Front. Chem. Sci. Eng.
2013, 7(3): 329–337
DOI 10.1007/s11705-013-1339-0
RESEARCH ARTICLE
Preparation of manganese (III) acetylacetonate nanoparticles
via an environmentally benign route
M. S. Shalaby (✉), H. Abdallah
National Research Center, El Buhouth St., Dokki, Cairo, Egypt
© Higher Education Press and Springer-Verlag Berlin Heidelberg 2013
Abstract With the hope of overcoming the generation of
hazardous materials to human health and environment,
serious and great endeavor have been made in catalyst
fabrication using green chemistry technology. In this paper,
the manganese (III) acetylacetonate nanoparticles with
diameters of about 146 nm were prepared by a simple and
environmentally benign route based on hydrolysis of
KMnO4 followed by reaction with acetylacetone in rapid
stirring rate or ultrasonication. The as-prepared samples
were characterized by X-ray diffraction, energy dispersive
X-ray fluorescence (EDIX), Fourier transfer infrared
spectroscopy and scanning electron microscope. Various
parameters were investigated, and the pure and stable
crystals of manganese (III) acetylacetonate could be
obtained in 98% conversion at a molar ratio 7∶1 of
acetylacetone to KMnO4 and 75°C after 60 min. We
further proposed a mathematical model, and the predicted
results from model were in good agreement with
experimental results.
Keywords green chemistry, manganese (III) acetylaceto-
nate, reaction conversion, Mathematical model
1 Introduction
Metal acetylacetonate complexes are widely used as
catalyst and co-catalysts in many chemical reactions such
as oligomerization, polymerization, isomerization, hydro-
genation, and coupling. Also, they are used in rubber
technology for vulcanization [1,2].
The unique properties of these coordination complexes
have made them multi-field researches such as stereo-
isomerism, where the tris-chelate complexes occurs due to
the fundamental difference in two possible ligand bonding
configurations. Likewise, coordination compounds arise
Received December 24, 2012; accepted April 26, 2013
E-mail: marwashalaby_4@yahoo.com
when a metal cation is bonded to one or more anions
through coordinate covalent bonds [3].
According to that, metal acetylacetonates are stated to
promise precursor of heterogeneous catalysts [4–6].
Volatility of some acetylacetonates (Cr(acac)3, Al(acac)3,
V(acac)3, Pt(acac)2 or Cu(acac)2) makes possible their
vapour phase to deposite on support surface. Thermally
unstable acetylacetonates (Co(acac)2, Fe(acac)3 or
Mn(acac)3) can be deposited by adsorption from organic
solvents. High dispersion degree of supported metal
acetylacetonetes is achievable due to their H-bonding
with surface groups of support or ligand substitution [7–
11]. Also, manganese (III) acetylacetonate (Mn(acac)3) has
been employed as efficient constituent in electrolyte of
single-metal redox flow battery (RFB) for applications
including storage of the large amounts of energy produced
by intermittent sources such as wind turbines and solar
cells. However, Mn(acac)3 was chosen as source material
for preparation of LiMn2O4 thin films, which are used as a
cathode material in microbatteries [7]. However, these
compounds can be used in polymeric coatings as stabilizer
of cross-linking reaction [12–14], catalyst of drying
process [9,10] and toughening agent [11].
Green chemistry has attracted more attention in the past
century to use non-toxic or less toxic raw materials and
solvents to produce environmentally benign chemicals,
because its definition is invention, design, development
and application of chemical products and processes to
reduce or eliminate the use and generation of substances
hazardous to human health and environment [4–6]. Metal
acetylacetonate complexes can be produced by green
chemistry using acetylacetonate anion and metal ions,
usually transition metal compounds.
The present study investigates the production of
Mn(acac)3 with a green chemistry technique; it does not
use any hazardous solvent other than water, in which the
product is insoluble and thus can be easily separated. Also,
this process uses one source of manganese that has a high
oxidizing power to maximize reaction yield, and could be
330 Front. Chem. Sci. Eng. 2013, 7(3): 329–337
an alternative for non-green traditional technique. Another
benefit of this green technique is the high purity of
produced Mn(acac)3 due to the absence of any contami-
