Applied Catalysis B: Environmental 46 (2003) 293–305

Iron-containing silicalites for phenol catalytic wet peroxidation

Nicolas Crowther, Faı̈çal Larachi∗
Department of Chemical Engineering & CERPIC, LAVAL University, Ste-Foy, Que., Canada G1K 7P4
Received 8 December 2002; received in revised form 18 April 2003; accepted 21 May 2003

Abstract
Heterogeneous catalytic wet peroxidation (CWPO), involving the mineralization (i.e. complete conversion to CO2 and
H2 O) of organic compounds is a possible path for the treatment of toxic and/or bio-refractory wastewater streams. The aim of
the present work was to synthesize and characterize five solid-phase catalyst formulations featuring iron(III) species supported
on silica-based mesoporous molecular sieves of the MCM-41 and HMS-types. These materials were tested for the CWPO of
aqueous phenol in a batch slurry reactor using hydrogen peroxide, as an oxidant, under very mild conditions (P = 1 atm and
T = 80 ◦ C). The five materials were produced according to four recipes. Structural data was provided by XRD and nitrogen
adsorption–desorption, the iron content was assessed by atomic absorption. The freshly obtained catalysts, with embedded
templates within pores, were activated either by calcination or through solvent extraction, then used for CWPO. The spent
catalysts were recovered and characterized before thermal re-activation and re-exposure to fresh phenol-containing solutions.
For all materials, in the first run, the conversion of phenol was total and rapid (less than 15 min), and the removal of total
pollution plateaued between 55 and 85% in 180 min with mineralization selectivities of ca. 95%. The materials underwent
leaching of the iron, from 6% (w/w) to total. It was possible to perform successful CWPO reactions with some recycled
materials. In terms of activity as well as robustness in the reaction conditions, one catalyst was able to remove 81% of the
organic load with a selectivity of 93%, and simultaneously leaching 6% iron off. During the second run, it showed less activity
but endured 2% leaching only. Surprisingly, the structure of this best catalyst was not mesoporous nor microporous and
exhibited a very low specific surface area.
© 2003 Elsevier B.V. All rights reserved.
Keywords: Heterogeneous catalytic wet peroxidation; Wastewater treatment; Mesoporous silicalite; Iron; Hydrogen peroxide; Phenol; Leaching

1. Introduction carbon dioxide and/or other harmless species. Cata-

The increasingly stringent water quality regula-
tions and demand for water reuse after treatment
have stimulated strong research efforts aimed at the
development of cheap and efficient routes to destroy
toxic and/or bio-refractory organic compounds from
liquid streams. One possible path is the complete
oxidation (or mineralization) of these compounds to
∗ Corresponding author. Tel.: +1-418-656-3566;
fax: +1-418-656-5993.
E-mail address: faical.larachi@gch.ulaval.ca (F. Larachi).
lysts are certainly expected to occupy a central place
in such processes [1–3]. Therefore, the design of new
catalyst formulations is actively pursued in industry
and academia to meet market demands driven by
increasingly tight profit margins, especially because
no immediate dollar profits are expected in cleaning
“end-of-pipe” wastewater streams.
Several successful processes can be applied at
various stages of water treatment, and undoubtedly
catalytic wet oxidation (CWO), using pure oxygen or
air for oxidant, has proven its worth for wastewater
treatment, particularly when organic contaminants at

