Environmental Science and Pollution Research

https://doi.org/10.1007/s11356-020-10484-x

RESEARCH ARTICLE

Preparation of the Mn/Co mixed oxide catalysts for low-temperature

CO oxidation reaction
Mojtaba Ghiassee 1 & Mehran Rezaei 2 & Fereshteh Meshkani 1,3 & Sajad Mobini 3

Received: 4 June 2020 / Accepted: 10 August 2020

# Springer-Verlag GmbH Germany, part of Springer Nature 2020

Abstract
The Mn/Co mixed powders with various Mn/Co molar ratios were prepared by the coprecipitation method and used in low-
temperature CO oxidation. The physicochemical characteristics of these powders were characterized using the Brunauer-
Emmett-Teller (BET), X-ray diffraction (XRD), temperature-programmed reduction (TPR), and scanning electron microscopy
(SEM) analyses. The results demonstrated that the Mn/Co molar ratio significantly affected both the textural and catalytic
properties and the sample with a Mn/Co = 1:1 possessed a BET area of 123.7 m2g−1 with a small mean pore size of 6.44 nm.
The catalytic results revealed that the pure cobalt and manganese catalysts possessed the low catalytic activity and the pure Co
catalyst is not active at temperatures lower than 140 °C. The highest catalytic activity was observed for the catalyst with a Mn/Co
= 1. The obtained results showed that the incorporation of Pd into the Mn/Co catalyst significantly enhanced the catalytic activity
for oxidation of carbon monoxide and the highest CO conversion was observed for the catalyst with 1 wt.% Pd and this catalyst
exhibited a CO conversion of 100% at 80 °C.

Keywords CO oxidation . Cobalt-manganese oxides . Palladium . Low temperature . Catalyst

Introduction
Carbon monoxide (CO) is a major cause of poisoning in many
developed countries (Venkataswamy et al. 2015; Solomon et al.
2019). The most common source of CO is the exhaust emissions
of motor vehicles (Otsmeier et al. 2012; Amini et al. 2013). The
removal of CO has attracted considerable attention in recent
years and is a challenging topic in catalysis. In catalytic removal
of CO, catalysts play a very important role and the catalytic
oxidation is an effective method in reducing the content of CO
Responsible editor: Santiago V. Luis
* Mehran Rezaei
mrezaei@iust.ac.ir
1
Institute of Nanoscience and Nanotechnology, University of Kashan,
P.O. Box 8731751117, Kashan, Iran
2
School of Chemical, Petroleum and Gas Engineering, Iran University
of Science and Technology (IUST), P.O. Box 16765-163,
Tehran, Iran
3
Catalyst and Advanced Materials Research Laboratory, Chemical
Engineering Department, Faculty of Engineering, University of
Kashan, P.O. Box 8731751117, Kashan, Iran
(Zhang et al. 2002; Kowsari and Abdpour 2017). In recent years,
many studies have been performed to prepare catalysts with high
activity and stability at low temperatures (Devendrasinh Darbar
2017; Liu et al. 2017; Shanmugavadivel et al. 2019). Different
catalysts have been employed in this reaction. Among them,
MnCo2O4 is one of the employed catalysts in carbon monoxide
oxidation (Devendrasinh Darbar 2017; Liu et al. 2017;
Shanmugavadivel et al. 2019). The MnCo2O4 catalyst has a very
porous structure and therefore has an active level suitable for the
oxidation process of carbon monoxide. Also, this catalyst pos-
sessed higher adsorption energy for CO and also low energy for
the formation of oxygen vacancy (Arun et al. 2013; Ghiassee
et al. 2019). The structure of MnCo2O4 consists of a combination
of two metal oxides, each of them has a significant effect on
carbon monoxide oxidation (Liang et al. 2013; Cao et al.
2014). The various types of Mn phases such as MnO2, Mn2O3,
and Mn3O4 have been employed in several applications, because
of the various oxidation states (Pahalagedara et al. 2017; Zhang
et al. 2018a; Lei et al. 2020). Lakshitha et al. (Pahalagedara et al.
2017) studied the CO oxidation behavior of manganese oxides
with different phases and all these phases showed 100% CO
conversion when the temperature increased up to 200 °C.
Based on the reported characteristics of the Mn components in
CO oxidation, the manganese oxide has a high ability to activate

