Applied Catalysis A: General 286 (2005) 211–220

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Hydrotalcite like compounds with low Mo-loading active catalysts

for selective oxidation of cyclohexene with hydrogen peroxide
Rodica Zǎvoianu a,*, Ruxandra Bı̂rjega b, Octavian Dumitru Pavel a,
Anca Cruceanu a, Mihai Alifanti a
a
Department of Chemical Technology and Catalysis, Faculty of Chemistry, University of Bucharest,
Bd. Regina Elisabeta No. 4-12, S3, Bucharest 030018, Romania
b
ZECASIN S.A., Bucharest, Splaiul Independentei, No. 202 A, S6, Bucharest, Romania
Received 29 October 2004; received in revised form 28 February 2005; accepted 8 March 2005

Abstract

Several Mo-containing hydrotalcite-like compounds (HTlcs-Mo) were prepared by different ionic exchange procedures using as parent a
synthetic hydrotalcite Mg3Al(OH)8(CO3)0.5
2H2O with a composition similar to the natural occurring mineral. Their physico-chemical
properties determined by chemical and TG–DTA analyses, XRD, BET, FTIR, SEM-EDX, DR–UV–vis and Raman spectroscopy, were
compared to those of two HTlcs-Mo prepared by direct synthesis at constant pH = 10 and low or respectively high supersaturation. The
catalytic activity of these solids towards cyclohexene oxidation with hydrogen peroxide was investigated. The catalytic activity was mainly
influenced by the basic properties of the catalysts, which varied depending on the preparation procedure. The best catalysts for
hydroperoxidation were found to be those having a low Mo content (about 2.5–2.8%) in the form of MoO42 species, and higher Mg
concentration in the brucite layer. The catalysts containing also Mo7O246 species were more active for epoxidation.
# 2005 Elsevier B.V. All rights reserved.

Keywords: Layered double hydroxide; Hydrotalcite; Molybdate; Heptamolybdate; Cyclohexene oxidation; Hydrogen peroxide

1. Introduction A large number of hydrotalcite-like compounds (HTlcs)

Since 1990’s there is a growing interest for the study of
natural or synthetic hydrotalcite-like anionic clays due to their
special properties, which allow wide-scale applications as
polymer stabilizers, ion-exchangers, adsorbents or catalysts
[1–5]. This class of materials is defined by the general formula:
zþ
½M1x Mx3þ ðOHÞ2 bþ ½An
b=n 
mH2O, (M = metal, A = inter-
layer anion, b = x or 2x  1, for z = 2 or 1). Structural studies
showed that these solids have a laminar structure consisting of
positively charged brucite-type metal hydroxide layers with
balancing anions and water molecules in the interlayer space.
The most representative natural occurring solid of this type is
the mineral hydrotalcite (HT–CO32) having the formula
Mg3Al(OH)8(CO3)0.5
2H2O [1–6].
* Corresponding author. Tel.: +40 21 4103178x143; fax: +40 21 3159249.
E-mail address: zavoianu.rodica@unibuc.ro (R. Zǎvoianu).
may be synthesised by varying either the nature of the
cations or the nature of the compensation anions. In this way,
new materials can be tailored in order to fulfil specific
requirements. The simplest method to obtain modified
HTlcs is to replace the cations in the brucite-type layer with
other bivalent or trivalent cations that have an ionic radius
similar to Mg or Al and can adopt the same octahedral
arrangement. Meanwhile, metals that are not compatible
with the octahedral sites of the brucite-type sheet, such as
Mo, may be introduced in the interlayer space of these solids
in their anionic form [6–10]. Using this method, new
catalysts having outstanding properties due to the high
dispersion and the possibility of migration and rearrange-
ment of the active species can be obtained.
Several Mo-containing HTlcs were proved to be active
catalysts for selective olefin oxidation [11–13], oxidative
dehydrogenation of propane [14], alkoxylation reactions

