Reac Kinet Mech Cat (2012) 105:145–162

DOI 10.1007/s11144-011-0398-9

Oxidation of tert-butanethiol with air using Mo-

containing hydrotalcite-like compounds and their
derived mixed oxides as catalysts

Rodica Zăvoianu • Anca Cruceanu •

Octavian Dumitru Pavel • Emilian Angelescu •

Ana Paula Soares Dias • Ruxandra Bı̂rjega

Received: 2 June 2011 / Accepted: 31 October 2011 / Published online: 16 November 2011
Ó Akadémiai Kiadó, Budapest, Hungary 2011

Abstract This contribution presents several aspects concerning the production

and characterization of hydrotalcite-like compounds containing Mo-species in the
interlayer region (Mo-HT), the corresponding derived mixed oxides (Mo-CHT) and
their catalytic activity in the demercaptanization of gasoline contaminated by tert-
butanethiol. Mo-HT samples were obtained using two different molybdenum
sources, e.g. Na2MoO4 or (NH4)6Mo7O24 and two preparation procedures: (i) ionic
exchange and (ii) coprecipitation at pH 10 under high supersaturation. The derived
mixed oxides were obtained by calcination at 450 °C during 24 h. The solids have
been characterized by chemical analysis, TG/DTA, XRD, SEM–EDX, FTIR, DR-
UV–Vis and Raman spectroscopy as well as determination of base sites. The spe-
cific area of the solids was determined using the BET method. The best catalysts
were found to be those containing higher amounts of Mo species with tetrahedral
coordination obtained by calcination of the Mo-HT precursors prepared at pH 10,
either by ionic exchange or by co-precipitation using Na2MoO4 as a molybdenum
source. Meanwhile, the catalysts containing mainly octahedrally coordinated Mo
species (obtained from Mo-HT prepared at pH 10 using (NH4)6Mo7O246H2O as
molybdenum source) were characterized by a higher concentration of molybdenum
species with octahedral coordination, lower number of base sites, smaller surface
area, and a poor catalytic activity.

R. Zăvoianu (&)  A. Cruceanu  O. D. Pavel  E. Angelescu

Department of Organic Chemistry, Biochemistry and Catalysis, Faculty of Chemistry,
University of Bucharest, Bd. Regina Elisabeta, No. 4-12, S3, 030018 Bucharest, Romania
e-mail: rodicazavoianu@gmail.com
URL: http://www.unibuc.ro/prof/zavoianu_r/

A. P. S. Dias
ICEMS-UQUIMAF-GRECAT, Instituto Superior Técnico, Technical University of Lisbon,
Av. Rovisco Pais, s/n, 1049-001 Lisbon, Portugal

R. Bı̂rjega
National Institute for Physics of Laser, Plasma and Radiation, Bucharest, Romania

123
146 R. Zăvoianu et al.

Keywords Molybdenum mixed oxides  Demercaptanization 

Hydrotalcite-like compounds  Tert-butanethiol oxidation

Introduction

The removal of sulfur from petroleum cuts is a priority in oil processing due to the
exigencies imposed by environmental protection regulations. Among the sulfur-
containing compounds, thiols are among the less desirable since they cause foul
odor, deterioration of additives in finished products, poisoning of the catalysts used
in oil processing and corrosion. Therefore, it is necessary to remove them, either
by extraction or by their subsequent transforming to inoffensive alkyl disulfides. In
the petroleum industry, such processes are usually called ‘‘sweetening’’. The most
widely used sweetening process is Merox developed by UOP [1–3], which is based
on the aerobic oxidation of alkane thiols to dialkyl disulfides at 25–40 °C, in
alkaline environment (NaOH aqueous solution 10%wt.) in the presence of a soluble
Co(II) complex catalyst with oxygen carrier properties (e.g. disodium Co(II)phta-
locyanine-disulfonate), according to the reactions:
2RSH þ 2NaOH , 2RSNa þ 2H2 O ð1Þ
2RSNa þ H2 O þ ½O ! R  S  S  R þ 2NaOH ð2Þ
2RSH þ ½O ! R  S  S  R þ H2 O ð3Þ
The addition of a base is necessary (pH = 9–9.5) because in the initial step a
mercaptide ion has to be formed [4]. The sweetening process is highly efficient in
demercaptanization since in the case of alkyl radicals R with more than 3 carbon
atoms the disulfides which are not soluble in gasoline precipitate thus facilitating
their complete removal from gasoline. However, the presence of the base solution
raises serious problems due to its caustic character. Therefore, a special attention
has been granted to the replacement of homogeneous sweetening catalysts with
solid catalysts, such as those obtained by impregnation of an activated carbon with
the Merox catalyst and the base compound. Several studies reported also the
catalytic activity of metal complexes immobilized into layered double hydroxides
(LDH) supports, especially Co(II)phtalocyanine-tetrasulfonate [Co(PcTS]4- for the
auto-oxidation of thiols with O2 [5–7]. The immobilization of the transition metal
complex into LDH has three main effects on the catalytic behavior. First, the
activity of Co complex is improved by heterogenization; second, the catalyst is
more stable in time than the homogeneous homologue, and third, the LDH or the
mixed oxides obtained from LDHs precursors not only act as a carrier but also as a
solid base [8, 9], favoring the dissociation of thiols while playing a role similar to
the one of the alkaline solutions used in homogeneous conditions.
The first report concerning the oxidation of thiols by molecular oxygen in the
presence of a molybdenum compound entrapped in a LDH host (e.g. Zn–Al) was
published by Corma et al. [10]. Layered double hydroxides defined by the general
formula: [Mz? 3? b? n-
1-xMx (OH)2] [Ab/n] m H2O, (M = metal, A = interlayer anion,
b = x or 2x-1, for z = 2 or 1), are anionic clays with laminar structure consisting

