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Catalysis Today
journal homepage: www.elsevier.com/locate/cattod

Catalytic performance for toluene abatement over Al-rich Beta zeolite

supported manganese oxides
⁎
Yuexin Penga, Ling Zhanga, Long Chenb, Dingzhong Yuana,b, Guoxiong Wanga, Xiangju Menga, ,
⁎
Feng-Shou Xiaoa,
a
Key Laboratory of Applied Chemistry of Zhejiang Province, Zhejiang University, Hangzhou 310028, China
b
Faculty of Chemistry Biology and Materials Science, East China Institute of Technology, Fuzhou 344000, China

A R T I C L E I N F O A B S T R A C T

Keywords: Catalytic combustion of toluene has been widely investigated due to importance of abatement of volatile organic
VOCs abatement compounds (VOCs), and in this work we have successfully prepared highly efficient heterogeneous catalysts for
Zeolite supported manganese oxides toluene combustion by impregnation of manganese oxides with Al-rich Beta zeolites (Beta-SDS) with H-form
Al-rich Beta zeolite (MnOx/H-Beta-SDS) and K-form (MnOx/K-Beta-SDS) as well as pure siliceous Beta zeolite (MnOx/Si-Beta).
Toluene combustion
Catalytic tests show that these zeolite-supported catalysts have higher activities than alumina-supported
Oxygen species
manganese oxides (MnOx/Al2O3). By comprehensive consideration of reducibility, adsorbed oxygen species,
and lattice oxygen species in the catalysts, it is shown that the adsorbed oxygen species play more important
roles than others for the catalytic activity. The good catalytic performance and understanding of active sites over
the MnOx/H-Beta-SDS might be helpful for preparation of catalysts in VOCs abatement.

1. Introduction
The emission of volatile organic compounds (VOCs) is proved as one
of the main contributors of air pollution [1–3], which becomes a
notable and widespread problem due to their endangerments to natural
environment and human health [4–7]. Catalytic combustion is one of
the most effective techniques for removal of VOCs, which can com-
pletely transform organic contaminant into harmless species like CO2
and H2O at relatively low temperatures [8,9]. Supported noble metals
such as Pt, Pd [10,11], transition metal oxides such as CeO2 and MnOx,
as well as mixed oxides are all quite active during VOC combustion
process [12–15]. Generally, supported noble metal catalysts show
excellent performance for VOCs abatement, but the wide applications
are always limited by their high cost and susceptibility to poisoning
[16–19]. As a result, transition metal oxides draw a great attention and
interest because of economic viability in industrial applications
[18,20].
Manganese can form a number of oxides with the different oxidation
states, which exhibits interesting catalytic properties by generating
redox couple via the Mars-Van-Krevelen mechanism [21]. Both sup-
ported and unsupported of them show particularly superior catalytic
activities in VOCs oxidations [22,23]. In particular, complex oxides
containing Mn such as manganite perovskites with excellent perfor-
mance have been paid much attentions [24–26]. Nonetheless, there are
still challenges for the manganese oxides such as relatively low surface
areas and difficult control of the active sites. Thus, it is suggested useful
strategies to enhance the catalytic performance by the use of appro-
priate supports [27–29], control of crystalline morphology [30], and
addition of promoters [19,23,31].
Zeolites with advantages of large surface areas, high adsorption
capacity, high stability, and tailored wettability and mesoporosity have
been regarded as one of the most potential supports for the VOCs
abatement [32,33]. For examples, Meng et al. designed a one-pot route
to prepared Mn-ZSM-5 catalyst for catalytic oxidation of toluene with
65% total conversion of toluene to carbon dioxide [34]; Gülin et al.
prepared supported metal oxides as catalysts for catalytic combustion of
toluene in air [15]; Wang et al. synthesized HZSM-5 supported Ag and
Ce catalysts for eliminating flue gas with low-concentration of toluene
[35]. In these examples, it is strongly desirable to enhance the catalytic
activities in industrial applications.
In the previous study, we have prepared a series of zeolite supported
Pt catalysts, and it is found that the abundant framework Al and the
presence of K+ in the zeolites are favorable for improving catalytic
activities in the VOCs abatement [36–40]. In this work, we prepared Al-
rich Beta zeolite supported manganese oxides, exhibiting superior
activity and long life in catalytic combustion of toluene.

