Journal Pre-proof

Acidic H2O2 treatment of LaCoO3 towards highly dispersed

Co3O4 nanoparticles with excellent catalytic performance for
C3H8 combustion

Junxuan Yao, Huaiqian Lu, Bo Hou, Litao Jia, Yong Xiao, Debao
Li

PII: S1566-7367(19)30292-4
DOI: https://doi.org/10.1016/j.catcom.2019.105830
Reference: CATCOM 105830

To appear in: Catalysis Communications

Received date: 31 July 2019

Revised date: 21 September 2019
Accepted date: 23 September 2019

Please cite this article as: J. Yao, H. Lu, B. Hou, et al., Acidic H2O2 treatment of LaCoO3
towards highly dispersed Co3O4 nanoparticles with excellent catalytic performance for
C3H8 combustion, Catalysis Communications (2018), https://doi.org/10.1016/
j.catcom.2019.105830

This is a PDF file of an article that has undergone enhancements after acceptance, such
as the addition of a cover page and metadata, and formatting for readability, but it is
not yet the definitive version of record. This version will undergo additional copyediting,
typesetting and review before it is published in its final form, but we are providing this
version to give early visibility of the article. Please note that, during the production
process, errors may be discovered which could affect the content, and all legal disclaimers
that apply to the journal pertain.

© 2018 Published by Elsevier.

 Journal Pre-proof

Acidic H2O2 treatment of LaCoO3 towards highly dispersed

Co3O4 nanoparticles with excellent catalytic performance for
C3H8 combustion

JunxuanYaoa,b, Huaiqian Lua, Bo Houa, Litao Jiaa, Yong Xiao*a, Debao Li* a

f
oo
a
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, The Chinese
pr
Academy of Sciences, 030001 Taiyuan, PR China.
e-
b
University of Chinese Academy of Sciences, 100049 Beijing, PR China.
Pr

*
Corresponding authors: Prof. Yong Xiao, E-mail: xiaoyong@sxicc.ac.cn;
al
rn

Prof. Debao Li, E-mail: dbli@sxicc.ac.cn

u
Jo
 Journal Pre-proof

Abstract

The acidic H2O2 solution employed in the treatment of LaCoO3 resulted in an

improved porosity and the formation of Co3O4 nanoparticles highly dispersed on the

surface of LaCoO3. The resulting solid exhibited superior catalytic activity towards

propane combustion with T50 as low as 254 oC, high stability with time on stream (up

to 48 h) and excellent water tolerance. This catalytic behavior was associated with

f
oo
the increase in the concentration of oxygen vacancies in the formed perovskite solid

support.
pr
e-
Keywords: LaCoO3; Co3O4; Propane combustion; H2O2; Oxygen vacancy.
Pr
al
u rn
Jo
 Journal Pre-proof

1． Introduction

Volatile organic compounds (VOCs) as typical air pollutants have been

confirmed to cause various environmental problems and human health risks [1].

Among VOCs, light hydrocarbons with high C-H bond energy are difficult to be

converted into other harmless compounds and their emissions should be controlled

through appropriate methods. Catalytic combustion is considered to be one of the

f
most efficient routes for light hydrocarbons treatment in gas emissions [2].

oo
Currently, two types of catalysts are employed in catalytic combustion, namely,

pr
supported noble metal and non-noble metal oxide catalysts. The supported noble
e-
metal catalysts usually exhibit high activity towards catalytic combustion but due to
Pr

the high cost, low stability [3] and poor resistance to poisoning [4] always limit their

large-scale applications. Non-noble metal oxide catalysts, especially the

al

perovskite-type catalysts, such as LaCoO3 [5-7] and LaMnO3 [7, 8-10] have attracted
rn

much attention for their investigation towards combustion reactions. Due to the
u

variable valence states of transition metal ions, the perovskite-type catalysts usually
Jo

exhibit excellent redox properties, which is conducive to the catalytic combustion.

Moreover, as the formation of perovskite structure can only occur under high

temperatures, the perovskite-type catalysts possess high thermal stability, which is

also important during the exothermic combustion reaction [11]. On the other hand,

the low specific surface area (< 20 m2 g-1) and surface enrichment of La cations

usually result in low activity [12, 13]. Therefore, it is necessary to improve the

catalytic performance of the perovskite-type catalysts through appropriate

 Journal Pre-proof

modifications.