123
Oxidation of tert-butanethiol with air 147

of positively charged brucite-type metal hydroxide layers with balancing anions and
water molecules in the interlayer space. The most representative naturally occurring
solid of this type is the mineral hydrotalcite (HT-CO32-) having the formula
Mg3Al(OH)8(CO3)0.52H2O [11–16]. This type of solid is known to be a useful solid
base catalyst. Its composition may be modified in order to obtain catalysts with both
redox and base properties, yielding the so-called hydrotalcite-like compounds (HTlc).
One of the methods used for the obtaining of HTlc is the replacement of Mg2? or Al3?
cations from the brucite-type layer with other bivalent or trivalent transition metal
cations having similar cationic radius and coordination preference. Another method
implies the exchange of the carbonate anions from the structure with oxometallate or
polyoxometallate anions. This method is applied for the modification with metals that
are not compatible with the octahedral sites of the brucite-type sheet, such as Mo, or W
[16–20]. HTlcs containing interlayer oxometallate or polyoxometallate anions can be
used as precursors for obtaining new catalysts with outstanding properties due to the
high dispersion and the possibility of migration and rearrangement of the active
species [14, 16, 18]. Several Mo-containing HTlcs were proved to be active catalysts
for different oxidation reactions such as selective olefin oxidation [21–23] or
oxidative dehydrogenation of propane [24]. 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 [16, 17, 20–25]. Generally,
these solids were prepared at low pH values in order to stabilize the Mo7O246- anions.
Recently, several methods have been developed for producing hydrotalcite-like
materials containing molybdate (MoO42-) anions (Mo-HT), which are good
catalysts for selective oxidations under mild conditions [26–28]. The dispersion, the
accessibility and the coordination state of Mo in the active sites as well as its redox
behavior are among the factors that influence strongly the catalytic activity. These
characteristics are mainly determined by the preparation conditions (composition of
the reaction mixture, pH, temperature, ageing treatment) used to obtain the catalyst.
Based on the above-mentioned facts, the aim of this contribution is to investigate
the catalytic performances of Mo-containing HTlc (Mo-HT) and their derived
mixed oxides (Mo-CHT) in the oxidation of tert-butanethiol (t-BuSH) with air. This
test reaction has been selected since t-BuSH is one of the impurities difficult to
be removed by catalytic sweetening from naphta gasoline. The influence of the
preparation method as well as of the molybdenum source on the structural and
physico-chemical properties of the solids is going to be analyzed in correlation with
their catalytic activity.

Experimental

Preparation of the catalysts

Three Mo-containing HTlcs samples (Mo-HT) were obtained at constant pH 10

following two different procedures: ionic exchange (IE) without the presence of an
organic swelling agent, or coprecipitation at high supersaturation using Mg(NO3)2,

123
148 R. Zăvoianu et al.

Al(NO3)3 and two different molybdenum sources, Na2MoO4, and (NH4)6Mo7

O24NaOH and HNO3 aqueous solutions (1.5 M) were used for pH adjustment. All
reagents were purchased at high chemical purities ([98%) from Merck. Decarbon-
ated distilled water was used for the preparation of the aqueous solutions. Both the
ionic exchange and the direct synthesis were performed under inert atmosphere in
order to avoid the contamination with CO2.
For the preparation by ionic exchange according to the method previously
developed by Kwon [29], an amount of Na2MoO4 solution (7.5910-3 M) containing
a number of MoO42- anions equal to the half of the anionic exchange capacity (AEC)
of a parent hydrotalcite Mg3Al(OH)8(NO3)2H2O (HT-NO3) synthesized by
coprecipitation at constant pH = 10 and low supersaturation [11, 26] had been
used. The pH was adjusted to 10 using a 1.5 M aqueous solution of NaOH.
The preparation by co-precipitation at pH = 10 and high supersaturation [11,
28], was performed by adding a Mg and Al-nitrates solution (1.5 M (Mg?Al), ratio
Mg/Al = 3 initial pH = 4.5) with a constant flow rate of 1mL/min to a base
solution (initial pH = 10.5) containing the appropriate amount of a molybdenum
salt (e.g. Na2MoO4, or (NH4)6Mo7O24) aiming at a composition of Mg:Al:Mo =
3:1:0.25. The concentration of Mo in the aqueous base solution was 0.1 M. Aqueous
NaOH solution (1.5 M) was used for the pH adjustment in the preparation with
Na2MoO4 [28], while a NH4OH solution (25%wt. NH3) was used for the pH
adjustment in the preparation with (NH4)6Mo7O24.
All the samples were submitted to an aging treatment at 65–70 °C during 18 h,
followed by filtration, washing with decarbonated distilled water (up to pH = 7),
and drying 18 h at 90 °C. Depending on the preparation procedure (PP) and the
molybdenum source (S) used for obtaining the precursors, their names had been
abbreviated as Mo-HTPP-S: (i) Mo-HTIE-Na2MoO4 (IE=ionic exchange at pH 10); (ii)
Mo-HTHS-Na2MoO4 (HS = direct synthesis at constant pH = 10 and high supersat-
uration and (iii) Mo-HTHS-(NH4)6Mo7O24.
The mixed oxide catalysts (Mo-CHT) were obtained following the calcinations
of the above-mentioned Mo-HT precursors under air-flow at 450 °C during 24 h.
The names of these samples are defined by replacing the suffix HT with CHT in
the name of the precursor, e.g. Mo-CHTIE-Na2MoO4, Mo-CHTHS-Na2MoO4 and
Mo-CHTHS-(NH4)6Mo7O24, respectively.

Characterization

The physico-chemical properties of the prepared solids were determined by

chemical and TG-DTA analyses, XRD, BET, SEM–EDS, FTIR, DR-UV–Vis and
Raman spectroscopy.
The metal content in the samples was determined by atomic absorption
spectrometry (AAS) using a VARIAN AAS apparatus, while the carbon and
nitrogen content of the samples was determined by elemental analysis performed
with Carlo Erba automatic analyzer. The obtained results are presented in Table 1.
TG-DTA analyses were performed by heating the catalyst samples (50 mg) from
50 °C up to 800 °C (1 °C/min) under N2 flow (50 mL/min) using SETARAM TG-
DTA apparatus for recording TG and DTG curves and a-Al2O3 as standard.

123
Oxidation of tert-butanethiol with air 149

Table 1 The chemical compositions of the catalysts

Samples Mg Al Mo wt. % N wt. % C wt. % Mg:Al:Mo H2O*
wt. % wt. % Atomic ratio (wt. %)

Mo-HTHS-Na2MoO4 17.4 7.2 2.8 2.6 0.1 2.68:1:0.11 12.0

Mo-HTIE-Na2MoO4 22.8 9.2 2.7 1.0 0.2 2.75:1:0.08 12.3
Mo-HTHS-(NH4)6Mo7O24 12.5 8.7 21.7 2.7 0.1 1.6:1:0.7 6.2
Mo-CHTHS-Na2MoO4 28.5 11.3 4.4 – 0.2 2.8:1:0.1 8
Mo-CHTIE-Na2MoO4 35.1 14.8 4.4 – 0.1 2.6:1:0.08 7.5
Mo-CHTHS-(NH4)6Mo7O24 16.2 10.5 27.9 – 0.1 1.7:1:0.75 4.2