0926-3373/$ – see front matter © 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0926-3373(03)00224-8
294 N. Crowther, F. Larachi / Applied Catalysis B: Environmental 46 (2003) 293–305
low or moderate loads are concerned. CWO is usually
practiced between 100 and 300 ◦ C and at pressures
in the 1–10 MPa range. These severe conditions are
required for minimizing the impact of CWO intrinsic
main limitations which are the oxygen low solubil-
ity in water and the hindered oxygen supply to the
liquid-phase due to the gas- and liquid-side mass
transfer resistances. Circumventing completely the
limited-solubility as well as the interfacial resistance
barriers of the oxidant implies increasing temperature
and pressure above the water critical point (374 ◦ C,
218 atm) yielding limitless O2 -water miscibility and
resulting in a collapse of the gas–liquid interface [4,5].
Another far more economical alternative route to su-
percritical wet oxidation is to opt for a liquid-phase
oxidant, such as hydrogen peroxide, that would allow
the (wet peroxidation) conditions to decrease dramat-
ically to atmospheric pressure and sub-boiling water
temperature [6,7].
The use of wet peroxidation homogeneous catalysts
like the Fenton catalysts Fe2+ /Fe3+ , or other dissolved
transition metal cations, e.g. Cu2+ , Mn2+ , and Co2+ ,
has proven to be quite efficient [8,9], but this neces-
sitates a tight pH control to prevent precipitation and
extra steps for the recuperation and the reuse of the
catalyst [10]. The alternative is the development of
solid-phase catalysts, which feature efficiency as well
as stability under the reaction conditions.
The aim of the present work is to synthesize and
characterize a series of heterogeneous catalysts for
the catalytic wet peroxidation (CWPO) of organic
compounds in water. Phenol was chosen as a model
reactant for comparison with available literature on
CWPO. Hydrogen peroxide was chosen as the oxi-
dant, having both advantages of being relatively in-
expensive and a liquid-phase compound. The catalyst
features iron(III) species supported on silica-based
mesoporous molecular sieves (MCM and HMS hexag-
onal structures). The expected characteristics are
higher specific surface area together with large pore
size which is expected to enhance intraparticle dif-
fusion when compared to microporous materials like
zeolites. Iron doping was chosen for its cheapness as
well as for its known participation in the conventional
Fenton/Haber–Weiss homogeneous reaction pathway.
It has been shown that the final stability, especially
the hydrothermal stability of the mesoporous network
depends on the synthesis conditions [11]. In particular
the pH of the gel greatly influences the thickness of the
pore walls. Gels with a high pH frequently possess thin
and fragile walls, as opposed to thick ones obtained
for neutral pH.
There are two ways in which the iron can mod-
ify the silica structure. The metal may simply be in
contact with the surface of the pore walls, and upon
calcination, nanoclusters of octagonal crystalline iron
oxide (Fe2 O3 ) are formed. This extra-framework iron
is retained to the support only by weak Van der Waals
bonds. The iron oxide clusters are prone to easily leach
off and/or be washed out during the CWPO treating.
In the second way, the iron may well be incorporated
by substitution into the silica framework, and thus be
attached by covalent bonds. Iron lies in a tetragonal
geometry and is referred to as framework iron. Iron can
be incorporated in the silica framework through direct
synthesis by introducing an appropriate iron precursor
in the synthesis gel as done for other atoms such as
titanium or boron [12]. In this way, iron atoms present
at the edge of the pore walls are likely to represent
resistant active centers.
Substitution is more difficult than simple contact
to the surface and there is often a mixture of both
framework and extra-framework metal species when
substitution is intended. Some works report that iron
oxide clusters color the materials in shades of brown,
whereas framework iron is colorless [13–15]. Finally,
a maximum limit of 0.9–1.0 wt.% for framework po-
sitions was established by Wang et al. [15].
Some works report that the presence in the synthe-
sis gel of fluoride anions maximizes the proportion of
framework-substituted metals [16–18]. Besides being
widely used as condensation agents in sol–gel synthe-
sized silica [18], fluorides are thought to form soluble
complexes with iron(III) at the pH values prevailing
in the synthesis [19].
Previous studies in our group have shown that
CWO catalysts may undergo some deactivation via
the obstruction of the catalytic sites by adsorption
and/or polymerization of the organics present [20–22].
The fraction of carbon actually converted to CO2 ,
will be measured to evaluate the mineralization selec-
tivity of the synthesized materials. Deactivation can
also occur via the leaching of the active species out
of the material. This phenomenon may be attributed
to several factors. The first of which is that the pH
of the CWPO reaction medium is acidic. Iron and
 N. Crowther, F. Larachi / Applied Catalysis B: Environmental 46 (2003) 293–305
particularly extra-framework iron oxide are readily
dissolved in an acidic environment. Secondly, strong
complexing and solvolytic properties of the oxidant
and/or intermediate products (e.g. catechol) may rup-
ture the metal-oxygen bonds [23,24]. Finally, the pH
range corresponds to the stability zone of Fe3+ in
aqueous solution [19].
2. Experimental
2.1. Catalyst preparation
The formation of hexagonal mesoporous silica
structures, based on a sol–gel process, is a relatively
complex phenomenon and has been thoroughly de-
tailed in numerous articles since their discovery [25].
It implies a hydrothermal sol–gel process involving