It has been reported that the fabrication of MOx/LaMO3 structure through the

in-situ treatment of LaMO3 can efficiently promote the catalytic performance of

perovskite-type catalysts. Compared with the traditional synthetic strategy of

supported catalysts, the in-situ treatment of LaMO3 can achieve better dispersion of

MOx species much more feasible through the in-situ formation, which is able to

f
improve the redox properties of the perovskite more effectively. Moreover, as the

oo
preservation of perovskite structure, the modified catalysts can still exhibit excellent

pr
structural and thermal stability. Li et al. [14] utilized nitric acid solution to synthesize
e-
the MnO2/LaMnO3 catalyst which was much more active than pristine LaMnO3
Pr

towards toluene combustion. Unfortunately, the nitric acid treatment cannot be

applied in the treatment of LaCoO3, as the Co species can also be dissolved at the
al

same time [15]. Chen et al. [16] employed an alkaline treatment to fabricate a
rn

La2O3/Co3O4/LaCoO3 catalyst, which exhibited excellent performance towards

u

benzene oxidation. However, the excess La2O3 could cover the Co3O4 and lead to a
Jo

decrease of activity.

It is well known that H2O2 has certain reducibility properties. It may be utilized

to reduce Co species in LaCoO3 with the aid of an acidic solution. Therefore, in this

work, we adopted an acidic H2O2 aqueous solution to fabricate the Co3O4/LaCoO3

structure. After such treatment, highly dispersed Co3O4 nanoparticles were formed on

the LaCoO3 surface. The new catalyst exhibited superior activity towards propane

combustion with T50 as low as 254 oC. Various characterization methods were
 Journal Pre-proof

employed to investigate the effect of acidic H2O2 treatment on the structural and redox

properties of LaCoO3 catalyst, and the important role of Co 3O4 formed after treatment

was revealed.

2． Experimental

Acidic H2O2 was employed in the treatment of LaCoO3 to fabricate

f
Co3O4/LaCoO3 catalyst. The new catalyst was characterized by various methods such

oo
as XRD, SEM, TEM, FTIR, EPR, XPS, H2-TPR and TPSR. Catalytic evaluation was

pr
conducted using a fix-bed reactor. The inlet and outlet gas was analyzed by gas
e-
chromatography equipped with a FID detector.
Pr

Details of catalysts preparation, characterization and evaluation of catalysts

performance for propane combustion reaction are given in the Electronic Supporting
al

Information (ESI).
rn

3． Results and discussion

u

3.1．Catalysts structure and morphology

Jo

The powder XRD patterns of catalysts are shown in Fig. S1 (ESI). It can be seen

that all diffraction patterns are well indexed to the perovskite LaCoO3 (JCPDS

00-048-0123), indicating the preservation of LaCoO3 structure after the acetic acid

and acidic H2O2 treatments. As seen in the insertion of Fig. S1, LCO-AH shows

smaller separation between the peaks around 2θ = 33o than other samples, indicating

the incorporation of heteroatoms into the perovskite structure after acetic acid

treatment [17], which may lead to the formation of solid solution.

 Journal Pre-proof

The textural properties of catalysts were characterized by N2

adsorption-desorption measurements. As illustrated in Fig. S2 (ESI), all samples

exhibit the similar type-IV isotherm with a hysteresis loop at high relative pressures.

The size of hysteresis loops varies in the order: LCO < LCO-AA < LCO-AH,

indicating that the acidic H2O2 treatment can effectively improve the porosity of

LaCoO3 catalyst. As listed in Table 1, the specific surface areas and pore volumes

LCO (6.1 m2 g-1, 0.012 cm3 g-1) < LCO-AA (11.0 m2 g-1, 0.031

f
both show the order:

oo
cm3 g-1) < LCO-AH (13.6 m2 g-1, 0.040 cm3 g-1), confirming the improved textural

pr
properties of LCO-AH, which can facilitate the accessibility of surface active sites.
e-
Fig. S3 (ESI) shows the SEM, TEM and HRTEM images of catalysts. It can be
Pr

seen that the LCO exhibits the aggregation of irregular shaped particles. According to

the HRTEM images, the particles are confirmed as LaCoO3 with the lattice space of
al

