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Functional Materials Letters
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Article Title: Noble-metal-free catalysts based on apatite-type lanthanum silicate for

complete toluene combustion

Author(s): Kenji Matsuo, Naoyoshi Nunotani, Nobuhito Imanaka

DOI: 10.1142/S1793604720500356

Received: 08 May 2020

Funct. Mater. Lett. Downloaded from www.worldscientific.com

Accepted: 29 August 2020

To be cited as: Kenji Matsuo, Naoyoshi Nunotani, Nobuhito Imanaka, Noble-

metal-free catalysts based on apatite-type lanthanum silicate for
complete toluene combustion, Functional Materials Letters, doi:
10.1142/S1793604720500356

Link to final version: https://doi.org/10.1142/S1793604720500356

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Functional Materials Letters
Vol. 1, No. 1 (2015) 1–4
World Scientific Publishing Company

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Noble-metal-free catalysts based on apatite-type lanthanum silicate for complete toluene
combustion
by UNIVERSITY OF NEW ENGLAND on 09/06/20. Re-use and distribution is strictly not permitted, except for Open Access articles.

Kenji Matsuo, Naoyoshi Nunotani, and Nobuhito Imanaka*

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Department of Applied Chemistry, Faculty of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan
*imanaka@chem.eng.osaka-u.ac.jp

Received Day Month Year; Revised Day Month Year

Noble-metal-free LaCoO3/La10Si5CoO27−/-Al2O3 catalysts were developed for complete toluene combustion, and their catalytic
activities were investigated. The active oxygen supply from the apatite-type La10Si5CoO27− promoter successfully improved the

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oxidation ability of the LaCoO3 activator, and the highest catalytic activity was obtained for the 10 wt.% LaCoO3/20 wt.%
Funct. Mater. Lett. Downloaded from www.worldscientific.com

La10Si5CoO27−/-Al2O3 catalyst, which oxidized toluene completely at the temperature as low as 300°C.

Keywords: Noble-metal-free catalyst; toluene combustion; lanthanum silicate

Toluene has been generally used in chemical industry as
organic solvent for paints, adhesives, printing inks, etc.
However, toluene is one of the well-known volatile organic
compounds (VOCs), which contribute to air pollution
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meaning oxygen release and storage abilities. When active
oxygen species is supplied from promoters to activators, the
oxygen species is considered to migrate in the promoter
lattice, suggesting that the oxide ion conducting property is

including photochemical smog.1 According to Ministry of the
Environment in Japan, toluene is the highest rate released to
the environment among the PRTR (Pollutant Release and
Transfer Register) substances in 2017. For human health,
toluene vapor has harmful effects on nervous system, and
may also cause sick building syndrome and multiple
chemical sensitivity syndrome by the accumulative exposure
even in trace amounts.2 In order to protect our health and
environment, therefore, it is necessary to remove toluene
emitted into the atmosphere.
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an important issue. In addition to the oxide ion conducting
characteristics, the redox ability is a key factor, because the
redox reaction occurs in the oxygen release and storage
processes. Based on these concepts, we have recently
developed the novel La10Si5CoO27− promoter with the
apatite-type structure,9,10 which has a one-dimensional tunnel
structure suitable for oxide ion migration11 and the redox
property owing to the valence change of Co2+/3+. The oxygen
release and storage abilities of the La10Si5CoO27− promoter
facilitated the oxidation of methane and toluene over the

To date, various methods for the removal of toluene have
been investigated, and in particular, catalytic combustion is
regarded as the ideal technology owing to its low operating
cost and simple process.3 For the catalysts, while platinum
based catalysts are well-known to effective for toluene
combustion,4,5 platinum is scarce and expensive resource;
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noble-metal based catalysts.9,10 Even in the case of the noble-
metal-free catalysts based on LaCoO3, therefore, the
La10Si5CoO27− promoter is expected to accelerate the
oxidation of toluene. In this study, we prepared
LaCoO3/La10Si5CoO27−/γ-Al2O3 catalysts by loading the
LaCoO3 activator and the La10Si5CoO27− promoter on γ-

therefore, the development of noble-metal-free based
catalysts with high catalytic activity is requested. Among
noble-metal-free based catalysts, LaCoO3 has been reported
to be effective for toluene combustion,6 which might be
related to its electronic conducting property above 230°C; 7,8
however, LaCoO3 requires the elevated temperature of 410°C
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Al2O3 with high surface area, and their catalytic activities for
toluene combustion were investigated.
The La10Si5CoO27− promoter was synthesized according
to our previous study.9 Stoichiometric amount mixture of
La(NO3)3·6H2O (FUJIFILM Wako Pure Chemical
Industries), Co(NO3)2·6H2O (FUJIFILM Wako Pure

to oxidize toluene completely. Chemical Industries), and Si(OC2H5)4 (Kishida Chemical)

