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CERAMICS
INTERNATIONAL
Ceramics International 41 (2015) 595601
www.elsevier.com/locate/ceramint

Synthesis of MnO, Mn2O3 and Mn3O4 nanocrystal clusters by thermal

decomposition of manganese glycerolate
Ondej Jankovska, David Sedmidubska, Petr imeka, Zdenk Sofera,
Pavel Ulbrichb, Vilm Bartnka,n
a
Department of Inorganic Chemistry, Faculty of Chemical Technology, Institute of Chemical Technology, Technick 5, 166 28 Prague 6, Czech Republic
b
Department of Biochemistry and Microbiology, Faculty of Food and Biochemical Technology, Institute of Chemical Technology, Technick 3, 166 28 Prague 6,
Czech Republic
Received 19 August 2014; received in revised form 23 August 2014; accepted 26 August 2014
Available online 3 September 2014

Abstract

We successfully prepared MnO, Mn2O3 and Mn3O4 nanoparticles by thermal decomposition of manganese (II) glycerolate in air or inert
atmosphere at various temperatures. The thermal behavior during decomposition was analyzed by simultaneous thermal analysis. The manganese
precursor was analyzed by X-Ray diffraction, SEM, SEM-EDS and X-Ray photoelectron spectroscopy to evaluate exact composition. The
particle size of the obtained nanoparticles was determined from XRD patterns using Scherrer equation and also by transmission electron
microscopy. Thanks to the extremely low sizes, such nanoparticles can be used at large-scales for industrial use.
& 2014 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Keywords: Nanoparticles; Manganese oxides; Glycerolate; Thermal decomposition; Nanocrystals

1. Introduction as electrode materials in batteries employing pseudocapacitive

behavior [11] or for potential use in supercapacitors [12,13].
The group of TM-oxide nanomaterials is interesting for Moreover manganese oxides based substances are useful for
applications in sensors, data and energy storage as well as in ionic absorption [14].
catalysis [1,2]. Numerous different processes for the nanopar- MnO, Mn2O3 and Mn3O4 nanoparticles have been already
ticles synthesis have been already reported, however, only a prepared from nanorods of manganese oxalate [15]. Under
few of them fulll the basic requirements for industrial use [3]. solvothermal conditions the decomposition of manganese
For large-scale synthesis it is important to nd simple and cupferronate in the presence of trioctylphosphine oxide led
cost-effective method for the production of nanoparticles to the synthesis of MnO nanoparticles with unique magnetic
with tunable particle size and also with high purity. Thermal
decomposition of organic-TM precursors seems to be one of
the most suitable candidates [46].
Manganese oxides have been intensively studied due to their
catalytic properties. A large number of catalytic processes
assisted by these catalysts has been already in use, for instance
oxidation reactions [79] or various organic syntheses [10],
and many other interesting applications can be envisaged such

n
Corresponding author. Tel.: 420 220443765.
E-mail address: vilem.bartunek@vscht.cz (V. Bartnk). Fig. 1. XRD pattern of manganese (II) glycerolate (Mn-GLY).

http://dx.doi.org/10.1016/j.ceramint.2014.08.108
0272-8842/& 2014 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
 596 O. Jankovsk et al. / Ceramics International 41 (2015) 595601

properties [16]. Magnetic and microstructural properties of
antiferromagnetic MnO nanoparticles wrapped in ferrimagnetic
Mn3O4 shells have been reported by Berkowitz et al. [17]
Mn2O3 was synthesized by solgel method using methanol as
a solvent [18] and also by the solvothermal route [19].
Compared to previously published papers, our method is
very simple. We present a two-step procedure of MnO, Mn2O3
and Mn3O4 nanoparticles synthesis from a single precursor.
In the rst step we prepared the manganese (II) glycerolate
which was subsequently thermally decomposed in air or in inert

Fig. 2. SEM images of manganese (II) glycerolate.

Fig. 3. XPS survey spectrum and high-resolution details of C 1s, O 1s and Mn 2p of manganese (II) glycerolate. Fitting of C 1s shows possible carbon stages.
 O. Jankovsk et al. / Ceramics International 41 (2015) 595601 597

