Applied Catalysis B: Environmental 61 (2005) 12–20

www.elsevier.com/locate/apcatb

Plasma-assisted catalysis for volatile organic compounds abatement

Monica Magureanu a,*, Nicolae B. Mandache a, Pierre Eloy b,
Eric M. Gaigneaux b, Vasile I. Parvulescu c,*
a
National Institute for Lasers, Plasma and Radiation Physics, Plasma Physics and Nuclear Fusion Department,
Str. Atomistilor 409, C.P. MG-36, 76900 Bucharest, Romania
b
Catholic University of Louvain, Unité de Catalyse et Chimie des Matériaux Divisés, Croix du Sud 2/17, B-1348 Louvain-la Neuve, Belgium
c
University of Bucharest, Department of Chemical Technology and Catalysis, B-dul Regina Elisabeta 4-12, 030016 Bucharest, Romania
Received 11 February 2005; received in revised form 15 April 2005; accepted 19 April 2005
Available online 23 May 2005

Abstract

A dielectric barrier discharge (DBD) combined with Mn-based phosphate catalysts placed downstream of the plasma reactor was
investigated experimentally for total oxidation of toluene in air. The discharge was initiated by high voltage pulses of 18 kVamplitude and 12–
13 ns rise time. The pulse frequency increased from 14 to 80 Hz, for applied voltages in the range 18–28 kV. Discharge currents up to 100 A
and approximately 50 ns duration were obtained. No other hydrocarbons except toluene were detected in the effluent gas. The yield of carbon
dioxide formed in the discharge was up to 24%. As catalysts, MnPO4, Mn-APO-5 and Mn-SAPO-11 were tested, for temperatures up to
400 8C. Under purely catalytic conditions, the best behavior for toluene total oxidation was found for Mn-SAPO-11, with a CO2 yield up to
33%, at 400 8C. The combined application of plasma and catalysis showed a remarkable synergetic effect, even at low temperature, up to
100 8C, where the catalysts alone are not active. In this range, the CO2 yield increased up to 41%, for the Mn-SAPO catalyst. At 400 8C the
highest CO2 yield was obtained for MnPO4, reaching 68%. The synergetic effect observed for the plasma–catalyst combination is attributed to
ozone radicals formed in the discharge, which decompose on the catalyst surface, greatly contributing to toluene total oxidation.
# 2005 Elsevier B.V. All rights reserved.

Keywords: Volatile organic compounds; Plasma; Dielectric barrier discharge; Heterogeneous catalysis

1. Introduction adhesives, represent also an important source of VOC

Volatile organic compounds (VOC) are aliphatic and
aromatic hydrocarbons, which may contain also hetero-
atoms, like oxygen, nitrogen, sulfur, halogens. They are
characterized by a very high vapor pressure, exceeding
0.5 kPa at 25 8C.
The main source of VOC emission in the atmosphere is
transportation, by emissions from motor vehicles and
aircraft, evaporative losses from automobile service stations,
and also by evaporation from gasoline marketing activities.
Industrial processes involving the use of solvents, including
various chemical processes, the use of paints, glues,
* Corresponding authors. Tel.: +40 213320588; fax: +40 213320588.
E-mail addresses: monimag@infim.ro (M. Magureanu),
v_parvulescu@chem.unibuc.ro (V.I. Parvulescu).
emission. Losses in the production processes can contribute
also to VOC pollution, however, to a smaller extent.
These compounds are harmful to the environment and to
human health. They are precursors of photochemical smog,
leading in the presence of UV light, to the formation of
ozone and other oxidizing compounds in the low atmo-
sphere, and contribute also to the depletion of stratospheric
ozone. Regarding the medical risks, it is known that many
VOC are toxic, and some were proved to be carcinogenic.
Therefore, the abatement of VOC, with high efficiency
and at low cost, is a very important issue. Conventional
techniques for the removal of these pollutants are thermal
and catalytic oxidation and carbon adsorption. Thermal
oxidation destroys VOC from contaminated air streams at
high operating temperatures, in the range 700–900 8C. The
addition of a catalyst accelerates the rate of oxidation and

