Journal of Hazardous Materials 397 (2020) 122577

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Journal of Hazardous Materials

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Catalytic ozonation of toluene using Mn–M bimetallic HZSM-5 (M: Fe, Cu, T
Ru, Ag) catalysts at room temperature
Jihee Kima,1, Jung Eun Leea,1, Hyung Won Leea,1, Jong-Ki Jeonb, JiHyeon Songc,
Sang-Chul Jungd, Yiu Fai Tsange, Young-Kwon Parka,*
a
School of Environmental Engineering, University of Seoul, Seoul 02504, South Korea
b
Department of Chemical Engineering, Kongju National University, Cheonan 31080, South Korea
c
Department of Civil and Environmental Engineering, Sejong University, Seoul 05006, South Korea
d
Department of Environmental Engineering, Sunchon National University, Suncheon 57922, South Korea
e
Department of Science and Environmental Studies, The Education University of Hong Kong, Tai Po, New Territories, Hong Kong

G R A P H I C A L A B S T R A C T

A R T I C LE I N FO A B S T R A C T

Editor: Rinklebe Jörg We investigated the catalytic efficiency of Mn-based bimetallic oxides in degrading toluene and ozone at room
Keywords: temperature. The room temperature-active bimetallic oxide catalysts were prepared by the addition of Fe, Cu,
Toluene Ru, and Ag precursors to Mn/HZSM-5. We obtained H2-temperature-programmed reduction (H2-TPR) profiles,
Ozone X-ray diffraction patterns, and X-ray photoelectron spectra to investigate the characteristics of the prepared
Mn bimetallic oxide catalysts catalysts. The catalytic efficiency of Mn-based bimetallic oxide catalysts in degrading toluene and ozone at room
HZSM-5 temperature was mostly improved by the addition of the secondary metals. The prepared bimetallic oxide
Catalytic ozonation catalysts, Cu-Mn/HZSM-5, Fe-Mn/HZSM-5, Ru-Mn/HZSM-5, and Ag-Mn/HZSM-5, enhanced efficiency for to-
luene removal compared to Mn/HZSM-5. The H2-TPR profiles of the Mn-based bimetallic oxide catalysts showed
stronger and broader adsorption-desorption bands at lower temperatures than the profile of Mn/HZSM-5.
Additionally, the ratio of the surface defective oxygen over the lattice oxygen on the bimetallic oxide catalysts
was higher than that of Mn-only catalysts; the ratio of Mn3+ over Mn4+ was higher for all bimetallic oxide
catalysts, as well. Among the bimetallic oxide catalysts, Ru-Mn/HZSM-5 showed the highest efficiency for the
removal of toluene to COx due to the synergetic effect of the oxidation state and reducible potential at room
temperature.

⁎
Corresponding author.
E-mail address: catalica@uos.ac.kr (Y.-K. Park).
1
Co-first authors.