*As calculated considering the loss of weight determined by TG-DTA analysis in the range 105–200 °C
[11]

The X-ray diffraction patterns of the samples were recorded using a DRON 3
´
diffractometer equipped with a graphite monochromator (kCuKa = 1.5418 Å). The
samples were scanned from 7 to 70° (2h) in steps of 0.05° 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 cm-1 were recorded on BioRad FTS 135
spectrometer using the KBr pellets technique. The concentration of the solid sample
in the KBr matrix was 0.1 wt%.
Micro Raman spectra of the catalysts in the range 1424–196 cm-1 were recorded
with 1 scan/8 s using SPEX 1877 triplemate spectrophotometer and the laser line
514.5360 nm as exciting radiation.
The specific surface area of the solids was determined by BET method from
nitrogen adsorption–desorption isotherms at -196 °C using a Carlo-Erba instru-
ment. Prior to the determination, the samples were degassed at 90 °C during 24 h
under a pressure of 0.1 Pa.
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). The samples
were analyzed from 15 mm working distance, with a resolution of 12 nm.
The surface base sites of the catalysts were determined on the basis of the
irreversible adsorption of organic acids, such as acrylic acid, pKa = 4.2 and phenol
pKa = 9.9, using a method that is suitable for both dried and calcined samples
which was described in detail in a previous publication [30]. The amount of
adsorbed phenol is related to the number of strong surface base sites while the
amount of adsorbed acrylic acid is related to the total number of base sites. The
number of weak base sites is given by the difference between the amount of
adsorbed acrylic acid and the adsorbed phenol. Before base site measurements, all
catalysts were thoroughly degassed under vacuum at room temperature.

123
150 R. Zăvoianu et al.

Catalytic tests

In order to select the best catalysts, preliminary catalytic tests were performed by
contacting synthetic samples of gasoline (100 mL) containing 128.5 ppm t-BuSH
with the catalysts (1.3 g) under air flow (5 L/h) at ambient temperature and
pressure, under continuous stirring during 4 h. For the series of catalysts presenting
higher activity, the effects of the catalyst concentration, the air flow rate and the
reaction time were also investigated. Another set of experiments aimed to
investigate the resistance of the catalysts under operating conditions and the
possibility of using them in six repeated reaction cycles (4 h each). The catalyst
used in one reaction cycle was separated from the reaction mixture, washed with
diethyl ether and dried under air flow during 1 h at 90 °C, before being introduced
in the next cycle. The concentration of t-BuSH in the reaction mixture was
determined by gas chromatography using a GC K072320 Thermo-Quest chromato-
graph equipped with a FID detector and a capillary column of 30 m length with
DB5 stationary phase.

Results and discussions

The data presented in Table 1 show that both the ratio Mg/Al and the Mo uptake are
different depending on the preparation conditions and the molybdenum source.
All the samples presented traces of carbon suggesting that carbonate is still
present no matter what precautions are taken. For both Mo-HT samples prepared
using Na2MoO4 as a molybdenum source either by ionic exchange or by co-
precipitation at high supersaturation, the Mo-uptake was lower than the expected
value considering the atomic ratio in the preparation mixture Mg:Al:Mo in the
reaction mixture 3:1:0.25. For the sample prepared by ionic exchange this could be
expected since the true exchange capacity of anionic clays (e. g. 1.0–1.5 meq g-1) is
usually much lower than the theoretical one (3.3 meq g-1 for HT-NO3-) [14, 16].
The atomic ratio Mg:Al was also slightly lower than 3, indicating that for these
samples, there is probably a leaching of Mg during the washing stage. The
differences in the Mg/Al ratios were also confirmed by the results of the XRD and
SEM–EDX analyses (see Table 2). The chemical composition of the sample
prepared using (NH4)6Mo7O24 as a molybdenum source was very different from that
expected considering the composition of the reaction mixture, indicating that a high
amount of molybdenum is incorporated in the structure in this case, but there is also
a pronounced loss of Mg during the washing step since the ratio Mg/Al is much
lower than 3 (e.g. 1.6). Compared to Mo-HTHS-Na2MO4, Mo-HTHS-(NH4)6Mo7O24 also
presents a different behavior during thermal decomposition as it may be seen from
the results of the thermal analysis presented in Fig. 1. Thus, the total loss of weight
during the thermal decomposition of Mo-HTHS-Na2MO4 was 39 wt% (typical for a
hydrotalcite-like compound) whereas for Mo-HTHS-(NH4)6Mo7O24, this loss of weight
was only 23 wt%, indicating a higher thermal stability. Mo-HTHS-Na2MO4 which
has a low concentration of Mo presents two weight losses accompanied by
strong endothermic effects at 235 and 419 °C respectively, while the sample

123
Oxidation of tert-butanethiol with air 151

Table 2 Results of XRD, SEM–EDX and BET analyses for Mo-HT samples
Mo-HT Lattice IFS I003
I110
Mg/Al Mg/Al/Mo D003b D-110b Ssp
Samples parameters

a (Å) c (Å) (Å) (XRD)a (SEM–EDX) (Å) (Å) (m2/g)

Mo-HTIE-Na2MoO4 3.060 23.521 2.93 5.98 2.75 2.72/1/0.11 78 166 58

Mo-HTIE-Na2MoO4 3.060 23.521 2.93 5.98 2.75 2.72/1/0.11 78 166 58
Mo-HTHS-Na2MoO4 3.058 23.310 2.97 7.53 2.71 2.7/1/0.12 119 182 47
C
Mo-HTHS-(NH4)6Mo7O24 – – – – – 1.72/1/0.9 – – 35
(1.2/0/0.5)*
Reference material 3.065 23.716 3.10 8.29 3.00 3/1/0 77 145 65
Mg3Al-CO32-

*Traces in the less homogeneous samples

a
The ratios Mg/Al were calculated using the values of the lattice constant a, and Vegard’s law [11]
b ´
D003 (Å) and D110 (Å) are the sizes of the crystals determined using Debye-Sherrer formula for two directions
perpendicular to the planes (003) and (110), respectively
c
For Mo-HTHS-(NH4)6Mo7O24 due to the low crystallinity the values of the lattice parameters have not been
calculated

