removal efficiency. AOPs are defined as
those which involved with the generation of hydroxyl radicals by
many techniques such as ultrasound, plasma and electro-oxidation
along with Fenton process. These above methods except Fenton
process suffer from high operation costs, which limits its industrial
application. However, Fenton process is a low-cost and high-
efficiency technology for NO oxidation and quite suitable for the
oxidation-absorption process.
Ding et al. (2014b) proposed a novel NO oxidation approach by
Fenton process, which utilized the injection of hydroxyl radicals
from the catalytic decomposition of gas-phase H2O2, and the hy-
droxyl radicals are powerful, non-selective oxidants with the ability
of converting NO in flue gas to more easily dissolved NO2. More
importantly, H2O2 is an environmentally friendly oxidant since it
decomposed to hydroxyl radicals without producing byproducts,
which are detrimental to the absorption process (Rui et al., 2013).
Ding et al. mixed the gas-phase H2O2 catalyzed by FeOx catalyst
with the simulated flue gas to achieve the simultaneous removal of
NO and SO2, and found that the NO removal efficiency is closely
related to the H2O2 flow and the temperature of the simulated flue
gas (Ding et al., 2014b). They further investigated the effect of
calcination temperature during the preparation of the catalyst by Fe
(NO3)3$9H2O on NO removal efficiency and suggested that higher
calcination temperature benefits the generation of oxygen va-
cancies, which had more apparent promotional effect on the cata-
lytic efficiency (Ding et al., 2014a). Wu et al. proposed a novel NO
removal approach with hydroxyl radicals from catalytic decompo-
sition of gas-phase H2O2 over La1-xCaxFeO3 oxides and found that
the surface hydroxyl group density and the oxygen vacancy con-
centration increased with the Ca stoichiometry increased (Wu and
Xiong, 2018). In catalytic gas-phase H2O2 oxidation of NO, most of
papers focused on the effect of processing conditions and surface
properties of active species on NO oxidation; but less attention has
been given to the effect of supports of Fe-based catalyst. Never-
theless, it is well known that suitable supports can facilitate catalyst
to exhibit efficient and stable catalytic performance.
The aim of this work is to develop solid supports for the active Fe
species on the NO oxidation through Fenton process. Catalytic wet
peroxide oxidation (CWPO) in the presence of Fe-based catalysts
has been widely used in the treatment of organic compounds in
wastewater (Gao et al., 2014). So far, several supports have been
used, like zeolites, pillared clays, alumina, silica, mesostructured
SBA-15 and activated carbon (Bautista et al., 2010). Herein, referring
to the above supports, g-alumina, K-10 andZSM-5 were used as
supports to prepare Fe-based catalysts in this work. The NO
oxidation experiments were tested to analyze the catalytic activity
of catalysts. In addition, physicochemical properties of catalysts
were characterized and attempts were made to correlate them with
their catalytic performance.
303
2. Experimental
2.1. Experimental apparatus
The experimental apparatus for the NO removal in oxidation-
absorption device is shown in Fig. S1. The simulated flue gases
are supplied by compressed gas cylinders filled with NO and N2.
The total flow is 250 mL/min, and NO content is 300 ppm. Atomized
H2O2 is produced by a homemade ultrasonic H2O2 atomizer and
carried into the reaction tube by N2. The volume flow of the
atomized H2O2 is about 0.07 mg/min 2 mol/L H2O2 are prepared by
diluting 30% H2O2 (Tianjin ZhiYuan Reagent Co., Ltd.) with deion-
ized water. The oxidation is occurred in a fixed bed reactor made of
quartz with a quartz partition supporting the 0.2 g catalyst, and the
temperature is measured by a K-type thermocouple. The absorp-
tion is occurred in an airtight glass bottles filled with saturated
calcium hydroxide solution. The atomized H2O2 is rapidly vapor-
ized after entering the reactor with higher temperature and
decomposed into hydroxyl radicals over Fe-based catalysts.