0.38 nm, corresponding to the {012} planes. After acetic acid treatment, the
rn

morphology is almost unchanged except that the surface of LaCoO3 particles seems to
u

become rougher. With the introduction of H2O2, a significant morphological evolution

Jo

is observed. LaCoO3 particles with clear edges and corners appear. The particles

connect with each other and assemble into the honeycomb-like structures, which

significantly improve the porosity. Moreover, as seen in Fig. S3f (ESI), some

nanoparticles with the average size of  5 nm are also observed on the surface of

honeycomb-like structures. As confirmed by HRTEM, the small nanoparticles are

verified as Co3O4 with the lattice space of 0.23 and 0.28 nm, corresponding to the

{022} and {222} planes, respectively. These results demonstrate that the acidic H2O2
 Journal Pre-proof

treatment cannot only modify the textural properties of LaCoO 3 catalyst, but also

fabricate highly dispersed Co 3O4 nanoparticles placed on the LaCoO3 surface. It has

been reported [15] that the La-O bonds are more easily to be attacked by acid

solution. Therefore, it is reasonable to deduce that the acetic acid solution can

dissolve La3+ cations preferentially, and leave the unstable lattice structure

containing Co3+ and O2- on the surface, which can further be reduced by H2O2

f
forming Co3O4.

oo
Fig. S4 (ESI) shows FTIR spectra of the investigated catalysts. Three IR bands

pr
located at 420, 560 and 598 cm-1 can be observed in each spectrum, which are
e-
attributed to the stretching vibrational mode of Co-O in LaCoO3 [18]. As seen in the
Pr

insertion of Fig. S1 (ESI), the IR band at 598 cm-1 slightly red shifts to 594 cm-1 in

the LCO-AH solid. It has been reported that the IR absoption band of Co-O
al

stretching vibrational mode in Co3O4 is located at 567 cm-1 [19], lower than that in
rn

LaCoO3. Therefore, the red shift of the IR band is possible to be related with the small
u

amount of Co3O4 in the solid sample.

Jo

3.2．Redox properties of catalysts

The reducibility of catalysts was characterized by H2-TPR. As depicted in Fig. 1,

all samples exhibit two reduction peaks, which are assigned to the stepwise reduction

of LaCoO3 [20, 21]. It should be noticed that a broadened H2 consumption trace at

450-500 oC (where the arrow is marked) and the obviously lowered initial reduction

temperature of the second reduction peak (see insertion in Fig. 1) are observed in

the trace of LCO-AH, which are associated with the reduction of surface Co 3O4
 Journal Pre-proof

[16]. The reduction temperatures of LCO-AA and LCO-AH are obviously lower than

that of LCO. The lower reduction temperature of LCO-AA can be due to their higher

lattice oxygen activity and mobility [22, 23], while the lower reduction temperature of

LCO-AH can be associated with the more active lattice oxygen and the formation of

Co3O4. The ratios of the two reduction peak areas (A2/A1) were estimated and are

listed in Table 1. It can be seen that the A2/A1 of LCO-AA is 2.20, higher than that of

LCO (2.04), indicating more Co 2+ in LCO-AA after acetic acid treatment [11].

f
oo
Moreover, after acidic H2O2 treatment, the A2/A1 ratio of LCO-AH further increases

pr
to 2.29, implying that the introduction of H2O2 can induce the formation of Co 3O4 and
e-
lead to more abundant Co2+. The increase in Co2+ content can facilitate the
Pr

formation of oxygen vacancies [24, 25], which is conducive to the catalytic activity.

The EPR spectra shown in Fig. S5 show much stronger peak intensity in LCO-AH,
al

indicating the abundance of Co2+, which implies more oxygen vacancies in the
rn

catalyst [26].
u

XPS was used to analyze the surface cobalt valance state and surface oxygen
Jo

species in the catalysts. Fig. S6a shows the Co 2p XPS spectra of catalysts. The

peaks at ~ 780 eV and 781~782 eV are attributed to Co 3+ and Co2+, respectively [27].

