Applied Catalysis B: Environmental 74 (2007) 223–232

www.elsevier.com/locate/apcatb

On the impact of the choice of model VOC in the evaluation of V-based

catalysts for the total oxidation of dioxins: Furan vs. chlorobenzene
D.P. Debecker, F. Bertinchamps, N. Blangenois, P. Eloy, E.M. Gaigneaux *
Université catholique de Louvain, Unité de catalyse et chimie des matériaux divisés, Croix du Sud 2/17, B-1348 Louvain-la-Neuve, Belgium
Received 30 November 2006; received in revised form 21 February 2007; accepted 22 February 2007
Available online 25 February 2007

Abstract
V-based catalysts, widely developed for the catalytic abatement of dioxins, are usually studied and optimized by investigating the oxidation of
model chlorinated aromatic compounds (e.g. chlorobenzene). Even though the oxygenated function included in the central aromatic ring of the
molecular structure of a dioxin could influence major aspects of the catalytic process, it has never been taken into account in the reported works. In
this study, furan is chosen as a model for the central oxygenated ring of a polychlorinated dibenzo furan (PCDF) and its oxidation is compared to the
case of chlorobenzene. The strategy was to check systematically if the improvements of formulations enlightened from our previous investigation
on chlorobenzene also remain beneficial with furan. It turned out that the use of a sulfate containing TiO2 as support for the active VOx phase as well
as the doping of the formulation with Mo or W oxides had very different impacts in the two cases. Some improvement strategies prove to be
inefficient or deleterious in the case of furan. Competition tests further suggest that the adsorption behavior of dioxin could be better imitated by
furan than by chlorobenzene. These observations highlight, in the case for which working with the target pollutant is difficult (as with dioxins), that
the choice of the model molecule is critical.
# 2007 Elsevier B.V. All rights reserved.

Keywords: Dioxin; Chlorobenzene; Furan; Catalytic oxidation; VOC combustion; VOx/TiO2

1. Introduction towards harmless products and can operate at relatively low

In the field of atmospheric pollution, it is evident that
polychlorinated hydrocarbons, and in particular dioxins,
constitute a major concern. The word ‘‘dioxin’’ collectively
refers to polychlorinated dibenzo furans (PCDF) and poly-
chlorinated dibenzo dioxins (PCDD). Dioxins are very stable
structures consisting in three aromatic cycles. The central ring
includes one (PCDF) or two (PCDD) oxygen atoms and the
external cycles are substituted with chlorine atoms at various
positions (Fig. 1). These compounds are formed during
incineration and combustion processes [1]. As a response to
their high persistence and their subsequent toxicity, catalysis is
the most promising solution since it allows to directly destroy
these pollutants at the source of emission [1–3]. Moreover, the
catalytic total oxidation can exhibit an excellent selectivity
* Corresponding author. Tel.: +3210473665; fax: +3210473649.
E-mail address: gaigneaux@cata.ucl.ac.be (E.M. Gaigneaux).
0926-3373/$ – see front matter # 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcatb.2007.02.016
destruction temperature [2,4–6].
For this application, two families of catalysts have been
developed. Noble metal-based catalysts are highly active [7–
10] but suffer from high cost and low stability toward the
produced HCl and Cl2 [2,11–13]. Moreover, they also catalyze
the further poly-chlorination of the pollutants [14]. Transition
metal-based catalysts are the alternative. In particular, vanadia-
based catalysts are recognized as active and stable in a chlorine-
containing environment [2,15,16]. Indeed, Bertinchamps et al.
showed that their activity in benzene oxidation was the same as
in chlorobenzene oxidation [17]. So, V-based formulations
constitute a promising solution for dioxin total oxidation and
efforts are made to improve their formulation. A large number
of fundamental works have been done in order to understand the
oxidation mechanism that is involved during total oxidation of
dioxins on V-based catalysts. However, very few authors have
reported works realized directly on real dioxins [18–20]. Real
dioxins are usually not used in mechanistic studies because they
are hard to handle and of course very toxic. Model volatile
organic compounds (VOC) are thus often used. The chosen
224 D.P. Debecker et al. / Applied Catalysis B: Environmental 74 (2007) 223–232
Fig. 1. Molecular structures of PCDD, PCDF, chlorobenzene and furan.
models need to be structurally similar to dioxins, less toxic and
easier to handle. Even if they always differ in some ways from
the target compound, model compounds prove to be essential in
order to test and optimize the proposed formulations.
Classically the authors want to evaluate the activity of the
catalyst in the oxidation of an aromatic ring, as well as its
resistance to chlorine poisoning. Therefore, simple chlorinated
aromatic compounds (e.g. chlorobenzene) are very often
chosen [1,11,12,15,17,21–25]. As interesting lines to optimiza-
tion of the catalysts for such model VOCs, it has been found that
titania supports are able to spread the vanadia very well on their
surface, which leads to high activity [22,24]. Sulfate containing
TiO2 are also claimed to be even more efficient [15,17,24].
Additionally, several authors have shown that other transition
metal oxides (essentially MoOx, WOx) can act as dope for the
active phase of VOx [11,17,21,23,26–29].
Molecules like chlorobenzene are useful models for dioxins.