and provide oxygen, which is effective in the CO oxidation
reaction (Kunkalekar and Salker 2012; Mobini et al. 2018).
Cobalt oxide (Co3O4) is an efficient catalyst for CO oxidation
(Jansson et al. 2001; Fujita et al. 2003; Sa et al. 2013; Mu et al.
2018). The catalytic activity of a series of Co3O4 catalysts is
reported and the results indicated a full conversion of CO at
ambient temperature (Sa et al. 2013; Wu et al. 2019). Xie et al.
(Zhang et al. 2018b) reported that the Co3O4 nanorods calcined
at 450 °C could catalyze CO oxidation at low temperatures
(Mahammadunnisa et al. 2016; Zhang et al. 2018b). Honghong
Yi et al. (Yi et al. 2017) reported a higher activity for nano-
Co3O4, which was related to the smaller particle size, higher
Brunauer-Emmett-Teller (BET) area, higher ratios of the Co2+/
Co3+ and Olatt/Oads (Yi et al. 2017). Due to the mentioned prop-
erties of the cobalt and manganese phases, the combination of
these two metal oxides can be interesting in developing a highly
active and stable catalyst for the oxidation of CO. The use of the
promoters can affect the catalytic activity at low temperature. It is
known that the addition of the Pd, Pt, Rh, and Au can affect the
catalytic activity in CO oxidation reaction at low temperatures
(Bunluesin et al. 1996; Christou and Efstathiou 2007; Bratan
et al. 2017). Among these promoters, Pd-promoted catalysts
exhibiting high activity in the oxidation of CO at low tempera-
tures. Also, the supported Pd catalysts exhibited high activity for
the selective catalytic oxidation of CO (El et al. 2016; Li et al.
2019). The results indicated that the competitive adsorption of
CO and O2 on the Pd surface inhibits the CO oxidation at lower
temperatures (El et al. 2016). In this work, Mn/Co mixed oxide
powders with various ratios of Mn/Co were synthesized and used
as a catalyst for the CO oxidation reaction. To improve the ac-
tivity of the catalyst at low temperatures, the influence of the Pd
promoter on the textural and catalytic properties was investigated
Experimental
Starting materials
For the preparation of the samples, C 2 H 3 NaO 2 .3H 2 O,
Mn(NO3)2.4H2O, Co(NO3)2.6H2O, PdCl2, and NaOH are
used as starting materials.
Catalyst preparation
The various samples with different Mn/Co molar ratios were
prepared with the coprecipitation method. For this purpose,
depending on the Mn/Co molar ratio, appropriate contents of
Mn and Co metal salts and C2H3NaO2.3H2O (0.68 g) were
dissolved in deionized water and NaOH solution was added to
this solution, and the pH was set to 9. The prepared slurry was
kept under these conditions for 2 h and then filtered and
washed with warm distilled water. The filter cake was then
dried at 90 °C for 12 h and calcined at 300 °C for 4 h (3
Environ Sci Pollut Res
°C/min.). The Pd-promoted catalysts were prepared using
the wetness impregnation method. The selected catalyst pow-
der with determined Mn/Co molar ratio was immersed in an