the condensation of silica species (soluble or col-
loidal), with uptake of other inorganic compounds if
present, on the surface of ordered micelles of surfac-
tant acting as template. This eventually leads to the
precipitation of the solid-phase which is recovered.
Five iron-loaded hexagonal or lamellar mesoporous
catalysts were prepared with iron loading between 1.2
and 16.6% (w/w). Samples A–D were expected to dis-
play a MCM structure (ionic surfactant), and for sam-
ple E, HMS composition (neutral template).
Synthesis of catalyst A was performed using a
procedure described by Alves and Pastore [16].
First, a “silica source” was prepared by adjusting a
commercial sodium silicate solution (Aldrich 27%
SiO2 , 14% NaOH, d = 1.390) to give a 90 g/l SiO2 ;
180 g/l NaOH solution. To 66 ml of the silica source
brought to a temperature of 75 ◦ C approximately, was
slowly added 12.7 g of a 33 wt.% aqueous solution of
cetyltrimethylammonium bromide (CTAB, Aldrich)
under stirring. After further stirring for 30 min, the
pH was slowly lowered to 12 with concentrated
hydrofluoric acid (EM Science) used as received.
Then, approximately 72 ml of a 0.07 mol/l solution of
iron(III) potassium oxalate (Alfa Aesar) was added
to the gel. The molar composition of the gel mixture
was 0.1SiO2 ·0.005Fe·0.011CTAB·100H2 O. After 4 h
of stirring, the final pH was around 11.6. The gel was
allowed to age in Teflon® lined stainless steel auto-
claves at 150 ◦ C for 66 h. After this, the precipitate
was filtered, washed extensively with deionised water
295
then a small amount of ethanol, and dried overnight
at 80 ◦ C. The “fresh” form of the obtained catalyst A
is denoted A-f.
Catalyst B was produced in a similar way, except
that the iron potassium oxalate complex was replaced
by an iron potassium EDTA complex, prepared from
an appropriate amount of K2 EDTA (EDTA 1:2 KOH)
combined with Fe(NO3 )3 ·9H2 O (Aldrich) in a 1:1 mo-
lar proportion in water.
Catalyst C was synthesized as reported by Pasqua
et al. [17]. A first solution was prepared from
7.65 g of CTAB, 14.81 g of NH4 F and 197.1 g of
water. After solubilization, 2.02 g Fe(NO3 )3 ·9H2 O
with 65.7 g water were added. Then, 20.85 g of
tetraethylorthosilicate (TEOS, Aldrich) was added
slowly. The gel had the following molar composition:
0.1SiO2 ·0.005Fe·0.021CTAB·0.4NH4 F·146H2 O. Pre-
cipitation was readily observed, and the gel was left
to stir for 4 h at room temperature, before being trans-
ferred to a Teflon® lined stainless steel autoclave to
age statically at 105 ◦ C for 24 h. The pH remained
around 7.7 throughout the process. The precipitate
was then filtered, washed with water and a dash of
ethanol and left to dry at 80 ◦ C overnight.
Catalyst D was prepared according to Reddy
and Song [26]. First, 4 g of Cab-O-Sil were dis-
persed in 25.7 g of water. Secondly, 11.6 g of
tetramethylammonium-silicate solution (Aldrich) was
mixed with 5.5 g of sodium silicate solution (Aldrich)
then added to the Cab-O-Sil and left 15 min to stir.
Thirdly, a solution of 0.67 g of iron nitrate (Aldrich)
and 10 g of water was slowly added to the previ-
ous mixture. Finally, a solution of 12.9 g of CTAB
in 77 g of water was added to form the gel. The
gel molar composition was: 1SiO2 ·0.025Fe·0.3124-
CTAB·0.1728NaOH·0.0876TMA·63.3H2 O. The gel
was allowed to stir for 2 h, and was transferred to the
Teflon® lined stainless steel autoclave to age stati-
cally at 100 ◦ C for 24 h. The precipitate was filtered,
washed and left to dry at 100 ◦ C overnight.
Catalyst E preparation was similar to that detailed
in Ruel and Gontier [27]. A solution of 17.69 g TEOS,
24.76 g ethanol and 4.95 g isopropyl alcohol was
placed in a beaker. Slowly added to it was a second
solution of 1.5 ml aqueous HCl 1 M, 54.25 g water,
4.13 g dodecylamine (Aldrich) and 0.84 g iron nitrate.
The gel had the following composition: 1SiO2 ·0.025-
Fe·0.26DDA·6.3EtOH·0.97IPA·0.02HCl·36H2 O. Af-
296 N. Crowther, F. Larachi / Applied Catalysis B: Environmental 46 (2003) 293–305
ter stirring for 1 h, it was left to stand overnight, then
the precipitate was filtered, washed and left to dry at
100 ◦ C overnight.
All the materials described above are referred as
“fresh”. In this form, the template remained trapped
inside the pores. In order for the catalyst to be ready for
use, the template was removed either by calcination,
or by extraction with appropriate template solvents.
For calcination, the samples were placed in an oven
and the temperature was raised from room to 550 ◦ C
in 6 h under nitrogen, and kept up for six more hours
under dry air. Extraction was performed by dispersing
the fresh catalyst in a mixture of ethanol and water
under stirring, aided with small amounts of NaCl or
HCl, for 3–4 h. The extracted catalysts were recovered
by filtration, washing and drying at 80 ◦ C overnight.
These materials then are referred to as “activated”.
2.2. Catalyst characterization
To identify the structure and the distance between
(1 0 0) diffraction lattice planes, X-ray powder diffrac-
tion (XRD) patterns were recorded on a Siemens
D5000 diffractometer using the Cu K␣ radiation at
40 kV to 30 mA (λ = 1.54184 Å), at 1 ◦ /min [2θ] over
the range 1–8◦ . The specific BET surface areas and the
pore size distribution were determined using N2 ad-
sorption and the BET model. The nitrogen adsorption
isotherms at 77 K were measured on an OMNISORP
100 or a QUANTACHROME Autosorp-1 device, af-
ter pre-treatment under vacuum at 250 ◦ C to a residual
pressure of about 10−5 Torr. The total iron content
of the calcined samples was measured by atomic
absorption spectroscopy (AAS), on a Perkin-Elmer
AAnalyst100 or with a Perkin-Elmer Optima3000
inductively coupled plasma spectrometer, ICP. The
samples were first dissolved in an aqueous HCl–HF
mixture. Catalysts were investigated for their carbon
content with a Carlo-Erba 1106 CHN analyzer and