As listed in Table 1, the Co2+/Co3+ ratio of LCO-AA is 0.69, higher than that of LCO

(0.63), indicating that the acetic acid treatment can increase the Co 2+ content. When

H2O2 is introduced, the Co2+/Co3+ ratio further increases to 0.72, indicating an

increased content of Co2+ in the LCO-AH, which is considered to promote the

formation of oxygen vacancies and improve oxygen activation.

 Journal Pre-proof

According to the IR spectra shown in Fig. S7, there are some carbonates

(1000~1600 cm-1) and hydroxyls (2850~3000 cm-1) on the catalysts surface.

Therefore, we fitted the O 1s XPS peak of each sample into four components. As seen

in Fig. S6b, the peaks located at 529.9, 530.2, 531.4 and 533.3 eV are attributed to

surface lattice oxygens (Olatt), surface adsorbed oxygen species (Oads), surface

adsorbed OH, and oxygens in surface adsorbed water or carbonates, respectively [24].

f
As listed in Table 1, the Oads/Olatt values increase in the order: LCO < LCO-AA <

oo
LCO-AH, indicating that LCO-AH with more oxygen vacancies can facilitate the

adsorption of oxygen species more effectively. pr

e-
Fig. 2 shows the O2-TPSR profiles of the three samples. The signals of both O2
Pr

(m/z=32) and CO2 (m/z=44) were detected during the experiments. As seen in the

profiles of LCO and LCO-AA, the oxygen consumption peaks correspond to the CO2
al

production peaks, strongly suggesting that O2 reacts with preadsorbed C3H8 to

rn

produce CO2. However, in the profile of LCO-AH, another consumption peak in the
u

O2 signal is also observed at relatively lower temperatures. It is interesting to notice

Jo

that there is no CO2 production peak at the corresponding temperature, which

implies that the low-temperature O2 peak might be associated with the replenish of

oxygen vacancies in the solid sample. These results further confirm that the acidic

H2O2 treatment can significantly increase the oxygen vacancies. Moreover, the

amount of produced CO2 increases in the order: LCO < LCO-AA < LCO-AH,

indicating that the acidic H2O2 treatment can improve the adsorption of C3H8 and

facilitate the combustion reaction.

 Journal Pre-proof

Fig. S8 (ESI) presents the C3H8-TPSR profiles of the three catalysts. It is

observed that the peak temperatures of the three solids increase in the order: LCO <

LCO-AA < LCO-AH, which means that surface oxygens in the LCO-AH solid are

more active. This can be due to the abundant oxygen vacancies present in LCO-AH,

which are able to provide channels for oxygen diffusion and make oxygen species to

be more accessible during reaction [28].

3.3．Catalytic performance

f
oo
The catalytic activity performance of samples is shown in Fig. 3a. It is noticed

pr
that the catalytic activity increases in the order: LCO < LCO-AA < LCO-AH.
e-
LCO-AH exhibits the best catalytic activity with T50 and T90 as low as 254 and 312 oC,
Pr

respectively. As seen in Table 2, the LCO-AH shows high activity in terms of T50 and

T90 compared with the catalysts reported elsewhere, confirming the excellent
al

catalytic performance of the modified catalyst.

rn

It is well known that oxygen vacancies play a crucial role in the catalytic
u

combustion. The enrichment of oxygen vacancies can not only improve the adsorption
Jo

of oxygen species but also promote the activity and mobility of lattice oxygens. As a

result, large amount of oxygen species is more accessible in the reaction, which can

then increase the catalytic activity. The acid treatment applied can dissolve surface

La cations but cannot create oxygen vacancies effectively. On the other hand, the

acidic H2O2 treatment can dissolve La cations and then reduce the unstable Co

species to Co3O4, which leads to the formation of abundant oxygen vacancies. The

oxygen vacancies are able to facilitate accessibility of oxygen species on the

 Journal Pre-proof

catalyst surface, which finally contributes to the excellent catalytic combustion

activity.