0926-3373/$ – see front matter # 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcatb.2005.04.007
 M. Magureanu et al. / Applied Catalysis B: Environmental 61 (2005) 12–20
enables the reaction to occur at lower temperatures, 300–
600 8C. Supported noble metals: Pt, Pd, or metal oxides (Ni,
Cu, Mn) are currently reported for such applications [1–3].
However, catalyst poisoning by sulfur, chlorinated com-
pounds or heavy particle loadings, which may be present in
the gas stream limits the performances of these catalysts due
to catalyst deactivation.
In the carbon adsorption technique, the VOC are removed
from the air stream by physical adsorption onto activated
carbon grains. However, this method is not recommendable
to remove high contaminant concentrations and there are
several other factors that affect the adsorption, including
temperature, type of carbon and of contaminant, and
residence time. In addition, the spent carbon must be
disposed of and the adsorbed contaminants must be
destroyed. This often involves thermal treatment, which
increases the cost of the air cleaning process. Therefore, a
non-thermal approach, involving lower costs, would be
desirable.
As an alternative to conventional techniques for VOC
abatement, non-thermal (non-equilibrium) plasma, gener-
ated in atmospheric pressure discharges, had been investi-
gated [4–8]. The advantage of these plasmas consists in the
ability to generate high-energy electrons, while keeping the
background gas close to room temperature [8,9]. Typical
electron temperatures are in the range 2–10 eV (1 eV –
11 000 K) and gas temperatures between room temperature
and 200 8C [9–12]. The energetic electrons excite, dissociate
and ionize the gas molecules producing chemically active
species. Thus, a highly reactive environment is created
without spending energy on gas heating as in thermal
processes. However, plasma activation tends to be less
selective than catalytic processes, and undesirable by-
products may be formed. Especially the formation of toxic
carbon monoxide in discharges in mixtures of air and
hydrocarbons was often reported [1,13].
It is hoped that by combining plasma and heterogeneous
catalysis, the high efficiency of non-thermal activation and
the high selectivity of catalysts will result in a synergetic
effect. Promising results in this direction were already
reported [2,3,13–17], however, at the present state of
development, the large energy required hinder the broad
application of non-thermal plasma technology for cleaning
of VOC-contaminated effluent streams. Therefore, the
Fig. 1. (a) Experimental set-up; (b) discharge reactor and electrical circuit.
13
investigation of such a plasma–catalyst synergy could be
the key to improving the efficiency and lowering the costs of
VOC removal.
In the present investigation, a dielectric barrier discharge
(DBD) at atmospheric pressure, combined with hetero-
geneous catalysis was used for the oxidation of small
amounts of toluene in air. The electrical characteristics of the
discharge and the ability of the plasma to decompose toluene
were studied. Several catalysts based on Mn were tested for
temperatures up to 400 8C, in the absence and in the
presence of the discharge.
2. Experimental
The experimental set-up is illustrated in Fig. 1a. Toluene
was introduced via a bubbler and was afterwards diluted by a
stream of ambient air. The flow rate through the bubbler and
the flow of ambient air were adjusted by mass flow
controllers (MFC-1, MFC-2). The input concentration of
toluene could be varied by controlling the flow rate of air
passing through the bubbler and the flow rate of ambient air.
In most experiments the flow through the bubbler was set to
5 ml/min and the flow of ambient air to 45 ml/min. Under
these conditions, the toluene concentration at the inlet of the
discharge reactor was 560 ppm. In other experiments, both
flow rates were varied, keeping their ratio constant,
therefore, the total flow was varied at constant toluene
concentration. A dielectric barrier discharge reactor was
used at atmospheric pressure and ambient temperature. The
catalysts were placed in a cylindrical reactor, downstream of
the plasma reactor, in a temperature-controlled oven. The
oven temperature was varied between room temperature and
400 8C. Toluene conversion was determined by gas
chromatography (GC) using a gas chromatograph (Hew-
lett-Packard 5890 series II) with flame ionization detector
(FID) and a CP-Sil2 CB column (50 m length, 0.32 mm
diameter). The presence of hydrocarbons in the effluent gas,
as reaction products from toluene decomposition was also
one-line determined by GC. A gas analyzer (Fisher
Rosemount, type MLT 4T IR-IR-UV-IR) was coupled on-
line to monitor continuously the concentration of carbon
dioxide resulting from the complete oxidation of toluene, as
well as nitrogen oxides (NO and NO2) formed in the plasma.
14 M. Magureanu et al. / Applied Catalysis B: Environmental 61 (2005) 12–20
