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Received 29 November 2001; received in revised form 18 March 2002; accepted 18 March 2002
Abstract
The need for highly concentrated hydrogen peroxide solutions to fuel spacecraft propulsion systems necessitates the
development of new catalytic formulations mainly based on supported manganese oxides. In order to improve the preparation
of such catalysts, the thermal decomposition and the hydrothermal reduction of different permanganate precursors were studied,
as well as the effect of washing on the products. The test samples were characterized by X-ray power diffraction (XRD) and
surface area determination, and compared for their catalytic activity towards H2 O2 decomposition using a constant pressure
reactor (for 1.71% H2 O2 ) and a constant volume reactor (for 50% H2 O2 ). The catalysts prepared by thermal decomposition
of KMnO4 or NaMnO4 ·H2 O have shown the intermediate formation of potassium (or sodium) manganate, and its partial
dissolution during washing with water; higher catalytic activity and larger surface area were observed for the decomposition
products of KMnO4 . The hydrothermal reduction yielded products exhibiting larger surface area and higher specific catalytic
activity when carried out under stoichiometric conditions. Comparable kinetic parameters were determined using both catalytic
reactors. Unsupported and alumina supported catalysts displayed comparable activity per gram of manganese.
© 2002 Elsevier Science B.V. All rights reserved.
Keywords: Hydrogen peroxide decomposition; Manganese oxide catalysts; Potassium permanganate; Sodium permanganate; Permanganate
reduction; Thermal decomposition
1. Introduction
夽 These results were originally presented at the 3rd Interna-
tional Hydrogen Peroxide Propulsion Conference, Gulfport, MS, The use of more concentrated hydrogen peroxide
November 2000 (Conference proceedings CD). solutions (i.e. up to 98%) leads to a strong increase of
∗ Corresponding author. Tel.: +33-5-49-453860;
the adiabatic decomposition temperature (632 ◦ C for
fax: +33-5-49-454020. 85%; 755 ◦ C for 90%; 953 ◦ C for 98%), which is in-
E-mail address: charles.kappenstein@univ-poitiers.fr
(C. Kappenstein).
adequate for long-term application of conventional sil-
1 Present address: Chemistry Department, Faculty of Science, ver or silver plated screen catalysts. The melting point
Minia University, Egypt. of silver (962 ◦ C) is near the adiabatic temperature
0926-860X/02/$ – see front matter © 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 6 - 8 6 0 X ( 0 2 ) 0 0 2 2 0 - X
146 C. Kappenstein et al. / Applied Catalysis A: General 234 (2002) 145–153
and the formation of silver oxides will preclude the hydrothermal reduction of different permanganate
long-term use of such type of catalysts. Other cat- precursors in bulk state (unsupported samples), as a
alytic formulations have been proposed to replace the model for the precursor–precursor interactions, which
silver catalysts [1]; most of them are based on man- may occur inside the support pores of supported cat-
ganese oxides supported on alumina (MnOx /Al2 O3 ), alysts, (ii) to follow the effect of washing with water
silica (MnOx /SiO2 ) or cordierite monolith honeycomb on the active phases, and (iii) to compare the cat-
(MnOx /2MgO·2Al2 O3 ·5SiO2 ). alytic activity of the different manganese oxide sam-
The impregnation procedure is important for a good ples, thus, produced towards H2 O2 decomposition in
anchorage of the active phase onto the support, and the solution.
most efficient catalyst precursor compounds are the
permanganates of potassium, sodium, calcium or am-
monium [2,3], or even permanganic acid HMnO4 [4]. 2. Experimental
Formation of the manganese oxides can be effected
either by thermal decomposition of the precursor in 2.1. Preparation of test catalysts
the solid state, or chemical reduction of the MnO4 −
anions in aqueous or non-aqueous solutions. Decomposition of potassium permanganate (KM-
The preparation course of a supported manganese nO4 , analytical grade, Labosi, France; 2 g in a flat
oxide catalyst often involves three main processes: covered porcelain crucible) or sodium permanganate
(i) wet impregnation of the support with an aque- (NaMnO4 ·H2 O, 98% pure, Strem Chemicals, USA)
ous solution containing manganese precursor species was performed in static air at 400 ◦ C for 1 or 9 h at
at a given concentration; (ii) drying at 80–120 ◦ C; a heating rate of 23 ◦ C min−1 . After calcination and
(iii) calcination at 400–700 ◦ C, in oxidative (air), in- cooling to ambient temperature, the solid residues
ert (N2 , Ar) or reductive gas atmosphere (H2 , CO). were washed with 250 ml distilled water, dried at
Process (ii) can be described as a combination of 110 ◦ C for 5 h, and calcined further at 600 ◦ C for 5 h.