aqueous solution of PdCl2 with the desired concentration to
achieve the determined weight percentage of Pd (1, 2, and 3
wt.%). The impregnation was performed at room temperature
and under stirring for 2 h. After impregnation, the suspension
was dried at 90 °C for 12 h and the dried sample was heat-
treated at 300 °C for 4 h.
Catalytic tests
For the catalytic reaction, 0.1 g of the catalyst particles (0.25–
0.5 mm) was loaded into a quartz fixed-bed microreactor (ID 7
× 500 mm height). Before the catalytic tests, the samples were
pretreated using an oxidizing gas stream (20% O2–80% Ar) at
300 °C for 1 h. The mass flow controllers (BROOKS 5850S)
were used to control the flow rates of reactive gases (Ar, O2,
and CO). During the reaction, the catalyst bed temperature
was monitored with a K-type thermocouple. After pretreat-
ment of the catalyst at oxidizing atmosphere, the reactant gas
mixture containing 4% CO, 20% O2, and 76% Ar with a
GHSV value of 60,000 ml/(h.gcat.) was introduced into the
reactor. The catalytic tests were performed in the temperature
range of 40 to 200 °C. A gas chromatograph was used for
determining the composition of the outlet stream. The CO
conversion was determined using Eq. 1:
CO conversion ð%Þ ¼ ½ðCOin −COout Þ=COin   100 ð1Þ
Catalyst characterization
The BET area, pore volume, pore size, and its distribution
were determined using a Belsorp mini II instrument. The re-
duction characteristics of the samples were studied using a
Chemisorb 2750 instrument by the temperature-programmed
reduction (TPR) analysis. The details of the analysis were
reported in our published article (Ghiassee et al. 2019). The
X-ray diffraction (XRD) analysis was conducted using a
PANalytical X’Pert-Pro diffractometer.
Results and discussion
The XRD diffractograms of the samples are displayed in Fig.
1. The prepared Mn/Co catalysts showed a crystalline struc-
ture with higher crystallinity compared with the pure Mn and
Co catalysts. The diffraction peaks observed at 2θ = 31.42,
36.96, 59.0, and 65.06° are related to the MnCo2O4 spinel
structure according to the JCPDS # 00-023-1237 reference
number. Also, the presence of the peaks confirmed the exis-
tence of the several diffraction phases. The diffraction peaks at
Environ Sci Pollut Res
Fig. 1 XRD patterns of the Mn/
Co mixed samples. MnCo2O4
(♣), Mn3O4 (♠), Co3O4 (♦), CoO
(×), PdO (□), MnO2 (*) and
Mn2O3 (+) with various Mn/Co
molar ratios
2θ = 32, 36.96, and 59.38° are assigned to the formation of the
Mn3O4 phase. The diffraction peaks of the Co3O4 phase were
also detected at 2θ = 31.33, 36.96, 59.38, and 65.25° (JCPDS
# 01-073-1701). For the pure cobalt catalyst, the diffraction
peaks at 2θ = 36.96, 45, 59.38, and 65.06° are related to the
presence of Co3O4 (JCPDS # 01-073-1701) and the observed
diffraction peaks at 2θ = 36.96 and 60° are assigned to the
formation of CoO (JCPDS # 01-075-0418). The pure Mn