The concentration of ozone generated in the plasma was
measured by the iodometric method [18].
The discharge reactor and the electrical circuit are shown
in Fig. 1b. The dielectric barrier discharge was generated in a
cylindrical reactor made of glass, with the outer diameter of
14 and 1.5 mm wall thickness. The inner electrode was a
metallic rod of 8 mm diameter. The outer electrode was
made of copper stripes wrapped around the glass tube. The
discharge gap was, therefore, about 1.5 mm, and the length
was 12 cm, resulting in a volume for the plasma of 5.3 cm3.
The discharge was operated in pulsed mode. Under these
conditions reactive species are formed at a high rate during
the pulses, maintaining a low average power input. The
voltage pulses were produced by charging a capacitor
(C = 1 nF) at high voltage, which is subsequently discharged
by a self-triggered spark-gap switch (SG). Due to technical
reasons, the high voltage of negative polarity was applied on
the outer electrode and the inner electrode was grounded in
the plasma–catalytic tests. Similar results were obtained
with a positive high voltage applied to the inner electrode
and the outer electrode grounded. The discharge voltage was
measured by a high voltage probe (Tektronix P6015A) with
a resistance RHVprobe = 100 MV, connected in parallel with
the discharge. The discharge current was measured from the
voltage fall on a 4 V resistor, connected in series with the
inner electrode. The current and voltage waveforms were
monitored by an oscilloscope (Tektronix TDS320).
Several Mn-based phosphate catalysts were tested:
MnPO4, Mn-APO-5 and Mn-SAPO-11. MnAPO-5 and
Mn-SAPO-11 were prepared according to literature proce-
dures [19–21]. MnPO4 has been prepared by mixing
0.06 moles MnO2 with H3PO4 (molar ratio 1:1) in 50 ml
H2O for 2 h at room temperature under vigorous mixing.
After that, 5 ml dimethylaminoethanol were added, and the
mixture was stirred for another 60 h, and than it was
thermally treated at 170 8C for 48 h in a teflon-lined stainless
steel autoclave. The resulting precipitate was washed with
demineralized water and calcined at 400 8C.
The above catalysts were characterized by adsorption–
desorption isotherms of N2 at
196 8C, XRD, O2-TPO,
XPS. Adsorption and desorption curves of N2 at
196 8C
were obtained with a Micromeritics ASAP 2000 apparatus
after degassing the samples at 150 8C for 12 h under
vacuum.
The XRD patterns were recorded by a SIEMENS D-5000
diffractometer at 40 kV, 50 mA, and equipped with a
variable-slit diffracted-beam monochromator and scintilla-
tion counter. The diffractograms were recorded in the range
0–808 at a rate of 28 min
1 using Cu Ka radiation
(l = 1.54183 Å).
The TPD measurements with O2 were carried out in the
same fixed bed quartz microreactor as that used for the
catalytic testing. Four hundred milligrams of sample were
heated from room temperature to 500 8C at a rate of
1 8C min
1 in a diluted flow of O2 (40% O2 in He at
27 ml min
1) and kept at 500 8C for 8 h. After cooling to
room temperature under O2 flow, the sample was purged
with He (15 ml min
1) for 3 h. The temperature was then
increased at a rate of 5 8C min
1 up to 500 8C under the
same He flow. The O2 desorbed was analyzed by a Balzers
Quadrupole QMG 311 mass spectrometer.
The XPS spectra were recorded using a SSI X probe
FISONS spectrometer (SSX-100/206) with monochromated
Al Ka radiation. The spectrometer energy scale was
calibrated using the Au 4f7/2 peak (binding energy
84.0 eV). The samples were moderately heated by a quartz
lamp in the introduction chamber of the spectrometer to
promote degassing, thus, improving the vacuum in the
analysis chamber. For the calculation of the binding
energies, the C1s peak of the C–(C, H) component at
284.8 eV was used as an internal standard. The surface
composition of the investigated samples was determined
using the bands assigned to Mn2p3, P2p, Al2p, O1s, N1s, and
Si2p, respectively.
3. Results and discussion
3.1. Discharge characterization
Typical voltage and current waveforms are shown in
Fig. 2a and b, respectively, for applied voltages in the range
18–28 kV.
The rise time of the voltage (from 10 to 90%) after the SG
breakdown is 12–13 ns (Fig. 2a), resulting in a voltage rise
rate of approximately 1.5 kV/ns. The voltage decay is slow,
being determined by the time needed to discharge the
capacitance of the electrode system through the resistance of
the high voltage probe. Consequently, the voltage pulses are
long, of the order of tens of ms. The amplitude of the pulses
is determined by the distance between the electrodes of the
spark-gap switch (gap length of the switch). In the present
experiments a gap length of 7 mm was used. Under these
conditions, a potential difference of about 18 kV between
the electrodes of the switch is sufficient for spark breakdown
Fig. 2. (a) Voltage waveforms; (b) current waveforms, for applied voltages
of 18–28 kV.
 M. Magureanu et al. / Applied Catalysis B: Environmental 61 (2005) 12–20 15