nants and easily recycling of unreacted reactants [15,16].
Traditionally, Mn(acac)3 is prepared by non-green techni-
que in the presence of sodium acetate as a neutralizing
agent in reaction mixture; the reaction begins with
MnCl2$4H2O and acetylacetone to form a complex of
Mn(II) which in turn reacts with Mn(IV) from KMnO4 to
provide Mn(acac)3. The resulting product will require extra
washing and separation techniques before final application.
Moreover, sodium acetate, unreacted manganese sources
and acetylacetone in the final filtrate are difficult to
separate, recycle and reuse [17].
The objective of this work is to develop a reliable
production technology to produce pure crystals of
Mn(acac)3 in nanostructure. Quality control test on the
resulted products are introduced to guarantee its promising
industrial application as an efficient nano-scale catalyst.
Also, this work provides an improved, economical and
environmentally benign green process for the development
of Mn(acac)3.
2 Materials and methods
2.1 Materials
Technical grade acetylacetone was purchased from Fluka,
potassium permanganate (KMnO4) was obtained from
Sigma-Aldrich. Chemicals were used as received unless
stated otherwise.
2.2 Synthesis of manganese acetylacetonate
Mn(acac)3 was synthesized by dissolving 5 g of KMnO4 in
50 mL of distilled water with continuous stirring in batch
system, while the heating of reaction was carried out by a
water bath. After dissolution was completed; distilled
acetylacetone was added to the solution with continuous
stirring. A white crystalline precipitates were observed
during the reaction. Therefore, it was important to keep the
whole mixture to cool for 10 minutes in order to complete
the crystals deposition. The formed dark shiny crystals of
Mn(acac)3 was filtered off and dried in vacuum over fused
CaCl2 for 15 minutes.
A parametric study was conducted to investigate the
influence of molar ratio of acetylacetone to KMnO4,
reaction temperature, and reaction time. Production of
Mn(acac)3 was accomplished without any neutralizing
agent to prevent contamination so the product purity and
stability upon storage increased [17–20].
2.3 Product characterization
A variety of instrumentation analyses were performed to
detect and evaluate the quality of final product (Mn(acac)3
crystals), allowing the formulation of an integrated full
product assay by Fourier transfer infrared spectroscopy
(FTIR), scanning electron microscope (SEM), energy
dispersive X-ray fluorescence (EDIX) and X-ray diffrac-
tion (XRD).
2.3.1 Determination of reaction conversion using HPLC
After the reaction was completed, the produced solution
was filtered to separate the dark shiny crystals of
Mn(acac)3 from unreacted solutions. Then, the unreacted
manganese in reaction solution was analyzed by HPLC
Agilent 1200 series, made in Germany, using methanol as
mobile phase and Eclipse XDB-C18 (5 μm, 4.6
150
mm) as the stationary phase. Finally, the reaction
conversion can be calculated according to this formula:
½Mnin -Mnunreacted 
x¼
100,
½Mnin 
where x is the reaction conversion, Mnin is the moles of
inlet manganese according to KMnO4 amount, and
Mnunreacted is the unreacted moles of manganese which
was obtained from HPLC analysis of produced unreacted
solution.
2.3.2 SEM and EDIX
Mn(acac)3 crystals samples were grinded and coated with
gold sputtering to provide electrical conductivity. The
micrographs were taken on a JEOL 5410 scanning electron
microscope at 20 kV. EDIX was used to measure the
elemental analysis of Mn(acac)3 crystal samples, using the
energy-dispersive X-ray fluorescence (EDIX) device
contains DET, area-10 mm2, window (ATW2) model
6587, made in Oxford.
2.3.3 FTIR
Samples of Mn(acac)3 crystals were also characterized by
FTIR analysis at 16 scans per minute with resolution of 4
cm–1 and absorbance 400–4000 cm–1. The IR data were
collected using JASCO FTIR-6100 model, made in Japan.
2.3.4 XRD
XRD analysis was used to identify the mineralogical
composition of Mn(acac)3 crystal samples. The XRD-
spectrum (Brukurd 8 advance, CuK, target with secondary
mono chromator λυ = 40, mA = 40, Germany) was used for
Mn(acac)3 crystals identification and estimation of the
anastase-to-rutile ratio. XRD patterns were obtained at
room temperature by using X-ray generator (Shimata XD-
D1, Japan).
 M. S. Shalaby et al. Preparation of manganese (III) acetylacetonate nanoparticles 331