2.2. Preparation of catalysts
K10, g-alumina, ferric nitrate, Fe2O3 and Fe3O4 were purchased
from Aladdin Reagent Co., Ltd., and ZSM-5 zeolite was purchased
from Catalyst Plant of Nankai University, Tianjin, China. The ZSM-5
zeolite is H type and the ratio of silicon to aluminum is 80. These
were used as received without any further purification unless
otherwise mentioned. The Fe/ZSM-5, Fe/K10 and Fe/g-alumina
were prepared by incipient wetness impregnation of ZSM-5, K10
and g-alumina with an aqueous solution of Fe (NO3)3$9H2O in order
to obtain a 4% Fe wt.% nominal load. Afterwards, all the catalysts
were calcined at 300  C for 4 h.
2.3. Data process
NO removal efficiencies of catalysts were obtained after 1 h at
steady state and the efficiencies were calculated by Eq. (1).
Cin Cout
h¼  100% (1)
Cin
h is the removal efficiency, Cin and Cout is the inlet and outlet of
NO content, respectively. The value is tested for three times by
using testo 350 portable emission analyzer.
2.4. Characterization of catalyst
The power X-ray diffraction (XRD) measurement was carried
out with an automated X-ray diffractometer (Model ULTIMA Ⅳ,
Rigaku, Japan) using Cu Ka radiation (l ¼ 1.5418 Å), 40 kV voltage,
40 mA electrical current, 2q from 5 to 85 . The Fourier trans-
formation infrared (FTIR) spectroscopy were recorded on a Bia-Rad
FTS 165 spectrophotometer by dispersing the samples in KBr pel-
lets. Specific surface area was measured using nitrogen adsorption
at 196  C and determined by BET method using a Quantachrome
SI automated gas sorption system. The X-ray photoelectron spec-
troscopy (XPS) was carried out on a Thermo ESCALAB 250X
(America) electron spectrometer using 150 W Al Ka X-ray source.
The electron spin resonance (ESR) measurements were made using
a Bruker EMX-10/12-type spectrometer in the X-band. The acidity
of the samples was measured by ammonia temperature-
programmed desorption (NH3-TPD). Hydrogen temperature pro-
grammed reduction (H2-TPR) was performed in quartz U-tube
reactor on an automated chemisorption analyzer (Quantachrome
Instruments) by the GC method. The acid sites (Brønsted or Lewis)
304 R. Cui et al. / Chemosphere 234 (2019) 302e309

of the samples were determined by FTIR studies using pyridine as a
probe in a Nicolet-380 spectrophotometer and spectra were
recorded in the range of 1400e1600 cm1 following the reported
literature. In-situ IR measurements were conducted using the
Bruker VERTEX 70 FTIR spectrometer equipped with an in situ
diffuse-reflectance cell.
3. Result and discussion
3.1. Characterization of catalysts
The crystallographic structures of supports and catalysts were
studied by XRD patterns, as shown in Fig. 1 (a). The XRD patterns of
ZSM-5 zeolite show peaks at the ranges of 2q ¼ 7.9 , 8.8 , 23.1,
23.9 , 24.5 , which correspond to the specific peaks of the standard
MFI-structure ZSM-5 zeolite (Yan et al., 2015). In can be seen that
K10 shows the layered structure in crystalline form with sodium
and quartz-rich elements (Daud and Hameed, 2010). The diffraction
peaks observed in g-alumina were broad and diffuse indicating that
the g-alumina particles are of nanosized and the peaks are assigned
to the-alumina phase (JCPDS NO: 1-1307). No other peaks could be
observed in the patterns of these supports purchased, which
confirm the phase purity of them. The XRD patterns of Fe/g-
alumina, Fe/K-10 and Fe/ZSM-5showed that the supports loaded
with iron maintained the original crystal structure of supports. No
peak for iron oxides is observed because the Fe load is less than 5%
and Fe species are well dispersed on the surface of the supports (Qi
and Yang, 2005). The intensities of Fe/g-alumina, Fe/K-10remain
unchanged compared to those of g-alumina and K-10. However,
decrease of the intensity for the Fe/ZSM-5 is indicative of the
presence of iron in the impregnated catalyst. Fig. S2 shows the SEM
images of supports and catalysts. Not much change on the
morphology can be visualized although after supports were
impregnated with Fe.
