Synthesis, characterization and testing of a new V2O 5/Al2O3-MgO catalyst for butane dehydrogenation and limonene oxidation

Article abstract of DOI:10.1039/c3dt32954b

We report the synthesis and characterization of new V₂O ₅/Al₂O₃-MgO catalysts and their application in oxidative dehydrogenation and epoxidation reactions. The materials were prepared by wet impregnation under excess acid conditions. Anchoring of the desired species on the support occurs via an exchange reaction between the vanadium complex and surface hydroxyl groups. The IR and UV-Vis spectra of these catalysts indicate the presence of monomeric vanadium species at 5 wt% V ₂O₅ loading, along with small amounts of polymeric species at 5 and 10 wt% V₂O₅ loadings. Electron paramagnetic resonance (EPR) spectroscopy reveals the presence of ferromagnetic VO ²⁺ dimers following calcination at 773 K. The catalysts were then tested in two reactions, namely the gas phase oxidative dehydrogenation of n-butane under flow conditions at 773 K and the liquid phase epoxidation of limonene with H₂O₂. The dehydrogenation reaction gave butenes and 1,3-butadiene in moderate selectivity at 8-10% conversion. The epoxidation of limonene was less successful, giving 50-70% selectivity to the 1,2-epoxide at 10-20% conversion.

Full text of DOI:10.1039/c3dt32954b

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Synthesis, characterization and testing of a new
V2O5/Al2O3–MgO catalyst for butane dehydrogenation
and limonene oxidation†
Cite this: DOI: 10.1039/c3dt32954b
Zea Strassberger, Enrique V. Ramos-Fernandez, Agnes Boonstra, Remy Jorna,
Stefania Tanase* and Gadi Rothenberg*
We report the synthesis and characterization of new V2O5/Al2O3–MgO catalysts and their application in
oxidative dehydrogenation and epoxidation reactions. The materials were prepared by wet impregnation
under excess acid conditions. Anchoring of the desired species on the support occurs via an exchange
reaction between the vanadium complex and surface hydroxyl groups. The IR and UV-Vis spectra of these
catalysts indicate the presence of monomeric vanadium species at 5 wt% V2O5 loading, along with small
amounts of polymeric species at 5 and 10 wt% V2O5 loadings. Electron paramagnetic resonance (EPR)
spectroscopy reveals the presence of ferromagnetic VO2+ dimers following calcination at 773 K. The cata-
lysts were then tested in two reactions, namely the gas phase oxidative dehydrogenation of n-butane
under flow conditions at 773 K and the liquid phase epoxidation of limonene with H2O2. The dehydro-
genation reaction gave butenes and 1,3-butadiene in moderate selectivity at 8–10% conversion. The
epoxidation of limonene was less successful, giving 50–70% selectivity to the 1,2-epoxide at 10–20%
conversion.
Received 9th December 2012,
Accepted 31st January 2013
DOI: 10.1039/c3dt32954b
www.rsc.org/dalton
loadings. These species are often good catalysts, thanks to
their accessibility and high activity.10,11
1. Introduction
Heterogeneous catalysis is somewhere between art, science
In this paper, we report the synthesis and characterization
and technology. The science part is more obvious to the of a new type of vanadium catalyst supported on a combined
general observer. Solid catalysts are ubiquitous in the chemical acid–base support: Al2O3–MgO. The advantages of this bifunc-
industry (over 90% by volume of all chemicals are made using tional support are detailed elsewhere.12 We elucidate the
heterogeneous catalysis).1–4 Despite this, and notwithstanding oxidation states at the active site using electron paramagnetic
the many years of research into the mechanisms of reactions resonance (EPR) and study the nanometric properties of the
on surfaces, we still do not know how most catalysts actually catalyst using a variety of surface and bulk techniques. These
work.5 In fact, catalyst discovery is often serendipitous.6–9
catalysts were then tested in two types of reactions: gas-phase
In this respect, the left side of the periodic table is some- oxidative dehydrogenation of n-butane under flow conditions
what neglected. Most catalytic studies concentrate on the elec- at 773 K and liquid-phase epoxidation of limonene with H2O2.
tron-rich transition metals. The reason is that many of these
metals can easily switch between two relatively stable oxidation
states, making them ideal active site candidates. However,
there are exceptions on the basic side. Vanadium, for example,
2. Experimental section
is stable as V2+, V3+, V4+, and V5+. The V5+ state is found in
The V2O5 precursors used were high-purity oxalic acid and
tetrahedral (VO4), pentahedral (VO5) and octahedral (VO6) forms
and tends to form polyoxoanions. Surface V5+ sites are usually
present as isolated monomeric VO4 species at low vanadium
ammonium metavanadate (Sigma-Aldrich; ≥99% pure). As
oxide support we used Al2O3–MgO (a gift sample from
Eurosupport).13 All products were identified by comparing
their GC retention times to those of authentic samples.