However, one should bear in mind that the central aromatic ring
of a dioxin molecule is oxygenated. In a PCDF this ring is a
furan (Fig. 1). This essential characteristic is not taken into
account when a simple chlorinated VOC like chlorobenzene is
chosen as a model. Nevertheless this moiety can influence
major aspects of the catalytic process (adsorption of the
pollutant, coking, etc.) as it is suggested from the DRIFTS
study of Larrubia and Busca [30] on the adsorption of various
compounds on a VOx–WOx/TiO2 catalyst. Taralunga [31] also
intended to take this oxygenated moiety of dioxins into account
when investigating the oxidation of benzofuran in addition to
the oxidation of dichlorobenzene over zeolite and noble metal-
based catalysts. To our knowledge though, no other reported
study did investigate the importance of this central ring in the
catalytic abatement of dioxins on V-based catalysts. Improve-
ments of the catalyst formulations are proposed but they are
never checked in the perspective of an oxygenated model. We
thus, propose a comparative study of the oxidation of
chlorobenzene – as a chlorinated aromatic model molecule –
and the oxidation of furan—as an oxygenated aromatic model
molecule.
It should be noted that the issue of the total oxidation of
oxygenated VOC is already well documented in the literature.
Studies on ketones [32–38], alcohols [38–41] or esters [42–44]
total oxidation show that O-compounds are quite easily
destroyed and that the behavior of the VOC differ with their
structure. In this paper, the total oxidation of an aromatic O-
compound is addressed. Even though it can be expected that our
catalyst would destroy furan easily, this remained to be
checked. Also, the basic oxygen of furan is likely to play an
important role in the adsorption of the pollutant on the acid
VOx/TiO2 based catalyst. Since the adsorption of this polar
group (similar to those present in PCDD and PCDF) can
influence major aspects of the catalytic process it is important to
have a better insight on this matter.
Besides, the main goal of this comparative study is to check
the beneficial effect brought by ‘‘improved’’ formulations of V-
based catalysts in the case of the oxidation of furan. In
particular, two parameters of the formulation are studied: (i) the
use of a sulfate containing TiO2 support instead of the classical
TiO2 support and (ii) the use of Mo and W oxides as doping
phases of the active phase of vanadium. Therefore, the catalytic
performances of V-based catalysts supported on two different
supports and possibly upgraded with MoOx or WOx are
investigated in the oxidation of chlorobenzene and furan. Also,
in addition to the one-pollutant tests, the respective behaviors of
the two models are investigated in the course of a competition
test, namely a test involving both pollutant models simulta-
neously.
The observed performances are correlated with the results of
various characterizations. FTIR analysis with adsorbed
pyridine allowed us to study the acidity of the catalysts. As
suggested by Larrubia and Busca [30], the acidity of the
catalyst should indeed play a crucial role in the adsorption of
the VOCs on the surface of the catalyst. The tendency of the
various impregnated oxides to spread on the supports is
considered thanks to XPS and XRD analysis. The weight
loadings (ICP-AES) and the surface area (N2 adsorption) are
also measured.
2. Experimental
2.1. Preparation of the catalysts
Catalysts are supported on two different TiO2 supports: a
70% anatase-30% rutile TiO2 (Degussa P25: 48 m2/g, denoted
hereafter T) and a pure anatase TiO2 containing 1.4% wt of
sulfate (Millenium PC 100: 91 m2/g, denoted hereafter Ts).
The active phase is VOx (V) and the secondary phases are
MoOx (Mo) and WOx (W). The precursors of these oxides are
respectively NH4VO3 (Vel, 99.9%); (NH4)6Mo7O244H2O
(Aldrich, >99%); and (NH4)2WO4 (Aldrich, 99.99%). To
obtain the impregnation solutions, the precursors are dissolved
in distilled water and complexed with 2 moles of oxalic acid for
1 mole of transition metal. All impregnation solutions had a pH
below 3. A classical wet impregnation method was used and the
amounts of precursor were calculated in order to obtain 0.75
theoretical monolayer of transition metal oxide on the surface
of each support. The theoretical monolayer coverage was
calculated based on the cross sectional area of a unit composed
of one transition metal atom and its oxygen coordination
sphere. The values are 12 Å2 for VOx, 17 Å2 for MoOx and
15 Å2 for WOx [24]. The suspension of support in the
 D.P. Debecker et al. / Applied Catalysis B: Environmental 74 (2007) 223–232
Table 1
Abbreviation and compositions of the catalysts
Name Support Active phase Doping phase
(0.75 mL) (0.75 mL)
TV TiO2 VOx / accurate within a range of about 1% (in relative) for the
TVMo TiO2 VOx MoOx
TVW TiO2 VOx WOx
TsV Sulfated containing TiO2 VOx /
TsVMo Sulfated containing TiO2 VOx MoOx
TsVW Sulfated containing TiO2 VOx WOx
TMo TiO2 / MoOx
TW TiO2 / WOx
impregnation solution was stirred for 2 h at room temperature
before the solvent was evaporated under reduced pressure in a
rotavapor at 45 8C. The obtained solids were dried overnight in
an oven at 110 8C and then calcined at 400 8C at atmospheric
pressure in air for 20 h in a muffle furnace.