The IR spectrum of Fe/g-alumina, Fe/K-10 and Fe/ZSM-5 are
shown in Fig. 1 (b). Broad bands at 3433 cm1 are indicative of
water adsorbed on catalysts, and its presence was confirmed by the
deformation band at 1634 cm1. The bands at 3648 and 3675 cm1
are relative to the stretching of hydroxyls groups and cations from
the octahedral sheet of Fe/K-10 and Fe/ZSM-5, respectively. In Fe/g-
alumina, the bands at 760 and 556 cm1 correspond to the vibra-
tion mode of AlO6 octahedra (Ji et al., 2012). The 1300-400 cm1
region indicates the framework vibration of lattice cell (T-O-T unit,
T is SiO4or AlO4 tetrahedron). Fe/K-10 has similar spectral features
to Fe/ZSM-5. The bands at 1079 cm1 correspond to the stretching
vibrations of silica-oxygen tetrahedrons as (Si-O-Si) and the bands
at 802 cm1 correspond to Al-O vibrations. The bands at 552 and
455 cm1 are attributed to Si-O-Si and Al-O-Si vibrations, respec-
tively (Taketa et al., 2015). Stretches relating to iron oxide were not
found in catalysts (Wei et al., 2012; Safari et al., 2016).

Fig. 1. (a) XRD profiles of g-alumina, K-10, ZSM-5, Fe/g-alumina, Fe/K-10 and Fe/ZSM-5. (b) The FTIR spectrum of Fe/g-alumina, Fe/K-10 and Fe/ZSM-5. (c) N2 adsorption-desorption
isotherms of Fe/g-alumina, Fe/K-10 and Fe/ZSM-5. (d) H2-TPR profiles of Fe/g-alumina, Fe/K-10 and Fe/ZSM-5.
 R. Cui et al. / Chemosphere 234 (2019) 302e309
Specific surface areas and porosity properties of Fe/g-alumina,
Fe/K-10 and Fe/ZSM-5 were determined by N2 adsorption-
desorption. Fig. 1 (c) displays the N2 adsorption-desorption iso-
therms of the samples, and their BET surface area and pore prop-
erties are summarized in Table 1. As can be seen in Fig. 1 (c), the N2
adsorption-desorption isotherms of Fe/g-alumina shows a hyster-
esis loop at a high relative pressure fit for type IV of adsorption
isotherms, which illustrates the existence of mesopores (Zielin  ski
et al., 2010). The isotherms of Fe/K10 was categorized as type IV
and hysteresis loop H3 typical of slit-shaped pores (Zhang et al.,
2006). However, the N2 adsorption-desorption isotherms of Fe/
ZSM-5 fit for a typical feature of microporous material (type I
adsorption isotherm). As can be seen in Table 1, Fe/g-alumina
shows much higher BET specific area (261.23 m2/g), total pore
volume (0.98 cm3/g) and average pore size (15.04 nm) than Fe/
ZSM-5 and Fe/K10, which is beneficial to the adsorption and
diffusion of reactants.