3 Mathematical model Table 1 Effect of various molar ratio on reaction conversion of

Mn(acac)3 production after 60 min
Mathematical model was developed using MATLAB Molar ratio Reaction conversion/% Yield/gm
Simulink (Mathworks, Release 2008a) and the batch (acetylacetone∶KMnO4)
processes were studied with respect to different parameters 1∶1 64.7 3.00
(molar ratio, temperature, and reaction time). The model 2∶1 88.3 4.60
was verified by comparing experimental results with 4∶1 91.6 5.00
predicted results from the model.
5∶1 93.86 5.06
7∶1 94 5.63
4 Results and discussion 10∶1 94.4 5.67

4.1 Effect of reactant molar ratio on reaction conversion

A series of experiments were carried out using different

molar ratios (1∶1 to 10∶1) of acetylacetone to KMnO4. The
other conditions were fixed at 45°C and 60 min for reaction
time. Samples were taken from the reactor flask after 10
min during the reaction time. Fig. 1 indicates unreacted
Mn% in produced filtrate solution, where the lowest
weight percent of Mn in the filtrate was 1.74% at molar
ratio 10∶1 of acetylacetone to KMnO4 which increases to
Fig. 2 Effect of reaction time on product yield at molar ratio 7∶1
be 1.79% and 1.84% at molar ratios 7∶1 and 5∶1 of acetylacetone to KMnO4 and reaction temperature 45°C
respectively. It was obvious from these experiments that
excess molar ratio between the reacting species greatly
affects the reaction conversion and product yield as shown is common in reactions of strong inorganic oxidizing
in Table 1. The molar ratio 7∶1 other than 10∶1 was chosen reagents with organic compounds [16] and this was also
to be optimum because the corresponding reaction verified with the following mathematical model. The
conversions are approximately close to each other. optimum reaction time was 60 min, which was long
enough for the optimization process by minimizing the
unreacted compounds and increasing process economic.

4.3 Effect of reaction temperature on reaction conversion

In order to use less energy and reduce the chemical reaction

costs, experiments were carried out at 25°C, 45°C, 55°C,
65°C and 75°C, respectively, with a 7∶1 molar ratio of
acetylacetone to KMnO4 and reaction time being 60 min.
Figure 3 reveals that unreacted Mn% in filtrate liquid phase
is always decreased to reach a minimum of 0.49% at 75°C
compared with 1.79% at 45°C.
These results indicate that by increasing reaction

Fig. 1 Effect of various reactant molar ratios on unreacted Mn%

in filtrate liquid phase

4.2 Effect of reaction time on product yield

To further optimize the reaction conditions, different

reaction times (5 min, 15 min, 25 min, 35 min, 45 min
and 60 min) were tested. In these experiments, the other
reaction conditions were fixed at molar ratio 7∶1 of
acetylacetone to KMnO4 and at 45°C. Figure 2 illustrates
yield of Mn(acac)3 at various reaction time, where the yield
reached 7.5 gm after only 5 min and increased to 10.62 gm Fig. 3 Effect of reaction temperature on unreacted Mn% in
after 60 min. Increasing the yield during the reaction time filtrate liquid phase
332 Front. Chem. Sci. Eng. 2013, 7(3): 329–337

temperature the reaction conversion could be increased to

94% at reaction temperature 45ºC and about 98% at 75ºC.
However, increasing temperature (up to 75ºC) could cause
excessive control on reaction vessel design due to
accessibility to foam formation at higher temperature,
and increase operating cost of required energy consumed.