According to the reported reaction mechanism [33], a possible reaction pathway

over the LCO-AH catalyst can be deduced. First, LaCoO3 support activates gas

phase oxygen into surface adsorbed oxygen species (Oads). This process is positively

influenced by surface oxygen vacancies. Then, Oads on the modified support

f
diffuses towards the surface active sites of Co3O4 phase and react with adsorbed

oo
intermediates formed upon C3H8 dissociative adsorption on Co 3O4. It is also noted the

pr
presence of Oads at the interface between the perovskite support and the Co 3O4
e-
particles of likely different activity towards propane combution.
Pr

Fig. 3b shows Arrhenius plots for the three investigated catalysts. It can be

seen that the Ea values follow the order: LCO-AH (97 kJ mol-1) < LCO-AA (106 kJ
al

mol-1) < LCO (121 kJ mol-1). The LCO-AH exhibits the lowest Ea, suggesting the
rn

presence of more active sites on the surface. Moreover, the specific reaction rate,
u

normalized to the specific surface area, was also estimated as shown in Fig. 3c. It
Jo

is obvious that the LCO-AH shows the highest specific reaction rate in the 220-260

o
C range, which confirms the best catalytic activity exhibited by the LCO-AH solid.

Finally, the stability of LCO-AH was tested and results are shown in Fig. S9a

(ESI). The activity of LCO-AH only decreases slightly (< 5% propane conversion)

under the applied reaction conditions (T=320 oC, 48 h on reaction stream),

demonstrating the high stability of LCO-AH with time on stream towards propane

combustion. Fig. S10 (ESI) shows TEM images of LCO-AH before and after the
 Journal Pre-proof

stability test. It is observed that no agglomeration of Co3O4 nanoparticles was found

after reaction, and an average particle size of about 5.6 nm is seen, only slightly

larger than that before reaction, in harmony with the high stability of catalyst.

Fig. S9b shows the effect of water vapor on the stability of LCO-AH. Only a

slight decrease from 88.9 to 81.5% is observed upon the introduction of 3 vol% water

vapor, demonstrating the good stability of LCO-AH under wet conditions in the feed

f
stream. Moreover, once the water vapor was cut off, the conversion almost recovered

oo
to the initial level, indicating that the inhibition of activity by the water vapor was

reversible. pr
e-
Pr

4. Conclusions

In this study, LaCoO3 was treated in an acidic H2O2 solution and the
al

obtained catalyst (LCO-AH) consisted of highly dispersed Co3O4 nanoparticles on the

rn

surface of LaCoO3. The latter catalytic system exhibited superior activity towards
u

propane combustion with T50 and T90 as low as 254 and 312 oC, respectivly. Except
Jo

for the improved textural properties, the excellent catalytic performance was mainly

associated with an increased concentration of oxygen vacancies compared to the

original LaCoO3. The stability test showed that the LCO-AH was highly stable with

long time on stream (ca. 48 h). Moreover, the slight decrease of activity from 88.9 to

81.5% under wet reaction conditions (3 vol% H2O) also demonstrated an excellent

water tolerance for the given catalyst composition.

 Journal Pre-proof

Acknowledgements

This work was financially supported by Shanxi Provincial Research Foundation for

Basic Research (Grant No. 201601D021044, 201701D121037, 201701D221056), and

the Coal-base Key Technologies R&D Program of Shanxi Province (Grant No.

MH2014-13).

f
oo
pr
e-
Pr
al
u rn
Jo
 Journal Pre-proof

References

[1] M.S. Kamal, S.A. Razzak, M.M. Hossain, Catalytic oxidation of volatile organic

compounds (VOCs) – A review, Atmospheric Environment, 140 (2016) 117-134.

[2] L.F. Liotta, Catalytic oxidation of volatile organic compounds on supported noble

metals, Applied Catalysis B-Environmental, 100 (2010) 403-412.