H2 temperature-programmed reduction (TPR) experiments
were conducted on Fe/g-alumina, Fe/K-10 and Fe/ZSM-5. The re-
sults are shown in Fig. 1 (d). As can be seen in the figure, the TPR
spectrum of Fe/g-alumina and Fe/K-10 exhibit three main peaks
centered at about 385  C, 542  C and 645  C. The peaks at about
385  C correspond to the reduction of Fe2O3 to Fe3O4 (peakI), peaks
at 542  C are assigned to the reduction of Fe3O4 to FeO (peakII), and
the peaks at 645  C are attributed to the reduction of FeO to Fe
(peakIII), respectively (Zielin ski et al., 2010). However, the TPR
spectrum of Fe/g-alumina shows only one reduction peak at 395  C,
which corresponds to the reduction of Fe2O3 to Fe3O4 (peakI). The
higher temperature of the peak I and no peaks observed at higher
temperature in Fe/g-alumina suggest that there is a strong inter-
action between Fe and-alumina, which results in the reduction of
Fe2O3 to Fe3O4 at a higher temperature, stabilizes the Fe3O4 phase
and further suppresses the transformation of Fe3O4 to FeO (Zhang
et al., 2006). Similarly, the relatively weak H2 consumption peaks
of Fe/K10 at higher temperature are also due to that Fe3þ in Fe/K10
formed Fe-O-Si bond with montmorillonite K10 and were harder to
be reduced (Yuan et al., 2018). According to the H2 consumption of
the peak I of the catalysts, we can know that the content of Fe2O3 in
Fe/K10 is much larger than that in Fe/g-alumina and Fe/ZSM-5. In
addition, the reduction of FeOx in Fe/ZSM-5 ends at FeO phase
rather than Fe.
To make clear the chemical state of Fe species in different sup-
ports and the interaction between Fe species and supports, XPS
technique was applied. Fig. 2 (a) shows the Fe 2p XPS spectra of
catalysts. The binding energies of Fe species for the three catalysts
are split into three peaks. For Fe/K10, Fe/g-alumina and Fe/ZSM-5,
the binding energies centered at 710.3 eV and 709.9 eV can be
assigned to Fe2þ in FeOFe structure, the binding energies centered
at 712.3 eV, 711.6 eV and 711.0 eV are attributed to Fe3þ in FeOFe
structure, and the binding energies centered at 715.1eV, 713.3 eV
and 712.9 eV are corresponding to Fe3þ in FeOH (Munoz et al., 2013;
Huang et al., 2015). Compared to Fe/ZSM-5, the Fe2þ and Fe3þ in
FeOFe for Fe/g-alumina and Fe/K10 shift to higher binding energies,
indicating that the Fe atoms in Fe/g-alumina and Fe/K10 show
lower density of electron cloud (Huang et al., 2015). Table 1 shows
Table 1
BET surface, pore properties, surface Fe atomic content and acidity of catalysts.
Catalysts Surface area and pore structure parameters
Surface Area (m2/g) Pore Size (nm) Pore Volume (cm3/g)
Fe/ZSM-5 244.75 3.29 0.20
Fe/g-alumina 261.23 15.04 0.98
Fe/K-10 190.05 6.00 0.29
305
the surface Fe atomic concentration of different catalysts. It can be
obtained that the Fe loading in catalysts are consistent with the
calculated value. From the Fe3þ/Fe2þ ratios of catalysts, we can see
that Fe species exist on the surface of Fe/K10 mainly in the form of
Fe2O3, whereas Fe species exist mainly in the form of Fe3O4 for Fe/
ZSM-5 and Fe/g-alumina.
Fig. 2 (b) shows the O1s spectra of catalysts. It can be clearly seen
that O1s peak of catalysts can be decomposed to different peaks
indicating that different types of oxygen species exist in catalyst
surface. The spectrum of Fe/K10 is composed of three peaks
centered at 531.6 eV, 532.5 eV and 533.1 eV, which could be
assigned to the Fe-O bond in FeOx, chemisorbed oxygen and Si-O
bond in montmorillonite (Zhu et al., 2015). The spectrum of Fe/g-
alumina can be fitted into three peaks: one peak at 532.5 eV can be
attributed to the chemisorbed oxygen on the surface; the moderate
peak at 531.4 eV is due to the lattice oxygen of Al2O3, and the last
peak at 530.6 eV is assigned to the lattice oxygen of FeOx (Liu and
Sun, 2007). The spectrum of Fe/ZSM-5 can be decomposed to four
peaks. The peak at 533.8 eV is attributed to hydroxyl species from
Brønsted acid sites. It is worth noting that the binding energy of Fe-
O bond in Fe/K10 is shifted to 531.6 eV due to strong interaction
between silica and Fe2O3, indicating that a portion of the iron
inserted into the clay structure is deposited on the surface, inter-
acting with the tetrahedral sheets of the clay (Coelho et al., 2014).