Mo-HTHS-(NH4)6Mo7O24, which has a high concentration of Mo, shows four stages of

weight loss accompanied by endothermic effects at 177, 445, 526, and 571 °C. The
effects noticed at temperatures higher than 500 °C are ascribed to the thermal
decomposition of the paramolybdate anions [31].
The calcined samples Mo-CHT have higher Mg, Al, Mo concentrations since the
nitrate anions and most of the hydroxyl groups are lost during calcination. However,
since calcination takes place under air flow, traces of carbonate are also found.
The XRD patterns of Mo-HT samples prepared by ionic exchange or co-
precipitation at high supersaturation using Na2MoO4 as a molybdenum source
(Fig. 2Ia, b) exhibit a typical hydrotalcite structure with sharp and symmetric
reflections for (003), (006), (110) and (113) planes and broad asymmetric peaks for
(012), (015) and (018) planes (JCPDS 70-2151) [11]. The reflections were indexed
in a hexagonal lattice with R3m rhombohedral symmetry. The cell parameters are
given by a = 2 9 d110 and c =32 x (d003 ? 2 d006). The interlayer free spacing (IFS)
´
was calculated by subtracting the brucite sheet thickness (e.g. 4.8 Å as reported by
c
Miyata [32]) from 3 values. These samples have a homogeneous 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 which are mainly NO3-. The (0kl) peaks are less asymmetric compared to
those of the reference pattern of the natural mineral HT-CO32-, showing less
turbostratic disorder effects. In their case the decrease of the Mg/Al ratio compared
to the standard HT-CO32- 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.
The diffraction pattern of Mo-HTHS-(NH4)6Mo7O24 (Fig. 2Ic) shows a considerably
disordered structure with broader and less defined peaks. The maximum of the

123
152 R. Zăvoianu et al.

0 50 0,5 50
Mo-HTHS-Na2MoO4 40 Mo-HTHS-Na2MoO4
40

dh/dt (meV/min)
-10 30

dm/dt (mg/min)
20 DTG

HF (meV)
0 30
TG (%)

-20 10
HF 0 20
-30 -10
-20 -0,5 10
TG DHF
-40 -30 0
-40
-50 -50 -1 -10
0 200 400 600 800 0 200 400 600 800
T (ºC) T (ºC)

0 10 0,5 8
Mo-HTHS-(NH4)6Mo7O24 Mo-HTHS-(NH4)6Mo7O24
-10 0

dh/dt (mEv/min)
dm/dt (mg/min)
-10 0
HF (meV)
-20 TG DTG
TG (%)

-20 3
-30
-30 -0,5
HF DHF
-40 -40
-50 -50 -1 -2
0 200 400 600 800 0 200 400 600 800
T (ºC) T (ºC)

Fig. 1 TG and HF profiles for Mo-HTHS-Na2MoO4, and Mo-HTHS-(NH4)6Mo7O24

(003)

(I) (200) (II)

(006)

(220)
(012)

(110)
(113)
(015)

(018)
I (a.u.)

I (a.u.)

(111)
(a)
(d)
(b) (e)
(*)
(c) (f)

10 20 30 40 50 60 70 10 20 30 40 50 60 70
2θ (degrees) 2θ (degrees)

Fig. 2 XRD patterns of the catalysts: (I) Mo-HT precursors: a Mo-HTHS-Na2MoO4, b Mo-HTIE-Na2MoO4,
c Mo-HTHS-(NH4)6Mo7O24, (II) Mo-CHT mixed oxides: d Mo-CHTHS-Na2MoO4, e Mo-CHTIE-Na2MoO4,
f Mo-CHTHS-(NH4)6Mo7O24, * diffraction lines of Mo compounds impurities

reflection corresponding to (003) plane shifted to lower values of 2h suggests the

location of the paramolybdate species in the interlayer. The significant broadening
of the second diffraction line (006), which is also shifted to lower values of 2h,
highlights the disorder in the stacking of the planes (00l) due to the presence of the
Mo species similarly to the phenomenon reported in the case of the intercalation of
metavanadate species [33, 34]. The wide basal peaks and the broad diffraction
band corresponding to the (110) plane suggest the presence of small crystallites.

123
Oxidation of tert-butanethiol with air 153

Normally, the smaller size of the crystallites would lead to a larger surface area.
However as it may be seen from Table 2, this sample has the lowest surface area.
This fact was also confirmed by the SEM microphotographs presented in Fig. 3
where it may be seen that at the same magnification level (e.g. 2700), the particles
of Mo-HTHS-(NH4)6Mo7O24 exhibit a quasi-flat surface with small excrescences while
the particles of Mo-HTHS-Na2MoO4, which has a well-defined diffraction pattern,
show a porous layered structure. Therefore it may be assumed that the poor
crystallinity of Mo-HTHS-(NH4)6Mo7O24 may be due to the presence of a compact
amorphous phase covered with small crystallites. The less homogeneous compo-
sition of Mo-HTHS-(NH4)6Mo7O24 was also revealed by the results of SEM–EDX
analysis presented in Table 2.
The XRD patterns of Mo-CHTIE-Na2MoO4 and Mo-CHTHS-Na2MoO4 (Fig. 2IId, e)
present the typical features of Mg(Al)O mixed oxide with periclase structure
(a = 4.184 and 4.193Å, respectively) and no traces of polymolybdate species have
been noticed. Meanwhile, the pattern of Mo-CHTHS-(NH4)6Mo7O24 (Fig. 2IIf) shows a
high amount of amorphous phase with several diffraction lines corresponding
to molybdenum compounds. The unit cell parameter and the mean crystallite size
were evaluated assuming a Voigt profile function. The mean crystallite size was
determined using the Debye–Scherrer formula:
D ¼ ðk  k=bcoshÞ ð4Þ

Fig. 3 SEM microphotographs of Mo-HTHS-Na2MoO4, Mo-HTHS-(NH4)6Mo7O24 and Mo-CHTHS-Na2MoO4

123
154 R. Zăvoianu et al.