4.4 Product characterization

4.4.1 SEM and EDXRF

Mn(acac)3 crystals precipitated from solution was sub-

jected to full chemical analysis to confirm its structure and
purity. Scanning electron micrographs were used for
Mn(acac)3 crystal surface views with the magnification
120000 and 100000 respectively in the micrographs (a) &
(b) as shown in Fig. 4. The SEM images indicate that Mn
(acac)3 was uniform fine particles with particle size of 146
nm and wall thickness 60 nm without using sophisticated
experimental technique in mixing and ultrasonication,
which could lead to the formation of crystalline aggregates
of this product. This means that slight modifications using
ultrasonic homogenizer can form small nano-particles of
this product which can be applied in catalysis of chemical
processes.
Also, the metallic content of Mn% in solid crystals of
product was 14.7%, as confirmed by EDXRF, whereas the
organic carbon content was 50.21% as analyzed by the
elemental analysis Fig. 5 showed the EDIX chart for
produced crystals, agreeing with the published literature
[19]. The result from HPLC was 14% Mn, which is also in
agreement with analysis in previous literatures [20–22].

4.4.2 FTIR
Fig. 4 SEM micrographs of (a) crystal size of manganese (III)
The produced Mn(acac)3 crystals were characterized by acetylacetonate, and (b) wall thickness of manganese (III)
FTIR. Its FTIR-spectrum (Fig. 6) was super-imposable on acetylacetonate crystals

Fig. 5 EDIX chart for manganese (III) acetylacetonate crystals

 M. S. Shalaby et al. Preparation of manganese (III) acetylacetonate nanoparticles 333

Fig. 6 FTIR for produced manganese (III) crystals

that of the authentic sample particularly in the figure print
region (1500–650 cm–1). The main distinguishing features
were: (i) the presence of strong absorption bands (peaks
nos. 14, 15, and 16) at 1588, 1514.8, and 1384.6 cm–1
respectively (C–O, carboxylate), (ii) peak No. 23 at 753.5
cm–1, and (iii) peak No. 26 at 565 cm–1 (Mn–O, stretching).
Fig. 5 proves excellent agreement with published literature
[21].
4.4.3 XRD
Figure 7 illustrates the XRD-spectrum that reflects the
amorphous state of the final product nano-molecules. The
2nd and 3rd peaks (d = 5.877 and d = 5.48040) appear
correspond to the associated organic impurities, while the
1st major sharp peak (d = 8.05609) belongs to the main
product. The developing XRD-monograph is really

Fig. 7 XRD chart for manganese (III) acetylacetonate crystals

334 Front. Chem. Sci. Eng. 2013, 7(3): 329–337

 
considered as figure-prints for product identification. – Ea
However, the XRD results were in agreement with the k ¼ A:exp : (4)
RT
published literature [23].
Equilibrium constant (K) is also function of temperature
and can be expressed by Van’t Hoff equation [25].
5 Mathematical model  
– ΔH
K ¼ K 0 :exp , (5)
5.1 Model development RT
 
The overall reaction equation was – ΔGo0
K 0  exp , (6)
KMnO4 þ 8C5 H8 O2 ↕ ↓MnðC5 H7 O2 Þ3 RT 0
 