https://doi.org/10.1016/j.jhazmat.2020.122577
Received 23 January 2020; Received in revised form 20 March 2020; Accepted 21 March 2020
Available online 05 May 2020
0304-3894/ © 2020 Elsevier B.V. All rights reserved.
J. Kim, et al.
1. Introduction
Environmental pollution is increasingly raising public concerns
(Hwang et al., 2019; Xu and Shan, 2018). Volatile organic compounds
(VOCs) which are liquids at room temperature with boiling points in the
range of 50–260 °C are some of the most prominent sources of pollution
(Senthilnathan et al., 2018; Huang and Zhang, 2019; Tanaka et al.,
2019). Aromatic compounds and their derivatives, such as toluene and
phenol, are detrimental to human health and animal. Majority of or-
ganic pollutants are controlled under a litany of rules and regulations in
many countries. In general, when harmful organic molecules are
emitted during various industrial or household processes, they need to
be treated before dispersing into the air (Jeon et al., 2018; Lee et al.,
2018; Kumar et al., 2019). Toluene is one of the most widely used
solvents in printing factories and chemical industries (Sultana et al.,
2015; Veerapandian et al., 2019). One of the most serious effects of
toluene exposure is known to be the influences on the central nervous
system (CNS). Acute exposure to low or moderate levels of toluene may
result in fatigue, headaches, and nausea, while exposure to high levels
of toluene or its ingestion will cause CNS depression and death (Agency
for Toxic Substances and Disease Registry (ATSDR, 2000; U.S. EPA,
2005). There have been tremendous attempts to abate the emission of
toluene and other harmful organic pollutants using catalysis (Wu et al.,
2013; Huang et al., 2015; Jung and Suh, 2018), photolysis (Li et al.,
2018; Zou et al., 2019), plasma discharge (Lee et al., 2020a; Feng et al.,
2020), adsorption (Sultana et al., 2015; Hwang et al., 2018; Jeon and
Jeon, 2018), and hybrid treatment (Qin et al., 2018, 2019; Jafari et al.,
2019; Lee et al., 2020b; Wang et al., 2020). Among them, catalytic
oxidation of organic molecules is regarded as one of the most feasible
and eco-friendly methods. In past several decades, noble metals, such as
Ag, Au, Pd, and Pt (Burgos et al., 2002; Radic et al., 2004) were em-
ployed to remove organic pollutants and reported to enhance the effi-
ciency of catalysts in removing VOCs (Liotta, 2010). In order to over-
come the defects of noble metals, such as deactivation and high cost (Li
et al., 2009; Huang et al., 2015), modified transition metal-based cat-
alysts (Chen et al., 2018; Yang et al., 2018; Wei et al., 2019) were also
applied to combined with plasma (Li et al., 2015; Zhu et al., 2020) or
photolysis (Li et al., 2019b; Shu et al., 2019) to abate the emission of
VOCs. Catalytic oxidation using a bimetallic oxide component (CoOx-
CeO2) with a multistage plasma system was employed to investigate
more active catalysts and the degradation mechanism of toluene (Jiang
et al., 2019). Li et al. (2019b) performed toluene degradation using a
CeO2/LaMnO3 catalyst under IR irradiation and obtained 89% con-
version of toluene. Among several transition metals, Mn oxides are ef-
fective in removing toluene in the presence of ozone at low tempera-
tures (Dhandapani and Oyama, 1997). Mn-based multi-metal-loaded
catalysts were developed and were superior to mono-transition metal
catalysts (Rezaei et al., 2013; Piumetti et al., 2015). Wei et al. (2019)
performed toluene removal using a Cu-Mn catalyst and converted to-
luene by 90% at 227 °C.
Although various attempts of investigation over enhancing catalytic
efficiency and adjusting experimental conditions have been performed
in order to abate emitted toluene at room temperature, the removal of
toluene by catalytic oxidation could not reach at satisfied goals without
combination of plasma or photolysis at room temperature. The catalytic
activity using metal oxides for the removal of VOCs shows high effi-
ciency at relatively high temperature although under UV-irradiation or
plasma discharge (Shu et al., 2019). Chen et al. (2018) utilized the Ce-
Mn binary oxides for toluene removal and obtained complete oxidation
of toluene at 280 °C.
Additionally, the physical and chemical properties of a catalyst