catalyst also possessed two crystalline phases, MnO2 and
Mn2O3, at 2θ = 28.55°, 31.52°, and 56.00° (JCPDS # 01-
081-2261) and 2θ = 37.06, 66.33, and 55.01° (JCPDS # 01-
076-0150), respectively. The PdO (□) phase is detected at the
2θ = 31.40, 45, and 56° according to the reference number
(JCPDS # 00-046-1211). According to Fig. 1, the addition of
Pd and the difference in Mn/Co molar ratio did not change the
intensity of the diffraction peaks and also the detected phases
of the samples. The results indicated that the size of the crys-
tals can be affected by the preparation conditions.
The effect of the reaction temperature on the CO conver-
sion of the catalysts with different Mn/Co molar ratios is
shown in Fig. 2. The results revealed that the pure cobalt
and manganese catalysts possessed the low catalytic activity
and the pure Co catalyst is not active at temperatures lower
than 140 °C. The highest catalytic activity was observed for
the catalyst with a Mn/Co molar ratio of 1 (Mn/Co = 1:1).
To improve the activity of the catalyst at low temperature,
the Pd was added to the catalyst and its influence on the tex-
tural and catalytic properties was investigated. The catalytic
results indicated that the MnCo2O4-1 wt.% Pd sample showed
higher activity compared with other prepared catalysts (Fig.
3). As can be seen, the catalysts containing 1 and 2 wt.% Pd
exhibited higher activity compared with the Mn/Co = 1:1
catalyst. The catalyst with 3 wt.% Pd possessed almost similar
catalytic activity with Mn/Co = 1:1 catalyst.
According to the IUPAC classification, the samples con-
taining Co showed the type IV isotherm with H2-shaped hys-
teresis loop (Cook et al. 2012). This type of the hysteresis loop
is related to catalyst structure containing particles with cylin-
drical pore shape (Biabani et al. 2012). The Mn/Co = 1:0
catalyst also possessed type IV isotherm with type H1 hyster-
esis loop, related to the mesoporous materials comprising
nearly spherical-shaped agglomerates or compacts. The Pd-
promoted catalysts also showed type IV isotherm with type
H1 hysteresis loop. The formation of the hysteresis loop at
lower relative pressure for the Mn/Co = 1:2, Mn/Co = 1:1,
and Mn/Co = 2:1 indicates the presence of smaller pores com-
pared with the Mn and Co catalysts (Table 1). The hysteresis
loop was also observed at lower relative pressures for Pd-
promoted catalysts compared with Mn/Co = 1:0 and Mn/Co
= 0:1 catalysts, confirming the pores are smaller in size com-
pared with Mn/Co = 1:0 and Mn/Co = 0:1 catalysts. The pore
size distributions of the samples are also shown in Fig. 4b. The
results clearly showed that the pore distribution is located in
the smaller region in Mn/Co = 1:2, Mn/Co = 1:1, and Mn/Co
= 2:1 catalysts compared with Mn/Co = 1:0 and Mn/Co = 0:1
catalysts.
The textural characteristics of the catalysts are reported in
Table 1. It is seen that the Mn/Co = 1:1 catalyst possessed the
 Environ Sci Pollut Res