[3] R. Strobel, J.D. Grunwaldt, A. Camenzind, S.E. Pratsinis, A. Baiker, Flame-made

f
alumina supported Pd-Pt nanoparticles: Structural properties and catalytic behavior in

oo
methane combustion, Catalysis Letters, 104 (2005) 9-16.

pr
[4] P. Gelin, M. Primet, Complete oxidation of methane at low temperature over noble
e-
metal based catalysts: a review, Applied Catalysis B-Environmental, 39 (2002) 1-37.
Pr

[5] M. Alifanti, M. Florea, V.I. Parvulescu, Ceria-based oxides as supports for

LaCoO3 perovskite; catalysts for total oxidation of VOC, Applied Catalysis

al

B-Environmental, 70 (2007) 400-405.

rn

[6] J. Xu, J. Liu, Z. Zhao, C. Xu, J. Zheng, A. Duan, G. Jiang, Easy synthesis of
u

three-dimensionally ordered macroporous La1-xKxCoO3 catalysts and their high

Jo

activities for the catalytic combustion of soot, Journal of Catalysis, 282 (2011) 1-12.

[7] R. Spinicci, M. Faticanti, P. Marini, S. De Rossi, P. Porta, Catalytic activity of

LaMnO3 and LaCoO3 perovskites towards VOCs combustion, Journal of Molecular

Catalysis a-Chemical, 197 (2003) 147-155.

[8] S. Ponce, M.A. Pena, J.L.G. Fierro, Surface properties and catalytic performance

in methane combustion of Sr-substituted lanthanum manganites, Applied Catalysis

B-Environmental, 24 (2000) 193-205.

 Journal Pre-proof

[9] C. Zhang, C. Wang, W. Zhan, Y. Guo, Y. Guo, G. Lu, A. Baylet, A. Giroir-Fendler,

Catalytic oxidation of vinyl chloride emission over LaMnO 3 and LaB0.2Mn0.8O3 (B =

Co, Ni, Fe) catalysts, Applied Catalysis B-Environmental, 129 (2013) 509-516.

[10] H. Arandiyan, H. Dai, J. Deng, Y. Liu, B. Bai, Y. Wang, X. Li, S. Xie, J. Li,

Three-dimensionally ordered macroporous La0.6Sr0.4MnO3 with high surface areas:

Active catalysts for the combustion of methane, Journal of Catalysis, 307 (2013)

f
327-339.

oo
[11] Q. Yang, D. Wang, C. Wang, X. Li, K. Li, Y. Peng, J. Li, Facile surface

pr
improvement method for LaCoO3 for toluene oxidation, Catalysis Science &
e-
Technology, 8 (2018) 3166-3173.
Pr

[12] B. Li, Q. Yang, Y. Peng, J. Chen, L. Deng, D. Wang, X. Hong, J. Li, Enhanced

low-temperature activity of LaMnO3 for toluene oxidation: The effect of treatment

al

with an acidic KMnO4, Chemical Engineering Journal, 366 (2019) 92-99.

rn

[13] N.A. Merino, B.P. Barbero, P. Grange, L.E. Cadus, La 1-xCaxCoO3 perovskite-type
u

oxides: preparation, characterisation, stability, and catalytic potentiality for the total
Jo

oxidation of propane, Journal of Catalysis, 231 (2005) 232-244.

[14] W. Si, Y. Wang, S. Zhao, F. Hu, J. Li, A Facile Method for in Situ Preparation of

the MnO2/LaMnO3 Catalyst for the Removal of Toluene, Environmental Science &

Technology, 50 (2016) 4572-4578.

[15] Y. Peng, W. Si, J. Luo, W. Su, H. Chang, J. Li, J. Hao, J. Crittenden, Surface

Tuning of La0.5Sr0.5CoO3 Perovskite Catalysts by Acetic Acid for NOx Storage and

Reduction, Environmental Science & Technology, 50 (2016) 6442-6448.

 Journal Pre-proof

[16] Y. Luo, K. Wang, J. Zuo, Q. Qian, Y. Xu, X. Liu, H. Xue, Q. Chen, Selective

corrosion of LaCoO3 by NaOH: structural evolution and enhanced activity for

benzene oxidation, Catalysis Science & Technology, 7 (2017) 496-501.