þ 2½ðCH3 COÞ2 CH2 þ 4H2 O þ KC5 H7 O2 : (1) ΔS
K 0 ¼ exp , (7)
R
In order to obtain kinetic equation of the reaction, the
experimental results were correlated to kinetic model for
the reaction which was carried out in a glass batch system ΔG ¼ ΔH – T ΔS, (8)
of 200 mL capacity. Therefore, the feed of reaction was where, ΔH, ΔG can be calculated from Eqs. (5–8).
charged to reactor and then heated to the desired reaction The rate of reaction is calculated according to overall
temperature which was kept constant within 0.5 K. reaction Eq. (9):
The kinetic reaction was conducted by withdrawing
samples at regular time intervals that were analyzed by – d½MnOþ
4
¼ k½MnOþ
4 : (9)
HPLC to determine unreacted KMnO4 and thus reaction dt
conversion.
The reacted amount of KMnO4 and the produced
Assumptions used to develop the model included:
amount of Mn(III) acetylacetonate can be calculated
 The reaction rate was defined as the change in the rate of
from Eqs. (10), and (11), respectively.
moles for component i with time gmol$sec–1. The rate of
reaction was expressed in terms of the moles of the ½MnOþ þ
4  ¼ ½MnO4 0 ð1 – xÞ, (10)
different components.
 The reaction was considered pseudo first order reaction,
½MnðC5 H7 O2 Þ3  ¼ ½MnOþ þ
4 0 – ½MnO4 : (11)
where the acetylacetonate was used in excess amount
(acetylacetone /KMnO4). The reaction conversion can be calculated from Eq. (12).
 KMnO4 was used as oxidizing agent, where the
permanganate ion MnO4– in which manganese has its dx
¼ kð1 – xÞ: (12)
highest oxidation state of + 7. dt
 The presence of excess acetylacetone can reduce Mno4–
to Mn2+ which can be oxidized again by excess amount of 5.2 Model verification
acetylacetone to produce Mn(III) acetylacetonate.
 Increasing amount of produced water can dissolve the
5.2.1 Effect of reactant molar ratio on reaction conversion
byproducts and reverse the reaction. In aqueous solution,
Mn (III) can readily hydrolyze according to Eq. (2) but it is
the most stable in acid solutions. Manganese (III) is also The effect of molar ratio of acetylacetone to KMnO4 on the
slowly reduced by water as in Eq. (3). reaction conversion was investigated at 1∶1, 2∶1, 4∶1, 5∶1,
7∶1, and 10∶1, respectively. The results show that the
Mn3þ þ2H2 O ↔ MnðOHÞ2 þHþ , (2) unreacted Mn decreased as the molar ratio increased.
However, molar ratio 7∶1 was chosen for the highest
conversion (94%) after 60 min at 45°C which were close to
4Mn3þ þ2H2 O ↔ 4Mn2þ þ4Hþ þO2 : (3)
the reaction conversion at molar ratio 10∶1. The compar-
So, the molar ratio of acetylacetonate to KMnO4 must be ison between predicted unreacted Mn from model and
high enough to keep acetylacetonate concentration con- experimental results using molar ratio 7∶1 is shown in
stant throughout the process, where using excess amount Fig. 8, indicating a good match with experimental results.
of acetylacetonate can break thermodynamic equilibrium The heat of reaction was calculated to be – 4336 J/mol, the
of the reversible reaction according to LeChâtelier change in Gibbs free energy was – 7326.6 J/mol and
principle [24]. entropy change was 9.4 J/mol$K. Table 2 illustrates
The reaction rate constant (k) as function of temperature parameters calculated by model.
can be expressed by the Arrhenius equation. Figure 9 illustrates comparison between predicted
 M. S. Shalaby et al. Preparation of manganese (III) acetylacetonate nanoparticles 335

5.2.2 Effect of reaction temperature on reaction conversion

The effect of temperature on the rate of reaction was

studied by conducting the reaction at 25°C, 45°C, 55°C,
65°C and 75°C, respectively. The molar ratio of acetyla-
cetone to KMnO4 was fixed at 7∶1 with reaction time
60 min. The results show that the reaction conversion
increases as the temperature increases, thus the productiv-
ity of Mn(acac)3 increases. Fig. 10 illustrates comparison
between predicted results and experimental results accord-
ing to reaction conversion at temperature 75°C, showing a
Fig. 8 Comparison between predicted unreactant with model fair match between predicted model results and experi-
and experimental results (molar ratio of acetylacetone∶KMnO4 = mental data. Model parameters at various temperatures
7∶1) were calculated and illustrated in Table 3. The change in
heat of reaction change, Gibbs free energy and change in
Table 2 The model parameter at different molar ratios entropy were calculated at different temperatures.
Ea/(J$mol–1) k/(mol$min–1) Molar ratio
3940 0.2255 1∶1
4080 0.2139 2∶1
4170 0.2068 4∶1
4380 0.1910 5∶1
4680 0.1705 7∶1
4890 0.1608 10∶1

Fig. 10 Comparison between predicted model of produced

Mn(acac)3 and experimental results at 75°C (molar ratio of
acetylacetone : KMnO4 = 7∶1)

When the kinetic model was fitted to all experimental

results, the results were in good agreement.