Fig. 2 CO conversion (%) of the

samples with various Mn/Co mo-
lar ratios. Reaction conditions:
4% CO and 20% O2 balanced
with Ar, GHSV = 60,000 ml/g.h,
pretreated in the oxidative
atmosphere

highest BET area (123.72 m2/g) and the smallest pore size
(6.44 nm) among the prepared catalysts. The results demon-
strated that the incorporation of Pd into the Mn/Co = 1:1
catalyst decreased the BET area, which could be due to the
partial blockage of the pores with the Pd clusters.
The TPR profiles of the samples are shown in Fig. 5. The
Mn/Co = 0:1 catalyst showed two major reduction peaks at a
temperature lower than 600 °C. It is known that the Co3O4 is
reduced to CoO at a temperature higher than 300 °C and then
CoO is subsequently reduced to Co at around 400 °C
(Meshkani and Rezaei 2015; Pu et al. 2017). In some cases,
a single peak was obtained for the reduction of Co3O4 at 330
°C (Jirátová et al. 2018).
The profile of the Mn/Co = 0:1 catalyst (Fig. 5d) includes
two major reduction peaks between 200 and 500 °C. Based on
other previous TPR studies of pure Co, these two main

Fig. 3 CO conversion (%) of the

samples with various Pd contents.
Reaction conditions: 4% CO and
20% O2 balanced with Ar, GHSV
= 60,000 ml/g.h, pretreated in the
oxidative atmosphere
Environ Sci Pollut Res
Table 1 Textural properties of the catalysts
Catalyst SBET (m2/g)
Mn/Co = 1:2 108.42
Mn/Co = 1:1 123.72
Mn/Co = 2:1 121.99
Mn/Co = 1:0 73.87
Mn/Co = 0:1 34.51
MnCo2O4-1 wt.% Pd 90.68
MnCo2O4-2 wt.% Pd 89.11
MnCo2O4-3 wt.% Pd 84.23
reduction peaks are assigned to the reduction of Co3O4 to CoO
and CoO to Co (Cook et al. 2012). The shift of the reduction
peaks of the Mn/Co = 1:0 catalyst (Fig. 5d) to lower temper-
atures might be due to the bulk phase of the pure cobalt oxide
compared with the dispersed cobalt oxide particles on the
surface of the catalyst support in the supported catalysts
(Jacobs et al. 2007). Regardless of the difference in the reduc-
tion temperature, all of the reduction profiles are almost sim-
ilar. Most of the TPR profiles (Fig. 5) exhibited two peaks at
300 and 600 °C, respectively. In accordance with Fig. 5, these
reduction peaks are correlated to the multistage reduction of
the structural spinel Mn/Co (Li et al. 2014). The reduction
peak observed at 200–400 °C (Fig. 5a, 5b, and 5c) is assigned
to the low-temperature reduction of Co3+ → Co2+ and Mn4+
→ Mn3+ and the peak at 400–700 °C (Fig. 5a,b, and c) is
related to the high-temperature reduction of Co2+ → Co0
and Mn3+ → Mn2+ (Zener 1951; Mousavi et al. 2014; Li
et al. 2017; Bhairi et al. 2018). For the Mn/Co = 1:0 catalyst
(Fig. 5e), a distinction between the two reduction stages of
Mn-mixed oxides is possible, which consists of the reduction
process of Mn species in MnOx (Trivedi and Prasad 2016) and
it could be related to the reduction of Mn-mixed oxide due to
the synthesis of the sample in the absence of Co, because with
the addition of cobalt content, the first peaks shifted to higher
Fig. 4 (a) Nitrogen adsorption/
desorption isotherms and (b) pore
size distributions of the prepared
sample with various Mn/Co
molar ratios
Pore volume (cm3/g) Pore size (nm)
0.25 9.44
0.19 6.44
0.21 6.89
0.28 15.15
0.21 24.87
0.21 9.52
0.23 10.14
0.21 10.11
temperature initially and then move back to the lower temper-
ature sharply (Zheng et al. 2018).
According to the TPR profiles of the MnCo2O4-1 wt.% Pd
sample (Fig. 5f), the two reduction peaks of the Mn oxides by
the Pd-doped shifted to lower temperatures. This confirms the
increase in the mobility of oxygen in the spinel phase of man-
ganese oxide (de la Peña and Álvarez-Galván 2005; de la Peña
O’Shea and Alvarez-Galvan 2007). Adding palladium to the
catalyst structure seems to weaken the Mn-O bond, which
leads to an increase in the mobility of oxygen molecules in
the lattice (V.A. de la Pen a O’Shea 2005).
As shown in Fig. 6, the activity of the MnCo2O4-1 wt.% Pd
catalyst was measured under different pre-processing condi-
tions at 300 °C for 3 h. A gas stream containing 20% O2–80%
Ar, Ar, and 20% H2 in Ar were used as oxidative, inert, and
reductive atmosphere, respectively.
According to Fig. 6, the pretreated catalyst under an oxidizing
stream exhibited the highest activity (Fig. 6a). The oxidative
atmosphere can enhance the adsorption of the active superficial
O2 species, which can improve the activity of the catalyst
(Mobini et al. 2017). The catalyst pretreated in the inert gas
stream possessed high conversion at low temperatures (Fig. 6b).
The catalyst pretreated under the hydrogen stream (Fig.
6c) shows lower CO conversion than the catalyst
 Environ Sci Pollut Res