where h is the Bragg angle, b is the fullwidth at half maximum of the peak corrected
by the instrumental broadness, k is the X-ray wavelength (kCuKa = 1.5418 Å) and k
is the structural factor (taken as 0.9 for the cubic structure of MgO). The mean
crystallite size was calculated as an average value given by the FWHM of (200) and
(220) peaks. The results are presented in Table 3.
The surface areas of the calcined samples presented in Table 3 are larger than
those corresponding to the dried precursors, while respecting the same variation
order (e.g. the largest surface area is exhibited by the samples prepared by ionic
exchange with Na2MoO4, followed by the sample prepared by co-precipitation at
high supersaturation with Na2MoO4 and the lowest surface area is characteristic of
the sample prepared at high supersaturation with (NH4)6Mo7O24). The effect of
calcination on the surface modification is illustrated by the SEM microphotographs
in Fig. 3, where it may be seen that at the same magnification level (e.g. 3500)
the dimensions of the particles in Mo-CHTHS-Na2MoO4 are smaller than those in
Mo-HTHS-Na2MoO4.
The FTIR spectra of the molybdenum containing catalysts are presented in
Fig. 4.
The FTIR spectra of the Mo-HT samples (Fig. 4a, c, e) show broad adsorption
bands suggesting a high disorder of the molecules in the galleries. Meanwhile, the
band corresponding to Mo–O–Mo stretching vibrations at 665 cm-1, the one related
to MoO42- at 856 cm-1 and the band for Mo=O stretching at 914 cm-1 [25, 35]
appear in the same region as those characteristic for a typical HT structure.
Therefore, due to the overlapping, it is difficult to comment the nature of Mo species
in the modified HTlcs. The most significant difference between the FTIR spectra of
the samples Mo-HTHS-Na2MOO4 and Mo-HTHS-(NH4)6Mo7O24 is the higher intensity of
the peak at 1400 cm-1 ascribed to the presence of NO3- anions [36] in the spectrum
of Mo-HTHS-Na2MOO4. 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. The effect of the ionic exchange for the sample
Mo-HTIE-Na2MoO4 is noticed due to the lowering of the band corresponding to
NO3-vibrations compared to the band in the spectrum of Mo-HTHS-Na2MoO4.
In the FTIR spectra of the calcined samples (Fig. 4b, d, f) the decrease of the
intensity of the band corresponding to the hydroxyl groups at 3460 cm-1 compared
to the spectra of Mo-HT samples was noticed. The FTIR spectrum of Mo-CHTHS-
(NH4)6Mo7O24 indicates that this sample has a lower amount of hydroxilic groups and
a higher amount of Mo incorporated compared to Mo-CHTHS-Na2MoO4, whose

Table 3 Results of XRD, SEM–EDX and BET analyses for Mo-CHT samples
Sample Unit cell parameter Mean crystallite Mg/Al/Mo SBET
(a) (Å) size (Å) (SEM–EDX) (m2/g)

Mo-CHTHS-Na2MoO4 4.193 36 2.81/1/0.09 100

Mo-CHTIE-Na2MoO4 4.184 38 2.65/1/0.1 150
Mo-CHTHS-(NH4)6Mo7O24 4.171 32 1.7/1/0.9 82

123
Oxidation of tert-butanethiol with air 155

Fig. 4 FTIR spectra of Mo-

containing samples (a Mo-
HTHS-Na2MoO4, b Mo-CHTHS-
Na2MoO4, c Mo-HTIE-Na2MoO4,
d Mo-CHTIE-Na2MoO4,
(f)

Transmittance (a.u.)
e Mo-HTHS-(NH4)6Mo7O24,
f Mo-CHTHS-(NH4)6Mo7O24,
—856 cm-1) (e)

(d)

(c)

(b)
(a)

400 1000 1600 2200 2800 3400 4000

Wavenumber (cm-1)

(a) (b) (c)

260

Kubelka Munk (a.u.)

Kubelka Munk (a.u.)
Kubelka Munk (a.u.)

270
275

313
calcined
290

360
calcined
calcined
323
260

dried
394
260

dried
309

dried
320

200 300 400 500 200 300 400 500 200 300 400 500
Wavelength (nm) Wavelength (nm) Wavelength (nm)

Fig. 5 DR-UV–Vis spectra of Mo-containing samples a dried—Mo-HTHS-Na2MoO4; calcined—

Mo-CHTHS-Na2MoO4; b dried—Mo-HTIE-Na2MoO4, calcined—Mo-CHTIE-Na2MoO4; c dried—Mo-HTHS-
(NH4)6Mo7O24, calcined—Mo-CHTHS-(NH4)6Mo7O24

spectrum displays higher intensity bands corresponding to hydroxyl groups while

the bands corresponding to Mo–O bonds are noticed as shoulders.
Fig. 5 displays the DR-UV–Vis spectra of the Mo containing catalysts in the
region 220–500 nm where the absorption bands characteristics to Mo species
appear.
According to literature data, the isolated MoO42- species with Mo in tetrahedral
coordination present absorption bands in the region 260–280 nm, while the bands in
the region 300–320 nm are due to Mo7O246- and isolated MoO3 species with Mo6?
in octahedral coordination [37, 38]. As it may be seen from Fig. 5, all the samples
contain both Mo in tetrahedral and octahedral coordination. However, in the
samples prepared with Na2MoO4, (Fig. 5a, b) the amounts of tetrahedrally

123
156 R. Zăvoianu et al.

coordinated species are prevailing whereas in the samples prepared from

(NH4)6Mo7O24 (Fig. 5c) the octahedrally coordinated species prevail.
The results obtained by DR-UV–Vis were confirmed by those of Raman
spectroscopy analysis illustrated by the spectra presented in Fig. 6.
The Raman spectra revealed the presence of the most intense absorption band
corresponding to Mo–O symmetrical stretching vibration in MoO42- at 896 cm-1
and the one corresponding to d(Mo=O) in MoO42- at 320 cm-1 [21, 26] in all
the calcined samples, even if in the case of Mo-CHTHS-(NH4)6Mo7O24 (Fig. 6c)
the intensity of these bands was much lower. The bands characteristic for Mo7O246-
at 940 cm-1 (highest intensity), 564 and 219 cm-1 (Mo–O-Mo m and d vibrations)
and 340 cm-1 (d(Mo=O)) [39] could be discerned clearly in the spectrum of
Mo-CHTHS-(NH4)6Mo7O24, while in the spectra of Mo-CHTIE-Na2MoO4 and Mo-
CHTHS-Na2MoO4 (Fig. 6a, b), only the band at 940 cm-1 could be noticed as a
shoulder.
The results of the preliminary catalytic tests (Fig. 7) performed by contacting the
catalysts with synthetic samples of gasoline contaminated with 128.5 ppm t-BuSH
under air flow at ambient temperature and pressure showed that for all Mo-HT
samples the conversions of t-BuSH were lower by 10–25% than those obtained in
the presence of the corresponding derived mixed oxides Mo-CHT. At a first glance,
this fact should be explainable by the increase of the surface area in the mixed oxide
samples (see Table 3) compared to the hydrotalcite-type precursors (see Table 2).
However, it was surprising to notice that the lowest conversion level was
obtained in the presence of the samples containing the highest concentration of Mo,
e.g. Mo-HTHS-(NH4)6Mo27O24 and Mo-CHTHS-(NH4)6Mo27O24, which yielded only 15
and 24% conversion of t-BuSH. These conversion values are less than half of the
conversions reached with the catalysts prepared using Na2MoO4 as a molybdenum
source, which have a concentration of Mo sites that is 6-8 times lower than in Mo-
HTHS-(NH4)6Mo27O24 and Mo-CHTHS-(NH4)6Mo27O24 samples. Meanwhile, the specific
surface areas of these catalysts (35 and 82 m2/g, respectively) are only approxi-
mately  lower than those of the samples Mo-HTHS-Na2MoO4 and Mo-CHTHS-
Na2MoO4. One fact revealed clearly by the characterization of the samples that might
be related to the poor catalytic activity of Mo-HTHS-(NH4)6Mo27O24 and Mo-CHTHS-
(NH4)6Mo27O24 could be the low amount of Mo species with tetrahedral coordination
included in these samples. Another fact that could be accounted as responsible for

Fig. 6 Raman spectra of Mo- (O)

CHT samples (a Mo-CHTHS- (O) (O)
(T)
Absorbance (a.u.)