[17] Q. Wu, L. Zhao, M. Wu, W. Yao, M. Qi, X. Shi, Fabrication of nanofibrous A- or

B-sites substituted LaCoO3 perovskites with macroscopic structures and their catalytic

applications, Materials Research Bulletin, 51 (2014) 295-301.

f
[18] M. Sun, Y. Jiang, F. Li, M. Xia, B. Xue, D. Liu, Dye Degradation Activity and

oo
Stability of Perovskite-Type LaCoO3-x (x=0 similar to 0.075), Materials Transactions,

51 (2010) 2208-2214. pr
e-
[19] D.D.M. Prabaharan, K. Sadaiyandi, M. Mahendran, S. Sagadevan, Precipitation
Pr

method and characterization of cobalt oxide nanoparticles, Applied Physics

a-Materials Science & Processing, 123 (2017).

al

[20] R.N.S.H. Magalhaes, F.S. Toniolo, V.T. da Silva, M. Schmal, Selective CO

rn

oxidation reaction (SELOX) over cerium-doped LaCoO3 perovskite catalysts, Applied

u

Catalysis a-General, 388 (2010) 216-224.

Jo

[21] I. Rossetti, C. Biffi, L. Forni, Oxygen non-stoichiometry in perovskitic catalysts:

Impact on activity for the flameless combustion of methane, Chemical Engineering

Journal, 162 (2010) 768-775.

[22] Y. Lou, L. Wang, Z. Zhao, Y. Zhang, Z. Zhang, G. Lu, Y. Guo, Y. Guo,

Low-temperature CO oxidation over Co 3O4-based catalysts: Significant promoting

effect of Bi2O3 on Co3O4 catalyst, Applied Catalysis B-Environmental, 146 (2014)

43-49.
 Journal Pre-proof

[23] B. Levasseur, S. Kaliaguine, Effects of iron and cerium in La 1-yCeyCo1-xFexO3

perovskites as catalysts for VOC oxidation, Applied Catalysis B-Environmental, 88

(2009) 305-314.

[24] Z. Pu, Y. Liu, H. Zhou, W. Huang, Y. Zheng, X. Li, Catalytic combustion of lean

methane at low temperature over ZrO2-modified Co3O4 catalysts, Applied Surface

Science, 422 (2017) 85-93.

f
[25] Y. Luo, J. Zuo, X. Feng, Q. Qian, Y. Zheng, D. Lin, B. Huang, Q. Chen, Good

oo
interaction between well dispersed Pt and LaCoO3 nanorods achieved rapid Co 3+/Co2+

pr
redox cycle for total propane oxidation, Chemical Engineering Journal, 357 (2019)
e-
395-403.
Pr

[26] Y. Lou, L. Wang, Y. Zhang, Z. Zhao, Z. Zhang, G. Lu, Y. Guo, The effects of

Bi2O3 on the CO oxidation over Co 3O4, Catalysis Today, 175 (2011) 610-614.
al

[27] X. Wang, J. Zuo, Y. Luo, L. Jiang, New route to CeO 2/LaCoO3 with high oxygen
rn

mobility for total benzene oxidation, Applied Surface Science, 396 (2017) 95-101.
u

[28] Z. Shang, M. Sun, S. Chang, X. Che, X. Cao, L. Wang, Y. Guo, W. Zhan, Y. Guo,
Jo

G. Lu, Activity and stability of Co 3O4-based catalysts for soot oxidation: The

enhanced effect of Bi2O3 on activation and transfer of oxygen, Applied Catalysis

B-Environmental, 209 (2017) 33-44.

[29] T. Asada, T. Kayama, H. Kusaba, H. Einaga, Y. Teraoka, Preparation of

alumina-supported LaFeO3 catalysts and their catalytic activity for propane

combustion, Catalysis Today, 139 (2008) 37-42.

[30] M. Alifanti, J. Kirchnerova, B. Delmon, D. Klvana, Methane and propane

 Journal Pre-proof

combustion over lanthanum transition-metal perovskites: role of oxygen mobility,

Applied Catalysis a-General, 262 (2004) 167-176.

[31] D. Klvana, K.S. Song, J. Kirchnerova, Catalytic performance of

La0.66Sr0.34C0.2Fe0.8O3 perovskite in propane combustion: Effect of preparation and

specific surface area, Korean Journal of Chemical Engineering, 19 (2002) 932-939.