a FT-IR spectrometer (Nicolet), allowing to evaluate
the fraction of carbon removed from the liquid-phase
but not converted to CO2 during CWPO.
Catalysts for reuse were recovered by filtration from
the reaction medium, then dried at 100 ◦ C overnight
and underwent complete calcination cycle just like for
the activation. The materials ready for reuse were an-
alyzed for their structure by XRD, and for their total
iron content by AAS or ICP.
The materials will be referred to by their letter
followed by -f, -c, -e, -r, respectively, for “fresh”,
“calcined”, “extracted”, and “reused”.
2.3. Oxidation reaction
Phenol oxidation was carried out in a double-jacket
glass batch reactor. The entire reactor volume was
first sparged by flushing with industrial grade he-
lium (Praxair), then closed and kept under slight He
overpressure. An aqueous phenol solution at 0.260 g/l
corresponding to 200 mg/l of carbon (ppm C) was
prepared by dissolving phenol (EM Science) into
deionized water brought to pH 3.5 with sulfuric acid
(EM Science), then sonically degassed. The deionized
water was obtained from a Culligan Model E1 Plus
purification system (electrical conductance < 1 ␮S).
The total volume of liquid (phenol and hydrogen per-
oxide solutions) being 300 ml, the adequate amount
of phenol solution was poured into the reactor. The
catalyst (0.15 g, i.e. load of 0.5 g/l) was then contacted
with the solution, and both were allowed to reach the
experimental temperature of 80 ◦ C in approximately
30 min. The volume of 1 mol/l hydrogen peroxide
commercial solution (EM Science) to add was cal-
culated by considering the stoichiometric amount of
H2 O2 required to convert phenol to CO2 (14 mol per
mol of phenol) plus an excess of 50–60% above the
stoichiometric needs. The reaction time reference was
taken when the volume of hydrogen peroxide solution
was injected in one shot into the reactor.
Samples of the reaction medium were analyzed
in order to obtain the total organic carbon (TOC),
the phenol and the hydrogen peroxide conversions,
and to monitor the pH evolution and the potentially
leached off iron from the catalyst. TOC of acidified
samples (to remove dissolved CO2 ) was measured
using a combustion/non-dispersive infrared gas ana-
lyzer (model Shimadzu 5050 TOC analyzer, Mandel
Scientific Inc., Montréal, PQ).
Disappearance of phenol, the parent pollutant, was
monitored using a high-performance liquid chromato-
graph (HPLC), which consisted of a combination
of model 510 Waters dual-solvent delivery system,
a model 490 programmable multi-wavelength ultra-
violet absorbance detector, an automated gradient
controller, and a Phenomenex Bondclone® C18,
300 mm × 3.9 mm × 10 ␮m. The unit was operated
 N. Crowther, F. Larachi / Applied Catalysis B: Environmental 46 (2003) 293–305
isocratically at 0.8 ml min−1 using as a mobile phase
50:50 (volume ratio) water:methanol. UV detection
was performed at 254 nm. Peak area recording and
integration was achieved using a Hewlett-Packard in-
tegrator (HP 3390 A). HPLC calibration was achieved
by using phenol concentrated solutions from which
daughter solutions were obtained by successive di-
lutions. The main intermediate oxidation products,
detected but not quantitated, were catechol, hydro-
quinone, quinones, muconic acid, maleic acid, oxalic
acid and acetic acid [6]. H2 O2 consumption was
given by the iodine–thiosulfate titration method. The
content of metal ions was determined by AAS or ICP,
described previously.
3. Results
3.1. Oxidation reaction
The pH starting value of the reaction medium was
set to 3.5 because previous studies showed that this
was the optimal value for phenol oxidation by hydro-
gen peroxide in the presence of iron [6,7]. Though
pH was left out of control during reaction, for all
catalytic tests performed, no significant change was
noted.
Blank tests were preliminarily carried out prior to
the actual heterogeneous catalytic tests, in the absence
100
90
Relative residual concentration
80
70
60
50
40
30
20
10
0
0 50
Time (min)
Fig. 1. Relative residual number of moles for TOC, phenol and H2 O2 . CWPO over B-c catalyst. Conditions: temperature 80 ◦ C; phenol
initial concentration 170 ppm C; 163% H2 O2 (excess stoichiometric ratio); catalyst load 0.5 g/l; Fe 25.3 mg.
297
of one or the other of the reactants, in the experimen-
tal conditions described previously. In the absence of
iron, no significant consumption of phenol or hydro-
gen peroxide was noticed. Homogeneous iron at a con-
centration of 12 ppm (equivalent to 0.5 g/l of catalyst
with 2.5% (w/w) iron loading) was contacted with a
phenol-free solution of hydrogen peroxide. A 35% de-
crease in the amount of oxidant was observed in the
space of 1 h. Thus, free iron(III) cations were effective
in activating hydrogen peroxide.
Fig. 1 presents a typical time course of the relative
residual concentrations for total organic carbon, phe-
nol and hydrogen peroxide obtained for catalyst B-c.
The trends exhibited in Fig. 1 are also representative
of the catalytic behavior for the other catalysts A-c
through D-c.
Table 1 summarizes the TOC, phenol and peroxide
relative residues for all the catalysts, as well as figures
characterizing the performance of the oxidant. All cat-
alysts were able to completely oxidize the parent pol-
lutant, phenol, in the space of ca. 10 min. There was a
significant decrease in the total organic carbon content
of the reaction medium. This indicated that most of
the organic load was removed from the liquid-phase.
Deeper removal of the organic load was impeded, as
observed by other groups [6,7], by the accumulation
of refractory organic byproduct acids that were sta-
ble in the reaction medium because they were already
highly oxidized molecules.
TOC
PhOH
H2O2
100 150
298 N. Crowther, F. Larachi / Applied Catalysis B: Environmental 46 (2003) 293–305