the following two competitive solid–solid interac- For simplicity, the catalysts thus obtained are denoted
tions: (a) a precursor–support surface interaction, below by the chemical symbols of the alkali metal
leading to strong anchorage of the precursor species and manganese atoms, followed by the successive
onto the support; and (b) a precursor–precursor bulk designations: an Arabic numeral indicating the time
interaction within the support pores, leading to crys- duration (in hours) of the calcinations at 400 ◦ C, w
tallization of the precursor followed by its thermal if washed with water, and 600 if calcined further at
decomposition throughout the calcination process 600 ◦ C for 5 h. Thus, KMn9h indicates the 400 ◦ C cal-
(iii). Stronger precursor–precursor interactions than cination product of KMnO4 for 9 h, whereas KMn9hw
precursor–support interactions lead to weakly bound signifies the same product following washing with
precursor species, which could be dissolved in the water and drying at 110 ◦ C for 5 h.
H2 O2 solution and washed away during the first Reduction of the permanganate precursors was
pulses. This may obviously be promoted by the strong performed in an autoclave implementing the Guyard
solvation capacity of the hydrogen peroxide, which is (redox) reaction [7] with manganous ions in aque-
close to that of water. ous solution (at pH 1 or 7) containing foreign ion
Another way to prevent the partial dissolution of the additives, under controlled hydrothermal conditions
calcined precursor is to perform a direct redox reac- (100 ◦ C, 120 kPa, 16 h). The amount of the reac-
tion between permanganate and a mild reductant under tants and details of the reaction variables have been
controlled hydrothermal conditions, in the presence of reported elsewhere [5]. Following cooling to ambient
appropriate foreign ion additives. This procedure has temperature, the resulting precipitates were filtered,
been studied in the bulk state with manganous ions as washed with distilled water, dried at 120 ◦ C for
a reductant and led to the formation of a variety of 16 h, and ground to pass through a standard sieve of
tunnel-structured MnO2 [5,6]. 250 mesh. Designations of the different test catalysts
Therefore, the main objectives of the present work thus obtained are given corresponding to a preparation
were: (i) to study the thermal decomposition or briefing in Table 1.
C. Kappenstein et al. / Applied Catalysis A: General 234 (2002) 145–153 147
Table 1
Designation, preparation conditions and characteristics of the different test samples
Samples Preparation XRD phasea SBET (m2 g−1 )
Thermal decomposition
KMn1h Calcination of KMnO4 , 400 ◦ C, 1 h K2 MnO4 + K2 Mn4 O8 (?) 7.6
KMn9h Calcination of KMnO4 , 400 ◦ C, 9 h K2 MnO4 + K2 Mn4 O8 (?) 6.5
KMn1hw KMn1h washed, water, dried 110 ◦ C K2 Mn4 O8 (?) 24
KMn9hw KMn9h washed, water, dried 110 ◦ C K2 Mn4 O8 (?) 22
KMn9hw600 KMn9hw calcined, 600 ◦ C, 5 h K2−x Mn8 O16 12
NaMn9h NaMnO4 ·H2 O calcined, 400 ◦ C, 9 h Na0.7 MnO2 2.8
NaMn9hw600 NaMn9h washed, calcined 600 ◦ C, 5 h Na0.7 MnO2 + Mn7 O13 ·5H2 O 2.1
Hydrothermal reductionb
S1 MnSO4 + excess KMnO4 , pH 1 ␣-MnO2 (fibrils) 71
S2 Excess MnSO4 + KMnO4 , pH 1 ␣-MnO2 (fibrils) 85
S3 MnSO4 + NaMnO4 , stoichiometric, pH 1 ␥-MnO2 + -MnO2 (minor) 127
S4 MnSO4 + KMnO4 , stoichiometric, pH 7 Amorphous-MnO2 165
S5 Excess MnSO4 + NaMnO4 + Ca(NO3 )2 , pH 1 t-MnO2 62
2−x Mn8 O16 (␣-MnO2 ) 44–1386; Na0.7 MnO2 27–751; Mn7 O13 ·5H2 O 23–1239;
a PDF number: K MnO 12–264; K Mn O 16–205; K
2 4 2 4 8
␥-MnO2 17–510; -MnO2 24–735; t-MnO2 (todorokite) 38–475.