Six different V-based catalysts have thus been prepared.
Their compositions are described in Table 1. The reference
catalyst contains 0.75 monolayer (ML) of the active phase wet-
impregnated on TiO2 (TV). Doped formulations were obtained
by simultaneous impregnation of vanadium oxide with
molybdenum or tungsten oxides on TiO2 in order to obtain
0.75 theoretical ML of each deposited oxides (TVMo and
TVW). The same preparation protocol has been applied to the
sulfate containing support, leading to the three formulations
denoted TsV, TsVMo and TsVW. Also, the two doping oxides
have been impregnated alone on T (TMo and TW).
2.2. Catalytic tests
All the catalytic tests were performed in a metallic fixed-bed
micro-reactor (PID ENG & Tech, Spain, Madrid) operating at
atmospheric pressure. The reactor was made of an inconel tube
of 1 cm internal diameter. The catalytic bed was composed of
200 mg of catalyst powder selected within the granulometric
fraction 200–315 mm and diluted in 800 mg of inactive glass
spheres with diameters in the range 315–500 mm. The gas
stream contained 100 ppm of chlorobenzene or/and 150 ppm of
furan in He (Praxair), 20% of O2 (Praxair; 99.995%) and He
(Praxair; 99.996%) as diluting gas to obtain 200 ml/min
(VVH = 37000 h1). The reaction was run from 100 to 400 8C
in a step mode. At each temperature investigated, the catalyst
was stabilized for 150 min. Two start-up procedures have been
envisaged. In the ‘‘direct’’ procedure, the test is readily started
from 100 8C and proceeds to the next temperature steps. In the
‘‘sat’’ procedure, the catalyst is first contacted with a
concentrated flow of the VOC (750 ppm) for 4 h at 100 8C.
After this period, the composition of the flow is stabilized at the
usual concentration and the usual temperature-programmed test
proceeds.
Analysis of reactants and products was continuously
performed by on-line gas chromatography (GC). The CP-
3800 gas chromatography apparatus from Varian equipped with
four columns (one Hayesep G, one Hayesep T, one Molsieve
and one CP-Sil 8CB), a methaniser and three detectors (one
225
TCD and two FID) was used with He as carrier gas in order to
quantify chlorobenzene, furan, O2, CO, CO2 and to detect other
hydrocarbons. The analysis parameters were set as to allow one
analysis each 15 min and to obtain measured performances
conversion of chlorobenzene and furan. To calculate the
conversion at a given temperature, only the concentrations of
reactants measured and averaged in the period of time from 100
to 150 min after stabilization were taken into account. The
conversion is defined as the ratio reactant transformed/reactant
in the inlet.
2.3. Characterization
X-ray diffraction (XRD) measurements were performed on
the fresh catalysts with a Siemens D5000 difractometer using
the Ka radiation of Cu (l = 1.5418 Å). The 2u range was
recorded between 5 and 758 at a rate of 0.028 s1. The ICDD-
JCPDS database was used to identify the crystalline phases.
X-ray photoelectron spectroscopy (XPS) was performed on
a SSI X-probe (SSX-100/206) spectrometer from Surface
Science Instruments working with a monochromatic Al Ka
(1486.6 eV) radiation (10 kV, 22 mA). The analysis chamber
was operated under ultrahigh vacuum with a pressure close to
5  109 Torr. Charge compensation was achieved by using an
electron flood gun adjusted at 8 eV and placing a nickel grid
3.0 mm above the sample. Pass energy for the analyzer was
150 eV and the spot size was approximately 1.4 mm2. For these
measurements, the binding energy (BE) values were referred to
the C-(C, H) contribution of the C 1s peak at 284.8 eV. The
surface atomic concentrations were calculated by correcting the
intensities with theoretical sensitivity factors based on Scofield
cross sections [45]. Peak decomposition was performed using
curves with 85% Gaussian type and 15% Lorentzian type, and a
Shirley non-linear sigmoid-type baseline. The following peaks
were used for the quantitative analysis: O 1s, C 1s, V 2p, Ti 2p,
Cl 2p, Mo 3d and W 4d. Based on the XPS analysis, we
estimated the surface ratio impregnated oxide/support by the
formula:
atomic concentration of impregnated metal ð%Þ
XPS ratio ¼
atomic concentration of Ti ð%Þ
Fourier Transformed Infra Red spectra of pre-adsorbed
pyridine (FTIR-pyridine) were recorded using an IFS55
Equinox spectrometer (Brücker) equipped with a MCT detector
and working with a resolution of 4 cm1. The amount of
Brønsted and Lewis sites is determined by the integration of the
area of the peaks at 1537 and 1446 cm1, corresponding
respectively to pyridine adsorbed on Brønsted sites and Lewis
sites. The details of this experiment are given elsewhere [17].
The estimation of the weight percentages of V, Mo, W and Ti
was performed through inductively coupled plasma-atomic
emission spectroscopy (ICP-AES) on an Iris Advantage
apparatus from Jarrell Ash Corporation.