0926-860X/$ – see front matter # 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2005.03.009
212 R. Zǎvoianu et al. / Applied Catalysis A: General 286 (2005) 211–220
[15], or oxidation of thiols [16]. The dispersion, the
accessibility and the coordination state of Mo in the active
sites as well as its redox behaviour are among the factors that
influence strongly the catalytic activity. These character-
istics are mainly determined by the preparation conditions
(composition of the reaction mixture, pH, temperature and
aging treatment) used to obtain the catalyst. Most of the
studies were directed towards HTlcs where Mo was present
as heptamolybdate (Mo7O246) species acting as pillars that
expanded the distance between the brucite-type sheets
[6,7,10–15]. Generally, these solids were prepared at low pH
values in order to stabilise the Mo7O246 anions. Up to now
only few studies concerning the preparation of molybdate
(MoO42) containing HTlcs at pH 10 have been published
[17,18]. HTlcs with Mo7O246 in the interlayer space
contain usually higher amounts of Mo than those with
MoO42. Thus, considering that in the formula of the natural
hydrotalcite (HT–CO32), CO32 anions are exchanged by
Mo7O246, the resulting HTlc would have the formula:
Mg3Al(OH)8(Mo7O24)0.166
2H2O (e.g. 24.93 wt.% Mo),
while if CO32 anions are exchanged by MoO42 the
Mo-HTlc would have the formula Mg3Al(OH)8
(MoO4)0.5
2H2O (e.g.13.63 wt.% Mo).
As indicated by literature data, cyclohexene or alkylcy-
clohexene oxidation with hydrogen peroxide (H2O2) can be
conducted on both types of HTlcs-Mo [11–13,17,18]. The
selectivity and the yield to different oxidation products are
related to the nature of Mo active sites, the ratio between the
reactants as well as to the nature of the solvent. HTlcs with a
high Mo-loading as Mo7O246 (e.g. 21.8–25.3 wt.% Mo;
HTlcs: Zn2Al and Mg2Al, respectively), presented a rather
low activity for cyclohexene oxidation to epoxide (1.9%) or
diols (3.2–4%) when using (BuO)3PO as solvent at 73 8C, and
equimolar amounts of H2O2 and cyclohexene [11]. The low
activity was related to the inaccessibility of the gallery Mo
sites under the reaction conditions [11,12]. Better catalysts for
the oxidation of cycloolefins with H2O2 seemed to be Mg–Al–
HTlcs having lower Mo-loading (e.g. in the range 2–8 wt.%
Mo) mainly as MoO42 sites. In their presence the yields to
cycloolefinic hydroperoxides were higher than 65% when
using molar ratios H2O2:cycloolefin = 2:1, and acetonitrile or
dimethylformamide (DMF) as solvent [17]. The activity of
these catalysts was assumed to be a consequence of their
ability to generate singlet molecular oxygen 1O2 upon contact
with H2O2 according to the reaction [17,19]:
HTðMgAlMoO2
4 Þ
2H2 O2 ! 1 1
2H2 O þ O2 ð Dg Þ (1)
The authors proposed a sequential mechanism involving
the successive formation of monoperoxomolybdate
MoO3(O2)2, diperoxomolybdate MoO2(O2)22, triper-
103 M);
oxomolybdate MoO(O2)32 and tetraperoxodimolybdate
Mo2O3(O2)42 species on the surface of the catalyst. It
was shown that the yield to hydroperoxides is higher and
103 M) and
the generation of 1O2 is faster under the most favourable
conditions for the formation of triperoxomolybdate species
(pH 10, ratio H2O2/Mo 3/1, T = 35 8C). Meanwhile, the
authors stated that the yield to epoxides was higher at lower
pH and H2O2/Mo ratios when monoperoxomolybdate
species prevailed.
The preparation of the HTlc-(MoO42) described by Laar
et al. [17,18] implied the use of a parent HT with NO3 or
Cl as compensation anion that was submitted to ionic
exchange (at pH 10) either with Na2MoO4 or with a mixture
of Na2MoO4 and para-toluene sulfonic acid ( pTOS).
However, the influence of using a hydrotalcite with a
similar composition to the natural occurring mineral in the
obtaining of this type of catalysts was not studied. Until
now, even if HTlcs-(Mo7O246) have been successfully
prepared by direct synthesis [14], there are no reports
concerning the application of this method for the obtaining
of HTlc-(MoO42).
Based on these limitations, the main goal of this work was
the selection of the most advantageous preparation method
for the obtaining of HTlc-(MoO42) highly active for the
oxidation of cyclohexene with H2O2. For this purpose,
several HTlcs with low Mo-loading were prepared at pH 10
using different methods and their physico-chemical and their
catalytic properties have been compared.
2. Experimental
2.1. Catalysts preparation
Five HTlcs samples with low Mo loading (in the range
2.5–9.3 wt.%) were obtained by procedures based either on
the principle of ionic exchange (with/without the presence of
an organic swelling agent), or on the principle of direct
synthesis from Mg(NO3)2, Al(NO3)3 and Na2MoO4. NaOH
and HNO3 aqueous solutions (1 M) were used for pH
adjustment. All reagents were purchased at high chemical
purities (>98%) from Merck. Decarbonated distilled water
was used for the preparation of the aqueous solutions. For
the preparations by ionic exchange, an amount of Na2MoO4
solution containing a number of MoO42 anions equal to
half of the anionic exchange capacity (AEC) of the parent
hydrotalcite has been used. Further on the Mo-containing
HTLcs samples are referred to as: HTMo(IE), HT–Mo–
pTOS(B), HTMo–pTOS(AB), HTMo(HS), HTMo(LS).
(i) HTMo(IE) was obtained by ionic exchange according to
the procedure first described by Kwon et al. [20], between
a parent hydrotalcite Mg3Al(OH)8(CO3)0.5
2H2O (HT–
CO32) previously synthesized by coprecipitation at
constant pH = 10 and low supersaturation [21,22] and an
aqueous solution of Na2MoO4 (7.5
(ii) HTMo–pTOS(B) was prepared by competitive ionic