5.2.3 Production rate and scaling up

Fig. 9 Comparison between predicted model of produced
Mn(III) acetylacetonate and experimental results (molar ratio of
acetylacetone : KMnO4 = 7 ∶ 1)
produced Mn(acac)3 moles from model and experimental
results using molar ratio 7∶1 of acetylacetone to KMnO4,
indicating the experimental results fitted with the predicted
model.
The cumulative productivity of reaction was studied at
reaction temperature 75°C, molar ratio 7∶1. Figure 11(a)
demonstrates the cumulative productivity over 120 min of
operation. Figure 11(b) depicts the slope of the curve,
which shows that the maximum production rate of
0.000732 mol/ min was reached after 20 min. Therefore,
the optimum time to shift a new cycle can occur after

Table 3 Model parameters at various temperatures

Temperatures/°C ΔG/(J$mol–1) ΔS/(J$mol–1$K–1) ΔH/(J$mol–1) Ea/(J$mol–1) k/(J$min–1)
25 – 4070.34 2.2e-3 – 4071 4040 0.2000
45 – 7326.6 9.4 – 4344 4680 0.1705
55 – 8961 13.7 – 4480 4950 0.1664
65 – 10583 17.65 – 4617 5263 0.1571
75 – 12211 21.43 – 4754 6240 0.1182
336 Front. Chem. Sci. Eng. 2013, 7(3): 329–337
Fig. 11 (a) Change of cumulative productivity with time at 75°C
and molar ratio 7∶1; (b) The production rate versus time at 75°C
and molar ratio 7∶1
20 min. The scaling up of the reaction can be suggested to
use stainless steel batch reactor with three openings one for
condenser, one for feeding at the top of the reactor and the
last one for collecting product at the bottom of the reactor;
this can provide in a concurrent increase in the reactor area
from 200 mL to 10 L. The reactor must have temperature
controller and pressure gauge for safety. However,
increasing in reactor volume means high cumulative
productivity thus increasing in the product yield. The
system can be connected to filtration system to filter the
product from unreacted reactants and byproducts.
6 Conclusions
We have demonstrated that Mn(acac)3 nanoparticles could
be synthesized in aqueous medium through chemical
precipitation technique. Under the following conditions:
molar ratio 7∶1 of acetylacetonate to KMnO4, reaction
temperature 75°C, and reaction time 60 min, the highest
reaction conversion of about 98% was obtained.
The final product was analyzed by FTIR, SEM, EDIX
and XRD, and all analyses proves excellent agreement
with published literature [19]. The SEM images showed
that Mn(acac)3 was obtained as uniform fine nanoparticles
with particle size of 146 nm and wall thickness 60 nm
without using sophisticated experimental technique. The
mathematical model of the reaction was verified and
adjusted based on experimental results.
Nomenclature
K Rate reaction constant (gmol/min)
A Frequency factor
Ea Activation energy (J/mol)
R Gas constant (J/mol$K)
T Reaction temperature (K)
ΔH Change of heat of reaction (J/mol)
ΔG Change of Gibbs free energy of reaction (J/mol)
ΔS Entropy change of reaction (J/mol$K)
K Equilibrium reaction constant
K0 Equilibrium reaction constant at room temperature 25°C
½MnOþ
4 KMnO4 moles (gmol)
½MnðC5 H7 O2 Þ3  Mn(III) acetylacetonate moles (gmol)
X Reaction conversion
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