support affect the efficiencies of the catalytic oxidation of toluene
(Veerapandian et al., 2019; Zhokh et al., 2020). Various types of alu-
mina and zeolites have been employed as catalyst supports for the re-
moval of VOCs, owing to their large surface area and appropriate
geometrical structures that provide more feasible sites for the
2
Journal of Hazardous Materials 397 (2020) 122577
adsorption of VOCs. Zeolites can be classified according to pore dia-
meter, Si/Al ratio, and internal ring size. The hydrophilicity of zeolites
is affected by the Si/Al ratio; increasing this ratio results in decreased
hydrophilicity of zeolites. HZSM-5 is an aluminosilicate zeolite that has
been widely used as a support and adsorbent for the removal of ben-
zene-like aromatic pollutants, owing to its high adsorption capacity and
suitable pore size (Zhokh et al., 2020). ZSM-5 was recently employed as
an adsorbent of toluene in a non-thermal plasma system (Li et al.,
2019a; Veerapandian et al., 2019).
In this work, we employed HZSM-5 (SiO2/Al2O3 = 280) as a bi-
metallic oxide catalyst support because of its high hydrophobicity and
geometrical structure leading to provide the appropriate active sites for
the toluene adsorption. Mn-based bimetallic oxide catalysts, Fe-Mn/
HZSM-5 (FeMnZ), Cu-Mn/HZSM-5 (CuMnZ), Ru-Mn/HZSM-5 (RuMnZ),
and Ag-Mn/HZSM-5 (AgMnZ) were prepared and investigated for the
simultaneous removal of the 100 ppm toluene and 1000 ppm ozone at
room temperature. The physicochemical properties of the Mn-based
bimetallic oxides were analyzed by X-ray photoelectron spectroscopy
(XPS), X-ray diffraction (XRD) measurements, BET
(Brunauer–Emmett–Teller) surface area, and H2-TPR (H2-temperature-
programmed reduction) to understand the characteristics of more ac-
tive catalysts for toluene and ozone removal under the room tempera-
ture.
2. Experimental setup
2.1. Mn-based bimetallic oxide catalysts
HZSM-5 (SiO2/Al2O3 = 280, Zeolyst, USA) was widely employed
for the VOCs removal as a support of metal oxide catalysts; Mn and
various metals (Cu, Fe, Ru, Ag) were supported on HZSM-5. The metal
oxide catalysts were fabricated by wet impregnation method. In the first
stage of preparation of Mn/HZSM-5 (MnZ) primary template, a Mn
precursor, (CH3COO)2Mn∙4H2O (manganese acetate tetrahydrate,
Sigma-Aldrich, USA) was selected. Mn-loading of the MnZ catalyst was
fixed at 5 wt.%. At the second stage of preparation of secondary metal
added bimetallic oxide catalysts, we used FeN3O9∙9H2O (iron(III) ni-
trate nonahydrate, Sigma-Aldrich, USA), CuN2O6∙3H2O (copper(II) ni-
trate trihydrate, Sigma-Aldrich, USA), Cl3Ru∙xH2O (ruthenium(Ⅲ)
chloride hydrate, Sigma-Aldrich, USA), and CH3COOAg (silver acetate,
Sigma-Aldrich, USA) as precursors of FeMnZ, CuMnZ, RuMnZ, and
AgMnZ, respectively. The amount of Mn-loading and the amounts of
auxiliary metal (Fe, Cu, Ru, Ag) over the MnZ primary template were
fixed at 5 wt.% and 1 wt.%, respectively. Following a series of wet
impregnation processes, the prepared bimetallic oxide catalysts were
dried at 110 °C for 12 h and then calcined at 350 °C for 2 h. For the use
of catalytic oxidation of toluene and ozone, the bimetallic oxide cata-
lysts were formed as pelletizers with a size of 1.0–1.7 mm for the gas
flow.
2.2. Catalyst characterization
After pretreatment of the catalyst in vacuum at 200 °C for 12 h, the
N2 adsorption-desorption isotherms were carried out with a Belsorp
mini Ⅱ (BEL JAPAN, INC., Japan) nitrogen adsorption analyzer to de-
termine pore volume and the specific surface area of the catalysts. The
specific surface area of the sample was estimated using the BET method.
The XRD patterns for all samples were recorded on an Ultima Ⅲ
(Rigaku, JAPAN) diffractometer with Ni filtered Cu K α radiation. The
intensities of the XRD peaks were recorded in a 2θ range of 10°–90°.
XPS spectra were obtained with a MultiLab 2000 (VG, UK) using
non-monochromatic Al-K α radiation (1486.6 eV) for the evaluation of
the relative surface concentration of the metals and the elemental ionic
states. The C 1s line at 285 eV was referenced to the binding energies of
the elements.
H2-TPR analyses were performed with a BEL-CAT analyzer (BEL
J. Kim, et al. Journal of Hazardous Materials 397 (2020) 122577