N2 adsorption measurements have been performed at
196 8C, under a N2-partial pressure P/P0 = 0.3 on a
226 D.P. Debecker et al. / Applied Catalysis B: Environmental 74 (2007) 223–232
Micromeritics ASAP 2000 in order to determine the BET
surface area (SSA) of our catalysts and supports. Prior to the
measurement, the samples were degassed under N2/He
(30:70% vol.) at 120 8C for 1 h.
3. Results and discussion
3.1. Data on the catalytic tests
3.1.1. Effect of the start-up procedure
In the case of chlorobenzene, the start-up procedure did not
affect the performances measured afterwards. Fig. 2 shows the
GC results obtained during a test on chlorobenzene with the
‘‘direct’’ procedure. At each step of temperature a short
transition period leads to a stable plateau of observed
conversion. It is thus easy to evaluate an average conversion
for each investigated temperature.
For furan on the other hand, the two start-up procedures lead
to very different results. When the test is started with the
‘‘direct’’ procedure (Fig. 3), the conversion is almost complete
at the very beginning of the 100 8C-step and then it decreases
continuously. This decrease of the conversion is observed
during the whole temperature step. After 150 min, the
temperature is raised to the next step. As a consequence, the
conversion reaches a higher conversion and again decreases
progressively. Complementary tests have shown that this
instability lasts for more than 15 h. A similar long-lasting
transition period has also been reported in the oxidation of
butanol on noble metal based catalysts [3]. Thanks to the ‘‘sat’’
procedure, we were able to get rid of this instability. The
catalyst that has first been contacted with a concentrated flow of
furan for 4 h at 100 8C shows stable values of conversion for
each temperature (Fig. 4).
These observations reveal the occurrence of a strong
adsorption of furan on our catalysts. This is in agreement with
Spoto et al. [46] who already showed that furan interacts very
strongly with the acidic sites of a zeolite. In the ‘‘direct’’
procedure, our hypothesis is thus that furan is removed from the
flux both through real oxidation and through simple adsorption.
The surface is progressively covered with a carbonaceous
deposit. The extent of the elimination through adsorption is thus
Fig. 2. Evolution of the down-stream chlorobenzene concentration during a
catalytic test (‘‘direct’’ start-up procedure) on TsVMo.
Fig. 3. Evolution of the down-stream furan concentration during a catalytic test
(‘‘direct’’ start-up procedure) on TsVMo.
predominant at the beginning of the temperature plateau and
then decreases as the coverage of the surface is progressing.
This leads to a long-lasting transition period during which no
stable conversion can be measured. The effect of the ‘‘sat’’
start-up is to saturate the surface of the catalyst with furan. The
saturated catalysts acquire a pronounced brown-red color. This
was also observed on zeolites after adsorption of furan by Spoto
et al. [46]. The saturated catalysts exhibit a stable conversion
depending only on the applied temperature. It is noteworthy
that Paulis et al. [37] used a similar start-up procedure in order
to cope with the discrepancies observed in catalytic results and
caused by the strong adsorption of acetone on manganese
oxide-based catalysts.
The nature of the observed deposit has not been investigated
extensively. Yet, an enrichment of the atomic surface
concentration of carbon has been detected by XPS measure-
ments on saturated catalysts. The proportion of C linked to
oxygen atoms is also higher in saturated samples than in fresh
catalysts. This can originate from the presence of various O-
containing species produced from the reaction of furan on the
catalyst. The occurrence of polymerization of furan or its
derivatives on the catalyst surface would not be surprising as
Spoto et al. [46] evidenced the high reactivity of furan in
reactions.
Fig. 4. Evolution of the down-stream furan concentration during a catalytic test
(‘‘sat’’ start-up procedure) on TsVMo.
 D.P. Debecker et al. / Applied Catalysis B: Environmental 74 (2007) 223–232
3.1.2. Selectivity and carbon mass balance
In the case of chlorobenzene oxidation, CO2 is the main
oxidation product. The CO selectivity is comprised between 5
and 10%. Traces of maleic anhydride are also detected, which is
in agreement with the observations of Larrubia and Busca [30].
As the tests on furan are run in the ‘‘sat’’ procedure, the
catalyst surface is saturated with a carbonaceous deposit during
the test start-up. When the temperature is raised during the test,
this deposit is progressively burned. The outlet product
concentrations are thus the sum of (i) the products directly
formed from the oxidation of the entering furan and (ii) the
products formed or desorbed from the carbonaceous deposit.
Moreover, the outlet product concentrations are often unstable,
even at the end of the 150 min temperature plateau. It is thus
impossible to state a rigorous carbon mass balance in the tests
run on furan. Nevertheless, CO2 is the main oxidation product.
The estimation of the CO selectivity can vary between 5 and
30%. In addition, the outlet maleic anhydride concentration can
reach a few ppm. This partial oxidation activity is not surprising
since (i) it is known that VOx/TiO2 catalysts can produce maleic
anhydride during the oxidation of various VOC (benzene,
chlorobenzene, benzofuran) [30] and (ii) furan is a known
intermediate in the production of maleic anhydride from butene
on V2O5 containing catalysts [47–49].