exchange at pH 10, using HT–CO32 and an aqueous
solution containing Na2MoO4 (7.5
pTOS (0.03 M), ratio Mg:Al:Mo:pTOS = 3:1:0.25:0.5,
according to Van Laar et al. method [17,18];
 R. Zǎvoianu et al. / Applied Catalysis A: General 286 (2005) 211–220
(iii) HTMo–pTOS(AB), was synthesized following a proce-
dure based in principle on the method originally
developed by Drezdon [7,10]. First HT–CO32 was
submitted to the ionic exchange at pH 4.5 (adjusting
the pH with HNO3 1 M) with an organic swelling
agent (in our case pTOS – solution 0.03 M). After
1 h, the appropriate amount of molybdate solution
(7.5
103 M) corresponding to a ratio Mg:Al:Mo:p-
TOS = 3:1:0.25:0.79 in the reaction mixture was added
with a flow rate of 1 mL/min. The resulting slurry was
maintained at pH 4.5 under stirring during 24 h.
Afterwards the pH was adjusted to 10 using NaOH
solution 1 M.
(iv) HTMo(HS), has been directly synthesised at pH = 10
and high supersaturation [1,6], by the addition of the
Mg and Al-nitrates solution (1.5 M (Mg + Al), ratio
Mg/Al = 3) with a constant flow rate of 1 mL/min to the
molybdate solution (0.1 M) aiming a composition
Mg:Al:Mo = 3:1:0.25;
(v) HTMo(LS) was obtained by direct synthesis at pH = 10
and low supersaturation, by adding simultaneously
under strirring in 100 mL distiled decarbonated water,
the nitrates and molybdate solutions having the same
concentrations as those used in the previous pre-
paration. The amounts of solutions that were used
corresponded to a composition Mg:Al:Mo = 3:1:0.5.
Since the molybdate solution was more diluted than the
nitrates solution, aiming to respect the above-men-
tioned composition, their addition to the reaction
mixture was performed at different flow rates, e.g. 5 and
1 mL/min, respectively.
All the samples were submitted to an aging treatment at
65–70 8C during 18 h, followed by filtration, washing with
decarbonated distilled water (up to pH = 7), and drying 18 h
at 80 8C.
2.2. Catalysts characterization
The solids were characterized by chemical analysis,
XRD, DR–UV–vis and FTIR and Raman spectroscopy, TG–
DTA. The X-ray diffraction patterns of the samples were
recorded using DRON 3 diffractometer equipped with a
monochromator graphite crystal (lCu Ka1 ¼ 1:5406 Å). The
samples were scanned from 88 to 708 (2u) in steps of 0.058
with an acquisition time of 2 s at each point. The profile
fitting calculations were performed using Jandel Scientific
computer software and Voigt functions. The catalysts were
characterized by diffuse reflectance UV–vis spectroscopy in
the range 220–800 nm using SPECORD 80 UV–vis
spectrometer with an integration sphere coated with MgO
taken as reference. FTIR spectra in the range 400–
4000 cm1 were recorded on BioRad FTS 135 spectrometer
using the KBr pellets technique. Micro Raman spectra of the
catalysts in the range 1424–196 cm1 were recorded with
1 scan/8 s using SPEX 1877 triplemate spectrophotometer
213
and the laser line 514.5360 nm as exciting radiation. TG–
DTA analyses were performed by heating the catalyst
samples (50 mg) from 50 8C up to 800 8C (1 8C/min) under
N2 flow (50 mL/min) using SETARAM TG–DTA apparatus
for recording TG and DTG curves and a-Al2O3 as standard.
The specific surface area of the dried materials (activated by
heating during 1 h at 90 8C) was determined by BET method
from nitrogen adsorption-desorption isotherms at 196 8C
using a Carlo-Erba instrument.
The homogeneity of the samples was characterized by
SEM-EDX using a HITACHI S2400 scanning electron
microscope equipped with a RONTEC energy dispersive
X-ray high vacuum detector (W filament, E = 25 kV).
Samples were analysed from 15 mm working distance, with
a resolution of 12 nm.
The basic properties were determined by titration with
0.01 M benzoic acid solution in toluene using 0.15 g of
vacuum dried solid sample suspended in 2 mL of indicator
solution [17]. The indicator solution for the determination of
weak basic sites (pKa = 7.1) contained 0.01 g of Bromothy-
mol Blue in 100 mL toluene. The amount of strong basic
sites (pKa = 9.3) was determined in the presence of an
indicator solution containing 0.01 g of Phenolphthalein in
100 mL toluene.
2.3. Catalytic activity tests
The catalytic tests for cyclohexene oxidation with H2O2
were performed in a sealed reaction vessel where the
reaction mixture was maintained under vigorous stirring at
35 8C, during 3 h. For each test, 0.25 g of catalyst, 1.26 mL
cyclohexene (e.g. 12.5 mmoles) and 15 mL of dimethyl
formamide (DMF) solvent were used. The molar ratio
H2O2:cyclohexene varied in the range 1:1 and 2–1,
respectively. The reaction temperature was chosen in order
to favour the highest yield to 1O2 generation [12].
Cyclohexene (99%), H2O2 (30%) and DMF (99.5%) were
purchased from Merck. The reaction products were analyzed
by G.C. using a K072320 Termo-Quest chromatograph
equipped with a FID detector and a capillary column of 30 m
length and 0.324 mm diameter and DB-5 stationary phase.
Highly pure N2 (99.999%) was used as carrier gas. Prior to
chromatographic analysis the reaction mixtures were
reduced with an excess of PPh3 in order to transform the
cycloolefinic hydroperoxides in allylic alcohols.
3. Results and discussion
As it may be seen from the data presented in Table 1, the
chemical analysis showed that both the ratio Mg/Al and the
Mo uptake are different depending on the preparation
conditions. The differences in the Mg/Al ratios were also
confirmed by the results of the XRD and SEM-EDX
analyses (see Table 2). In all the preparations the Mo-uptake
was lower than the expected one.
214 R. Zǎvoianu et al. / Applied Catalysis A: General 286 (2005) 211–220