Fig. 1. The experimental setup.

JAPAN, INC., Japan). The samples were pretreated at 350 °C for 1 h in

He gas environment. Following cooling down to 23 °C. The cooled
catalysts were mixed with a 5% H2/He (30 mL/min) and heated with
the rate of 10 °C/min up to 700 °C.

2.3. Toluene removal by catalytic ozonation

Fig. 1 shows the experimental apparatus diagram. The toluene cy-

linder with N2 balance supplied toluene. The supply of ozone was
carried out by O2 injection into the O3 generator (Ozonetech, South
Korea). The initial concentrations of toluene and O3 were 100 ppm and
1000 ppm, respectively. Each gas flow rate was maintained at 1 L/min.
The Mn and Mn-based bimetallic oxide catalyst beds were prepared in a
2-inch stainless steel pipe, and the amount of charged catalyst was 1.5 g
for all species. The GHSV (gas hourly space velocity) was 4200 h−1. The
toluene degradation in the presence of ozone proceeded at ambient
temperature. The concentrations of toluene and COx in the outlet gas
going through the catalyst bed were analyzed by Fourier-transform
infrared (FTIR) spectroscopy (Thermo Scientific, USA) and an O3 ana-
lyzer (Ozonetech, South Korea), respectively. The analysis of by-pro-
ducts adsorbed on the catalyst surface was performed using a micro-
reactor (PY-2020iD, Frontier Laboratories, Japan) connected with a GC
(7280A, Agilent, USA)/MS (5977E, Agilent, USA). The vaporized pro-
duct was transferred to the column (Ultra-ALLOY-5, Frontier Labora-
tories, Japan) through an inlet of 350 °C with the split ratio of 20:1. The
material corresponding to the MS peak was identified by the NIST 05
library.

Fig. 2. The XRD patterns of bimetallic oxide catalysts.

3. Results and discussion

3.1. Characterization of catalysts Table 1

The surface area and the pore volume of Mn-based bimetallic oxide catalysts.
The XRD patterns of MnZ and Mn-based bimetallic oxides catalysts Catalyst BET surface area (m2/g) Pore volume (cm3/g)
were evaluated in the range of 10°–90° and shown in Fig. 2. Based on
the XRD patterns, there was no great difference between the MnZ and Mn/HZSM-5 365 0.23
Fe-Mn/HZSM-5 364 0.22
Mn-including bimetallic oxide catalysts, M-Mn/HZSM-5 (M: Fe, Cu, Ru,
Cu-Mn/HZSM-5 359 0.23
Ag) because the metal composite ratio was too low to detect. This result Ru-Mn/HZSM-5 358 0.21
implies that the bimetallic oxide particles were well-dispersed on the Ag-Mn/HZSM-5 357 0.21
surface.