Na2MoO4, b Mo-CHTIE-Na2MoO4, (O)

c Mo-CHTHS-(NH4)6Mo7O24,
(T)
T tetragonal, O octahedral) (c)

(T)
(a)

(T)
(b)

200 400 600 800 1000 1200 1400

Raman shift (cm-1)

123
Oxidation of tert-butanethiol with air 157

80

t -BuSH conversion (%)

70
60
50
Calcined
40 Precursors
30
20
10
0
1 2 3
Catalysts

Fig. 7 Comparison of the catalytic activities of precursors and calcined samples, air flow 5 L/h, 1.3 g
catalyst, 100 mL gasoline with Co t-BuSH = 128.5 ppm, 4 h reaction time. Precursors: 1 MoHTIE-Na2MoO4;
2 MoHTHS-Na2MoO4; 3 MoHTHS-(NH4)6Mo27O24; Calcined: 1 MoCHTIE-Na2MoO4; 2 MoHTHS-Na2MoO4; 3
MoHTHS-(NH4)6Mo27O24

their low activity would be a lower basicity of the surface which would lead to an
inefficient activation of the alkanethyol reactant.
In order to confirm this supposition, the surface base sites of the catalysts was
determined using a method based on the irreversible adsorption of organic acids,
(acrylic acid, pKa = 4.2 and phenol pKa = 9.9) that is suitable for both dried and
calcined samples [30]. The results presented in Table 4, show that undoubtedly the
samples prepared with (NH4)6Mo7O24 have the lowest number of base sites, while
the samples prepared either by ionic exchange or by co-precipitation with Na2MoO4
exhibit higher basicity. The values of the base sites numbers obtained for
Mo-HTIE-Na2MoO4 and Mo-HTHS-Na2MoO4 are slightly lower than those characteristic
to HT-CO32- (e.g. 6.47 mmol weak base sites/g and 0.26 mmol strong base sites/g
[30]). Meanwhile, those obtained for the corresponding Mo-CHT samples are also
just a little bit lower than those obtained for the mixed oxide CHT obtained from
HT-CO32- precursor (e.g. 7.98 mmol weak base sites/g and 0.38 mmol strong base
sites/g [30]).
Based on the above mentioned aspects it may be concluded that both the presence
of the base sites as well as the presence of tetrahedral coordinated Mo species are
required for the oxidation of t-BuSH. In the first stage, the t-BuSH molecule is
activated by dissociation in the presence of the base sites of the solid. In the case
of Mo-HT samples, the OH- ions in the interlayer act as Brønsted base sites with a
stronger basicity than MoO42-, or Mo7O246- and NO3- ions. In the case of
Mo-CHT samples, the base surface sites consist of OH- groups (low strength), M–O
pairs (medium strength) and O2- (strong) [40]. After the dissociation the t-BuSH-
anion is adsorbed preferentially on tetracoordinated Mo6? sites due to the fact that
these ones can undergo easily a change in their coordination state. The Mo6? is then
reduced to Mo5? and a radical t-BuSH* is generated. Two t-BuSH* radicals will
combine to generate the dialkyl disulfide t-Bu-S–S-t-Bu while the reoxidation of the
Mo sites will be ensured by the oxygen in the air flow. Further studies using XPS

123
158 R. Zăvoianu et al.

Table 4 Surface base sites of the samples determined in fully hydrated conditions and by irreversible
adsorption of organic acids
Sample Base properties in Base sites (mmol/g)
fully hydrated
conditions*
(pH) Weak base sitesa Strong base sitesb

Mo-HTIE-Na2MoO4 10 5.85 0.20

Mo-HTHS-Na2MoO4 9.8 5.79 0.17
Mo-HTHS-(NH4)6Mo7O24 7.2 2.72 0.05
Mo-CHTIE-Na2MoO4 10.2 6.88 0.32
Mo-CHTHS-Na2MoO4 10 6.71 0.26
Mo-CHTHS-(NH4)6Mo7O24 7.5 3.34 0.10

*Determined by pH measurement of a suspension containing 1.5 g solid sample in 100 mL distilled water
a
(moles of acrylic acid–moles of phenol) adsorbed/gram of catalyst
b
moles of phenol adsorbed/gram of catalyst

measurements in order to confirm the proposed mechanism are going to be

performed in the near future.
Since the calcined catalysts exhibited better catalytic activity, they were selected
for further testing in order to establish the optimal reaction conditions. In a first
series of tests, the influence of the concentration of catalyst in the reaction mixture
has been investigated. The results presented in Fig. 8a show that, for all catalysts,
the conversion of t-BuSH increases almost linearly when the concentration of
catalyst in the reaction mixture varies from 0.8 up to 1.3 wt%. A further increase
of the concentration of the catalyst does not lead to significant increases of the
conversion. The highest level of the conversion (80%) is reached with the catalyst
Mo-CHTIE-Na2MoO4. For the less active catalyst, the conversion does not exceed
30% even at the highest concentration of solid in the reaction mixture. Taking these
results into account, it may be concluded that a concentration of 1.5 wt% catalyst in
the reaction mixture would be preferable for obtaining high conversion levels.
In the second series of tests, the effect of the air flow rate on the conversion of t-
BuSH was investigated using the previously selected concentration of catalyst in the
reaction mixture. The results plotted in Fig. 8b show that the conversion of t-BuSH
increases sharply when the air flow rate varies from 1 up to 5 L/h, while the further
increase of the air flow rate does not lead to significant improvements. Therefore it
may be considered that an air flow rate of 6 L/h would be optimal for further
experiments.
In the third series of tests, the effect of the reaction time on the catalytic activity
was investigated using the optimal concentration of catalyst in the reaction mixture
and the optimal air flow rate selected. The results plotted in Fig. 8c show that after
4 h reaction time, almost stable values of the conversion of t-BuSH are obtained and
there is no decrease of the catalytic activity during 10 h. The fact that the total
conversion of this reactant cannot be reached even when the reaction time is
extended may be a consequence of two factors: (i) the lower reactivity of t-BuSH