Table 1
The chemical compositions of the catalysts
Sample Chemical composition (%)
Mg Al C H N S Mo H2Oa Mg/Al (at. ratio)
b
HT
Mg3Al(OH)8(CO3)0.5
2H2Oc 24.15 8.94 1.99 2.65 – – – 11.92 3.0
24.2 8.9 2 2.64 – – – 11.9 3.0
HTMo(IE)d
Mg3Al(OH)8(MoO4)0.25(CO3)0.25
2H2Oc 22.3 8.26 0.92 2.45 – – 7.34 11.01 3.0
23 9.3 0.9 2.7 – – 2.8 12.4 2.76
Mg2.75Al(OH)7.9(MoO4)0.09(CO3)0.21
2H2Oe 22.96 9.27 0.87 2.71 – – 2.9 12.38 2.75
HTMo–pTOS(B)d
Mg3Al(OH)8(MoO4)0.25( pTOS)0.5c 15.97 5.91 9.2 2.74 – 3.5 5.25 – 3.0
17.4 7.2 13.5 3.5 – 5.2 2.5 – 2.68
Mg2.7Al(OH)7.4(MoO4)0.1( pTOS)0.6(CO3)0.1e 17.43 7.17 13.7 3.4 – 5.1 2.55 – 2.7
HTMo–pTOS(AB)d
Mg3Al(OH)8(Mo7O24)0.036( pTOS)0.79c 17.24 6.38 15.69 3.57 – 5.98 5.67 – 3.0
15.6 6.9 17.9 3.7 – 6.8 4.2 – 2.51
Mg2.5Al(OH)7(Mo7O24)0.024( pTOS)0.83(CO3)0.012e 15.59 6.93 17.93 3.71 – 6.82 4.14 – 2.5
HTMo(HS)d
Mg3Al(OH)8(MoO4)0.25(NO3)0.5
2H2Oc 19.5 7.22 0 2.14 1.87 – 6.41 9.63 3.0
17.4 7.2 0.1 2.0 2.6 – 2.8 12.0 2.68
Mg2.7Al(OH)7.4(MoO4)0.11(NO3)0.7(CO3)0.04
2.5H2Oe 17.43 7.17 0.13 1.97 2.6 – 2.8 11.95 2.7
HTMo(LS)d
Mg3Al(OH)8(MoO4)0.5
2H2Oc 20.72 7.67 0 2.27 0 – 13.63 10.23 3.0
17.6 8.7 0.1 2.1 1.6 – 9.3 7.3 2.25
Mg2.25Al(OH)6.5(MoO4)0.3(NO3)0.36(CO3)0.02
1.25H2Oe 17.58 8.68 0.08 2.09 1.62 – 9.26 7.24 2.25
a
As calculated considering the loss of weight determined by TG–DTA analysis in the range 105–200 8C [1].
b
Values are calculated based on the expected formula (first row) and determined by chemical analyses (second row).
c
Expected formula (based on the composition of the reaction mixture during the synthesis of the corresponding HTlc).
d
Values are calculated based on the expected formula (first row), determined by chemical analyses (second row) and calculated based on the proposed
formula (third row).
e
Proposed formula.