3.2. Evaluation of the catalyst formulations
3.2.1. Catalytic conversion of chlorobenzene
Fig. 5 presents the light-off curves of the six catalysts
investigated in the course of total combustion of chlorobenzene
(‘‘direct’’ start-up procedure). The abatement of chlorobenzene
starts significantly at 150 8C. At 350 8C all the formulations
convert 100% of the chlorobenzene concentration. The inter-
polated temperature needed to convert 50% of the chlorobenzene
concentration (T50) is comprised between 185 and 230 8C. The
activity of the entire set of catalysts can be classified based on the
T50 as: TV (230 C8) < TVMo (220 8C) < TVW (215 8C)
< TsV (195 8C) < TsVW = TsVMo (185 8C). The three Ts-
supported formulations are more active than the corresponding
T-supported ones. The T50 decreases by about 35 8C for each
formulation when Ts is chosen instead of the classical TiO2. For
both supports, the formulations that contain MoOx or WOx are
Fig. 5. Chlorobenzene light-off curves (‘‘direct’’ procedure).
227
Fig. 6. Furan light-off curves (‘‘sat’’ procedure).
more active than the formulation containing only VOx. The co-
impregnation of the doping phases brings a beneficial effect by
decreasing the T50 by about 10–15 8C.
3.2.2. Catalytic conversion of furan
Fig. 6 presents the light-off curves of the catalysts in the
course of the total combustion of furan (‘‘sat’’ start-up
procedure). The abatement of furan starts already significantly
from 100 8C. At 250 8C, the six catalysts investigated convert
100% of the furan concentration. The 50% conversion is
reached at temperatures comprised between 135 and 180 8C.
The easy oxidation of furan, as compared to chlorobenzene,
was indeed expected as an oxygen-containing molecule is
intuitively easier to oxidize. But the most interesting data we
wish to enlighten is the fact that the T50 ranking of the catalysts
is obviously different from what is observed in the oxidation of
chlorobenzene: TVMo (180 C8) < TVW (170 8C) < TsVMo
(165 8C) < TsVW (160 8C) < TV (150 8C) < TsV (135 8C).
First, the three Ts-supported formulations are not collectively
better than the three T-supported ones. Nevertheless, as
regarding a given composition of impregnated oxides, the
Ts-supported formulations are still better. But the positive
effect is small (decrease of the T50 by about 10 8C for each
formulations) as compared to the effect observed in chlor-
obenzene oxidation. Secondly, doped formulations are system-
atically less active than the corresponding formulations that
were only impregnated with VOx. The negative effect is
obvious as the T50 increases by about 25 8C for MoOx or WOx-
containing formulations (for a given support). These two oxides
have also been tested when impregnated alone on T. Fig. 7
shows that WOx only has an effect above 250 8C. At lower
temperature, TW has the same low activity as the bare support.
MoOx on the other hand shows some activity, but is far from
competing the performances of the six V-based catalysts as
TMo has a T50 of about 210 8C only.
3.2.3. Surface acidity
Bertinchamps et al. already investigated the surface acidity
of identical catalysts [17]. Their main findings are crucial to the
understanding of our results and can be summarized as follows.
The study of the Lewis acidity revealed that (i) the sulfate
228 D.P. Debecker et al. / Applied Catalysis B: Environmental 74 (2007) 223–232
Fig. 7. Furan light-off curves on T, TMo and TW (‘‘sat’’ procedure).
containing support exhibits two times more Lewis sites than the
classical TiO2; (ii) the Lewis sites present at the surface of the
sulfate containing support are stronger than those of conven-
tional TiO2; (iii) the impregnated oxides either do not exhibit
any Lewis sites on their surface or exhibit less Lewis sites than
the bare support; and (iv) the decrease of the number of Lewis
sites that is observed when VOx, MoOx and WOx are
impregnated is due to a coverage effect. The study of the
Brønsted acidity revealed that (i) the classical support does not
exhibit any Brønsted sites, but Ts exhibits some of them (ii)
Brønsted sites are mainly brought by the impregnation of VOx,
MoOx and WOx and (iii) the amount of Brønsted sites brought
by the impregnated oxides is four times bigger in the case of Ts
than of T support. This latter was discussed as due to a better
spreading of the oxide phases on Ts and suggests that the
presence of stronger Lewis sites on the sulfate containing TiO2
promotes this spreading [17].
3.2.4. Other characterizations
For the entire set of catalysts, vanadium and molybdenum
oxides were not detected at all on XRD diffractograms. This
suggests the obtention of well-dispersed oxides, and likely the
formation of a homogeneous coverage of these phases as sub-
monolayers. WO3 crystallites on the other hand were detected
in the TVW and TsVW samples (JCPDS 32-1395). This is in
agreement with Leyrer et al. who explained the increasing
spreading of the oxides on TiO2 within the series:
WO3 < MoO3 < V2O5 [50]. Also, Bertinchamps et al. detected
the formation of WO3 crystallites on TiO2 at a theoretical
loading as low as 0.75 monolayer [15].