3
J. Kim, et al.
Fig. 3. The XPS spectra of Mn 2p (Mn 2p3/2; left, Mn 2p1/2; right) for the M-
Mn/HZSM-5 catalysts (M; Fe, Cu, Ru, Ag).
The surface area and pore volume of MnZ and Mn-based bimetallic
oxides are listed in Table 1. The surface area of MMnZ (M = Fe, Cu, Ru,
Ag) decreased more with the addition of secondary metals, following
the order Fe, Cu, Ru, and Ag to the range of 357–364 m2/g and became
lower than the BET surface area of MnZ (365 m2/g). The addition of a
transition or noble metal to manganese oxides resulted in the reduction
of the surface area of Mn-including bimetallic oxide catalysts. Although
there was a slight difference between the catalysts that included either
transition or noble metals, the surface areas of the Mn-including bi-
metallic oxide catalysts were assessed at 357–364 m2/g. The pore vo-
lumes of the bimetallic oxide catalysts were reduced to 0.21–0.23 cm3/
g by the addition of the secondary metals and did not differ greatly from
that of MnZ (0.23 cm3/g).
We recorded the XPS spectra of Mn 2p of the bimetallic oxide cat-
alysts to investigate the proportion of Mn3+ and Mn4+ following the
addition of a secondary metal to Mn (Fig. 3). The binding energies for
the Mn 2p3/2 and Mn 2p1/2 from the XPS spectra of Mn3+ in MnZ were
assigned in the range of 641.76–642.80 eV and 653.19–653.96 eV, re-
spectively (Liu et al., 2015). The binding energies of Mn 2p3/2 and Mn
2p1/2 from the XPS spectra of Mn4+ were assigned in the range of
644.14–646.39 eV and 655.77–657.5 eV, respectively (Liu et al., 2015).
Thus, the Mn3+ and Mn4+ state species coexisted in the Mn-based bi-
metallic oxide catalysts, but the Mn3+ state species was greater than the
Mn4+. The surface ratios of Mn3+ and Mn4+ for Mn bimetallic oxide
catalysts are listed in Table 2. We estimated that the concentration of
Mn3+ was higher than that of Mn4+ on the surface of the bimetallic
oxide catalysts. All bimetallic oxide catalysts showed a higher ratio of
Mn3+/Mn4+ than that of the Mn-only catalyst. FeMnZ and CuMnZ
showed similar Mn3+/Mn4+ values. RuMnZ and AgMnZ showed higher
values, 3.1 and 5.2, respectively, compared to the transition metal
4
Journal of Hazardous Materials 397 (2020) 122577
oxides.
Furthermore, the XPS spectra of O 1s for HZSM-5 support Mn-based
bimetallic oxides are shown in Fig. 4. The peaks in the 530.0–532.0 eV
and 532.0–533.0 eV ranges were assigned to the lattice oxygen (Olat)
and the surface vacancy oxygen (Ovac), respectively (Li et al., 2014).
The ratio of Ovac/Olat is shown in Table 2, as well. The Ovac/Olat ratio of
bimetallic oxide catalysts increased with the addition of auxiliary sec-
ondary metal except Ag.
The H2-TPR profiles of MnZ and Mn-based bimetallic oxide catalysts
with HZSM-5 support are shown in Fig. 5. The addition of the secondary
metals, Fe, Cu, Ru, and Ag to Mn oxides shifted the reduction tem-
peratures of the bimetallic oxide catalysts assigned at 332 °C and 448 °C
of MnZ to a lower temperature region. Specifically, the reduction
temperatures of RuMnZ were shifted to the lowest temperature region.
Moreover, the lower temperature region of RuMnZ had the largest peak
area. This observation implied that VOC oxidation might proceed easily
on RuMnZ because of its high reduction ability.
3.2. Degradation of toluene and ozone by Mn-based catalysts
The toluene removal efficiency of catalytic ozonation on Mn, Fe-Mn,
Cu-Mn, Ru-Mn, and Ag-Mn catalysts with HZSM-5 support is shown in
Fig. 6. Among the prepared metal oxides, RuMnZ showed the highest
toluene removal (36%), while CuMnZ showed the highest ozone re-
moval (70%). The toluene removals by Mn-based catalysts were as
follows: Ru- (36%) > Fe- (27.4%) ≈ Cu- (27.1%) > Ag- (23%) > only
Mn- (14%). The Mn-based bimetallic oxide catalysts showed improved
efficiency for toluene removal compared to MnZ.
The relation of ozone degradation and toluene removal using Mn-
based bimetallic oxides, M-MnZ (M: Fe, Cu, Ru, Ag), is plotted in Fig. 7;
the dependency of toluene removal over ozone degradation over metal
oxides at room temperature is described. The toluene degradation
tendency exhibited a roughly linear dependency on the ozone removal,
as shown in Fig. 7.
Moreover, we analyzed the concentration of COx (CO and CO2) in
the outlet gas using FTIR spectroscopy to estimate the amount of CO or
CO2 produced from the toluene degradation, as shown in Fig. 8. RuMnZ
showed the highest production of COx, indicating the highest activity of
RuMnZ; about 40% of the degraded toluene was converted into COx.
The highest catalytic activity of RuMnZ for converting toluene into COx
may be ascribed to the complementary effect of the oxidation state and
reducibility of Mn.
First, a lower oxidation state of the Mn catalyst was more effective
in decomposing benzene in the presence of O3 (Einaga and Ogata, 2009;
Ryu et al., 2019). The reductive lower oxidation states of Mn initiate the
decomposition of ozone by transforming its oxidized states, while Mn
moves to higher oxidation states. Ozone produces neutral oxygen and
oxygen radical anion by accepting an electron from the reaction with
reductive Mn. Experimental measurements using XANES (X-ray ab-
sorption near edge structure) and EXAFS (extended X-ray absorption
fine structure) showed that Mn3+ in the form of Mn2O3 was oxidized to
Mn4+ by the Mn-vicinal oxygen by altering the d electron for ozone and
VOCs (Aghbolaghy et al., 2018). Mn oxides were spread evenly on the
support, and they were more effective in the ozone degradation than
other metal oxides.
The binding energy of Mn3+ 2p3/2 in MnZ decreased with the ad-
dition of the secondary transition metal or noble metal, as shown in the
Mn 2p XPS spectra in Fig. 3. The binding energy of Mn3+ 2p3/2 in MnZ
(642.27 eV) was lowered to 642.11 eV, 641.76 eV, 642.06 eV, and
642.02 eV by the addition of Fe, Cu, Ru, and Ag, respectively. This
reduction implicated that the modified catalysts could be more favor-