in the switch. In this way, voltage pulses of 18 kV amplitude
were generated, regardless of the amplitude of the applied
voltage. When the applied voltage exceeds 18 kV, the
voltage does not decrease to zero between consecutive
pulses. The voltage waveforms consist of a ‘‘continuous’’
part of several kV, over which the pulses of 18 kV amplitude
are superimposed. When increasing the applied voltage, the
amplitude of the voltage pulses remains the same, only the
level of the continuous voltage increases, so the pulses are
shifted towards higher voltages.
The current pulses (Fig. 2b) consist of two peaks. The first
narrow peak is the displacement (or capacitive) current, and
represents the current charging the capacitance of the
electrode arrangement [22]. The amplitude of this current
peak is proportional to the time derivative of the voltage, and
its duration is equal to the voltage rise time. The capacitive
current appears regardless of the presence of the plasma and
does not contribute to the discharge ignition. The real
discharge current is the second current peak. This was
confirmed by the temporal correspondence with the visible
radiation emitted by the plasma, monitored by a photo-
multiplier [23]. Discharge currents up to 100 A were
obtained. A slight decrease in the amplitude of the current
pulses was observed with increasing the applied voltage.
This behavior is most likely the result of charges
accumulated on the dielectric due to the continuous voltage
mentioned earlier.
Fig. 3 illustrates the dependence on applied voltage of the
pulse repetition rate (a), the average discharge current (b),
the average power (c), and the energy per pulse (d).
The repetition rate of the pulses (n) is determined by the
applied voltage. Since the voltage decreases exponentially
with time, the pulse frequency is higher for higher applied
voltage. In the present experiments a linear dependence of
the frequency on applied voltage was found (Fig. 3a). A
maximum repetition rate of 80 Hz was obtained at 28 kV.
The average current was calculated from the relation:
Z
Ī ¼ n IðtÞ dt (1)
The increase in pulse frequency with applied voltage is more
pronounced than the slight decrease of the discharge current,
therefore, the average current increases towards higher
voltages (Fig. 3b). A linear dependence of the average
current on voltage was observed and values up to 200 mA
were obtained.
Due to the linear increase of the average current with
applied voltage, the average power shows a dependence as
the square of the voltage (Fig. 3c). In these experiments,
average powers in the range 0.5–5.5 W were obtained.
The energy per pulse was calculated by integrating the
product of current and voltage, for the second current peak,
the real discharge current:
Z
E ¼ IðtÞUðtÞ dt (2)
The energy per pulse increases also with increasing applied
voltage. The maximum value obtained was 68 mJ.
3.2. Catalyst characterization
3.2.1. Texture characterization
Mn-APO-5 and Mn-SAPO-11 had typical surface areas
for such kind of materials, respectively, 164 and 280 m2 g
1.
Manganese phosphate, prepared following the described
procedure, had a surface area of 89 m2 g
1.
3.2.2. XPS
Table 1 compiles the binding energies of Mn2p3/2, P2p3,
O1s, Al2p, and Si2p levels. For MnPO4 the binding energy of
the Mn2p3/2 level points to an oxidation state of less than 4+,
likely Mn3+, with Mn involved either as isolate species, or in
a MnO or Mn3O4 reduced environment [24,25]. Since the
synthesis of this phosphate used MnO2 as precursor, this
value indicates a reduction of manganese in the presence of
dimethyl-aminoethanol. In comparison with the binding
energies of Mn2p3/2 level for MnPO4 sample, the values
measured for aluminophosphate and silicoaluminopho-
sphate might correspond to a more oxidized state close to
Mn4+ [26]. But for these materials considerable evidence is
given in the literature that Mn in (silico-aluminophosphate is
in a Mn2+ state [27]. Some other authors also reported such
high values for the binding energy of the Mn2p3/2 level in
MnO [28,29]. Therefore, the values given in Table 1 could