⁎
Corresponding authors.
E-mail addresses: mengxj@zju.edu.cn (X. Meng), fsxiao@zju.edu.cn (F.-S. Xiao).

http://dx.doi.org/10.1016/j.cattod.2017.04.058
Received 16 November 2016; Received in revised form 10 February 2017; Accepted 29 April 2017
0920-5861/ © 2017 Elsevier B.V. All rights reserved.

Please cite this article as: Peng, Y., Catalysis Today (2017), http://dx.doi.org/10.1016/j.cattod.2017.04.058
Y. Peng et al.
2. Experimental section
2.1. Materials
NaAlO2, NaOH, and toluene were purchased from Sinopharm
Chemical Reagent, fumed silica (SiO2) was supplied from Shenyang
Chemical Co, Beta seeds (Si/Al = 12.50) were obtained from Nankai
University Catalyst Co. HF (40%), TEOS, TEAOH (40%), Mn
(NO3)2∙4H2O, KNO3, and NH4NO3 were received from Aladdin. All
these chemicals were of analytical-reagent grade and were used without
further purificatoin.
2.2. Catalyst preparation
The H- and K-form Al-rich Beta zeolite was carried out by ion-
exchange from as-synthesized Al-rich Beta (Beta-SDS), which was
synthesized according to literature [41]. In a typical run, 0.32 g of
NaAlO2 and 0.56 g of NaOH were dissolved in 6.8 mL of H2O, followed
by the addition of 2.0 g of fumed silica. After stirring overnight, 0.1 g of
Beta zeolite seeds was introduced into the gel and stirred for 10 min.
The resultant gel was transferred into an autoclave to crystallize at
120 °C for 90 h. The solid product was filtered, washed with water, and
dried at 80 °C in air for 12 h. For ion-exchange, 1.0 g as-synthesized
Beta zeolite was added into the 100 mL KNO3 or NH4NO3 solution
(0.1 M), stirring for 3 h at 80 °C. After filtering and washing with water,
dried in 80 °C for 12 h, the ion-exchanged sample was obtained. The
ion-exchange procedures were repeated for twice. After the solid
products were calcined in 550 °C for 4 h, the H- and K-form Al-rich
Beta zeolites were finally received, as denoted as H-Beta-SDS and K-
Beta-SDS, respectively.
The pure siliceous Beta zeolite was also prepared according to the
literature [42]. In a typical run, 8.47 g TEOS was added into 9.23 g
TEAOH solution under stirring for 8 h, followed by the addition of
0.915 g HF, stirring for 15 min. After evaporation to remove water at
50 °C, 0.34 g siliceous Beta seeds were added into the resultant gel and
then was transferred into an autoclave to crystallize at 140 °C for
7 days. After filtering, washing with water, drying at 80 °C, and
calcining at 550 °C for 6 h, the solid powder was finally obtained, as
denoted as Si-Beta.
The zeolite supported manganese oxide catalysts were prepared
from wet-impregnation using an appropriate amount of aqueous
solution of Mn(NO3)2·4H2O. After impregnation, the excess water was
removed in an evaporator at 80 °C, followed by calcination at 400 °C for
4 h. These catalysts are denoted as MnOx/H-Beta-SDS, MnOx/K-Beta-
SDS, and MnOx/Si-Beta, respectively.
2.3. Characterization
X-ray diffraction (XRD) patterns were obtained using a RIGAKU
Ultimate IV diffractometer with Cu Kα radiation. Nitrogen sorption
isotherms at −196 °C were measured using Micromeritics ASAP
2020 M system. The surface area was calculated by using the
Brunauer-Emmett-Teller (BET) method. The elemental composition of
the zeolites and the Mn content in the catalysts were determined by
inductively coupled plasma atomic emission spectrometry (ICP-AES)