XPS data were analyzed in term of atomic concentration
ratios (Table 2). In this way, an increase of the ratio V/Ti can be
correlated to a better spreading of the active phase [17]. The
slightly higher V/Ti ratio for TsV thus confirms the better
tendency of VOx to spread on sulfate containing TiO2. Table 2
also shows that the presence of a secondary phase leads to a
decrease of the ratio V/Ti. This could be related to a covering
effect of the secondary phase (Mo or W oxides) on the active
phase (VOx). But, Bertinchamps et al. rather demonstrated that
the spreading of Mo and W oxides on V oxide is almost absent
[17]. Thus the lower V/Ti ratios observed for the doped
Table 2
XPS ratios
V/Ti Mo/Ti W/Ti
TV 0.17 – –
TVMo 0.11 0.17 –
TVW 0.14 – 0.15
TsV 0.18 – –
TsVMo 0.10 0.17 –
TsVW 0.13 – 0.13
formulations is better accounted by the fact that, the secondary
phase prevents the active phase from spreading well on the
support. It can be noted that the effect is less important in the
case of WOx than in the case of MoOx. This is consistent with
the fact that WO3 crystallites are detected by XRD on our
catalysts, namely the fact the WOx is itself poorly spread on the
support and thus does not impede the spreading of VOx as
significantly as MoOx does.
ICP-AES loadings and specific surface area (SSA) are given
in Table 3.
3.2.5. Discussion on the effect of the sulfate containing
support
The use of Ts has a great positive impact on the
performances of the catalysts in the oxidation of chloroben-
zene. This effect can be attributed to the higher amount of
Brønsted sites present on Ts-supported catalysts [17]. Brønsted
sites seem to be implicated in the adsorption of chlorobenzene
on the surface of the catalyst, which is the first step of the
catalytic abatement process. This statement is in agreement
with Sinquin et al. [51] and Ramachandran et al. [52] who both
suggested that Brønsted sites are the adsorption sites of
chlorinated VOCs. The amount of Brønsted sites is thus a
crucial parameter. Their surface concentration should be high in
order to provide enough adsorbed chlorobenzene for the sites
that are involved in the combustion of the aromatic cycle. In this
view, Ts contributes in a direct, as well as in an indirect manner.
Ts bears some Brønsted sites on its surface (direct contribu-
tion). Nevertheless, the activation effect is mainly indirect, as
Ts – exhibiting a higher amount and strength of Lewis sites –
favors the spreading of the impregnated oxides. These well
spread oxides can in turn expose more Brønsted sites at the
surface of the catalyst, which leads to an enhancement of the
performances.
In the oxidation of furan, the use of the sulfate containing
support brings only a small beneficial effect. One should bear in
mind that Ts possesses a larger specific surface area than T
(Table 3). Also, we always impregnated 0.75 theoretical ML on
our catalysts and the catalytic tests are always run with the same
amount of catalyst (200 mg). As a result, when the reactor is
filled with a Ts-supported catalyst, it contains more active (and
doping) phase than when it is filled with a T-supported catalyst.
On one hand, this fact is not sufficient to explain the extent to
which Ts improves the performances in the oxidation of
chlorobenzene. On the other hand, this simple parameter could
account for the limited improvement observed in the oxidation
of furan. As a consequence, we should safely limit our
 D.P. Debecker et al. / Applied Catalysis B: Environmental 74 (2007) 223–232 229

Table 3
ICP-AES weight concentrations and ICP-AES ratios
SSA (m2 g1) V (%) Mo (%) W (%) V/X V2O5 (%) MoO3 (%) WO3 (%)
T 49.3 – – – – – – –
Ts 82.4 – – – – – – –
TV 45.7 2.55 – – – 4.55 – –
TVMo 44.9 2.11 2.82 – 0.75 3.76 4.25 –
TVW 43.1 1.96 – 5.95 0.32 3.49 – 7.50
TsV 68.8 3.93 – – – 7.01 – –
TsVMo 66.6 3.20 4.75 – 0.67 5.70 7.16 –
TsVW 56.7 3.48 – 10.91 0.32 6.20 – 13.75
TMo – 3.05 – – – 4.60 –
TW – – 6.55 – – –

interpretation to the fact that Ts has no chemical effect on the
oxidation of furan.
This is fully consistent with the observed strong tendency of
furan to adsorb on the surface of all of our catalysts. Moreover
we had to saturate the surface of our catalyst in the start-up of
the catalytic test in order to measure the real oxidation activity.
Consequently, the first step of the catalytic abatement process,
namely the adsorption, is certainly not a limiting step in the case
of furan. By increasing the Brønsted acidity of surface, Ts does
not promote the adsorption and does thus not have the
possibility to improve the entire catalytic process.
Though Fig. 7 shows that WOx is inactive, while MoOx is
moderately active, it is noteworthy that MoOx-doped catalysts
are even worse than WOx-doped ones. Nevertheless, XRD and
XPS results suggest that MoOx spreads more easily on TiO2
supports that WO3. As a consequence, the spreading of the VOx
phase is more affected in the case of co-impregnation of Mo
oxide. The higher activity of TVW and TsVW as compared to
TVMo and TsVMo, respectively suggests that the spreading of
the VOx phase is a crucial parameter. Moreover, it confirms the
fact that the sites that are active in the oxidation of furan are
located on the VOx phase.