Table 1 lishing that there was some parasitic self-degradation

Relative residual number of moles for TOC, phenol and H2 O2 of the hydrogen peroxide, especially in the early mo-
Catalyst Time Residual ψ (S in %) ments of the reaction where H2 O2 decomposition was
(min)
Phenol TOC H2 O2 at its highest. Similarly, the useful fraction of hydro-
(%) (%) (%) gen peroxide that contributed for the removal of the
A-c 10 2.2 69 58 5.3 (44) organic pollution (quantified in terms of a selectivity
20 0 48 47 4.0 (58) S = 2.33 × 100/ψ) indicates CWPO selectivity al-
60 0 24 28 3.7 (63) ways less than 100% (Table 1).
120 0 15 15 4.0 (58)
180 0 14 9 4.2 (56)
3.2. Catalyst stability to leaching and recycling, and
B-c 10 0.7 73 60 6.7 (35) mineralization selectivity
20 0 53 40 4.9 (48)
60 0 35 33 4.0 (58)
120 0 25 25 3.8 (61) To evaluate the contribution of homogeneous iron
180 0 19 19 3.9 (60) cations possibly leaching off from the solid catalysts,
C-c 10 0 58 60 3.6 (65)
an experiment in the same conditions was carried out
20 0 53 56 3.4 (69) using iron nitrate salts to mimic the leached cations.
60 0 46 41 3.6 (65) The iron concentration was chosen to be 5 ppm
150 0 35 28 3.8 (61) (1.5 mg/300 ml) which corresponded to the amount of
D-c 20 0.4 100 49 –
60 0 50 35 3.2 (73) Table 2
120 0 43 26 3.2 (73) Iron catalysts leaching patterns
150 0 37 24 3.0 (78) Catalyst Time Iron
(min)
D-e 20 0.4 86 76 6.0 (39) Initial Leacheda Max. leached
60 0 65 59 3.9 (60) (mg) (%) ± 0.5 conc. (ppm)b
130 0 60 54 3.9 (60) A-c 20 24.2 14 15
180 0 47 47 3.4 (69) 60 18
E-c 20 0 96 49 45.0 (0.05) 120 17
60 0 62 33 5.5 (42) 180 13
120 0 36 21 3.9 (60) B-c 20 25.3 2 5
180 0 27 11 3.8 (61) 60 5
Conditions: temperature 80 ◦ C, initial phenol: 180 ppm C, stoi- 120 5
chiometric ratio excess H2 O2 : 150%, catalyst load 0.5 g/l. 180 6
C-c 20 7.3 41 14
According to the mineralization reaction of phenol 60 54
by hydrogen peroxide: 150 56
D-c 20 2.2 64 5
C6 H5 OH + 14H2 O2 → 6CO2 + 17H2 O, 60 65
120 65
the molar ratio 150 66
n0H2 O2 − nH2 O2 (t) D-e 20 1.6 92 5
Ψ(t) = 60 100
n0TOC − nTOC (t) 130 100
180 84
measures the utilization of hydrogen peroxide ver-
sus the consumption of dissolved organic carbon as E-c 20 4.5 45 12
60 77
a function of time (Table 1). The ultimate value ex- 120 77
pected in the case of complete oxidation of phenol 180 75
and its intermediate organics and in the absence of
Conditions: see Table 1.
self-decomposition of the oxidant, would be 2.3. For a Leached amount is relative to the initial iron number of moles.
all catalysts, the values of ψ were over 2.3, estab- b Maximum amount of leached iron, expressed in mg/l.
 N. Crowther, F. Larachi / Applied Catalysis B: Environmental 46 (2003) 293–305 299

100
90
Relative residual concentration

80 TOC
70 PhOH
60 H2O2

50
40
30
20
10
0
0 50 100 150

Time (min)

Fig. 2. Relative residual concentrations for TOC, phenol and H2 O2 . Homogeneously ferric catalyzed phenol wet peroxidation. Conditions:
temperature 80 ◦ C; phenol initial concentration 175 ppm C; 162% H2 O2 (excess stoichiometric ratio); Fe 1.5 mg.

Fe leached from pristine B-c catalyst (Table 2). The
relative residual profiles for TOC, phenol and H2 O2
are illustrated in Fig. 2 for the homogeneously ferric
catalyzed wet peroxidation of phenol. Homogeneous
iron cations, which are entirely available catalytic
centers, yielded a similar pattern of total phenol
oxidation and partial phenol mineralization. Phenol
vanished in about 25 min (Fig. 2) compared to the
10 min required in the case of pristine B-c catalyst
(Fig. 1). In addition, after 150 min, ψ = 3.4 which
illustrates that here as well, the oxidant underwent
some self-degradation.
Summarized in Table 2 are the values of leached
iron amounts from the catalysts expressed in terms of
time course of Fe (%, w/w) with respect to the total
exhibited a lesser tendency to metal leaching. In par-
ticular, catalyst B-c was the one that exhibited the best
performance in terms of leaching (6% or 5 ppm), be-
sides being among the best to degrade phenol and to
reduce TOC (Table 1).
Although the expected maximum leaching would
occur at the end of the reaction periods, materials A-c
and D-e appeared to be an exception and showed max-
imum leaching during the course of CWPO. For sam-
ple D-e, this may be ascribed to the limited analytical
10
8
% Fe leaching