The Si2p spectra of Fe/K10 and Fe/ZSM-5 are shown in Fig. 2 (c). The
spectrum of the Fe/K10 and Fe/ZSM-5 are each fitted with a single
peak at 103.1 eV and 103.6 eV, respectively, which indicates only
one type of surface electronic level such as Si-O bonding. For the Fe/
K10, the binding energy of Si-O is lower than that of Fe/ZSM-5. This
again proves that there is a strong interaction between the iron
oxides and the silica matrix. Combined with H2-TPR and XPS re-
sults, we can conclude that both K10 and g-alumina have strong
interaction with iron oxides in the prepared catalysts, moreover,
K10 is stronger than g-alumina. The interaction between iron ox-
ides and supports cause Fe atoms show lower density of electron
cloud.
NH3-TPD was carried out to evaluate the acidic properties of the
catalysts. Ammonia was adsorbed on the acid sites of the catalysts
and removed by thermal desorption process. The temperature of
desorption peaks depends on strength of the bond between the
acid sites and NH3, and the desorption peaks can be classified as
weak, moderate and strong acid sites based on the desorption
temperature of 120e300, 300-500 and 500e700  C, respectively. In
addition, the amount of the acid sites base on the area of the NH3
desorption peaks Ramli and Amin (2015). The NH3-TPD profiles of
Fe/g-alumina, Fe/K-10 and Fe/ZSM-5 are displayed in Fig. 3 (a). The
NH3-TPD profile of Fe/K-10 and Fe/ZSM-5 display two desorption
peaks. The large desorption peaks at 137  C are attributed to weakly
bound NH3 and the higher temperature peaks around 424  C are
attributed to NH3 bound to moderate acid sites (Jia et al., 2009). The
NH3-TPD profile of Fe/g-alumina exhibits two weak acid peaks at
129 and 300  C. Generally, the peaks at lower temperature are
mainly related to Lewis acid sites, and the peaks at higher tem-
perature correspond to Brønsted acid sites (Jin and Li, 2009). In the
terms of acid amount, it is obvious that Fe/ZSM-5 has the highest
Fe atomic content FTIR of Pyridine
Fe3þ/Fe2þ Fe load Brønsted Conc.(CB) (mmol/g) Lewis Conc.(CL) (mmol/g) CB/CL
1.32 0.04 461.28 353.67 1.30
2.7 0.04 11.56 250.25 0.05
12.6 0.04 151.73 296.05 0.51
306 R. Cui et al. / Chemosphere 234 (2019) 302e309

Fig. 2. XPS curve fit of Fe2p (a), O1s (b) and Si2p (c) spectra of catalysts.

Fig. 3. (a) NH3-TPD profiles of Fe/g-alumina, Fe/K-10 and Fe/ZSM-5. (b) FTIR spectra of Pyridine adsorbed over Fe/g-alumina, Fe/K-10 and Fe/ZSM-5.

amount of weak acid and moderate acid. Secondly, Fe/K10 has a
relatively large amount of weak acid and a small amount of mod-
erate acid, and Fe/g-alumina has the least amount of weak acid.
The nature and strength of surface acid sites of Fe/g-alumina, Fe/
K-10 and Fe/ZSM-5 were determined by FTIR of adsorbed pyridine
after its adsorption at room temperature and sequential evacuation
at 150  C and 300  C. The FTIR spectra of the catalysts are shown in
Fig. 3 (b). The IR spectra in Fig. 3 (b) show that the catalysts exhibit
the characteristic peaks for pyridine adsorption at 1452 cm1 cor-
responding to Lewis acid sites and 1546 cm1 corresponding to
 R. Cui et al. / Chemosphere 234 (2019) 302e309
Brønsted acid sites. Moreover, a band at 1490 cm1 is correlated to
both Brønsted and Lewis acid sites (Ya'aini et al., 2013; Afreen et al.,
2017). The relative concentration of Lewis and Brønsted acid sites of
catalysts are listed in Table 1. It can be seen from Table 1 that all
catalysts contain a certain concentration of Lewis acid sites, but
their Brønsted acid sites concentration is obviously different, which
is mainly related to the acidity of the supports themselves. Among
them, Fe/ZSM-5 has the highest Brønsted acid sites content, fol-
lowed by Fe/K10.