b Precise amounts of the reactants and additives can be found in [5].
The test catalysts were characterized by X-ray pow- Two reactors were used to determine the activity
der diffractometry (XRD) and nitrogen sorptometry of the test catalysts towards the decomposition of
for BET surface area determination. The XRD was H2 O2 solutions. The first reactor was designed to
carried out at ambient temperature, using a D5000 work at constant pressure and temperature and has
Bruker diffractometer equipped with a source of back- been already described in a previous paper [9]. It can
monochromatized Cu K␣ radiation (λ = 0.15406 nm). be used to measure the volume of the evolved oxygen
The diffractometer was operated at 40 kV and 30 mA, up to 60 ml. Diluted H2 O2 (10 ml, 1.71 wt.%) was
and the data were acquired step-wise in the 2θ range placed in the reactor at 20 ◦ C and, then, the catalyst
5–80◦ with a step size of 0.02 or 0.04◦ , a time step (10–200 mg) was added to initiate the decomposition
of 1–10 s depending of the sample, and a divergence reaction. The second reactor is a constant volume
slit of 1◦ , using an online microcomputer. An auto- batch reactor (170 ml) with an operating pressure
matic PDF library search and match was conducted, between vacuum and 2 bar, the design of which has
using the standard SEARCH and DIFFRAC soft- been described in earlier communications [10,11]. A
ware (Bruker), for crystalline phase identification 200 mg portion of the test catalyst was placed inside
purposes. the reactor at ambient temperature, and the H2 O2
Nitrogen sorptometry was carried out at liquid nitro- solution (50 wt.%, Prolabo, France; 100 l) was in-
gen temperature (−195 ◦ C), using an automatic ASAP jected using a microsyringe.
2010 Micromeritics sorptometer with outgassing plat-
form and online data acquisition and handling system 3. Results and discussion
operating BET [8] analytical software for the adsorp-
tion data. The nitrogen gas was a 99.999% pure prod- 3.1. Thermal decomposition of KMnO4
uct of KOAC (Kuwait). A 300 mg portion of the test
catalyst was outgassed at 100 ◦ C and 10−5 Torr for The thermal decomposition of KMnO4 was fol-
12 h, prior to exposure to the nitrogen atmosphere. The lowed by XRD, the diffractograms obtained are dis-
reproducibility of the measurements was better than played in Fig. 1. The calcination at 400 ◦ C for 1 h is
98%. shown to result in the formation of a solid residue
148 C. Kappenstein et al. / Applied Catalysis A: General 234 (2002) 145–153
Table 2
Thermal decomposition of KMnO4 . Mass loss of the different steps observed, major XRD phase, crystallite size and oxidation number
of the Mn atoms [13]
Samples Mass lossa (%) Major crystalline phase Crystallite sizeb (nm) Mn oxidation number
Observedc Calculatedd
Table 3
Suggested reaction pathways for the thermal decomposition of the permanganate compounds, and derived mass losses
Thermal decomposition reaction Mass loss % (calculated)
loss of a part of the active phase (i.e. the water soluble the PDF database has not contained the corresponding
K2 MnO4 ). file.