For the samples prepared by ionic exchange this could be
expected since the true exchange capacity of anionic clays
(e.g. 1.0–1.5 meq g1) is usually much lower than the
theoretical one (3.3 meq g1 for HT–CO32) [4,6]. HTMo–
pTOS(AB) has the highest content of Mo among the samples
prepared by ionic exchange, confirming Miyata’s claim that
anionic clays strongly prefer multiple charged anions and
the selectivity for the exchange increases with increasing
anion charge density [6,23]. This catalyst has also a low
content of pTOS suggesting the difficulty of swelling since it
is known that the high charge density (4 e nm2) creates
strong electrostatic forces between the brucite type sheets
and the anions [4,6–8]. Even the samples prepared without
pTOS presented traces of carbon suggesting that carbonate is
still present whatever the precautions taken. This could be
expected since we used a parent HT–CO32 while the best
precursors for exchange reactions are known to be the
compounds containing nitrate or chloride anions [4,6–8].

Table 2
Results of XRD, SEM-EDX and BET analyses
Sample Lattice IFS (Å) I0 0 3 Mg/Al (XRD)a Mg/Al/Mo (SEM-EDX) D0 0 3 (Å)b D1 1 0 (Å)b Ssp (m2/g)
I1 1 0
parameters (Å)
a c
HT–CO32 3.065 23.716 3.10 8.29 3.00 3/1/0 77 145 65
HTMo(IE) 3.059 23.718 3.11 5.96 2.75 2.74/1/0.1 77 163 66
HTMo–pTOS(B) 3.053 23.361 2.99 6.19 2.67 2.66/1/0.1 75 149 67
HTMo–pTOS(AB) 3.052 23.829 3.14 3.19 2.50 2.48/1/0.05 (2.48/1/0.2)c 55 87 70
HTMo(HS) 3.058 23.310 2.97 7.53 2.71 2.7/1/0.12 119 182 47
HTMo(LS) 3.044 22.917 2.84 3.08 1.85 2.2/1/0.32 (1/0/0.9)c 72 101 75
a
The ratios Mg/Al were calculated using the values of the lattice constant a, and Vegard’s law [1].
b ´
D0 0 3 (Å) and D1 1 0 (Å) are the sizes of the crystals determined using Debye–Sherrer formula for two directions perpendicular to the planes (0 0 3) and
(1 1 0), respectively.
c
Traces in the less homogeneous samples.
 R. Zǎvoianu et al. / Applied Catalysis A: General 286 (2005) 211–220
Fig. 1. XRD patterns of Mo-containing hydrotalcites: (a) prepared by ionic exchange; (b) prepared by direct synthesis.
The XRD patterns of the samples prepared by ionic
exchange techniques (Fig. 1a) exhibit a typical HT–CO32
structure with sharp and symmetric reflections for (0 0 3),
(0 0 6), (1 1 0) and (1 1 3) planes and broad asymmetric peaks
for (0 1 2), (0 1 5) and (0 1 8) planes (JCPDS 70-2151) [1].
The reflections were indexed in a hexagonal lattice with R3m
rhombohedral symmetry. The cell parameters are given by
a = 2
d1 1 0 and c = 3/2
(d0 0 3 + 2d0 0 6), respectively. seems that the preference of the hydrotalcite for the anions
The interlayer free spacing (IFS) was calculated by
´
subtracting the brucite sheet thickness (e.g. 4.8 Å as reported
by Miyata [24]) from c/3 values.
The structural data calculated on the bases of XRD
analyses are included in Table 2. These data revealed a slight
decrease of the a cell parameter for all the Mo-containing
samples. According to Vegard’s law [1], this fact indicates a
depletion of the magnesium relative to the aluminium content.
Van Laar et al. using XPS measurements have evidenced the
enrichment of the surface with Al for several Mo-containing
HTlcs [17]. This phenomenon occurs probably due to some
local decreases of the pH during the preparation that lead to a
partial dissolution of Mg from the host layers [14].
The value of the lattice parameter c is influenced both by
the size of the compensation anion and the electrostatic
forces between the layers and the interlayer anions. The
intensity of these electrostatic forces is affected also by the
substitution degree of Mg2+ in the brucite-type sheet [4,6].
The results of SEM-EDX analysis presented in Table 2
indicated a homogenous composition of the two samples
prepared by ionic exchange at pH 10. In their case the
decrease of the Mg/Al ratio compared to the parent
hydrotalcite is accompanied by the decrease of c parameter
and consequently of the IFS. This fact indicates stronger
electrostatic interactions between layer and interlayer anions
due to the higher amount of Al3+ in the brucite sheet.
215
According to this result it may be suggested that in the case
of HT–CO32, the ionic exchange at pH 10 does not allow
the accommodation of larger anions such as Mo7O246, or
pTOS in the interlayer spaces. This fact is less surprising in
what concerns Mo7O246 since it is known that at basic pH
values this polyanion is converted to MoO42, which has
lower dimensions [7,8,17–19]. With respect to pTOS it
with increased charge density plays an important role in the
inhibition of the anionic exchange [23].
HTMo–pTOS(AB) presents an altered pattern with very
broad peaks suggesting that this sample suffered a dissolution/