The ESR spectrometer combining with DMPO was used to
verified the generation of hydroxyl radicals in H2O2/catalysts sys-
tem at 413K. Sample preparation process of different catalysts for
ESR detection is completely consistent. As shown in Fig. 4 (a), the
1:2:2:1 symmetrical four-line peaks in H2O2 and catalysts system
are the typical spectrum shape of DMPO-OH adducts (Wu and
Xiong, 2018). The hyperfine splitting constants (aN ¼ 1.50 mT and
aH ¼ 1.48 mT) is consistent with the data (aN ¼ 1.49 mT and
aH ¼ 1.49 mT) in the literature (Liu et al., 2016). Due to the parallel
ESR test of different catalysts, the yield of the hydroxyl radicals is
proportional to the peak intensity of ESR spectra. The ESR results
suggest that the yield of the hydroxyl radicals of Fe/K10 is signifi-
cantly higher than the other two catalysts, and Fe/g-alumina is
slightly higher than Fe/ZSM-5.
According to the Lin and Gurol mechanism, the valence state of
iron in the Fenton reaction switches between 2 þ and 3 þ charge, as
shown in Eqs. (2)e(4) (Lin and Gurol, 1998). The oxidation rate of
Fe2þ by H2O2 is known to be much faster than the reduction rate of
Fe3þ by H2O2 (Lee and Yoon, 2004). So, the reduction rate of Fe3þ is
the rate controlling step for the generation of hydroxyl radicals.
Combined with the characterization of the different catalysts
mentioned above, it can be considered that the Fe in Fe/K10 and Fe/
g-alumina show lower density of electron cloud due to the strong
interaction between the iron oxides and supports, and the lower
density of electron cloud of Fe3þ benefit the electron transfer from
the H2O2 to Fe3þ, thus favoring the production of hydroxyl radicals
by increasing the reaction rate of the rate controlling step Eq. (3)
(Huang et al., 2015). In addition, we suspect that Fe2O3 is a more
active catalyst than Fe3O4 in catalytic decomposition of gas-phase
H2O2, although Fe3O4 show more active than Fe2O3 in catalytic
wet H2O2 oxidation due to its unique characteristics (Pouran et al.,
2014). In order to verify the point that Fe2O3 is more active than
Fe3O4 in catalytic decomposition of gas-phase H2O2, the NO
removal experiments over purchased Fe2O3 and Fe3O4 at different
temperatures were carried out. As shown in Fig. S3, the tempera-
ture of 333K corresponds to wet H2O2, and the temperature of 413K
corresponds to gas-phase H2O2. The results show that when wet
H2O2 is added, the removal efficiency of Fe3O4 is higher than Fe2O3,
but the poor dispersion of wet H2O2 makes the two less efficient.
Fig. 4. (a) DMPO spin-trapping ESR spectra of Fe/g-alumina, Fe/K-10 and Fe/ZSM-5. (b) NO removal efficiencies of Fe/g-alumina, Fe/K-10 and Fe/ZSM-5. Conditions: NO content is
300 ppm, H2O2 flow is 0.07 mg/min, H2O2 concentration is 2 mol/L, temperature is 140  C. (c) In-situ IR spectra obtained over Fe/ZSM-5 with NO/H2O2 at 413K.
307
However, when gas-phase H2O2 is added, the removal efficiency of
Fe2O3 is higher than Fe3O4, which is consistent with our guess.