123
Oxidation of tert-butanethiol with air 159

Fig. 8 Results of catalytic tests (a) 90

for t-BuSH oxidation using
80
100 mL gasoline with
Co t-BuSH = 128.5ppm and 70

t-BuSH conversion (%)

Mo-containing catalysts
(filled square Mo-CHTHS- 60
Na2MoO4, filled diamond Mo-
CHTIE-Na2MoO4, filled triangle 50
Mo-CHTHS-(NH4)6Mo7O24); 40
a effect of catalyst concentration
(air flow rate 5 L/h, 4 h reaction 30
time); b effect of air flow rate
(concentration of catalyst 1.5 20
wt%, 4 h reaction time); c effect
10
of reaction time (concentration
of catalyst 1.5 wt%, air flow rate 0
6 L/h) 0 0,5 1 1,5 2
Catalyst concentration (wt. %)

(b) 90
80

t-BuSH conversion (%) 70

60

50

40

30

20

10

0
0 1 2 3 4 5 6 7 8
Air flow rate (L/h)

(c) 90

80

70
t-BuSH conversion (%)

60

50

40

30

20

10

0
0 1 2 3 4 5 6 7 8 9 1011
Reaction time (h)

123
160 R. Zăvoianu et al.

100

t -BuSH conversion (%)

90
80
70
60
50
40
30
20
10
0
Mo-CHTIE-Na2MoO4 Mo-CHTHS-Na2MoO4
Catalysts

Fig. 9 Results of catalytic tests for t-BuSH oxidation, air flow rate 6 L/h, concentration of catalyst 1.5
wt%, 100 mL gasoline with Cot-BuSH = 128.5 ppm, repeated reaction cycles

compared to the other light alkane thiols due to its molecular structure, (ii) the
partial screening of the active sites of the catalyst by the reaction products (disulfide
and water) during the process.
The fourth set of experiments aimed to investigate the resistance of the catalysts
under operating conditions and the possibility of using them in repeated reaction
cycles (4 h each). The results (Fig. 9) indicate that the catalytic activity decreases
gradually with about 8% after six reaction cycles. It may be supposed that the
deactivation occurs due to the adsorption of the reaction products on the surface of
the solids, even though the catalysts had been thoroughly washed with diethyl ether
in order to remove the adsorbed disulfide before being used in the next cycle.
The gasoline recovered after six reaction cycles was collected and submitted to
ICP-OES analysis (ASTM-E 1479-92) in order to examine the leaching of Mo,
Mg, and Al. For both catalysts Mo-CHTIE-Na2MoO4 and Mo-CHTHS-Na2MoO4, the
concentrations of Mg, Al and Mo in the recovered liquid phase were lower than the
detection limits (e.g. Mg \ 0.1 ppm, Al \ 0.02 ppm and Mo \ 0.05 ppm),
suggesting that leaching did not occur under reaction conditions.

Conclusions

The obtained results showed that the higher activity towards the oxidation of
t-BuSH is strongly related to two factors: (i) the presence of tetrahedral coordinated
Mo species well dispersed in the structure of the base solid, and (ii) the amount of
base sites in the solid. The preparation of Mo-HT solids at pH 10, using Na2MoO4
as molybdenum source allows the obtaining of crystalline materials with relatively
high basicity and fine dispersion of molybdate species. These solids exhibit the best
catalytic activity for the oxidation of t-BuSH (e.g. about 80% conversions). The
preparation of Mo-HT solids at pH 10, using (NH4)6Mo7O24 as molybdenum source
and NH4OH for pH adjustment, lead to less crystalline solids with smaller surface

123
Oxidation of tert-butanethiol with air 161

area and lower basicity. In these solids, which had the lowest catalytic activity, Mo
was present mainly as octahedral coordinated species.

Acknowledgments The Romanian authors express their gratitude to the Romanian National Agency for
Scientific Research for financial support through grant 71-043 ECOPAM under the framework of PNCDI
Partenerships program.

References

1. Alcaraz JJ, Arena BJ, Gillespie RD, Holmgren JS (1998) Solid base catalysts for mercaptan oxi-
dation. Catal Today 43:89–99
2. Jiang DE, Zhao BY, Xie YC, Pan GC, Ran GP, Min E (2001) Structure and basicity of gamma-
Al2O3-supported MgO and its application to mercaptan oxidation. Appl Catal A-Gen 219:69–78
3. Chatti I, Ghorbel A, Grange P, Colin JM (2002) Oxidation of mercaptans in light oil sweetening by
cobalt(II) phthalocyanine-hydrotalcite catalysts. Catal Today 75:113–117
4. Angelescu E, Cruceanu A, Zavoianu R, Angelescu A (2006) Transitional metals sulphonated pht-
alocyanines, catalysts for the demercaptanization of gasolines. Rev Chim-Bucharest 57:85–90
5. Iliev VI, Ileva AI, Dimitrov LD (1995) Catalytic oxidation of 2-mercaptoethanol by cobalt(II)-
phthalocyanine complexes intercalated in layered double hydroxides. Appl Catal A-Gen 126:
333–340
6. Iliev V (1993) Catalytic oxidation of mercaptans by charcoal-supported sterically hindered cobalt
(II)-phthalocyanines. J Mol Catal 85:L269–L273
7. Buck T, Bohlen H, Wohrle D, Schulz-Ekloff G, Andreev A (1993) Influence of substituents and
ligands of various cobalt (II) porphyrin derivatives coordinately bonded to silica on the oxidation of
mercaptan. J Mol Catal 80:253–267
8. De Vos DE, Jacobs PA (2001) Chapter 20 Zeolite-based supramolecular assemblies. In: van Bekkum
H, Flanigen EM, Jacobs PA, Jansen JC (eds) Introduction to Zeolite Science and Practice, Stud Surf
Sci Catal, vol 137. Elsevier, Amsterdam, pp 957–985
9. Perez-Bernal ME, Ruano-Casero R, Pinnavaia TJ (1991) Catalytic autoxidation of 1-decanethiol
by cobalt(II)phthalocyaninetetrasulfonate intercalated in a layered double hydroxide. Catal Lett
11:55–61
10. Corma A, Fornes V, Rey F, Cervilla A, Llopis E, Ribera A (1995) Catalytic air oxidation of thyols
mediated at a Mo(VI)O-2 complex center intercalated in a Zn(II)-Al(III) layered double hydroxyde
host. J Catal 152:237–242
11. Cavani F, Trifiro F, Vaccari A (1991) Hydrotalcite-type anionic clays: preparation, properties and
applications. Catal Today 11:173–301
12. Albertazzi S, Basile F, Vaccari A (2004) Catalytic Properties of Hydrotalcite-Type Anionic Clays. In:
Wypych F, Satyanarayana KG (eds) Clay Surfaces Fundamental and Applications, Interface Science
and Technology, vol 1. Elsevier, london, pp 497–546
13. Basile F, Vaccari A (2001) Chapter 10. In: Rives V (ed) Layered double hydroxides: present and
future. Nova Science Publisher, New York
14. Vaccari A (1999) Clays and catalysis: a promising future. Appl Clay Sci 14:161–198
15. Cheng S (1999) From layer compounds to catalytic materials. Catal Today 49:303–312
16. Trifiro F, Vaccari A (1996) Hydrotalcite-like Anionic Clays (Layered Double Hydroxides) in
Comprehensive Supramolecular Chemistry. In: Alberti G, Bein T (eds) Solid-State Supramolecular
Chemistry: two and Three-Dimensional Inorganic Networks, vol 7. Elsevier Science Ltd, Pergamon,
pp 251–291
17. Drezdon MA (1988) Synthesis of Isopolymetalate-Pillared Hydrotalcite via Organic-Anion-Pillared
Precursors. Inorg Chem 27:4628–4632
18. Rives V, Ulibarri MA (1999) Layered double hydroxides (LDH) intercalated with metal coordination
compounds and oxometalates. Coord Chem Rev 181:61–120
19. Ulibarri MA, Hermosin MC (2001) Chapter 9. In: Rives V (ed) Layered double hydroxides: present
and future. Nova Science Publisher, New York
20. Drezdon MA (1988) Pillared hydrotalcites. US Patent 4,774,212 Assignee to Amoco Corporation, 27
Sept 1998