reconstruction process. The results of SEM-EDX analysis
(Table 2) indicate that this sample has a less homogeneous
composition, mainly in what concerns the content of Mo.
Therefore the XRD pattern was solved considering a
disordered hydrotalcite-phase [6]. A significant decrease of
the basal peaks intensities (expressed as I0 0 3/I1 1 0 ratio) was
noticed. The IFS larger value obtained for this sample
accounts for the interlayer intercalation of Mo species.
However, this IFS is large enough to accommodate only
MoO42 species, while Mo7O246 are most probably located
at the edges of the layers. The presence of both Mo species
was further confirmed by the results of DR–UV–vis and
Raman spectroscopy. The significant broadening of the
second diffraction peak evidences a disorder in the periodicity
of the (0 0 l) planes. This disorder is most probably due to the
presence of the different Mo species as a consequence of the
pH variation during the preparation. A similar fact was
reported for metavanadate interlayer intercalation [25,26].
The broad basal spacing peaks accounted for the presence of
smaller crystallites.
The pattern of HTMo(HS) displays the structure of a well
crystallized HTlc (Fig. 1b). This sample has a homogeneous
216 R. Zǎvoianu et al. / Applied Catalysis A: General 286 (2005) 211–220
composition as indicated by SEM-EDX analysis. The
basal space peaks are very sharp and intense revealing
high stacking order along c axis due to a more compact
orientation of the anions. The (0 k l) peaks are less
asymmetric in comparison with HT–CO32, showing less
turbostratic disorder effects. The diffraction pattern of
HTMo(LS), shows a considerable disordered structure with
broader and less defined peaks. This indicates a smaller size
of the particles and consequently a larger surface area, as it
may be seen from Table 2. A very broad peak in the medium
angular region (denoted with (*) in figure) could be assigned
to MgMoO4 phase. The less homogeneous composition of
this sample was also revealed by the results of SEM-EDX
analysis presented in Table 2.
As it may be seen from Table 2, the crystals sizes of all the
samples are in accordance with the textural data. The lowest
BET surface area is obtained for the sample with the largest
crystal size (HTMo(HS)). The dimensions of the crystals
along (1 1 0) direction are less affected by the preparation
conditions than those along (0 0 3) direction, which is
perpendicular to the layers and is more sensitive to the
change of the anionic composition.
FTIR spectra of the molybdenum containing HTlc are
presented in Fig. 2.
The investigated samples show broader adsorption bands
than those of the parent HT–CO32 suggesting a higher
disorder of the molecules in the galleries. Meanwhile, the
band corresponding to Mo–O–Mo stretching vibrations at
665 cm1, the one related to MoO42 at 856 cm1 and the
band for Mo O stretching at 914 cm1 appear in the same
region as those characteristic for HT–CO32. Therefore, due
to the overlapping it is difficult to comment the nature of Mo
species in the modified HTlcs. However, the effect of the
ionic exchange for the samples HTMo(IE), HTMo–pTOS(B),
and HTMo–pTOS(AB), respectively, is noticed since the
bands corresponding to CO32 vibrations at 1386 cm1 are
broader and less intense [15,27,28].
In the spectrum of HTMo–pTOS(AB), the appearance of
two bands in the region 1230–1120 cm1 could be an
indication for the formation of metal sulfonates (due to the
presence of pTOS in the synthesis) [27]. These bands are less
demarked in the spectrum of HTMo–pTOS(B) when the ionic
exchange is realised at higher pH and they are absent in the
spectrum of HTMo(IE) whose preparation did not involve the
use of pTOS.
In the spectrum of HTMo(LS), the intensities of the bands
corresponding to crystallization water molecules (3460
and 1620 cm1) are lower compared to the spectrum of
HTMo(HS). For both samples prepared by direct synthesis,
the existence of the band at ca. 1400 cm1, indicates the
presence of (NO3) ions as compensation anions. This band
overlaps the one characteristic for the vibrations of CO32,
which is present in traces as it was shown by the results of the
chemical analysis presented in Table 1.
Fig. 3 displays the DR–UV–vis spectra of the Mo
containing hydrotalcites in the region 220–800 nm where
the absorption bands characteristics to Mo species appear.
The isolated MoO42 species with Mo in tetrahedral
coordination present absorption bands in the region 260–
280 nm. Meanwhile the bands in the region 300–320 nm are
due to Mo7O246 species with Mo6+ in octahedral coordina-
tion [29,30]. The spectra displayed in Fig. 3, show that
HTMo–pTOS(AB) presents the highest amount of molybde-
num octahedral coordinated species, while in the sample