To enhance the catalytic activity of the noble-metal-free was dissolved into the ethanol-acetic acid mixed solvent.
based catalyst, it is important to introduce promoters which Polyvinylpyrrolidone K25 (PVP K25; FUJIFILM Wako Pure
can supply active oxygen species toward the active sites, Chemical Industries) was added as a dispersant, and then the
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2 Author’s Name
solution was stirred at 80°C for 6 h. After stirring, the solvent
was evaporated at 180°C, followed by the preheating at
350°C to remove PVP. The resulting powder was calcined at
1000°C for 2 h under the air flow to obtain La10Si5CoO27−.
The La10Si5CoO27− solid was mixed with commercial -
Al2O3 (AxSorb AB, Nippon Light Metal) by wet ball milling
(Pulverisette 7, FRITSH GmbH) with ethanol, and then the
by UNIVERSITY OF NEW ENGLAND on 09/06/20. Re-use and distribution is strictly not permitted, except for Open Access articles.
mixture was heated at 500°C for 4 h to obtain x wt.%
La10Si5CoO27−/-Al2O3, where the La10Si5CoO27− amount
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(x) was adjusted in the range of 10-30 wt.%. Supported
LaCoO3 catalysts were prepared via the impregnation
process. Aqueous solutions of 0.1 mol·L−1 La(NO3)3 and 0.1
mol·L−1 Co(NO3)2 were mixed in stoichiometric amounts,
and then the solution was impregnated on x wt.%
La10Si5CoO27−/-Al2O3. After the impregnation, the sample
was dried at 180°C, followed by the calcination at 600°C for
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Funct. Mater. Lett. Downloaded from www.worldscientific.com
4 h in air to obtain y wt.% LaCoO3/x wt.% La10Si5CoO27−/-
Al2O3. Here, the LaCoO3 amount (y) was adjusted in the
range of 7-12 wt.%. For comparison, 10 wt.% LaCoO3/γ-
Al2O3 was prepared by similar method.
The obtained samples were identified using X-ray
powder diffraction (XRD; SmartLab, Rigaku) with Cu K
radiation (40 kV, 30 mA). The N2 adsorption-desorption
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measurement was conducted at −196°C to evaluate the
Brunauer-Emmett-Teller (BET) specific surface area and
Barrett-Joyner-Halenda (BJH) pore size distribution (TriStar
3000, Shimadzu). Temperature programmed reduction (TPR)
measurement was carried out under a flow of 5% hydrogen-
95% argon gas (50 mL·min−1) at a heating rate of 5°C·min−1
(BELCAT-B, MicrotracBEL).
The catalytic activity for toluene oxidation was carried
out in a conventional fixed-bed flow reactor with a 10-mm
diameter quartz glass tube by feeding 900 ppm toluene-
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99.91% air gas (20 mL·min−1) over 0.1 g of catalyst (space
velocity: 12,000 L·kg−1·h−1), where the catalyst was pre-
treated at 200°C for 2 h under a flow of argon (20 mL·min−1)
prior to the test. The amount of toluene passed through the
reactor was analyzed using gas chromatograph with a flame
ionization detector (FID; Shimadzu GC-8AIF) equipped with
the Sunpak-A column (Shinwa Chemical Industries), and the
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catalytic activity was evaluated in terms of toluene
conversion.
Figure 1 shows the XRD patterns of 10 wt.% LaCoO3/x
wt.% La10Si5CoO27−/-Al2O3 with the data of 10 wt.%
LaCoO3/-Al2O3, where these compositions are the feed
values. For the 10 wt.% LaCoO3/x wt.% La10Si5CoO27−/-
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Al2O3 catalysts, the apatite-type structure and -Al2O3 were
clearly observed, and the LaCoO3 phase could not be
detected, suggesting the high dispersion of LaCoO 3. Similar
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result was obtained for 10 wt.% LaCoO3/-Al2O3. The
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Fig. 1. XRD patterns of 10 wt.% LaCoO3/x wt.% La10Si5CoO27−/γ-
Al2O3 (x = 0, 10, 20, 30).
specific surface area of 10 wt.% LaCoO3/x wt.%
La10Si5CoO27−/-Al2O3 is summarized in Table 1, where the
N2 adsorption-desorption isotherms and the BJH pore size
distributions are shown in Figure S1. The surface area was
drastically decreased with the increase in the La10Si5CoO27−
amount (x), because the La10Si5CoO27− promoter has
significantly low surface area of 2.1 m2·g−1 compared to that
of -Al2O3 (256 m2·g−1). For the pore size, similar values (ca.
6 nm) were obtained (Figure S1).
Figure 2(a) shows the temperature dependences of
toluene conversion over 10 wt.% LaCoO3/x wt.%
La10Si5CoO27−/γ-Al2O3, and the effect of the La10Si5CoO27−
promoter amount (x) on the onset and the complete
combustion temperatures are presented in Figure 2(b). For
the catalysts with x ≤ 20, the complete combustion
temperature was obviously lowered with increasing x; i.e.,
the catalytic activity was improved by the introduction of the
La10Si5CoO27− promoter. This enhancement of the catalytic
activity is attributed to the supply of active oxygen species
from the La10Si5CoO27− promoter toward the LaCoO3
activator. As for the onset temperature, the catalysts with x ≤
20 showed almost the same values of ca. 220°C, because the
decrease of the surface area (Table 1) has an unfavorable
effect on the lowering of the onset temperature. In the case of
the catalyst with x = 30, the further decrease of the surface
area might predominantly contribute to the decrease of the
catalytic activity compared to the x = 20 case. Based on these
results, since toluene should be removed completely at a
temperature as low as possible from a practical standpoint,
Table 1. Specific surface area of 10 wt.% LaCoO3/x wt.%
La10Si5CoO27−/γ-Al2O3
x / wt.% Surface area / m2·g−1
0 135
10 113
20 87
30 64
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Fig. 2. (a) Temperature dependences of toluene conversion over 10 wt.% LaCoO3/x wt.% La10Si5CoO27−/γ-Al2O3 (x = 0, 10, 20, 30). (b) Onset temperature
and complete combustion temperature as a function of the La 10Si5CoO27− promoter amount (x) for 10 wt.% LaCoO3/x wt.% La10Si5CoO27− /γ-Al2O3.