123
162 R. Zăvoianu et al.

21. Gardner E, Pinnavaia TJ (1998) On the nature of selective olefin oxidation catalysts derived from
molybdate- and tungstate-intercalated layered double hydroxides. Appl Catal A-Gen 167:65–74
22. Pinnavaia TJ, Chibwe M, Constantino VRL, Yun SK (1995) Organic-chemical conversions catalyzed
by intercalated layered double hydroxides (LDHS). Appl Clay Sci 10:117–129
23. Tatsumi T, Yamamoto K, Tajima H, Tominga H (1992) Shape selective epoxidation of alkenes
catalyzed by polyoxometalate-intercalated hydrotalcite. Chem Lett 5:815–818
24. Mitchell PCH, Wass SA (2002) Propane dehydrogenation over molybdenum hydrotalcite catalysts.
Appl Catal A-Gen 225:153–165
25. Malherbe F, Depège C, Forano C, Besse JP, Atkins MP, Sharma B, Wade SR (1998) Alkoxylation
reaction catalysed by layered double hydroxides. Appl Clay Sci 13:451–466
26. van Laar FMPR, De Vos DE, Pierard F, Kirsch De-Mesmaeker A, Fiermans L, Jacobs PA (2001)
Generation of singlet molecular oxygen from H2O2 with molybdate-exchanged layered double
hydroxides: effects of catalyst composition and reaction conditions. J Catal 197:139–150
27. van Laar FMPR, De Vos DE, Vanoppen D, Sels B, Jacobs PA (1998) Heterogeneous molybdate
catalysts for the generation of singlet molecular oxygen (1Dg) from H2O2. Chem Commun 267–268
28. Zavoianu R, Birjega R, Pavel OD, Cruceanu A, Alifanti M (2005) Hydrotalcite like compounds with
low Mo-loading active catalysts for selective oxidation of cyclohexene with hydrogen peroxide. Appl
Catal A-Gen 286:211–220
29. Kwon T, Tsigdinos GA, Pinnavaia TJ (1988) Pillaring of layered double hydroxides (LDH’s) by
polyoxometalate anions. J Am Chem Soc 110:3653–3654
30. Ionescu R, Birjega R, Angelescu E, Pavel OD, Zavoianu R (2010) Epoxidation of cyclohexene with
H2O2 and acetonitrile catalyzed by Mg–Al hydrotalcite and cobalt modified hydrotalcites. Catal Lett
34:309–317
31. Rives V (2002) Characterisation of layered double hydroxides and their decomposition products.
Mater Chem Phys 75:19–25
32. Miyata S (1975) The syntheses of hydrotalcite-like compounds and their structures and physico-
chemical properties I: the systems Mg2?–Al3?–NO3-, Mg2?–Al3?–ClO4-, Ni2?–Al3?–Cl- and
Zn2?–Al3?–Cl-. Clay Clay Miner 23:369–375
33. Han KS, Guerlou-Demourgues L, Delmas C (1996) A new metavanadate inserted layered double
hydroxide prepared by ‘chimie douce’. Solid State Ionics 84:227–238
34. Menetrier M, Han KS, Guerlou-Demourgues L, Delmas C (1997) Vanadate-inserted layered double
hydroxides: a V-51 NMR investigation on the grafting process. Inorg Chem 36:2441–2445
35. Imamura S, Sasaki H, Shono M, Kanai H (1998) Structure of molybdenum supported on alpha-,
gamma-, and chi-aluminas in relation to its epoxidation activity. J Catal 177:72–81
36. Nakamoto K (2009) Infrared and Raman Spectra of Inorganic and Coordination Compounds Theory
and Applications in Inorganic Chemistry, 6th edn. Wiley, New York
37. Liu Z, Chen Y (1998) Spectroscopic studies on tetragonal ZrO2-supported MoO3 and NiO-MoO3
systems. J Catal 177:314–324
38. Faro AC, Grange P, dos Santos ACB (2002) Niobia-supported nickel molybdenum catalysts:
Characterisation on the oxide form. Phys Chem Chem Phys 4:3997–4007
39. Carriazo D, Domingo C, Martin C, Rives V (2006) Structural and texture evolution with temperature
of layered double hydroxides intercalated with paramolybdate anions. Inorg Chem 45:1243–1251
40. Corma A, Fornes V, Martin-Aranda MR, Rey F (1992) Determination of base properties of hydro-
talcites: condensation of benzaldehyde with ethyl acetoacetate. J Catal 134:58–65

123