Fig. 2. FTIR spectra of Mo-containing HTlcs compared to the spectrum of Fig. 3. DR-UVVIS spectra of Mo-containing HTlcs: () Mo in tetrahedral
the pure HT: () (NO3); (*) (pTOS). coordination; (*) Mo in octahedral coordination; (#) MoO3.
 R. Zǎvoianu et al. / Applied Catalysis A: General 286 (2005) 211–220 217

HTMo–pTOS(B) there is a higher amount of tetrahedral

coordinated species. This fact was expected since during the
preparation of the first sample the pH varied in the range 4.5–
10, while the second sample was prepared at pH 10.
It is interesting to notice that the spectrum of HTMo(IE)
exhibited also a shoulder in the region of the absorption
maximum for octahedral coordinated Mo species. For this
sample the maximums for both tetrahedral- and octahedral-
coordinated Mo species are shifted towards higher wave-
lengths. Beside the band assigned to MoO42, the spectrum of
HTMo(LS) shows a defined adsorption band corresponding to
Mo7O246 species as well as a shoulder around 340 nm
suggesting the presence of isolated MoO3 species. As XRD
pointed out, it is very likely that MoO3 forms a mixed oxide
with MgO. The presence of these different species in this
sample may be a consequence of the preparation method
considering the local phenomena that may occur during the
addition of the reactants in the reaction mixture. In the
spectrum of HTMo(HS) there is a broad adsorption band
characteristic to MoO42 species and two shoulders at
320–340 nm that indicate a very low amount of Mo7O246 Fig. 4. Raman spectra of Mo-containing HTlcs: O – (Mo7O24)6 species;
and isolated MoO3 species, respectively. The existence T – (MoO4)2- species.
of Mo7O246 traces in the solids prepared at pH 10 could
be due to some local decreases of the pH during the The results obtained by this complete set of analyses,
preparation. evidenced the coexistence of different molybdenum species
A better image upon the nature of the Mo species was in all the samples. Therefore we may conclude that the
obtained by Raman spectroscopy. The results of this analysis formulas proposed for the Mo-containing HTlcs in Table 1
illustrated by the spectra presented in Fig. 4 confirmed the are merely an approximation.
results obtained by DR–UV–vis spectroscopy. The basic properties of the catalysts determined by
The spectra clearly revealed the presence of the most benzoic acid titration of the basic sites in the presence of a
intense absorption band corresponding to Mo–O symmetrical pH indicator are presented in Table 3. The results indicate
stretching vibration in MoO42 at 896 cm1 and the one that the most basic Mo-containing hydrotalcite is HTMo(IE).
corresponding to Mo O in MoO at 320 cm1 in all the HTMo(HS) has a slightly lower basicity, probably due to the
samples [11,17]. The most intense band characteristic for presence of the nitrate ion in its composition. For the
Mo7O246, at 940 cm1 could be discerned in all spectra. catalysts prepared by direct synthesis, the basicity decreases
However, this band was more intense than the one with the increase of Mo-loading. The basicity of the
corresponding to MoO42 only in the spectrum of HTMo– catalysts prepared by ionic exchange in the presence of
pTOS(AB), which presented also the other bands characteristic pTOS is lower in the case of HTMo–pTOS(AB), which has
to Mo7O246, (e.g. Mo–O–Mo n and d vibrations at 564, and been prepared at variable pH.
219 cm1, Mo O bending at 340 cm1 [11]). In the spectra of The results of the catalytic tests involving cyclohexene
all the other samples the bands characteristic for octahedral- oxidation with H2O2 are presented in Fig. 5 and Table 4.
coordinated Mo species were less intense than those As it may be seen from Fig. 5, for all catalysts, both the
corresponding to the tetrahedral-coordinated Mo. turnover frequency (Fig. 5a) and the yield to allylic alcohol