the optimum La10Si5CoO27− amount (x) is determined to be clear that the optimum composition for toluene combustion

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x = 20, which showed the lowest complete combustion was 10 wt.% LaCoO3/20 wt.% La10Si5CoO27−/γ-Al2O3. This
Funct. Mater. Lett. Downloaded from www.worldscientific.com

temperature (300°C). catalyst can oxidize toluene completely at the temperature as

The effect of the LaCoO3 activator amount (y) on the
catalytic activity was also investigated. Figure 3(a) shows the
temperature dependences of toluene conversion over y wt.%
LaCoO3/20 wt.% La10Si5CoO27−/γ-Al2O3, and the onset and
the complete combustion temperatures as a function of the
LaCoO3 activator amount (y) are presented in Figure 3(b).
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low as 300°C, which is ca. 100°C lower than that of LaCoO 3
(complete combustion temperature: 410°C)9.
In order to discuss the effects of LaCoO3 and
La10Si5CoO27− on the catalytic activity, oxygen release
ability was investigated by the TPR measurement, and their
profiles are shown in Figure 4. For 10 wt.% LaCoO3/-Al2O3

The 20 wt.% La10Si5CoO27−/γ-Al2O3 sample without the
LaCoO3 activator showed no catalytic activity below 270°C.
By introducing the LaCoO3 activator, both the onset and the
complete combustion temperatures were obviously lowered
with increasing y up to y = 10, while the surface area was
decreased as listed in Table 2 where the pore structures were
almost the same (Figure S2). Thus, the introduction of the
active sites might enhance the catalytic activity. For the 12
wt.% LaCoO3/20 wt.% La10Si5CoO27−/γ-Al2O3 catalyst (y =
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without the La10Si5CoO27− promoter, there was no obvious
reduction peak. Nevertheless, the toluene combustion was
started at 220°C (Fig. 2(b)), and up to ca. 250°C, the activity
was almost the same as the 10 wt.% LaCoO3/20 wt.%
La10Si5CoO27−/γ-Al2O3 catalyst. This high catalytic activity
in the temperature below ca. 250°C indicates that LaCoO3
worked as the activator for toluene combustion. Owing to the
absence of the active oxygen supply from the promoter,
however, the 10 wt.% LaCoO3/γ-Al2O3 catalyst might require

12), the catalytic activity was decreased, because the excess elevated temperature of 390°C for the complete toluene
LaCoO3 doping might led to the further decrease of the combustion. In the case of 20 wt.% La10Si5CoO27−/γ-Al2O3
surface area which decreased the active sites. Therefore, it is without the LaCoO3 activator (Fig. 4), the reduction peak was
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Fig. 3. (a) Temperature dependences of toluene conversion over y wt.% LaCoO3/20 wt.% La10Si5CoO27−/γ-Al2O3 (y = 0, 7, 10, 12). (b) Onset temperature
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and complete combustion temperature as a function of the LaCoO3 activator amount (y) for y wt.% LaCoO3/20 wt.% La10Si5CoO27−/γ-Al2O3.
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Table 2. Specific surface area of y wt.% LaCoO3/20 wt.% amount of hydrogen consumption of 91 μmol·g−1 indicates
La10Si5CoO27−/γ-Al2O3 that Co3+ ions in the LaCoO3 activator were also reduced as