Fig. 5 H2-TPR analysis of the Mn/Co mixed oxide samples with different Mn/Co molar ratios calcined at 300 °C

pretreated under O2 stream, which could be due to the
partial reduction of the catalyst to species with lower O2
capacity (Zener 1951; de la Peña and Álvarez-Galván
2005; Shanmugavadivel et al. 2019).
The effect of GHSV and feed ratio (O2/CO) on the CO
conversion of the MnCo2O4-1 wt.% Pd was evaluated and
the results are displayed in Fig. 7. It is seen that the CO con-
version decreased with the increase of the GHSV. The
increment in GHSV value decreased the residence time of
the reactants with the catalyst surface, which consequently
decreased the conversion of CO (Feng et al. 2018).
The conversion of CO slightly improved with the incre-
ment in O2/CO ratio and the negative effect of the excess O2
was not observed on the catalytic performance. Therefore, the
increase in O2/CO did not change the catalytic performance of
the catalyst. Based on the “asymmetric inhibition” of CO

Fig. 6 Effect of pretreatment

atmosphere on the CO conversion
(%) of the MnCo2O4-1 wt.% Pd
catalyst. Reaction conditions: (a)
20% O2 in Ar, (b) 100% Ar, and
(c) 20% H2 in Ar at 300 °C for 3 h
Environ Sci Pollut Res

Fig. 7 Effect of GHSV on CO

conversion (%) (at CO/O2 = 1/10
molar ratio, red graph) and effect
of feed composition (blue graph)
on CO conversion (%) (GHSV =
60,000 ml/h.gcat), MnCo2O4-1
wt.% Pd catalyst, and reaction
temperature = 110 °C

oxidation, the adsorption of carbon monoxide is not affected decreased because of the limited access to O2 (Meshkani and
by excess oxygen, and the CO molecules are adsorbed by the Rezaei 2015; Pu et al. 2017).
sites which are always available. Under the stoichiometric The stability of the MnCo2O4-1 wt.% Pd catalyst was stud-
ratio of the CO/O2 in the feed stream, the conversion of CO ied at 110 °C for 25 h time on stream. Water vapor always has

Fig. 8 Stability test of the

MnCo2O4-1 wt.% Pd catalyst
under dry feed (4% CO and
20% O2) and wet feed (4% H2O,
4% CO, and 20% O2) at 110 °C

a negative influence on the stability (Yang et al. 2018).
Therefore, for investigation of the influence of the steam on
the catalytic stability (wet condition), the catalytic test was
conducted under the wet condition using a gas stream with 4
vol.% water vapor and the results are displayed in Fig. 8.
The results indicated that the catalyst exhibited high stabil-
ity under the dry and wet conditions (Fig. 8). The scanning
electron microscopy (SEM) images of the MnCo2O4-1 wt.%
Pd sample are displayed in Fig. 9. The SEM image of the
calcined catalyst showed the presence of the particles smaller
than 30 nm in this sample. The SEM images of the used
catalysts after the dry and wet stability tests are shown in
Fig. 9. SEM images of the MnCo2O4-1 wt.% Pd: (a) fresh catalyst, (b) spent catalyst after dry stability, (c) spent catalyst after wet stability test.
Environ Sci Pollut Res
Fig. 9b and 9c. According to the SEM images, no obvious
changes were observed in the morphology of the samples,
confirming the high stability of the textural properties of the
catalyst in this reaction.
Conclusions
In this study, the effect of the Pd addition on the catalytic
performance of the CO oxidation on MnCo2O4 catalyst was
studied. The results indicated that the MnCo2O4 containing 1
wt.% Pd showed higher activity than the MnCo2O4 catalyst.
Environ Sci Pollut Res
The results also showed that the sample pretreated under the
oxidizing atmosphere exhibited higher activity than the sam-
ple pretreated under the reductive atmosphere, which is related
to the higher oxygen adsorption capacity of the oxidized sam-
ple compared with partially reduced catalyst. The results also
indicated that the catalyst exhibited high stability under dry
and wet feed conditions and the SEM analysis also confirmed
that no dramatic changes in the morphology of the catalyst
were observed, confirming the high stability of the textural
properties of the catalyst during the reaction.
Acknowledgments The authors gratefully acknowledge the financial
support received from the Iran National Science Foundation (INSF) under
the grant number of 97017638.
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