Surface area measurements were performed by the BET
method using N2 at 77 K on a Thermo Scientific Surfer instru-
ment. Samples were dried in vacuum (1.10−3 mbar) for 3 h at
200 °C prior to the measurement.
Van ’t Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park
904, 1098XH Amsterdam, The Netherlands. E-mail: s.grecea@uva.nl,
g.rothenberg@uva.nl; http://www.hims.uva.nl/hcsc; Fax: (+)31 (0) 20 525 5604
†Electronic supplementary information (ESI)
available. See DOI:
10.1039/c3dt32954b
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Infrared spectra (4000–300 cm−1, resol. 0.5 cm−1) were 2.4. Procedure for n-butane oxidative dehydrogenation
recorded on a Varian 660 FTIR spectrometer equipped with a
Gladi ATR device, using the reflectance technique. Ligand field
spectra were obtained on a Perkin-Elmer Lambda 900 spectro-
photometer using the diffuse reflectance technique and MgO
as a reference. Electron paramagnetic resonance (EPR) spectra
were collected on a Brucker EMXplus instrument (magnetic
field calibrated with DPPH (g = 2.0036)).
GC analysis was done using an Interscience GC-8000 gas
chromatograph with a 14% cyanopropylphenyl/86% dimethyl
polysiloxane capillary column (Rtx-1701, 30 m; 25 mm ID;
1 μm df). Samples were diluted in 1 ml methanol. GC con-
ditions: isotherm at 50 °C (2 min); ramp at 2 °C min−1 to
70 °C; ramp at 70 °C min−1 to 140 °C; ramp at 10 °C min−1 to
260 °C; isotherm at 260 °C (2 min).
The catalyst was activated in situ before reaction in a flow of
45 ml min−1 N2 and 5 ml min−1 O2 at 500 °C. The reactions
were carried out at 1 atm and 500 °C in a continuous-flow
fixed-bed vertical quartz reactor (4 mm i.d.), which was con-
trolled with a fully automated system built in-house. The
partial pressures of C4H10, O2 and N2 were set up at
92 : 92 : 829 mbar respectively. The ratio of catalyst mass to
initial n-butane mass flow, so-called weight hourly space velo-
city, WHSV, was 7.7 h−1. A 3 mm quartz wool layer above the
catalyst served as a preheating zone. Isothermal conditions
were kept by diluting the catalyst bed with ground glass; the
reaction temperature was continuously monitored by a thermo-
couple at the catalyst bed. Reactor effluents were analyzed on-
line by using both an Interscience Compact GC equipped with
a TCD detector and a Porabond Q column and a mass
spectrometer. The measurement analytical repeatability was
better than 0.5%.
2.1 Procedure for TPR experiments
Hydrogen TPR studies were carried out for all catalysts.
Samples of ca. 50 mg were loaded into a quartz U-tube reactor
and pre-treated under nitrogen flow (40 ml min−1) at 473 K for
30 min. The samples were cooled to room temperature and the
gas stream was switched to 5% H2/N2 (40 ml min−1). The
samples were then heated to 1000 K (heating rate 10 K min−1).
Hydrogen consumption was determined quantitatively by a
thermal conductivity detector (TCD). A water trap was placed
before the TCD. Consequently, the TCD measures only the con-
sumed hydrogen quantity.
TOFs were calculated as mol of n-butane converted per
hour divided by the total mol of vanadium oxide. These calcu-
lations were based on the assumption that all catalysts have a
monolayer coverage of vanadium oxide. No estimation of the
active site was calculated.
3. Results and discussion
3.1 Catalyst synthesis
2.2 Procedure for catalyst synthesis
The catalysts were prepared by wet impregnation using stoi-
chiometric amounts of ammonium metavanadate and oxalic
acid (see the Experimental section for details). The maximum
amount of vanadium oxide that can form in a two-dimensional
layer, e.g. monolayer coverage, depends on both the support
surface area and the concentration of reactive surface hydroxyl
groups.11 Therefore, we selected three different V2O5 loadings.
Table 1 gives the catalyst composition and surface properties.
We observed that for a good impregnation, one must use an
excess of oxalic acid with respect to NH4VO3 (eqn (1)). This is
because the acid acts both as a reducing agent and a complex-
ing agent (eqn (1)).14 In these conditions, the sorption of
the vanadyl complex is carried out from acidic solutions.
Therefore, the surface hydroxyl groups are protonated and the
support surface has a positive charge (eqn (2), where x = the
number of functional groups at the oxide surface).11
Example: V2O5-350-5 (5% V2O5 on ESM 350, catalyst A). Oxalic
acid solution (0.75 g, 8.1 mmol, in 50 ml water) was added to a
solution of ammonium metavanadate (0.32 g, 2.7 mmol, in
100 ml water). The mixture was stirred at 900 rpm for ca.