Table 1
XPS binding energies of Mn 2p3/2, P2p3, O1s, Al2p, and Si2p levels
Catalyst Binding energy (eV)
Mn2p3/2 Mn2p3/2 P2p3 O1s O1s Al2p Si2p
MnPO4 641.2 644.7 133.0 530.4 531.1 – –
Fig. 3. (a) Pulse frequency; (b) average current; (c) average power; (d) Mn-APO-5 642.7 646.6 133.1 532.3 74.6
energy per pulse, as a function of applied voltage. Mn-SAPO-11 642.1 645.2 133.2 532.2 74.4 103.3
16 M. Magureanu et al. / Applied Catalysis B: Environmental 61 (2005) 12–20
Fig. 4. XRD pattern of MnPO4.
correspond indeed to a Mn2+ state. An additional support in
this sense may result from the values of the binding energy
of the Mn2p1/2 level. Data reported in literature [26,29] for
Mn3+ and Mn4+ species indicate much higher values than
those given in the Table 1. In a relative accordance with these
measurements, the band of the O1s level was symmetric.
However, it is far from sure that this is indicating only one
type of oxygen. For all the investigated phosphate catalysts
the binding energies of the P2p3 level was very similar, the
values being typical for inorganic phosphates [30].
3.2.3. XRD
XRD patterns recorded for Mn-APO-5 and Mn-SAPO-11
corresponded to those published in literature for such
compounds (Fig. 4) [31,32]. The XRD pattern of MnPO4
indicates an essentially amorphous solid, although it
contains very weak reflection lines corresponding to
manganese phosphate [33], and also some un-identified
peaks. These lines evidence that the crystalline fraction is
not a pure MnPO4 phase. As compared with the standard
patterns from the JCPDS-International Centre for Diffrac-
tion Data [33], it appears that the unidentified peaks could
correspond to reduced Mn oxides like Mn2O3, Mn5O8 or
Mn3O4, although it is not possible to fully ascertain that
these phases (or a combination of some of them) are indeed
present in the sample.
3.2.4. O2-TPD
O2-TPD profiles of the investigated catalysts in the
temperature range 100–500 8C evidenced very weak
oxygen-desorption capacity materials. The quantification
of the O2 released corresponded to less than 0.05 O atom/
Fig. 5. Temporal evolution of the CO2 concentration resulting from toluene
total oxidation in the discharge, for gas flow rates in the range 50–150 ml/
min.
Mns for all these catalysts, that confirms indeed a very weak
oxygen desorption capacity.
3.3. Plasma–catalytic tests
In order to separate the effect of the discharge from the
catalytic effect in toluene oxidation, experiments were
carried out: (a) under plasma conditions in the absence of
catalysts, at room temperature; (b) under purely catalytic
conditions, with the catalysts heated up to 400 8C, in the
absence of the plasma; and (c) for the plasma–catalyst
combination.
For all the experiments (plasma only and plasma
combined with catalysis) reported in this section, the
voltage applied to the discharge was 22 kV. This corresponds
to discharge pulses of 75 A peak current, with duration of
approximately 50 ns, and repetition rate of 40 Hz. Under
these conditions, the energy per pulse was 57 mJ, and the
resulting average power was 2.25 W. The input toluene
concentration was kept constant at 560 ppm in these
experiments.
Without catalyst, i.e. working with the plasma only, at
room temperature, the influence of the gas flow rate on the
concentration of carbon dioxide resulting from the total
oxidation of toluene in the discharge is shown in Fig. 5.
Toluene conversion, measured by GC, was in the range 45–
55%, roughly independent on flow rate in the range
investigated. This is most likely due to the filamentary
Fig. 6. CO2 yield obtained in the discharge, as a function of input energy.
 M. Magureanu et al. / Applied Catalysis B: Environmental 61 (2005) 12–20 17