Table 3
Basic properties of the samples determined in fully hydrated conditions and by titration with 0.01 M benzoic acid
Sample Basic properties in fully hydrated conditions (pH)a Basic sites (
104 mole/g)
Weak basic sitesb Strong basic sitesc
HT–CO32 10.2 1.6 1.0
HTMo(IE) 10 1.5 0.9
HTMo–pTOS(B) 9.5 1.3 0.5
HTMo–pTOS(AB) 9 1.0 0.3
HTMo(HS) 9.8 1.4 0.6
HTMo(LS) 9.3 1.2 0.3
a
Determined by pH measurement of a suspension containing 1.5 g solid sample in 100 mL distilled water.
b
pH indicator Bromothymol Blue, pKa = 7.1.
c
pH indicator Phenolphtalein, pKa = 9.3.
218 R. Zǎvoianu et al. / Applied Catalysis A: General 286 (2005) 211–220

This fact was expected since a higher amount of H2O2 would

enhance the rate of formation of triperoxomolybdate species
that favour the obtaining of cyclohexene-peroxide, which
converts upon reduction into cyclohexenol [12].
The catalytic performances seem to be strongly influenced
by the basicity of the solids since the activity of the catalysts as
well as the yields to cyclohexenol vary in the same order as the
basic properties: HTMo(IE) > HTMo(HS) > HTMo–pTOS(B)
> HTMo(HS) > HTMo–pTOS(AB).
The lowest activity exhibited by HTMo–pTOS(AB) could
be linked to the highest amount of polymolybdate observed
by spectroscopic methods. These species are responsible for
the lower dispersion of Mo sites as well as for steric
hindrances imposed to the molecular traffic of the reagents.
However, on this catalyst a yield of ca.15% to epoxycy-
clohexane was obtained. An explanation of such behaviour
can be the low basicity that favours the formation of
epoxycyclohexane as it was suggested by the mechanism
proposed by Van Laar et al. [17,18]. Indeed during its
preparation the pH was lowered up to 4.5, and in the brucite-
type sheet of this sample there is a lower amount of Mg,
hence a lower basicity. Among the catalysts prepared at pH
10, the lowest activity is presented by HTMo(LS). This
catalyst contains the highest Mo loading including
significant traces of Mo7O246 as well as a distinct phase
of MgMoO4 besides the prevailing MoO42 species. It has
also the lowest ratio Mg/Al in the brucite-type layer. These
characteristics could be responsible for the lower yield to
cyclohexenol compared to the yield to epoxycyclohexane
obtained in this case especially at an equimolar ratio H2O2:
cyclohexene. Thus, for the same amount of catalyst, (e.g.
0.25 g) HTMo(LS) contains 0.242 mmoles Mo compared to
0.073 mmoles in HTMo(HS), therefore the ratio H2O2:Mo is
lower and during the adsorption of H2O2, a larger amount of
Fig. 5. Comparison between catalytic performances of Mo-HTLc prepared
monoperoxomolybdate species, that promote the epoxida-
by different methods T = 35 8C, reaction time 3 h, 0.25 g catalyst, 15 mL tion may be formed [17,19].
DMF; (reaction mixtures reduced with PPh3 prior to chromatographic Another aspect that should be highlighted is that the most
analysis); (a) turnover frequency (TOF): mmol C6H10tr./mmol Mo/h; (b) active catalysts for cyclohexene hydroperoxidation were
yield to cyclohexenol; (c) yield to epoxycyclohexane. proved to be those containing lower amounts of Mo, for
which a better dispersion of MoO42 species is reached. The
best catalyst appears to be HTMo(IE). It led to 83.1% yield to
(Fig. 5b) obtained upon reduction of the samples with PPh3 cyclohexenol and respectively 9.2% yield to epoxycyclo-
increased with the ratio H2O2: cyclohexene. At the same hexane for a molar ratio H2O2:cyclohexene = 2:1. Under
time, the yield to epoxycyclohexane decreased (Fig. 5c). these conditions, very good performances were also
Table 4
Catalytic test results obtained in 4 consecutive reaction cycles; T = 35 8C, reaction time 3 h, 0.25 g catalyst, 15 mL DMF; H2O2/C6H10 = 1:1 (1.27 mL H2O2,
1.26 mL cyclohexene); reaction mixtures reduced with PPh3 prior to chromatographic analysis
Catalytic performance Cyclohexene conversion (%) Yield to cyclohexenol (%) Yield to epoxycyclohexane (%)
Cycle no. 1 2 3 4 1 2 3 4 1 2 3 4
Catalyst
HTMo(IE) 89.3 88.2 88.0 87.3 76.2 75.4 75.0 73.8 13.1 12.5 12.4 11.9
HTMo–pTOS(B) 53.1 52.5 51.8 50.5 34.5 33.7 32.8 32.3 15.9 15.3 14.8 14.2
HTMo–pTOS(AB) 21.9 20.8 20.1 19.7 4.4 4.1 3.6 2.6 17.5 16.7 16.5 15.7
HTMo(HS) 72.5 71.8 71.5 70.6 55.4 54.7 54.1 53.6 13.3 12.5 12.4 11.3
HTMo(LS) 35.9 35.2 34.6 33.8 19.8 19.2 18.8 18.2 14.4 13.9 13.2 12.8
The yield to unidentified compounds was less than 5%.
 R. Zǎvoianu et al. / Applied Catalysis A: General 286 (2005) 211–220
obtained with HTMo(HS), which led to 72.2% yield to
The preparation of HTMo(IE) requires the previous
cyclohexenol and 4.2% to epoxycyclohexane. The formation
of an allylic alcohol by the oxidation of 1-methyl-1-
2H2O, followed by the ionic exchange proce-
cyclohexene was reported also by Van Laar et al. [17]. They
obtained a yield of 66% in allylic alcohol and 0.2% in
epoxide when the reaction was carried out in similar
conditions. In their study, the catalyst leading to the above-
mentioned results was a Mo-containing HTlc prepared by
ionic exchange without pTOS (2 wt.% Mo and Mg/Al = 9/
1). The higher yield to epoxycylohexane obtained in our
study may be a consequence of the lower alkalinity and the
higher concentration of Mo in our catalysts. The differences
between the performances of two catalysts having similar
concentration of Mo and ratio Mg/Al, e.g. HTMo(IE) and
HTMo(HS) may be a consequence of their different
superficial properties. Thus, the fact that HTMo(IE), presents
a higher activity and selectivity for cyclohexenol may be due
to its higher basicity (see Table 3).
Under the same reaction conditions, HTMo–pTOS(B)
exhibited a 45.4% yield to cyclohexenol, and 15.1% for
epoxycyclohexane. The higher yield to epoxycyclohexane in
this case may be a consequence of the increased
hydrophobic character of this catalyst as well as of the
lower basicity [17,19].
The analyses of the reaction products and of the catalysts
after the catalytic tests show that no leaching of Mo occurs.
Also, the use of the catalysts in four consecutive reaction
cycles did not lead to a significant loss of their activity as it
may be seen from the results presented in Table 4. After each
reaction cycle the recovered catalyst was dried in an oven at
80 8C during 4 h.
4. Conclusions
In order to select the most advantageous method for
obtaining HT–MoO42 catalysts with high activity for the
hydroperoxidation of cyclohexene to cyclohexenperoxide
we considered the following aspects:
Only two of the preparation methods investigated in this
work lead to the obtaining of highly active catalysts: (i)
the direct ionic exchange at pH 10 between HT–CO32
and an aqueous solution of Na2MoO4 and (ii) the direct
synthesis at pH = 10 and high supersaturation. These
catalysts, namely HTMo(IE) and HTMo(HS), have the same
Mo-loading and a similar Mg/Al ratio. They have a
homogeneous composition and a well-defined diffraction
pattern characteristic to an HTlc structure. As it was
revealed by spectroscopic analyses, in these samples Mo
is present mainly as MoO42 known to be active for the
generation of singlet molecular oxygen 1O2. However,
in both catalysts traces of Mo7O246 are also present.
The higher basic properties and the prevalence of
well-dispersed MoO42 species in their structure are
responsible for their high activity.
219
synthesis of the parent hydrotalcite Mg3Al(OH)8(-
CO3)0.5
dure. The procedure is long lasting and it involves a large
consumption of reagents. Meanwhile, a lower consump-
tion of reagents is necessary for the preparation of
HTMo(HS), which is faster and less complicated.
However, both methods are more advantageous than
the procedure involving the ionic exchange using the
nitrate form of the hydrotalcite as starting material.
Based on the above-mentioned aspects, it may be con-
cluded that the most advantageous preparation procedure for
obtaining HT–MoO42 catalysts is the direct synthesis at pH
10 and high supersaturation.
Acknowledgements
The financial support of this research through the Grant 3-
106/2003 in the framework of the National Plan of Research,
Development and Innovation – CERES program of the
Romanian Minister of Education Research and Youth is
gratefully acknowledged. Also, authors express their
gratitude towards Associate Prof. Dr. Irinel Badea (Depart-
ment of Analytical Chemistry, Faculty of Chemistry,
University of Bucharest) for her assistance in analytical
determinations.
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