using a Perkin-Elmer plasma 8000 optical emission spectrometer. The
X-ray photoelectron spectra (XPS) of the catalysts were recorded using a
Thermo ESCALAB 250 instrument with Al Kα X-ray radiation for the X-
ray source. The binding energies were calibrated against the C1 s
(285.0 eV) peaks. High-resolution TEM (HRTEM) images were obtained
at 200 kV on a JEOL 2100F electron microscope.
H2 temperature-programmed reduction (H2-TPR) and O2 tempera-
ture-programmed desorption (O2-TPD) were performed on a Finetec
Finesorb-3010 instrument equipped with a thermal conductivity detec-
tor. Before starting the H2-TPR, 20 mg the sample was treated in
flowing Ar at 200 °C for 60 min. After cooling in flowing Ar, the H2-TPR
2
Catalysis Today xxx (xxxx) xxx–xxx
measurement was performed in 5 vol.% H2/Ar (50 mL/min) with
temperature rate of 10 °C/min. For O2-TPD, the sample was pre-treated
at 300 °C in He for 1 h. During the test, the gas flow was 50 mL/min−1.
After cooling down to room temperature, the sample was firstly
exposed to a 5% O2 gas flow for 1 h, then allowed to undergo
isothermal desorption under He for 30 min. The temperature rate in
the O2-TPD test was 10 °C/min.
2.4. Catalytic performance evaluation
Experiments for the catalytic combustion of 1000 ppm toluene were
performed at atmospheric pressure in a continuous-flow fixed-bed
micro-reactor consisting of a quartz tube (6 mm in diameter) filled
with the catalyst. The samples were per-treated at 350 °C for 2 h in the
air flow. As a typical experiment, 100 mg catalyst (0.45-0.90 mm size)
was used with a total flow-rate of feed gases (79% N2 + 21% O2) of
100 mL min−1. The concentration of toluene in the tail gases was
analyzed using a gas chromatograph (Fuli, GC9790) equipped with a
flame ionization detector and a 19091N-113 INNOWAX capillary
column (Agilent, 30 m × 0.32 mm × 0.25 mm). The concentration of
the oxidation products (CO2 and CO) in the tail gases was analyzed with
a gas chromatograph (Fuli, GC9790) equipped with a thermal con-
ductivity detector using a Carboxen packed column (Jie Dao,
2m × 2 mm). The conversion of toluene was calculated from the
difference in the inlet and outlet concentrations of toluene. The carbon
balance reached 100 ± 5% in this work.
3. Results and discussion
3.1. Characterization
Fig. 1 shows XRD patterns of MnOx/H-Beta-SDS, MnOx/K-Beta-SDS,
and MnOx/Si-Beta. They exhibit well-resolved characteristic peaks
associated with BEA structure [41,42]. These results suggest that the
BEA structure is stable during the process of impregnation and
calcination for the preparation of catalysts. In addition, a very weak
at 37° could be found, which should be attributed to the nanoparticles
of MnO2. The formation of MnO2 nanoparticles could be resulted from
the transformation of manganese nitrate precursors in the air. Fig. S1
shows nitrogen sorption isotherms of these samples, and their textual
parameters are presented in Table 1. The Si/Al ratios in MnOx/H-Beta-
SDS and MnOx/K-Beta-SDS were analyzed by ICP technique, giving
similar values at ca. 4.0–4.3.
Fig. 1. XRD patterns of (a) MnOx/H-Beta-SDS, (b) MnOx/K-Beta-SDS, and (c) MnOx/Si-
Beta.
Y. Peng et al. Catalysis Today xxx (xxxx) xxx–xxx

Table 1
Textural parameters, Si/Al ratios, and Mn loadings of the supports and catalysts.