The mass loss conceded by the different decom- Nevertheless, two crystalline phases in the cal-
position products of KMnO4 treatments, as well as cination products of NaMnO4 are in fair agree-
their crystallite size, and calculated and observed man- ment with standard diffraction data of Na0.7 MnO2.05
ganese oxidation numbers, are given in Table 2. It (27–751) and Mn7 O13 ·5H2 O (23–1239). The ef-
is obvious that the mean oxidation number of Mn in fected mass loss (24%) throughout the calcinations
the 400 ◦ C calcination products is about 5.0, which at 400 ◦ C is in fair agreement with the formation of
is compatible with a mixture of manganate (6.0) and a mixture consisting of Na2 MnO4 , and NaMn2 O4
MnO2 (4.0) or K2 Mn4 O8 (3.5). However, mass losses (Table 3; calculated loss = 24.6%). Following wash-
calculated on the basis of decomposition reactions ing, about one-fourth of the manganese is retrieved
suggested in Table 3 do not agree with the observed as MnO4 − (aq) ions. The calcination products are
ones (Table 2). A reasonable compromise would be shown (Table 1) to assume poor surface areas;
the formation at 400 ◦ C of a non-stoichiometric oxide
(MnO1.84 ). The calcination at 600 ◦ C led to a decrease
in the surface area from 22 to 12 m2 g−1 (Table 1) in
relation to the formation of crystalline cryptomelane.
Meanwhile, a slight mass loss of 3.5% and a signifi-
cant decrease in the oxidation number from 5.0 to 4.3
are shown (Table 2) to ensue.
Table 4
Rate constant values for the catalytic decomposition of H2 O2 . Zero-order kinetics for NaMnO4 based catalysts; first-order kinetics for
KMnO4 based catalysts
Sample Mass (mg) k0 (mol s−1 ) k0 (mol s−1 (g catalyst)−1 )
KMn9h 10 0.09 9
KMn9h 15 0.16 11
C. Kappenstein et al. / Applied Catalysis A: General 234 (2002) 145–153 151
Table 5
First-order rate constant values for H2 O2 decomposition on hydrothermal reduction products
Sample Mn Mass k1 k1 SBET k1 k1
(wt.%) (mg) (ml s−1 ) (ml s−1 g−1 ) (m2 g−1 ) (ml s−1 m−2 ) (ml s−1 (g Mn)−1 )
S1 47.3 13 0.13 10 71 0.14 21
S2 52.3 13 0.26 20 85 0.23 38
S3 57.6 8 0.22 28 127 0.22 49
S4 49.8 9 0.18 20 165 0.12 40
S5 46.5 12 0.21 18 62 0.29 39
KMn9hw600 51.4 15 0.16 11 12 0.90 21
MnOx /Al2 O3 1.6 177 0.17 1.0 – – 60
152 C. Kappenstein et al. / Applied Catalysis A: General 234 (2002) 145–153
Table 6
Decomposition of 50% H2 O2 . Successive pulses of 100 l H2 O2 on catalyst samples S1 and S3 (200 mg). Pressure increase and pressure
slope, initial and maximum temperature of the catalyst, temperature slope, maximum temperature of the gas phase
Sample Injection P increase P slope Tinitial Tmax T slope Tmax gas
number (mbar) (mbar s−1 ) (◦ C) catalyst (◦ C) (◦ C s−1 ) (◦ C)
S1 1 130 225 20 84 53 37
2 111 233 20 75 45 38
3 108 250 20 71 45 30
S3 1 133 255 20 95 47 52
2 109 271 20 98 80 59
3 105 317 20 97 85 35
temperature, are graphically presented for the sample oxide dose. For the first pulse, the pressure step is
S3 in Fig. 5. The pressure peaks are shown to be very highest, due to the liquid–vapour water equilibrium
sharp, indicating strong activity. A zoom at the results (23 mbar at 20 ◦ C). The pressure slope, the tempera-
obtained throughout the second injection is presented ture maxima and the temperature slopes are definitely
in Fig. 6; the three records display parallel variations higher for sample S3 than S1, thus indicating a higher
versus time, and the slope of each curve can be deter- activity for the former catalyst. The activity of the
mined. The results are reported in Table 6. The pres- S3 catalyst is, hence, comparable to the activity of
sure increase sequence after each injection is shown supported MnOx /Al2 O3 catalyst, but slightly lower
to be the same for both test catalysts, and corresponds than the activity of powdered Ag/Al2 O3 catalyst
to a complete decomposition of the hydrogen per- [9].
4. Conclusions