character of the discharge, since a part of the gas can by-pass

the micro-discharges, and therefore, exit un-reacted. The
CO2 concentration stabilized after several minutes, which
represent the response time of the system.
The specific energy input Ein is defined as the ratio
between the average power dissipated in the discharge and
the flow rate [34]:


J power ðWÞ
Ein ¼  6  104 (3)
l flowðml=minÞ

For the flow rates used in these experiments (50–150 ml/
min) the specific energy input varies in the range 2.7–0.9 kJ/
l. The CO2 concentration obtained shows a linear increase
with the energy input, reaching 950 ppm at the highest value
used.
A parameter which reflects the toluene total oxidation is
the yield of CO2 (YCO2 ), defined as the ratio between the
concentration of CO2 obtained in the experiment and the
CO2 concentration for total oxidation of the entire amount of
toluene introduced:
½CO2 out
YCO2 ð%Þ ¼  100 (4)
7  ½C7 H8 in
where [CO2out] is the output CO2 concentration, and
[C7H8in] is the input toluene concentration.
No other hydrocarbons except toluene were detected in
the effluent gas by gas chromatography. Nitrogen oxides
(NO and NO2) were formed in very small amounts in the
plasma, below 7 ppm. Ozone was detected after the
discharge reactor in concentrations of 7–8000 ppm, when
the plasma was operated in air. Carbonaceous deposits were
observed on the walls of the plasma reactor and on the inner
electrode. These by-products could not be analyzed in the
present experiments, however their yield was estimated by
weighing the discharge tube before and after the reaction and
does not exceed 5%.
Carbon monoxide and carbon dioxide were the only
gaseous reaction products resulting from toluene oxidation
in the plasma. Therefore, CO accounts for the rest of the
carbon needed to fulfill the carbon balance, since the solid
by-products were accounted for by weighing the discharge
tube. It is expected that the addition of catalysts would lead
to a shift in product distribution towards total oxidation
[1,2,7].
Fig. 6 shows the CO2 yield in the plasma, in the absence
of catalysts, as a function of input energy. The CO2 yield
increases linearly with input energy. A maximum value of
24% was obtained for the highest input energy used.
The following experiments were carried out in the
plasma–catalytic system, at 50 ml/min flow rate. The
toluene conversion was slightly enhanced by the addition
of the catalysts downstream the plasma zone, its values
being in the range 50–70%.
Figs. 7–9 illustrate comparatively the CO2 yield resulting
from toluene total oxidation in the discharge at room
Fig. 7. CO2 yield obtained in the discharge alone at room temperature, with
the catalyst alone, for the plasma–catalyst combination, and the calculated
sum of CO2 yields with plasma alone and with catalyst alone, as a function
of catalyst temperature for a MnPO4 catalyst and the toluene conversion for
the plasma–catalyst combination.
temperature, under purely catalytic conditions in the range
293–673 K, and for the plasma–catalyst combination in the
same range, as a function of the catalyst temperature, for the
three catalysts investigated. The plasma reactor was kept at
room temperature, only the catalysts, placed downstream,
were heated. The sum of CO2 yields obtained with the
plasma alone and under purely catalytic conditions is also
shown.
The MnPO4 catalyst became active around 200 8C. In the
absence of the discharge, the resulting CO2 concentration
increased as the catalyst temperature was increased.
However, relatively low values (maximum 680 ppm CO2
at 400 8C) were obtained in the temperature range
investigated, corresponding to a CO2 yield up to 17.3%.
For the plasma–catalyst combination, the resulting CO2
yield was enhanced as compared to that obtained with the
discharge alone, or with the catalyst alone, for the entire
temperature range used. After a strong initial increase with
catalyst temperature, the CO2 yield remained almost
constant when heating the catalyst from 100 to 300 8C,
and increased again considerably for higher temperatures.
At 400 8C the CO2 yield under these conditions was 67.6%.
Fig. 8. CO2 yield obtained in the discharge alone at room temperature, with
the catalyst alone, for the plasma–catalyst combination, and the calculated
sum of CO2 yields with plasma alone and with catalyst alone, as a function
of catalyst temperature, for a Mn-APO catalyst and the toluene conversion
for the plasma–catalyst combination.
18 M. Magureanu et al. / Applied Catalysis B: Environmental 61 (2005) 12–20
Fig. 9. CO2 yield obtained in the discharge alone at room temperature, with
the catalyst alone, for the plasma–catalyst combination, and the calculated
sum of CO2 yields with plasma alone and with catalyst alone, as a function
of catalyst temperature, for a Mn-SAPO catalyst and the toluene conversion
for the plasma–catalyst combination.