Samples Si/Ala Mna Ka BETb Vbmicro Vbmeso Vbtotal

wt% wt% m2 g−1 cm3 g−1 cm3 g−1 cm3 g−1

Beta-SDS 4.3 – – 621 0.28 0.06 0.34

Si-Beta ∞ – – 499 0.23 0.02 0.25
MnOx/H- 4.1 9.55 – 438 0.20 0.04 0.24
Beta-SDS
MnOx/K- 4.0 9.14 7.74 366 0.17 0.03 0.20
Beta-SDS
MnOx/Si-Beta ∞ 9.32 – 429 0.19 0.07 0.26

a
Determined from ICP technique.
b
Estimated from N2 sorption isotherms.

Fig. S2 shows large-scale TEM images of MnOx/H-Beta-SDS, MnOx/

K-Beta-SDS, and MnOx/Si-Beta, indicating that the MnOx nanoparticles
are mainly dispersed on the surface of Beta zeolite crystals. The high
resolution TEM images (Fig. 2) in these catalysts give well-resolved
lattice fringes of the manganese oxides, showing the lattice spacing of
the (201) crystal planes at 0.324 nm, which is in line with the
corresponding d value of standard MnO2 (JCPDS PDF# 65-1298).

3.2. H2-TPR and O2-TPD

Fig. 3 shows H2-TPR of MnOx/H-Beta-SDS, MnOx/K-Beta-SDS, and

MnOx/Si-Beta. In the profile of MnOx/H-Beta-SDS, two reduction peaks
centered 369 and 389 °C could be observed, where the lower peak is
assigned to the reduction Mn4+ to Mn3+, while the higher peak is
reasonably related to the reduction Mn3+ to Mn2+ [23,43]. In the
profile of MnOx/K-Beta-SDS, it is also given the two reduction peaks at
346 and 459 °C, but the difference between two peaks is larger. In
contrast, there is a broad reduction peak centered at 394 °C in MnOx/Si-
Beta, which suggests that the transformation from Mn4+ to Mn3+ then
Mn2+ occurs similar temperature [30]. These results indicate that the
zeolite supports with various cations strongly influence the reducibility
of the catalysts. Moreover, normal silica-aluminum zeolites are con-
sidered as the inert supports with non-reducibility [44]. As observed in
Fig. 3 for the transformation from Mn4+ to Mn3+, it is obvious that the
order for the reducibility of the catalysts is as follows: MnOx/K-Beta-
SDS > MnOx/H-Beta-SDS > MnOx/Si-Beta. The strong reducibility of
the MnOx/K-Beta-SDS might be related to the distortion of MnOx
octahedrons by addition of K+ promoter [45,46].
Fig. 4 shows O2-TPD profiles of MnOx/H-Beta-SDS, MnOx/K-Beta-
SDS, and MnOx/Si-Beta. In the curves of MnOx/H-Beta-SDS and MnOx/
K-Beta-SDS, both have two strong peaks, appearing at lower tempera-
ture of 236 and 285 °C and higher temperature of 547 and 544 °C,
respectively. In the curve of MnOx/Si-Beta, there is a major peak at
549 °C. Generally, the oxygen species in the supported manganese
oxides can be divided into adsorbed oxygen released at lower tempera-
ture (< 400 °C) and lattice oxygen released at higher temperature
(> 400 °C) [17]. Considering that there is no signal in O2-TPD profile of
the pure zeolite support [44], it is clear that MnOx/H-Beta-SDS and Fig. 2. TEM images of (a) MnOx/H-Beta-SDS, (b) MnOx/K-Beta-SDS, and (c) MnOx/Si-
MnOx/K-Beta-SDS exhibit much more adsorbed oxygen species than Beta.
MnOx/Si-Beta. The concentration of adsorbed oxygen species in the
catalysts is as follows: MnOx/H-Beta-SDS > MnOx/K-Beta-SDS > > are summarized in Table 2. Notably, MnOx/H-Beta-SDS has the Mn4+/
MnOx/Si-Beta. Mn3+ ratio at 0.38, while this ratio of MnOx/K-Beta-SDS and MnOx/Si-
Beta is 0.40 and 0.43, respectively. Clearly, the concentration of the
Mn3+ in MnOx/H-Beta-SDS is much larger than that of MnOx/K-Beta-
3.3. XPS
SDS and MnOx/Si-Beta, which could be due to the generation of Mn3+
species by dehydroxylation in the presence of acidic OH group in the
Fig. 5 shows Mn 2p3/2 spectra of MnOx/H-Beta-SDS, MnOx/K-Beta-
catalysts [49–51]. Relating to the concentration of adsorbed oxygen
SDS, and MnOx/Si-Beta. For MnOx/H-Beta-SDS, it is appeared two
species in the catalysts, it might be suggested that the Mn3+ plays an
peaks at 641.9 and 643.4 eV, which are attributed to Mn3+ and Mn4+
important role for the contribution of the adsorbed oxygen species.
species, respectively. For MnOx/K-Beta-SDS and MnOx/Si-Beta, there
Fig. 6 shows O1s spectra of MnOx/H-Beta-SDS, MnOx/K-Beta-SDS,
are two peaks at 641.6 and 643.0 eV, also assigned to Mn3+, and Mn4+,
and MnOx/Si-Beta, giving lower binding energy of 529.2 eV associated
respectively [30,47–49]. The Mn4+/Mn3+ ratios of various catalysts