able toward oxidation and reaction with ozone compared to MnZ be-
cause of their weakened bonding energy. Therefore, the appropriate Mn
bimetallic oxide catalysts on HZSM-5 support would show an improved
efficiency in removing ozone and toluene. As shown in Table 2, RuMnZ
and AgMnZ had higher Mn3+/Mn4+ ratios than the other catalysts.
J. Kim, et al.
Table 2
The surface atomic ratio of Mn ions and oxygen species based on the XPS spectra.
Catalyst Mn3+ (%) Mn4+ (%)
Mn/HZSM-5 11.1 4.9
Fe-Mn/HZSM-5 9.9 3.6
Cu-Mn/HZSM-5 6 2.2
Ru-Mn/HZSM-5 6.1 1.9
Ag-Mn/HZSM-5 14.1 2.7
a
The content of available vacancy oxygen on the catalyst surface position.
b
The content of lattice oxygen of each catalyst based on the XPS analysis.
Fig. 4. The O1 s XPS spectra of Mn-based bimetallic oxide catalysts for the
oxygen vacancy denoted as Ovacacy and the lattice oxygen denoted as Olattice.
Second, oxygen species such as lattice oxygen and oxygen vacancy
seemed imperative in the toluene oxidation. RuMnZ and CuMnZ
showed higher Ovac/Olat ratio than the other catalysts. Therefore, this
higher Ovac/Olat ratio might have induced the higher activity of the
catalysts for converting toluene to COx at room temperature. Many
researchers have reported that the oxygen vacancy is more important
than the lattice oxygen at lower temperature. Li et al. (2015) performed
acetaldehyde degradation using modified Mn catalysts (OMS-2) com-
bined with a plasma system and noticed enhanced catalytic activity
with Cu- and Co- added catalysts, Cu-OMS-2 and Co-OMS-2. They
proclaimed that the defective oxygen played a significant role in VOCs
degradation at low temperatures because of the enhanced mobility of
oxygen. Furthermore, Jiang et al. (2019) performed toluene degrada-
tion using catalytic oxidation combined with a multistage plasma
system. They employed CoOx-CeO2 bimetallic catalysts with 1:3, 1:1,
and 3:1 molar ratios of Co and Ce and explained that the oxygen va-
cancy was the cause of the high toluene degradation.
Moreover, toluene removal was improved by chemisorbed oxygen
rather than lattice oxygen in the presence of ozone (Li et al., 2014; Yuan
et al., 2020). Li et al. (2014) performed toluene degradation in the
presence of ozone at ambient temperature using Mn-Ag/HZSM-5, Ag/
HZSM-5, and Mn/HZSM-5 catalysts. They proclaimed that the abun-
dance of oxygen vacancies on the Mn-Ag/HZSM-5 catalyst was
5
Journal of Hazardous Materials 397 (2020) 122577
Mn3+/Mn4+ Ovac a
Olat b
Ovac/Olat
2.2 38.9 25.4 1.5
2.7 48.5 17.5 2.7
2.6 57.8 15.0 3.8
3.1 45.1 13.1 3.4
5.1 36.5 27 1.3
responsible for the improved catalytic activity for the removal of to-
luene.
Third, the highest reducibility of RuMnZ, as shown in the H2-TPR
profiles (Fig. 5), might have been another important reason for its
highest activity for the conversion of toluene into COx. Based on the H2-
TPR pattern, the interaction between the support and metals by the
addition of an auxiliary metal to Mn would not be stronger than that of
MnZ. The FeMnZ, CuMnZ, RuMnZ, and AgMnZ bimetallic oxide cata-
lysts, which were superior to MnZ in the ozone and toluene removal at
room temperature, showed a broad band and high intensity in relatively
lower temperature. The catalytic efficiency of Mn-based catalysts was
improved by the addition of appropriate reductive metals such as Fe,
Cu, Ag, or Ru, leading to more available active oxygen species to react
with ozone. The improved reducibility of Mn in CuMnZ, FeMnZ,
RuMnZ, and AgMnZ could enhance the catalytic activity for ozone and
toluene removal. Specifically, the TPR profile of RuMnZ had the highest
area at lower temperatures. This differentiation indicated that the lar-
gest amount of oxygen vacancy available during the toluene and ozone
conversion at room temperature existed on the surface of RuMnZ.
In summary, although RuMnZ had the second-highest Mn3+/Mn4+
and Ovac/Olat ratios, its lowest reduction temperature and highest H2
consumption area indicated that it might have had the largest oxygen
vacancy available at room temperature. Therefore, the highest catalytic
activity of RuMnZ might have been due to the proper combination of
the oxidation state and reducibility.
Additionally, we performed a GC/MS analysis of RuMnZ to detect
various products after the catalytic oxidation of toluene and ozone
(Fig. 9). The portion of degraded toluene over RuMnZ converted into
incompletely oxidized by-products such as aldehydes, organic acids,
and coupling products. Also, we observed coupling and dimerization
among various active radical species, such as phenyl radicals and me-
thyl radicals produced in the middle of the toluene degradation by
active oxygen species. Carbonaceous organic molecules, such as acetic
acid, benzaldehyde, and benzoic acid, were also observed.
The active oxygen species produced from the ozone degradation
should react with the methyl group or the unsaturated benzene ring of
toluene and lead to incompletely oxidized intermediates, such as ben-
zaldehyde, benzoic acid, methyl benzaldehyde, and acetic acid before
the formation of COx. Aghbolaghy et al. (2018) performed removal of
toluene, acetone, and their mixture, using MnOx/Al2O3 at 25 °C, 60 °C,
and 90 °C in the presence of O3 to investigate the synergetic effect of the
VOCs mixture. The catalytic ozonation of toluene by MnOx/Al2O3 at
25 °C could not convert toluene completely, generating various by-
products; however, raising the temperature improved the removal ef-
ficiency for both ozone and toluene and decreased the by-products
significantly. The low catalytic oxidation at low temperature was
caused by deactivation of the catalyst due to the adsorption of in-
completely oxidized carbonaceous compounds on the catalyst surface,
which blocked the active sites.
4. Conclusions
In this study, we performed catalytic ozonation of toluene using Mn-
based bimetallic oxide catalysts on HZSM-5 support by addition of 1 wt.
J. Kim, et al. Journal of Hazardous Materials 397 (2020) 122577