A similar behavior was observed for the Mn-APO
catalyst. In this case a maximum CO2 concentration of
530 ppm was obtained under purely catalytic conditions, at
400 8C, corresponding to a CO2 yield of 13.5%. In the
plasma–catalytic experiments, the CO2 yield increased in a
similar manner as for the MnPO4 catalyst, with a maximum
of 55.4% at 400 8C catalyst temperature.
When using the Mn-SAPO catalyst in the absence of the
discharge, 1310 ppm CO2 were obtained from toluene total
oxidation at 400 8C, resulting in a CO2 yield of 33.4%. The
plasma–catalyst combination led to an enhanced CO2 yield
especially at the lower catalyst temperatures used. The
maximum CO2 yield obtained under plasma–catalytic
conditions was 63.5% at 400 8C.
The combined application of plasma and catalysis shows
a remarkable synergetic effect if compared to the sum of the
individual effects. A synergy factor f can be defined as the
ratio between the CO2 yield obtained in the plasma–catalytic
system and the sum of yields obtained under purely catalytic
and purely plasma conditions:
ðYCO2 Þplasmaþcatalyst
f ¼ (5)
ðYCO2 Þplasma þ ðYCO2 Þcatalyst
Fig. 10 illustrates the synergy factor f, for the three catalysts
investigated, as a function of catalyst temperature.
At low temperature, up to 100 8C, where the catalysts are
not active, the best results were obtained with the Mn-SAPO
catalyst, with a synergy factor up to 1.85. For this catalyst
the synergy factor decreases with increasing temperature
until 1.16 at 400 8C. For the MnPO4 catalyst the synergy
factor was 1.63–1.74 over the entire temperature range
investigated, except at room temperature, where no synergy
was observed. The plasma–catalyst synergy for Mn-APO
was also less pronounced at room temperature ( f = 1.23),
and was enhanced at higher catalyst temperature, where f
varies in the range 1.58–1.81.
The toluene decomposition in the discharge can be due to
electron impact dissociation and to reactions with ozone and
Fig. 10. Synergy factor f as a function of the catalyst temperature for the
three catalysts investigated.
oxygen radicals, generated in the plasma. Since the toluene
concentration is very small, electron impact dissociation of
toluene molecules should be rather low, as compared to
radical reactions.
Oxygen radicals are generated by dissociation of
molecular oxygen according to the reaction:
e þ O2 ! e þ O þ O (R1)
Although atomic oxygen is a strong oxidizer, its stability is
very limited. Due to fast re-association processes, the life-
time of oxygen atoms is only a few microseconds at atmo-
spheric pressure [35].
Atomic oxygen reacts with molecular oxygen in three-
body collisions, forming ozone by the following reaction:
O þ O2 þ M ! O3 þ M (R2)
In air, M can be either molecular oxygen or molecular
nitrogen. The corresponding rate constants are: kN2 ¼
5:6  10
34  ðT=300Þ
2:8 cm3 s
1 mole
1 and kO2 ¼ 6
10
34  ðT=300Þ
2:8 cm3 s
1 mole
1, respectively [10].
Ozone is a more stable molecule; its lifetime at room
temperature is several days. It is also a strong oxidizing
agent, and oxidation with ozone usually starts at lower
temperatures than oxidation with oxygen.
Under purely catalytic conditions, toluene is decomposed
by reactions with oxygen on the catalyst surface. Such a
behavior is generally associated to the presence of oxygen
vacancies [36] which might be also the situation of these
catalysts, as far as manganese seems to be in a reduced
oxidation state. But the significant point of this study is that
while using Mn3O4 the formation of the intermediate
oxidation products has been observed [37,38], while in this
case only CO2, and presumably CO, have been detected.
In the plasma–catalytic system, only the long-lived
species formed in the discharge (the ozone radicals) can
reach the catalytic reactor and enhance toluene total
oxidation on the catalyst surface. The most likely
mechanism is the decomposition of ozone on the catalyst
surface, forming oxygen radicals (R3), which react further
with the toluene molecules. A similar mechanism is
proposed also in [2] for the decomposition of benzene by
means of a dielectric barrier discharge combined with MnO2
catalyst.
 M. Magureanu et al. / Applied Catalysis B: Environmental 61 (2005) 12–20
catalyst
O3
! O þ O2 (R3)
In the present experiments toluene, conversion was
slightly higher in the presence of catalysts as compared to
the values with the discharge alone, however, the major
effect of the catalyst was on the CO2 yield, which was
significantly enhanced by the addition of the catalysts. A
possible explanation for the shift of the product distribution
towards total oxidation in the presence of catalysts could be
the oxidation of some part of the CO formed in the plasma to
CO2, on the catalyst surface. At low temperature, this
reaction most likely proceeds via ozone, while at higher
temperature molecular oxygen probably plays a more