3
Y. Peng et al. Catalysis Today xxx (xxxx) xxx–xxx

Table 2
Surface elemental compositions of the catalysts.

catalyst molar ratio of molar ratio of oxygen species to total oxygen

Mn4+/Mn3+ species

Oad Olat

MnOx/H-Beta-SDS 0.38 0.39 0.07

MnOx/K-Beta-SDS 0.40 0.35 0.16
MnOx/Si-Beta 0.43 0.14 0.08

Fig. 3. H2-TPR profiles of (a) MnOx/H-Beta-SDS, (b) MnOx/K-Beta-SDS, and (c) MnOx/Si-
Beta.

Fig. 6. O1s XPS spectra of (a) MnOx/H-Beta-SDS, (b) MnOx/K-Beta-SDS, and (c) MnOx/
Si-Beta.

with the lattice oxygen and higher binding energy of 531.8 eV

associated with the surface adsorbed oxygen in the catalysts
[30,47,49,52–54]. By deconvolution, the concentration of adsorbed
oxygen and lattice oxygen in these catalysts are calculated, as presented
in Table 2. It is observed that concentration of the adsorbed oxygen in
the catalysts is in the following: MnOx/H-Beta-SDS > MnOx/K-Beta-
SDS > > MnOx/Si-Beta, while concentration of the lattice oxygen in
Fig. 4. O2-TPD profiles of (a) MnOx/H-Beta-SDS, (b) MnOx/K-Beta-SDS, and (c) MnOx/Si-
Beta.
the catalysts is in the following: MnOx/K-Beta-SDS > MnOx/Si-Beta >
MnOx/H-Beta-SDS. These results are well consistent with those
obtained from O2-TPD measurements.

3.4. Catalytic performance evaluation

Fig. 7 shows catalytic activities in toluene combustion over MnOx/

Fig. 5. Mn2p3/2 XPS spectra of (a) MnOx/H-Beta-SDS, (b) MnOx/K-Beta-SDS, and (c)
MnOx/Si-Beta.
H-Beta-SDS, MnOx/K-Beta-SDS, and MnOx/Si-Beta. Notably, Al2O3-
support manganese oxides give T90 and T50 (the conversion at 90%
toluene, the conversion at 50% toluene) at 343 °C and 312 °C. In
contrast, the zeolite-supported manganese oxides exhibit lower tem-
peratures for T90 and T50. The MnOx/H-Beta-SDS, MnOx/K-Beta-SDS,
and MnOx/Si-Beta give T90 at 285, 295, and 312 °C and T50 at 253 °C,
262 °C and 280 °C, respectively. These results indicate that the zeolites
are suitable supports for preparation of highly efficient catalysts for
VOCs abatement, which should be potentially important for VOCs
removal at large scale in the future.
It has been reported that the catalytic activity in toluene combustion
over the manganese oxide-based catalysts is dependent on the surface
oxygen species and reducibility, following the Mars-van Krevelen
mechanism [55]. Normally, organic molecules were totally oxidized
by the lattice oxygen in the transition metal oxides, generating the
oxygen vacancy, and latter being filled by adsorption of oxygen in the
gas-phase into the vacancy. In this mechanism, it is apparent that both
lattice oxygen species and adsorbed oxygen species as well as catalyst