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y / wt.% Surface area / m2·g−1 well as those in the La10Si5CoO27− promoter. Here, assuming
0 139 that the Co3+:Co2+ ratio of La10Si5CoO27− in 10 wt.%
7 93
10 87
LaCoO3/20 wt.% La10Si5CoO27−/γ-Al2O3 had the same value
12 77 as the 20 wt.% La10Si5CoO27−/γ-Al2O3 case (Co3+:Co2+ =
48:52), the reduced Co3+ amount in LaCoO3 was calculated
clearly observed at ca. 430°C, assigned as the reduction of
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to be 34 %. Such a reduction of LaCoO3 was not observed in

Co3+ to Co2+. This oxygen release ability facilitated the
the case of 10 wt.% LaCoO3/γ-Al2O3; that is, the reducibility

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toluene combustion even in the absence of the activator; that
of LaCoO3 was provided by the introduction of
is, 20 wt.% La10Si5CoO27−/γ-Al2O3 oxidized toluene
La10Si5CoO27−. From the results described above, it is
completely at 360°C (Fig. 3(b)), which is lower than the 10
demonstrated that the synergistic effect of the LaCoO3
wt.% LaCoO3/γ-Al2O3 case (390°C) as shown in Fig. 2(b).
activator and the La10Si5CoO27− promoter successfully
However, the onset temperature over 20 wt.%
improved the reducibility of the catalyst, which led to the
La10Si5CoO27−/γ-Al2O3 was 280°C; i.e., no catalytic activity
highest catalytic activity for the 10 wt.% LaCoO3/20 wt.%
was observed in the temperature below 270°C, while 10 wt.%
La10Si5CoO27−/γ-Al2O3 catalyst. Here, 10 wt.% LaCoO3/20
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LaCoO3/γ-Al2O3 can oxidize ca. 70% of toluene at 270°C.
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wt.% La10Si5CoO27−/γ-Al2O3 showed the high resistance

This behavior of 20 wt.% La10Si5CoO27−/γ-Al2O3 suggests
against coking (Figure S3). Although there is a possibility
that La10Si5CoO27− played the role of the promoter to supply
that less active CoAl2O412 was slightly formed because of the
the oxygen species for toluene combustion, rather than the
light pale blue color of the catalysts, further generation with
activator. By combining both the LaCoO3 activator and the
the color enhancement was not observed (Figure S3),
La10Si5CoO27− promoter (Fig. 4), the reduction peak top
indicating that the effect of CoAl2O4 is negligibly small.
temperature of 10 wt.% LaCoO3/20 wt.% La10Si5CoO27−/γ-
In summary, noble-metal-free catalysts of
Al2O3 (ca. 390°C) was lowered compared to that of 20 wt.%
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LaCoO3/La10Si5CoO27−/γ-Al2O3 were developed for the

La10Si5CoO27−/γ-Al2O3 (ca. 430°C), because the active sites
complete toluene combustion. Owing to the active oxygen
in the LaCoO3 activator might accelerate the oxygen release
supply from the apatite-type La10Si5CoO27− promoter, the
from the La10Si5CoO27− promoter. In addition, the total
toluene oxidation over the LaCoO3 activator was successfully
amount of hydrogen consumption for 10 wt.% LaCoO3/20
facilitated. Among the catalysts prepared, 10 wt.%
wt.% La10Si5CoO27−/γ-Al2O3 (91 μmol·g−1) was higher than
LaCoO3/20 wt.% La10Si5CoO27−/γ-Al2O3 exhibited the
that for 20 wt.% La10Si5CoO27−/γ-Al2O3 (24 μmol·g−1).
highest catalytic activity, and the complete combustion of
Based on the data of 20 wt.% La10Si5CoO27−/γ-Al2O3 (24
toluene was realized at the temperature as low as 300°C.
μmol·g−1), the Co3+:Co2+ ratio can be calculated to be 48:52,
under the assumption that all Co3+ ions were reduced to Co2+.
Acknowledgement
As for the 10 wt.% LaCoO3/20 wt.% La10Si5CoO27−/γ-Al2O3
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catalyst, if the Co3+:Co2+ ratio in La10Si5CoO27− was 100:0, This work was supported in part by Iwatani Corporation,
the amount of hydrogen consumption owing to the promoter JSPS KAKENHI Grant Number JP19H02435, and Steel
would be estimated as 45 μmol·g−1; therefore, the high Foundation for Environmental Protection Technology.

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Fig. 4. TPR profiles of 10 wt.% LaCoO3/20 wt.% La10Si5CoO27−/γ-
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Al2O3, 20 wt.% La10Si5CoO27−/γ-Al2O3, and 10 wt.% LaCoO3/γ-Al2O3.

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