iron content of the pristine catalysts, and of the ulti- 6

mate ppm concentration in the solutions. Fig. 3 shows
the leached amount of iron versus time for catalyst
4
B-c, and was typical of the profiles monitored for the
other materials. The information in Table 2 evidences
2
that iron in all tested catalysts had a tendency to par-
tially dissolve in the liquid.
Two trends deserve attention at this stage. It can be 0
discerned that materials prepared without fluorides in 0 50 100 150
Time (min)
the synthesis gel, such as catalysts D and E, lost vir-
tually almost their whole iron inventory very quickly Fig. 3. Percent iron leaching for catalyst B-c. Conditions: temper-
(66–100% Fe leach off). Conversely, catalysts A–C, ature 80 ◦ C; phenol initial concentration 170 ppm C; 163% H2 O2
for which fluorides were added to the synthesis gel, (excess stoichiometric ratio); catalyst load 0.5 g/l; Fe 25.3 mg.
300 N. Crowther, F. Larachi / Applied Catalysis B: Environmental 46 (2003) 293–305

Table 3
Carbon content of the catalysts after reaction, including recycled catalysts
Catalyst Removed carbon form liquid (mg/l) Deposited carbon on solid (mg/l) Mineralization selectivity (%)

A-c – – –
B-c 125 8.1 94
B-c recycled 40 2.5 94
C-c 131 10.0 92
C-c recycled 86 2.7 97
D-c – – –
D-e – – –
E-c – – –
Removed carbon is given by TOC measurement, deposited carbon, expressed as equivalent of carbon concentration in the liquid, is given
by elemental analysis. Mineralization selectivity represents the amount of carbon actually converted to CO2 .

accuracy considering the lowest iron loading of this
catalyst. At the other extreme, some re-adsorption of
iron to the catalyst might be at the origin of the slight
disturbance in the analysis of Fe from sample A-c.
The catalysts before and after reaction were also
investigated for their carbon content and thus for the
mineralization selectivity. The materials after initial
activation did not contain any carbon. Table 3 presents
the results of the carbon content detected in the mate-
rials after the reaction runs. The removed carbon con-
centration corresponds to the difference between the
initial (TOC0 ) and final TOC in the liquid. The de-
posited carbon (W) corresponds to the carbon that left
the aqueous solution but that did not convert to CO2 .
The catalyst mineralization selectivity is defined as the
mass of carbon converted to CO2 divided by the mass
of carbon eliminated from water: [(TOC0 − TOC −
W)/(TOC0 − TOC)] × 100, where W is the concentra-
tion of “solid” carbon on the catalyst expressed as the
mass of carbon per unit solution’s volume in mg/l.
As can be seen from Table 3, the mineralization se-
lectivity for catalysts B-c, B-c-r, C-c and C-c-r was
very high suggesting that the amount of carbon sus-
ceptible to build up on the catalyst was marginally low.
As no darkening of the materials was noticed during
the reaction, it is likely that catalyst deactivation, if it
was to occur, could not be ascribed to the deposition
of carbonaceous materials.
Table 4 shows the catalytic behavior of some reused
materials. All reused catalysts were calcined, just like

Table 4
Catalyst reuse after thermal reactivation
Recycled catalyst Time (min) Residual ψ Iron leaching