Fig. 5. The H2-TPR profiles of samples: (a) Mn/HZSM-5; (b) Fe-Mn/HZSM-5; (c) Cu-Mn/HZSM-5; (d) Ru-Mn/HZSM-5; (e) Ag-Mn/HZSM-5.

% of Fe, Cu, Ru, and Ag. Compared to MnZ, the Mn-based bimetallic
oxide catalysts showed improved efficiencies of toluene removal in the
presence of ozone at room temperature. The toluene removal effi-
ciencies by the bimetallic oxides were in line with those of the ozone
removal. Additionally, the defective oxygen influenced the removal of
ozone and toluene over the Mn-based bimetallic oxide catalysts. The
activity of the catalysts was related to the increased reducibility of Mn
and the defective oxygen sites; the addition of a reducible secondary
metal led to more active catalysts than MnZ. A high Mn3+/Mn4+ ratio
was also essential for toluene degdradation with ozone at room tem-
perature.
Fig. 6. The removal of toluene and ozone by the Mn-based M-Mn/HZSM-5 (M:
Fe, Cu, Ru, Ag) catalysts.
CRediT authorship contribution statement

Jihee Kim: Conceptualization, Investigation, Data curation,

Validation, Writing - original draft. Jung Eun Lee: Conceptualization,
Investigation, Data curation, Validation, Writing - original draft. Hyung
Won Lee: Conceptualization, Investigation, Data curation, Validation,
Writing - original draft. Jong-Ki Jeon: Data curation, Writing - review
& editing. JiHyeon Song: Data curation, Writing - review & editing,
Funding acquisition. Sang-Chul Jung: Data curation, Writing - review
& editing. Yiu Fai Tsang: Data curation, Writing - review & editing.
Young-Kwon Park: Conceptualization, Methodology, Writing - ori-
ginal draft, Writing - review & editing, Supervision, Project adminis-
tration, Funding acquisition.

Declaration of Competing Interest

Fig. 7. The plot of the toluene removal and ozone removal on the Mn-based
catalysts. The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.

6
J. Kim, et al. Journal of Hazardous Materials 397 (2020) 122577

Fig. 8. The concentration of CO and CO2 measured from the degradation of toluene and ozone.

Fig. 9. The GC/MS analysis of the by-products from the degradation of toluene and ozone over Ru-Mn/HZSM-5. (1) Carbon dioxide, (2) Benzene, (3) Acetic acid, (4)
Toluene, (5) 4-Methylbenzaldehyde, (6) Benzaldehyde, (7) Benzene carboxylic acid, (8) Diphenylmethane, (9) 2,2′-Dimethylbiphenyl.

Acknowledgment
This research was supported by the Technology Development
Program to Solve Climate Changes of the National Research Foundation
(NRF) funded by the Ministry of Science, ICT (2017M1A2A2086839).
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