atmosphere. We used several complementary analytical techniques
to describe the decomposition process and structure of the prepared
nanoparticles.
2. Experimental
In the rst step, manganese (II) glycerolate was prepared by a
reaction of water-free glycerol added in excess with Mn(NO3)2
under reux for 3 hours. After the heat treatment, solution was put
into distilled water. The formed solid phase was obtained by
centrifugation from the suspension, multiple washing by distilled
water and drying on evaporator. Thereafter manganese (II)
glycerolate was treated in the tube furnace in a dynamic puried
air atmosphere (pO2/p0 0.21, where p0 101.3 kPa) or in
dynamic argon atmosphere (pO2/p0  10  6) with a ow rate
50 mL.min  1. The precursors were then calcined at 750 K, 850 K
or 950 K for 5 min with the heating and cooling rate 10 K.min  1.
XRD patterns were collected at room temperature on X'Pert
PRO - powder diffractometer with parafocusing Bragg-Brentano
geometry using CuK radiation ( 1.5418 , U 40 kV, I 30
mA). Particle sizes were evaluated from the width in half height of
the most intensive single diffraction peak. X'Pert HighScore Plus
program was used for XRD data processing and the nanoparticle
sizes were calculated using Scherrer equation.
High resolution X-ray photoelectron spectroscopy (XPS)
was performed with ESCAProbeP (Omicron Nanotechnology
Ltd, Germany) spectrometer using a monochromatic aluminum
X-ray radiation source (1486.7 eV). The sample was attached
onto conductive holder made from high purity silver bar.
Wide-scan survey of all elements was recorded and the relative
sensitivity factors were used to evaluate the individual element
ratios from the survey spectra.
The morphology of synthetized materials was investigated
using scanning electron microscopy (SEM) with a FEG electron

Fig. 4. Elemental distribution maps of Mn, C and O recorded on manganese (II) glycerolate sample. The scale bar is 5 m.
598 O. Jankovsk et al. / Ceramics International 41 (2015) 595601

source (Tescan Lyra dual beam microscope). Elemental com-
position and mapping were performed using an energy dis-
persive spectroscopy (EDS) analyzer (X-MaxN) with a 20 mm2
SDD detector (Oxford instruments) and AZtecEnergy software.
To conduct the measurements, the samples were placed on a
carbon conductive tape. SEM and SEM-EDS measurements
were carried out using a 10 kV electron beam.
Thermal behavior was probed by simultaneous thermal analysis
(STA). The DTA and TG curves were recorded simultaneously on
a Linseis STA PT1600 apparatus at a heating rate of 10 K.min  1
in dynamic air or argon atmosphere with a ow rate 50 mL.min1
to imitate the real conditions during the thermal decomposition of
manganese (II) glycerolate in tube furnace.
The samples for transmission electron microscopy were
prepared by the deposition of a 6 ml drop of studied solution
onto carbon coated copper grid, excess of solution was
removed and grids were dried by Whatman ltration paper.
The samples were observed using the transmission electron
microscope JEOL JEM-1010 at accelerating voltage of 80 kV.
The micrographs were snapped by SIS MegaView III digital
camera (Soft Imaging Systems) and analyzed by means of
AnalySIS v. 2.0 software.
3. Results and discussion
MnO, Mn2O3 and Mn3O4 nanoparticles were successfully
prepared by thermal decomposition of manganese (II) glycer-
olate in a controlled air/argon atmosphere, for more details see
the experimental section.