Phenol (%) TOC (%) H2 O2 (%) Initial (mg) Maximum

% ppm in liquid

A-c-r 10 94 97 100 – 10.7 36 13

60 0 53 45 3.9
120 0 46 36 4.1
B-c-r 10 99 100 86 High 6.5 2 0.5
30 73 92 82 11.1
120 4 69 49 7.1
C-c-r 10 96 91 94 2.4 1.0 30 0.9
60 0 50 48 3.9
140 0 40 37 3.9
D-c-r 20 85 100 99 – 0.1 100 0.3
50 78 91 91 3.7
120 68 82 86 3.1
Conditions: see Tables 1 and 2.
 N. Crowther, F. Larachi / Applied Catalysis B: Environmental 46 (2003) 293–305
Table 5
Materials’ specific surface area and pore diameters
Catalysts Specific surface Pore size
area (m2 /g) distribution (Å)
A-c 100 – solvent extraction. This process is expected to increase
C-c 480 33
D-c 1058 30
D-e 866 30
E-c 895 – and D regardless of the activation method, revealing
for the activation, prior to recycling and contacting
with fresh phenolic solutions. It is noteworthy that the
catalyst amount, phenol feed concentration as well as
temperature were held under the same conditions as in
the testing of the fresh catalysts. However there was no
attempt to readjust the amount of catalyst to account
for the loss of iron between the fresh and the recycled
catalyst tests. For all the reused catalysts, a notice-
able activity loss was observed in comparison with the
activity using the pristine catalysts A-c through D-c.
Such activity loss in the case of spent sample D-c-r
was dramatic as phenol hardly converted and its min-
eralization very limited. All other materials were ca-
pable of performing, once more, complete elimination
of phenol as well as a notable TOC reduction.
In terms of leaching during the second run, sample
D-c-r lost completely its iron content. The poor cat-
alytic activity should here be attributed to the minute
amounts of iron in sample D-c-r (0.1 mg) which can-
not sustain high conversion of the pollutant (32% phe-
nol conversion and 18% TC conversion). In contrast,
sample B-c-r hardly lost any iron (2%) in the solution,
and its good robustness to retain iron in the second
run is to be paralleled with the one it exhibited during
the first run (6% iron loss).
3.3. Materials’ structural data
The structural data of the solids used for this study
included low-angle X-ray diffraction patterns to check
the crystalline phase (Fig. 4), nitrogen adsorption
isotherms (BET) for specific surface area and pore
size (Table 4), and total iron content (Table 5).
The materials obtained after filtration of the synthe-
sis gel, i.e. before activation, are referred to as fresh.
At this point, the template was still trapped within the
material. For all catalysts in the fresh form, the large
301
peak around 2θ = 2◦ was the d100 lattice plane, and
was typical of hexagonal mesoporous structures [28]
(Fig. 4a–d).
The template was removed either thermally or by
the contrast of the X-ray diffraction since the pores are
now empty. This was especially visible for catalysts C
hexagonal structure of the catalysts by emergence of
secondary diffraction peaks. Catalyst C was expected
to have very thick pore walls [17] and therefore the
secondary peaks were less obvious. In the case of sam-
ple E, only calcination revealed the hexagonal struc-
ture, whereas extraction led to pore breakdown. Upon
calcination, samples A and B underwent, respectively,
partial and complete collapse of their structure. This
occurred for instance in lamellar mesoporous phases
such as MCM-50 type materials [28]. It is possible to
reckon that B exhibits lamellar symmetry, and that A
displays a mixture of hexagonal (stable upon calcina-
tion) and lamellar structures.
XRD patterns were also taken after the first catalytic
run. This revealed how the structure was affected by
the reaction conditions. For catalysts C–E, the hexag-
onal network was retained, as evidenced by only lit-
tle changes in the respective XRD peaks’ height and
shape. Yet for A, complete collapse was observed.
BET measurements were performed on the fresh
and on the activated materials (Table 5). A high spe-
cific surface area is typical of mesoporous phases, es-
pecially for well structured hexagonal phases such as
sample D-c (see also XRD pattern). The pore diame-
ter being controlled by the template, sizes of 30–33 Å
correspond to the expected values for CTAB templat-
ing.
For sample A-c, no pore size distribution maxi-
mum could be established. Before calcination though,
a specific surface area of 261 m2 /g and a pore size
of 32 Å were determined. In a similar way, for sam-
ple B-c, BET measurement yielded 10 m2 /g, though
for the fresh uncalcined sample, a BET surface area
of 480 m2 /g and a pore size of ca. 30 Å were found.
For these two materials, the results corroborated the
XRD observations, i.e. that the inner-porous network
collapsed during activation by calcination.
Table 6 presents the iron weight content of the ma-
terials. For catalysts A and B, the iron loading in the
calcined form was much higher than expected, which
302 N. Crowther, F. Larachi / Applied Catalysis B: Environmental 46 (2003) 293–305

Fig. 4. X-ray diffractograms for materials A–E, fresh, calcined, extracted, and after CWPO reaction for the initially calcined materials.

was rather surprising for silica-based materials. For sis of 6 g of silica (see experimental section above).
the others, the content after activation was close to the Preparations C–E yielded around 6 g of activated ma-
expected value. For all catalysts prepared in this work, terial, whereas samples A and B, prepared using a very
the amount of each reagent was determined on a ba- similar method, produced approximately 1.7 g [16]. It
 N. Crowther, F. Larachi / Applied Catalysis B: Environmental 46 (2003) 293–305 303