important role, since ozone is easily decomposed at high
temperature.
When increasing temperature, ozone destruction in the
gas phase, especially by reaction with molecular oxygen
(R4), is enhanced:
O3 þ O2 ! O þ O2 þ O2 (R4)
The rate constant of this reaction kD = 73 
10
11 exp(
11400/T) cm3 s
1 mole
1 [39] depends
strongly on temperature. The decrease in ozone concentra-
tion with increasing temperature could explain the plateau in
the CO2 yield observed for the MnPO4 and Mn–APO
catalysts, in the temperature range 100–300 8C (Figs. 7
and 8). The rate constant for ozone destruction in the gas
phase increases with almost 5 orders of magnitude in this
range, from 3.9  10
23 at 100 8C to 1.7  10
18 at 300 8C.
On the other hand, the reactions on the catalyst surface are
accelerated when increasing temperature, as shown by the
tests performed under purely catalytic conditions. The bal-
ance of these two effects is the most likely cause of the
almost constant rate for toluene total oxidation observed for
catalyst temperatures in the range 100–300 8C. At higher
temperature, the toluene oxidation with molecular oxygen
on the catalyst surface is significantly enhanced (see Figs. 7
and 8 open symbols—purely catalytic conditions), therefore,
the CO2 yield increases again, despite the further decrease in
ozone concentration.
The Mn-SAPO catalyst promotes toluene total oxidation
with ozone even at low temperatures, below 100 8C. In the
absence of the discharge, toluene oxidation with oxygen on
the catalyst surface is more pronounced as compared to the
MnPO4 and Mn-APO catalysts. Consequently, for the
plasma–catalytic experiments the CO2 yield increases
continuously with temperature, despite the decreasing
ozone concentration.
At this moment it is hard to ascribe the differences
determined among the investigated catalysts. Since all the
catalysts desorb very little oxygen in the investigated
conditions, it may be speculated that not a redox mechanism
is governing such a behavior but more probably the
differences in the mode Mn is positioned on the external
surface. Such a hypothesis may also be supported by the
19
XPS results, which indicated a more oxidized Mn in the
incorporated APO and SAPO molecular sieves.
The plasma–catalyst synergy is expected to increase
when placing the catalyst in the discharge region. In this
case, in addition to oxidation with ozone, a contribution of
the short-lived species present in the plasma to toluene
oxidation on the catalyst surface is expected.
4. Conclusions
An experimental investigation of toluene total oxidation
was carried out in a plasma–catalytic system, formed by a
dielectric barrier discharge and Mn-based phosphate
catalysts, placed downstream the plasma reactor.
In the discharge, toluene decomposition is due to electron
impact dissociation and to reactions with ozone and oxygen
radicals generated in the plasma. The main reaction products
are CO2 and CO. Carbonaceous deposits were observed in
the plasma reactor, however, in relatively small amounts.
The CO2 yield in the plasma reached 24%.
Under purely catalytic conditions, toluene is decomposed
by reactions with oxygen on the catalyst surface. The
maximum CO2 yield, 33%, was obtained at 400 8C for Mn-
SAPO.
The combined application of plasma and catalysis led to a
slight increase in toluene conversion, the major effect being
the shift in product distribution towards total oxidation. The
addition of the catalyst showed a higher effect on toluene
total oxidation than the sum of individual steps. The
synergetic effect, was found even at temperatures up to
100 8C, where the catalysts are not active. In this case, the
CO2 yield increased up to 41%, for the Mn-SAPO catalyst.
In this temperature range, this effect is most likely due to
oxidation with ozone radicals of a part of the CO formed in
the plasma to CO2, on the catalyst surface. A further increase
in the plasma–catalyst synergy is expected by placing the
catalyst in the discharge region, when the short-lived species
produced in the plasma will most likely contribute to
oxidation on the catalyst surface.
Acknowledgements
This research was accomplished in the framework of a
bilateral research agreement of the ‘‘Commissariat Général
des Relations Internationales (CGRI)’’ office and of the
‘‘Direction des Relations Internationales (DRI)’’ office of
the Walloon Region of Belgium with Roumania. The authors
also thank the ‘‘Direction de la Recherche Scientifique
(DRS)’’ office for the program ‘‘Action de Recherches
Concertées’’ of the ‘‘Communauté Française de Belgique’’.
The authors thank European Project CONCORDE.
The work was partly financed by the Romanian Ministry
for Education and Research, under Program CERES, project
number 3-120.
20 M. Magureanu et al. / Applied Catalysis B: Environmental 61 (2005) 12–20
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