Fe3þ þH2 O2 /Fe3þ þHO,2 þHþ (2)
HO,2 þFe3þ /Fe2þ þO2 þHþ (3)
Fe2þ þH2 O2 / Fe3þ þOH þ , OH (4)
3.2. NO removal efficiency
The NO removal efficiencies of different catalysts were carried
out in a fixed bed reactor under the above reaction conditions in
order to investigate their catalytic performance. The resulting NO
removal efficiencies are presented in Fig. 4 (b). In contrast, the
removal efficiency of H2O2 was tested separately before the cata-
lysts was added. As shown in Fig. 4 (b), H2O2 combined with Ca
(OH)2 absorbent can achieve 9% NO removal efficiency, indicating
that the oxidation of H2O2 is weak for NO removal, and the removal
reaction is shown in Eqs. (5) and (6). The NO removal efficiencies of
Fe/g-alumina and Fe/K10 were 47.5% and 62.3%, respectively, which
is related to the amount of hydroxyl radicals because NO is mainly
oxidized by hydroxyl radicals through Eq. (7). It is worth pointing
out that Fe/ZSM-5 has the least amount of hydroxyl radicals in the
ESR test, but it's NO removal efficiency is the highest, which can
reach 90%. From the curve of NO concentration over time of Fe/
ZSM-5 as shown in Fig. S4, it can be seen that NO concentration
decreased from 300 ppm to 30 ppm in 2 min, while the NO2 con-
centration increased from 2 ppm to 7.5 ppm due to the incomplete
absorption of the self-made alkali absorption device. This result
demonstrates that in addition to the yield of hydroxyl radicals,
there are other factors that profoundly affect the NO removal effi-
ciency. By analyzing the above characterization, we found that the
acidity of Fe/ZSM-5 is quite different from the other two catalysts,
especially in the amount of Brønsted acid sites. Therefore, we
suspect that Brønsted acid sites play an important role in the NO
oxidation with gas-phase H2O2.
2NO þ 3H2 O2 /2HNO3 þ2H2 O (5)
2HNO3 þ CaðOHÞ2 /CaðNO3 Þ2 þ2H2 O (6)
NO þ , OH/HNO2 (7)
308 R. Cui et al. / Chemosphere 234 (2019) 302e309
3.3. In-situ IR
To investigate the role of Brønsted acid sites in Fe/ZSM-5 in the
reaction process, in-situ IR spectroscopy experiments were con-
ducted on Fe/ZSM-5 under gas mixture of NO and H2O2. Before in-
situ IR experiments, Fe/ZSM-5 was pre-treated for 2 h at 673K in
100 STP cm3/min He flow to remove adsorbed water and other
surface contaminants, and during the cool down to 413K: a back-
ground spectrum was recorded under He and then used as a
reference for the data conversion to absorbance units. Then, the gas
mixture was introduced, and IR spectra were collected after 5, 10, 15
and 20 min with a resolution of 2 cm1. As shown in Fig. 4 (c), bands
located in the 1700-1500 cm1, 2200-2100 cm1 and 3200-
2800 cm1 spectral regions appear after 5 min and then progres-
sively grow in intensity. In 1700-1500 cm1 range, multiple bands
are present, including two peaks centered at 1650 and 1608 cm1.
The bands in the 1700-1500 cm1 are typically attributed to nitrate
species formed on zeolites. In particular, the peak located at
1650 cm1 is attributed to a bridging nitrate complex, whereas the
peak centered at 1608 cm1 is assigned to bidentate nitrates (Hoost
et al., 1995; Hadjiivanov, 2000; Venkov et al., 2003). The band
centered around 2123 cm1 is assigned to NOþ by Jason A et al.