Table 6 Sample E-c exhibited a slightly better catalytic ac-

Materials’ iron content (expressed as weight percentage) at differ- tivity than sample D-c or D-e. HMS-type materials,
ent steps: in the synthesis media, calculated from the amounts of
formed by using neutral templates as opposed to ionic
iron source added to the gel; before first use; before re-use
templates, presented better features for catalytic ap-
Catalysts In synthesis After activation After reusing plication than well defined hexagonal structures [29].
gel (%) (%) (%)
While catalyst D-e let all its iron go, catalyst
A 5.0 15.1 (c) 12.2
D-c could retain 33% after one cycle of utilization.
B 5.0 16.6 (c) 15.6
C 5.0 4.9 (c) 2.2 Moreover, preparatory work, involving other solvent-
D 2.5 1.5 (c) 0.5 extracted MCM-41 type mesoporous materials were
1.2 (e) – tested for CWPO, confirmed an almost total loss of
E 2.5 2.3 (c) – Fe. It may be argued that the solvent extraction of
the template, when compared to calcination, does not
bring better anchoring of iron into the structure. As
far as iron stability into the structure was concerned,
is likely that the precipitation of the silica from the catalysts D-c, D-e and E-c should be discarded.
sol–gel medium was incomplete, and thus the solid ac-
tually formed was richer in iron than the synthesis gel. 4.2. Catalysts A-c, B-c and C-c
After reusing the catalysts, the iron loading dropped
due to leaching during the CWPO reaction. Before the first run and after calcination, the meso-
porous structure was well defined for C-c, it was
partially altered for A-c but totally destroyed for
4. Discussion B-c. During CWPO reaction, A-c structure collapsed
completely, whereas that of C-c remained stable. The
This study’s goal was to investigate the potential stability of C-c can be explained by the wall thick-
of iron-containing mesoporous silicalite materials for ness obtained for synthesis gel pH around neutral,
the heterogeneous CWPO of phenol. For this purpose, as opposed to the alkaline conditions for A and B
two decisive factors need to be met, namely, the cat- samples.
alyst activity and the catalyst stability in the reaction Materials A-c and B-c were capable to achieve ca.
medium. Catalyst stability can be envisioned through 85% pollution removal which was equivalent or better
three criteria: deactivation by fouling, deactivation by than the TOC conversions reported in previous stud-
leaching, and structure robustness. Deactivation by ies in the case of Fe-HZSM-5 zeolite or pillared clays
fouling was ruled out based on the high mineraliza- [6,30]. All three materials A-c, B-c and C-c enabled
tion selectivities shown in Table 3. Iron leaching off very rapid and complete destruction of the parent pol-
was the main factor for deactivation for the five cat- lutant in the first run, and still exhibited good activity
alyst preparation protocols (Tables 2 and 4) although after reuse.
addition of fluorides in the synthesis gel appeared to C-c sample lost 56% of its iron in the first run leav-
lower the extent of leaching. ing it as less appealing than A-c and B-c samples with
less than 15% Fe loss. After recycling, C-c and A-c
4.1. Catalysts D-c, D-e and E-c iron loss amounted to a further 30–40% as opposed
to 2% Fe loss of B-c sample. The acidic environment
Catalysts D-c, D-e and E-c were particularly prone was probably a major factor for the extraction of the
to iron leach off, and respectively, 66, 100 and 75% of metal from the support, and B-c catalyst appeared to
the active species were lost during the first CWPO run. be acid-proof in terms of iron retention.
It was impossible to assess unambiguously the cat- Catalysts A-c, B-c and C-c were prepared from gels
alytic activity contributed by the heterogeneous iron. containing fluoride, introduced as hydrofluoric acid
Especially for samples D-e and E-c, which lost nearly (A and B) or as ammonium fluoride (C). They were
all their active sites, they could not be reused in a sec- intentionally used to favor iron insertion into the silica
ond run. matrix, so it was expected to be tightly bound to the
304 N. Crowther, F. Larachi / Applied Catalysis B: Environmental 46 (2003) 293–305
support. On the other hand, it is anticipated that the
extra-framework iron will leach off first.
Catalyst B-c, freshly activated, was the solid that
offered the best catalytic activity, in spite of the little
estimated sites’ availability (low BET surface area). It
was investigated by XRD for microporosity and local
crystalline environments provided by iron oxide clus-
ters, from 2θ diffraction angles of 1–60◦ but no mi-
cropores or nanoclusters were detected. The change
in activity after recycling cannot be explained though
leaching deactivation due the low amounts of iron re-
leased in the solution. Besides, no change in color
was noticed. It is presumed that a structural change
occurred during the first and/or second runs that in-
volved the masking of some active centers without
migration of iron from framework to extra-framework
positions.
The leaching propensity of sample A-c in the two
runs was obvious. This may be correlated to the
fact that during calcination of spent catalyst, prior to
re-use, turned the material to dark brown color and
involved migration of Fe from framework to extra-
framework (i.e. exposed) positions prompting leach
off of iron in the course of the CWPO reaction.
Sample C-c was likely to exhibit better catalytic
activity because of well defined mesopores, thick
walls and high sites availability, compared to the
collapsed porous networks in A-c and B-c samples.
It was noticed, however, that the color turned pale
during CWPO but darkened upon activation cycles.
Migration of iron as in sample A-c might occur as a
consequence of calcination.
5. Conclusion
The best candidate for heterogeneous catalytic wet
peroxide oxidation of phenol, under mild conditions
(atmospheric pressure and 80 ◦ C), would be the cal-
cined catalyst B. In the space of 15 min, the parent
pollutant was totally degraded and after 180 min, 81%
of the organic load was removed from the liquid-phase
with a mineralization selectivity of 93%. It was also
possible to reuse B-c after re-calcination, although it
showed less catalytic activity. In terms of robustness,
B-c endured leaching of only 6% after the first cat-
alytic run, and when re-calcined for re-use, of only
2%.
The structure of catalyst B-c was not mesoporous
nor microporous, and exhibited a very low specific sur-
face area. Paradoxically, catalyst B-c displayed among
the best activity and leach-proof ability compared to
any equivalent iron-modified mesoporous support. On-
going work is in progress to investigate the nature of
the catalytic sites on catalyst B. The question of the
way iron is bound to the support, as framework (sub-
stituted into the silica matrix) or extra-framework (iron
nano-clusters trapped in the material) species could be
elucidated by ESR and Mössbauer spectroscopy cou-
pled with EXAFS. Also, the availability of iron to-
wards the incoming oxidant or organic molecules may
be clarified by TPR, TPO, TPD or TPA.
Acknowledgements
Financial support from the Natural Sciences and En-
gineering Research Council of Canada (NSERC) and
the Fonds Québécois de la Recherche sur la Nature
et les Technologies (FQRNT) is gratefully acknowl-
edged.
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