4
Y. Peng et al.
Fig. 7. Catalytic performances in toluene combustion over (a) MnOx/H-Beta-SDS, (b)
MnOx/K-Beta-SDS, (c) MnOx/Si-Beta and (d) MnOx/Al2O3.
Fig. 8. Catalytic performance in toluene combustion with GHSV of (a) 15,000, (b)
60,000, and (c) 120,000 mL (g h)−1 over MnOx/H-Beta-SDS.
Fig. 9. Dependence of catalytic activity on reaction time in toluene combustion with
GHSV = 120,000 mL (g h)−1 at 280 °C over MnOx/H-Beta-SDS.
5
Catalysis Today xxx (xxxx) xxx–xxx
reducibility is important. Recently, Luo et al. suggested that the lattice
oxygen atoms of manganese oxides are the active species for the
oxidation of organic species [56]; Santos et al. proposed that the lattice
oxygen in manganese oxides could be contributed as better catalytic
activity [57]. Nevertheless, Shi et al. reported that adsorbed oxygen
species play important roles for catalytic activity in the toluene
combustion [58]; Wang et al. suggested that the concentration of
adsorbed oxygen species related to the catalytic performance [30]. In
addition, Si et al. mentioned that the reducibility of manganese oxides
strongly influences the catalytic activity [55]. In this work, after
comparing the catalytic data with oxygen species and reducibility in
the catalysts, it is suggested that both lattice oxygen and adsorbed
oxygen species as well as catalyst reducibility contribute the catalytic
activity, but the adsorbed oxygen species are more important than the
lattice oxygen and catalyst reducibility because the MnOx/H-Beta-SDS
with the highest concentration of adsorbed oxygen species displays the
highest activity during these catalysts.
Fig. 8 shows dependences of catalytic activities in toluene combus-
tion on space velocity over MnOx/H-Beta-SDS. When the space velocity
is reduced to 15000 mL(g h)−1, this catalyst shows the T90 at 255 °C.
Fig. S3 shows dependences of catalytic activities in toluene combustion
on reaction temperature in the presence of 2% water and 5% carbon
dioxide. Obviously, the catalytic activities are reduced significantly,
which is due to the limitation of manganese oxide-based catalysts [59].
Fig. 9 shows on-steam toluene combustion with GHSV of 120000 mL
(g h)−1 at 280 °C over MnOx/H-Beta-SDS, giving stable activity. This
result indicates that this catalyst is durable.
4. Conclusion
Manganese oxides have been supported on H- and K-form Al-rich
Beta zeolites as well as pure siliceous Beta zeolite. They exhibit higher
activities in toluene combustion than alumina-supported manganese
oxides or themselves. Particularly, MnOx/H-Beta-SDS gives T90 at
285 °C, which is much lower than that (T90 at 330 °C) of alumina-
supported manganese oxides. The superior activity in the zeolite-
supported catalysts could be related to the contribution of both lattice
oxygen and adsorbed oxygen species as well as reducibility in the
manganese oxides of catalysts, but the adsorbed oxygen play more
important role than the lattice oxygen and reducibility for the activity.
The understanding of active oxygen species combined with extraordin-
ary activity in toluene combustion over the zeolite-supported catalysts
might be potentially important for designing and preparing highly
efficient heterogeneous catalysts for VOCs abatement in the future.
Acknowledgments
This work is supported by National Natural Science Foundation of
China (21333009, 21422306 and 21673205), Fundamental Research
Funds for the Central Universities (2015XZZX004-04) and Zhejiang
Provincial Natural Science Foundation of China under Grant No.
LR15B030001.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in the
online version, at http://dx.doi.org/10.1016/j.cattod.2017.04.058.
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