3.2.6. Discussion on the effect of the doping phase 3.3. Chlorobenzene versus furan in simultaneous reaction
The co-impregnation of MoOx or WOx brings an obvious
doping effect in the oxidation of chlorobenzene. We earlier 3.3.1. Competition test
showed that the doped formations present more acid Brønsted The adsorption behavior of furan is very different from what
sites than the catalysts containing only VOx [17]. These sites are is observed in the case of chlorobenzene. This has been showed
supposed to be involved in the adsorption step of chlorobenzene to have a dramatic effect on the entire catalytic process. An
[17,51,52]. The improved performances of doped catalysts can important remaining question is to know what will remain from
therefore be correlated with the higher amount of Brønsted sites these described behaviors if furan and chlorobenzene are
present on their surface. reacted together. It is known that the behaviors of the pollutants
In the oxidation of furan, however, the effect of the co- as well as the performances of the catalyst in their abatement
impregnation of MoOx and WOx is opposite. Three parameters are usually far from additive when mixtures are used. It is thus
have to be envisaged when trying to understand the effect of the useful to perform competition tests between the two VOC in
co-impregnation of secondary phases along with the active addition to the classical one-pollutant test.
phase. First, the presence of a secondary oxide prevents VOx Fig. 8 presents the light-off curves obtained in the course of
from spreading well on the support. As a consequence, the catalytic tests run on chlorobenzene and furan, alone and in
active phase could be less efficient. Secondly, MoOx and WOx competition. The tests were run in the ‘‘sat’’ procedure on
are not listed as good total oxidation catalysts in the literature
[1,9,11,12,22,43,44,53]. In a previous paper we showed that
these oxides are inactive in the oxidation of benzene [24]. Fig. 7
shows that TW is inefficient in furan oxidation. TMo, though
exhibiting some activity, is far from achieving the performances
of the V-based catalysts. Thirdly, as mentioned above, doped
catalysts exhibit a larger amount of Brønsted acidic sites on
their surface. This last parameter is crucial for the promotion of
the adsorption of chlorobenzene and seems to overcompensate
the two other parameters in the precise case of chlorobenzene.
However, the increase in the surface Brønsted acidity has no
influence in the oxidation of furan, since this VOC easily
adsorbs on all of our catalysts. As a consequence, the negative
effects brought by the two other parameters are not
compensated anymore. So, the co-impregnation of MoOx Fig. 8. Furan and chlorobenzene light-off curves alone and in competition on
and WOx is deleterious for the catalytic oxidation of furan. TsVW.
230 D.P. Debecker et al. / Applied Catalysis B: Environmental 74 (2007) 223–232
TsVW that was described as the most interesting formulation,
based on the study on chlorobenzene oxidation. Furan
oxidation is not significantly disturbed by the presence of
chlorobenzene. Chlorobenzene conversion, at the opposite, is
dramatically inhibited by the presence of furan in the flow.
When chlorobenzene is alone in the flow the conversion reaches
19%, 61% and 97% at 150 8C, 200 8C and 250 8C, respectively.
The total conversion is obtained at 300 8C. In the case of the
competition test, no chlorobenzene is removed from the flow,
even at 250 8C. The conversion only starts above 250 8C and
reaches 96% at 300 8C.
This means that furan and chlorobenzene compete for the
same active phase of the catalyst, namely the VOx phase. As
furan adsorption is fast, the active sites are blocked and
chlorobenzene cannot reach them. Chlorobenzene removal is
still inhibited after furan conversion has reached 100%. This is
due to the presence of the carbonaceous deposit formed by
furan and/or its products of partial oxidation. The sites are free
to accept chlorobenzene only at higher temperature, when the
ignition of the deposit has occurred.
3.3.2. Discussion on the possible role of the central ring of
dioxin
Whether the optimization of catalyst formulation is
envisaged on the basis of a chlorinated VOC or of an
oxygenated VOC will affect the decision of dioxins abatement
catalyst designers. The pertinent question is thus to know which
model is the most relevant. Knowing that a dioxin bears both an
oxygenated ring and two chlorinated rings, what can be the role
of these different moieties? The above-presented intermole-
cular competition results help us having an insight on the
possible role of the oxygenated ring of a dioxin in the course of
its abatement on a V-based catalyst.
Our results confirm that the oxygenated function of a furan
has a drastically higher affinity for V-based catalysts than the
chlorinated function of chlorobenzene. When these two
functions are present together in the flow, the oxygenated
one obviously wins the intermolecular competition. This
suggests that the central oxygenated ring of a dioxin could also
win the intramolecular competition against the chlorinated
moieties of the same molecule. The adsorption of the dioxin is
thus possibly directed by the oxygen atom(s) of the central ring
and likely not by the chlorinated ends. This hypothesis could
explain some observations that are reported in the literature.
Weber et al. [27] noteworthy showed that, in industrial plants,
dioxin removal proceeds under two distinct regimes: in the
lower temperature regime, removal mainly proceeds through
adsorption and in the higher temperature regime catalytic
oxidation is dominant. This behavior is similar to the behavior
we describe here in the case of furan and is not surprising in the
perspective of our hypothesis. Furthermore, Liljelind et al. [20]
note that the adsorption of dioxins is reversible. This means that
the molecular structure of the pollutant is not altered during the
very first step of the catalytic process. The dissociative
adsorption through the chlorine atom should thus not be
considered as the initial step during dioxin abatement and
certainly not as a spontaneous fast step as when chlorobenzene
is concerned. Also, the removal efficiency is always much
higher in dioxin abatement than in mono or poly chloroben-
zenes abatement [20,27]. For these latter models, the higher the
degree of chlorination, the lower the activation energy.