Fig. 5. Thermal decomposition of manganese (II) glycerolate in argon and air atmosphere at 750 K, 850 K and 950 K.
 O. Jankovsk et al. / Ceramics International 41 (2015) 595601
First we analyzed the formed manganese (II) glycerolate by
XRD (Fig. 1) [20]. Very intensive reection at 2 10.6 was
found, which is in good agreement with our previously
published data for cobalt (II) glycerolate prepared by similar
technique. However, manganese (II) glycerolate exhibits a
slightly more crystalline character if compared to almost
amorphous cobalt (II) glycerolate [21].
SEM images proved crystalline layered structure of manganese
(II) glycerolate. Individual platelets of dimensions 2  1 
10 m3 are randomly oriented as can be seen from Fig. 2.
In the next step, manganese (II) glycerolate was analyzed by
high resolution XPS (see Fig. 3). Peaks corresponding to Mn
2p, C 1s and O 1s were detected in XPS survey spectrum. The
twinning peak of Mn 2p at  644.9 eV for Mn 2p3/2 and
 656.7 for Mn 2p1/2 corresponds to Mn2 [22]. The C 1s
peak with an asymmetrical tail to lower energies at  289.2 eV
and a symmetrical O 1s peak at  534.5 eV were found.
Details of all peaks are also shown in Fig. 3. A relatively low
amount of Mn and O was calculated from the survey spectrum
yielding the resulting net formula Mn1C6.2O4.2 (Mn being
xed to 1). The deconvolution of C 1s peak conrmed the
presence of C-C/C-H and C-O bonds (Fig. 2), however, their
ratio is not quite consistent with the overall stoichiometry
probably due to charging effects [23,24].
The overall composition of manganese (II) glycerolate was
also determined by SEM-EDS. The obtained results showed
the presence of 36.7 7 0.2 wt. % of O, 35.97 0.2 wt. % of C
and 27.47 0.1 wt. % of Mn. No impurities were detected
within the sample. These results can be recalculated into
the empirical formula Mn1C6.0O4.4 which is in very good
agreement with the results obtained by XPS. Elemental
Fig. 6. XRD patterns of MnO, Mn2O3 and Mn3O4 nanoparticles.
599
distribution maps are shown in Fig. 4 conrming the homo-
genous distribution of all detected elements.
The decomposition process was analyzed by STA (Fig. 5).
DTA and TG curves revealed a different behavior in argon and
air atmosphere. Six samples were termed according to the
decomposition conditions as Ar-750, Ar-850, Ar-950, Air-750,
Air-850 and Air-950. In argon atmosphere the endothermic
peak at  660 K for all samples indicated the decomposition of
manganese (II) glycerolate to MnO, which was also conrmed
by TG. By contrast, a different behavior was observed in air
atmosphere where two exothermic peaks were detected; both
accompanied by the weight loss. The rst smaller peak at
 430K can be likely attributed to the oxidation of unreacted
sorbed glycerol on the manganese (II) glycerolate surface,
while the second exothermic peak at  535 K is associated
with the decomposition/oxidation of manganese (II) glycerolate.
Calculations based on TG estimated the molar mass in the range
between 120 and 130 for manganese (II) glycerolate. This value
is lower than expected and it can be explained by the presence
of sorbed glycerol. Similar results were obtained by XPS.
The XRD analysis conrmed successful formation of pure
nanocrystalline MnO in inert atmosphere (samples Ar-750, Ar-
850 and Ar-950), [25] while the results in air were surprising
(Fig. 6). The sample Air-750 was single phase and contained
only Mn3O4 [26], while the sample Air-850 contained a
mixture of Mn3O4 and Mn2O3. The last sample, Air-950,
was single-phase comprising uniquely Mn2O3 nanoparticles
[27]. The heating apparently leads to a gradual oxidation of
Mn from Mn2 to Mn2 /Mn3 and eventually to Mn3 .
Such behavior is in contrast with thermodynamic predictions,
where obviously Mn2O3 has to be stable at lower temperatures
600 O. Jankovsk et al. / Ceramics International 41 (2015) 595601

Fig. 7. TEM images of MnO, Mn2O3 and Mn3O4 nanoparticles. The scale bar is 200 nm.

compared to Mn3O4. Our observations can be explained in
terms of relatively low temperatures and short times of nal
heat treatment, where the reaction kinetics hinders the forma-
tion of thermodynamically stable nanoparticles. Moreover the
effective partial pressure of oxygen can be reduced due to
glycerolate oxidation and a slow removal of the oxidation
products from the reaction zone. Nevertheless, a thermodyna-
mically stable product, Mn2O3, has been obtained at the
highest temperature (950 K) in air atmosphere when the kinetic
barriers can be most easily overcome.
 O. Jankovsk et al. / Ceramics International 41 (2015) 595601
Calculations according to Scherrer equation conrmed the
assumed behavior for the decomposition of manganese (II)
glycerolate in argon atmosphere: higher temperatures led to a
formation of larger nanoparticles. Calculated particle sizes
of MnO were  15.8 nm for Ar-750,  17.2 nm for Ar-850
and  18.7 nm for Ar-950. The sample Air-750 contained
Mn3O4 nanoparticles with extremely low dimensions ( 12.2 nm)
while the sample Air-950 contained much larger Mn2O3 nano-
particles with a typical size  49.3 nm.
TEM images conrmed the calculated particles sizes. In the
case of Air-950 sample containing Mn2O3 the individual
nanoparticles were partially sintered, which is the reason
why much larger nanoparticles were observed compared to
all remaining samples. Moreover, a very interesting phenom-
enon was detected from TEM images. The shape of individual
2D nanoparticles clusters/agglomerates depends on the shape
of manganese (II) glycerolate (Fig. 7).
4. Conclusions
We prepared manganese oxide nanoparticles by thermal
decomposition of manganese (II) glycerolate. This process is
simple and cost-effective leading to the synthesis of nanopar-
ticles with uniform particle sizes. Tunable particle sizes of
MnO can be observed by changing time or temperature of the
decomposition process. The process of synthesis led to the
formation of nanoparticles with extremely low particles sizes
(1020 nm). In addition, unique structure of formed clusters
was observed. Such nanoparticle clusters can be used in
industry for the synthesis of catalysts exhibiting extremely
large surface area for hydrogen evolution, catalytic oxidation,
ionic extraction and many other applications.
Acknowledgment
This work was supported by Czech Science Foundation,
Grant No. 13-17538S, and by nancial support from specic
university research (MSMT No 20/2014).
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