(Loiland and Lobo, 2015) who pointed out that this species can be
generated on Brønsted acid bridging hydroxyl groups under
NO þ O2 adsorption. They also proposed the reaction mechanism
for the NO oxidation reaction as shown in Eqs. 8e11. The NOþ is
frequently observed because of its mechanistic importance in NH3-
SCR and NO oxidation, but there is still uncertainty about the
conditions under which it is stable and its precise role in the
mechanisms. NOþ is strongly electrophilic with a reversible redox
potential. Although there is no oxygen in the mixed gas, we can
speculate that H2O2 (its standard oxidation potential is 1.77 eV) and
hydroxyl radical (2.8 eV) as electron donor can react with
Si  O: ðNOþ Þ  Al like oxygen to achieve the oxidation of NO as
shown in Eqs. 12 and 13. Large amount of Brønsted acid sites on Fe/
ZSM-5 can provide rich absorption and activation sites for NO and
H2O2, which is the main reason why Fe/ZSM-5 exhibits the highest
removal efficiency.



Si  O NOþ Al þ O2 # Si  O NOþ
3  Al (8)

þ

Si  O NOþ 
3  Al þ NO# Si  O NO2 Al þ NO2 (9)

solegel method. Catal. Commun. 37, 105e108.
Si  O NOþ :
2  Al# Si  O Al þ NO2 (10)

Fe2O3/mesoporous silica catalysts prepared under mild conditions. Appl. Catal.
Si  O:  Al þ NO # Si  O NOþ  Al (11)

using ironeMontmorillonite K10 catalyst. J. Hazard Mater. 176, 1118e1121.
Si  O: NOþ  Al þ , OH# Si  O: Al þ HNO2 (12)


2Si  O: NOþ Al þ H2 O2 # 2Si  O: Al þ 2HNO2 (13)
To further verify the above conclusion, we modified the exper-
imental apparatus as shown in Fig. S5. In the new experimental
apparatus, NO may not be in direct contact with the catalyst.
Catalyst can only be used to catalyze the decomposition of H2O2
and the generated hydroxyl radicals were mixed with NO under the
quartz separator to oxidize it. The NO removal efficiencies over new
experimental apparatus are shown in Fig. S6. A similar trend to the
amount of hydroxyl radicals was observed in the NO removal effi-
ciencies, which indicated that in the new experimental system,
only hydroxyl radicals acted on the oxidation of NO. The reduction
in NO removal efficiency of Fe/ZSM-5 is most obvious, suggesting
that Fe/ZSM-5 are dual functional in oxidation of NO, that is,
whether both Fe ion sites and Brønsted acid sites collectively pro-
vide the catalytic functionality.
4. Conclusion
In this study, the Fe/g-alumina, Fe/K-10 and Fe/ZSM-5 were
prepared by incipient impregnation and used for the catalytic gas-
phase H2O2 oxidation of NO in a fixed bed reactor. ESR tests illus-
trate that Fe/K-10 has the highest generation rate of hydroxyl
radical, followed by Fe/g-alumina, then Fe/ZSM-5. The character-
ization results showed that Fe species were well dispersed on the
surface of the supports with 4% Fe loading. Fe species exist on the
surface of Fe/K10 mainly in the form of Fe2O3, whereas Fe species of
Fe/g-alumina and Fe/ZSM-5 exist mainly in the form of Fe3O4. The
Fe2O3 is more active than Fe3O4 in the catalytic decomposition of
gas-phase H2O2 into hydroxyl radicals. Fe3þ in Fe/K10 and Fe/g-
alumina show lower density of electron cloud due to a strong
interaction between Fe3þ and the support, which benefits the
electron transfer from the H2O2 to Fe3þ, thus favoring the produc-
tion of hydroxyl radicals. Fe/ZSM-5exhibits excellent surface acid-
ity, especially since it contains a large amount of Brønsted acid sites.
Interestingly, the NO removal efficiency of Fe/ZSM-5 is 90%, which
is much higher than 47.5% for Fe/g-alumina and 62.3% for Fe/K10.
In-situ IR results suggested that the Brønsted acid sites do play an
important role in NO oxidation with gas-phase H2O2 because they
can adsorb and activate NO to form NOþ which is strongly elec-
trophilic and easily oxidized by hydroxyl and H2O2, and a possible
reaction mechanism is proposed.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.chemosphere.2019.06.029.
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