[32] V.R. Choudhary, S. Banerjee, S.G. Pataskar, Combustion of dilute propane over

f
transition metal-doped ZrO2 (cubic) catalysts, Applied Catalysis A: General, 253

oo
(2003) 65-74.

pr
[33] Z. Hu, S. Qiu, Y. You, Y. Guo, Y. Guo, L. Wang, W. Zhan, G. Lu, Hydrothermal
e-
synthesis of NiCeOx nanosheets and its application to the total oxidation of propane,
Pr

Applied Catalysis B-Environmental, 225 (2018) 110-120.

[34] B. Solsona, T. Garcia, E. Aylon, A.M. Dejoz, I. Vazquez, S. Agouram, T.E.

al

Davies, S.H. Taylor, Promoting the activity and selectivity of high surface area
rn

Ni-Ce-O mixed oxides by gold deposition for VOC catalytic combustion, Chemical
u

Engineering Journal, 175 (2011) 271-278.

Jo
 Journal Pre-proof

Figure captions

Figure 1. H2-TPR profiles of investigated LCO-AH, LCO-AA and LCO catalysts.

Figure 2. O2-TPSR profiles of investigated LCO-AH, LCO-AA and LCO catalysts.

Figure 3. (a) Propane combustion activity vs temperature profiles; (b) Arrhenius plots

and (c) Specific reaction rates of propane combusiton of the investigated LCO-AH,

f
LCO-AA and LCO catalysts.

oo
pr
e-
Pr
al
u rn
Jo
 Journal Pre-proof

Figure 1

f
oo
pr
e-
Pr
al
rn
u
Jo
 Journal Pre-proof

Figure 2

f
oo
pr
e-
Pr
al
rn
u
Jo
 Journal Pre-proof

Figure 3

f
oo
pr
e-
Pr
al
rn
u
Jo
 Journal Pre-proof

Table 1. Textural properties, A2/A1 ratios, surface composition, catalytic activities and Ea of the LCO, LCO-AA and LCO-AH investigated
catalysts.

BET XPS results Catalytic activity

Average Pore
Catalyst crystallite
size (nm)a
surface
area
volume
(cm3 g-1)
A2/A1b

o f Ea
(kJ mol-1)
(m2 g-1) Co2+/Co3+ c

r o
Oads/Olattc T50d (oC) T90d (oC)

LCO 30.0 6.1 0.012 2.04 0.63

- p 0.41 338 408 127
LCO-AA 30.0 11.0 0.031 2.20
r0.66
e 0.46 270 332 106
LCO-AH
a
24.7 13.6
Calculated from powder XRD results.
0.040 2.29

l P 0.72 0.53 254 312 97

b
Calculated from peak areas in the H2-TPR traces.

n a
r
c
Calculated based on peaks area of XPS spectra.

u
d
The temperature at which the conversion is 50 or 90%.

J o
 Journal Pre-proof

Table 2. Catalytic activity testing reaction conditions (WHSV and propane concentration) and catalytic activity indicators (T 50 and T90 oC) of
the propane combustion over the present LCO-AH and other reported catalysts.

Catalyst
WHSV
(ml g-1 h-1)
C3H8 concentration, vol% T50, oC
o f T90, oC Reference

LCO-AH 100000 1%
r o 254 312 This work

- p
e
LaFeO3/Al2O3 9000 0.8% 400 470 [29]

La0.87Sr0.13Mn0.2Ni0.8O3−δ 48000

P
0.5%
r 315 350 [30]

La0.66Sr0.34Co0.2Fe0.8O3 12000

a l 1% 440 470 [31]

ZrO2 51000

r n 0.9% 310 370 [32]

NiCeOx 30000

o u 0.2% 250 290 [33]

NiCe
J
20000 0.8% 255 290 [34]
 Journal Pre-proof

Highlights

 Acidic H2O2 was firstly employed to treat the LaCoO3 catalyst.

 Highly dispersed Co3O4 nanoparticles formed on the LaCoO3 surface.


o f
o
Superior activity towards C3H8 combustion over the modified catalyst.

 Abundant oxygen vacancies for the high activity.

p r
e -
P r
a l
r n
o u
J
 Journal Pre-proof

Conflict of interest
We declare that they have no conflicts of interest to this work. We declare that we do not have any commercial or associative interest that
represents a conflict of interest in connection with the work submitted

o f
r o
- p
r e
l P
n a
u r
J o
Figure 1
Figure 2
Figure 3