Dichlorobenzene, for example, adsorbs more easily on the
catalyst than chlorobenzene because it bears two chlorine
atoms, which are involved in the adsorption step [21]. For
dioxins however, the destruction kinetics decreases with the
chlorination degree, which suggests again that the chlorine
atoms are not promoting the removal of the pollutant.
Moreover, for a given chlorination degree, the destruction
rates for PCDDs is always higher as compared to PCDFs [19].
This could be explained by the fact that PCDDs bear two
oxygen atoms in their central ring instead of one in PCDFs if we
consider that these oxine functions play a key role in the
initiation of the process.
It was shown that the improvements that are proposed after
optimization studies based on chlorobenzene oxidation are
useless or deleterious in the case of furan oxidation. Now we
suggest that this could also be the case in the course of dioxin
oxidation.
4. Conclusions
We compared the catalytic performances of V-based
catalysts in the oxidation of chlorobenzene and furan. The
behaviors of furan and chlorobenzene on V-based catalysts are
very different. This difference is linked to marked differences in
the adsorption behavior of the two VOCs. Since the adsorption
of the molecule on the catalyst is the first step of the entire
process of catalytic total oxidation it can dictate the
performances offered by the catalyst. As a consequence, given
preparation parameters will have different effects on the
conversion of two VOC that have a different adsorption
behavior.
Adsorption of chlorobenzene needs to be promoted and, in
this view the amount of Brønsted sites is critical. We confirm
here that it is possible to improve catalyst formulation by
increasing the amount of Brønsted surface acid sites. It can be
achieved by two ways:
- Using a sulfate containing TiO2 support with more Lewis sites
promotes the spreading of the impregnated phase. These
phases exhibit in turn a higher amount of Brønsted sites
required for the adsorption of chlorobenzene.
- Co-impregnating Mo or W oxides along with the active phase
of vanadium. These two oxides do not cover the active phase
of VOx and exhibit a huge number of Brønsted sites assisting
the adsorption of chlorobenzene.
The abatement of furan occurs at lower temperature than the
abatement of chlorobenzene. Furan adsorbs strongly on our
catalysts. At low temperature, a stable true conversion is only
achieved after the catalyst surface has been saturated with
adsorbed furan. This behavior is similar on all the formulations
tested. In other words, the adsorption of furan occurs easily
whatever the formulation. As a consequence, an attempt to
 D.P. Debecker et al. / Applied Catalysis B: Environmental 74 (2007) 223–232
improve the catalyst formulation through a promotion of its
adsorbent properties will not be efficient. In some cases, these
attempts can rather be deleterious. Hence;
- The sulfate containing support does not bring any significant
activation. The limited beneficial effect brought by Ts is
mainly due to its textural properties (higher specific surface
area) while the change in the surface chemistry (higher Lewis
and Brönsted acidity) does not improve the performance of
our catalysts in the oxidation of furan.
- Mo and W oxides, as secondary phases have a deleterious
effect on the performances of our catalysts. The fact that they
bring a huge quantity of Brönsted sites does not favor the
catalytic activity. Instead, as these oxides both are inefficient
in total oxidation of furan and prevent the active phase from
spreading well on the support, their presence inevitably leads
to a negative impact on the catalyst performances.
These observations can be of great importance in terms of
optimization of the catalysts formulations. If an upgraded
formulation is proposed, it will not necessarily be beneficial for
the abatement of different model molecules. And in turn, the
nature of the model molecule used in works that aim at the
optimization of catalyst formulation, will affect the decisions.
Similarly, changing a given parameter of the catalyst
preparation could have unpredicted effects when applied to
dioxin abatement.
Our results on the competition between furan and
chlorobenzene suggest that dioxins could behave in the same
way as furan. Indeed, the central oxygenated ring of the
molecule could win the intramolecular competiton against the
chlorinated moieties, just as furan does against chlorobenzene
in the case of intermolecular competition. The oxine function
could thus decisively dictate the nature of the pollutant-catalyst
interaction and hence the corresponding performances.
Acknowledgments
This work was supported by the ‘‘Direction Générale des
Technologies, de la Recherche et de l’Energie (DGTRE)’’ of
the ‘‘Région Wallonne’’ (Belgium) (convention no. 0114825),
the ‘‘Fonds National de la Recherche Scientifique (FNRS)’’ of
Belgium and the Université catholique de Louvain. The
involvement of the laboratory in the Coordinated Action
‘‘CONCORDE’’ as work package leader, in the Network of
Excellence ‘‘FAME’’ of the EU 6th FP, in the IUAP network:
‘‘Supramolecularity’’ sustained by the ‘‘Service public fédéral
de programmation politique scientifique’’ (Belgium) are also
acknowledged. D.P. Debecker also acknowledges the FNRS for
his position of Research Fellow.
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