10 min until an orange clear solution formed. This solution
was added to 5 g of ESM350 support (60 : 40 Al2O3–MgO) in a
250 ml round-bottomed flask and stirred 900 rpm for 10 min
at ambient temperature. The final suspension was evaporated
while stirring overnight on an oil bath at 100 °C, giving a white
powder. This was first dried at 120 °C for 24 h and then
calcined at 500 °C for 4 h (heating rate 2 °C min−1).
Catalysts B and C were similarly prepared using 5.4 mmol
(0.64 g) and 8.1 mmol (0.96 g) of ammonium metavanadate
and equivalent amounts of oxalic acid, respectively.
2.3 Procedure for limonene epoxidation
Table 1 Catalyst composition and properties
All reactions were run in stainless steel 40 ml autoclaves. A solu-
tion of 1.2 ml (6.2 mmol) limonene, 6 ml H2O2 (35% aq.),
1.3 ml (12.4 mmol) benzonitrile and 0.025 g of the catalyst in
40 ml acetone : 2-butanol (2 : 8) was charged in the reactor and
heated to 65 °C for 6 h. Blank experiments with or without the
support were performed in the same conditions. After the reac-
tion, the reactors were cooled down to room temperature using
an ice bath. Reactions were analysed by GC (anisole external
standard).
wt%
V atomsc
(nm2)
BET surface area Pore volume
b
Catalysta V2O5
(m2 g−1
)
(cm3 g−1
)
A
B
C
4.2
8.9
12.5
1.5
4.9
5.2
217
140
190
0.30
0.36
0.35
a In all cases, the support was 40 : 60 Al2O3–MgO, as 5 mm extrudates.
b Actual vanadium content determined by ICP. c The vanadium loading
divided by the surface area of the catalyst.
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NH4VO3 þ 3H2C2O4 ! H2½VOðC2O4Þ2ꢀ þ 2CO2 þ 2H2O
þ NH3 þ 1=2H2
Both Al2O3 and MgO tend to polarize and be surface
charged once suspended in an aqueous solution. However, the
surface charge depends on the pH of the solution.20 If this is
below the zero point charge (ZPC), the oxide surface is posi-
tively charged and will adsorb the negatively charged
vanadium complex. The ZPC is higher for MgO (pH =
12.1–12.7) than for Al2O3 (pH = 7.0–9.0). Therefore, the magne-
sia sites are more positively charged than the alumina ones.
Indeed, the pH of the solution is lower at higher vanadium
loadings (see ESI† for details). The measured pH of the solu-
tions at low loadings is higher than the ZPC. This means that
the surface would be more negatively charged than the
alumina site. Therefore, vanadium species bind to Al2O3 at low
loadings (5% and 10%) and to MgO at high loading (15%).
This is in agreement with the IR data discussed above.
ð1Þ
ð2Þ
S–OH þ Hþ ! ðS–OH2Þþ
2ꢁ
xðS–OH2Þþ þ ½VOðC2O4Þ ꢀ ! ðS–OÞ ½VOðC2O4Þ2ꢁxꢀ
2
x
þ xH2C2O4
ð3Þ
The attachment of the desired species on the support
occurs via an exchange reaction between the vanadium
complex and (protonated) surface hydroxyl groups (eqn (3)).
Importantly, ammonium and oxalate ions decompose fully,
leaving no traces on the catalyst surface after calcination at
500 °C.15 Note that the ICP vanadium loadings are consistently
lower than the nominal ones. This suggests that for a complete
complexation of vanadyl species a higher excess should be
used and thus the theoretical values would be reached.
The diffuse reflectance UV-visible (DRUV) spectra of the cata-
lysts A–C show a broad band with maxima around 260 nm,
290 nm and 315 nm, due to the ligand-to-metal charge transfer
(LMCT) transitions of V5+ (see Fig. 2). These bands originate
from VO4 species in tetrahedral coordination.21 The spectra of
B and C display a slight tail extending beyond 540 nm. This
indicates the presence of small amounts of polymeric species.
It also agrees with the results of Muylaert et al.,10 who reported
polymeric vanadium oxides at higher V loadings. The spectra
of A and B are almost identical in the UV range. We conclude
that the domain size of the dispersed vanadium species
remains unchanged, while the number of polymerized
vanadium species increases at higher vanadium loadings.
Vanadium oxide remains as a highly dispersed amorphous
monolayer phase at low loadings.22 This phase contains iso-
lated vanadium oxide species anchored to the surface. Our
support ESM350 (60 : 40 Al2O3–MgO) has a surface area of
3.2 Catalyst characterisation
We first investigated the catalyst surface structure by IR spec-
troscopy. Fig. 1 shows the spectra for the catalysts and the
plain support. The intensity of the hydroxyl group stretching
modes (at ca. 3000 cm−1) decreases upon addition of 5% and
10% V2O5 to the support (catalysts A and B, see Fig. S1† for
details). This indicates that the anchoring of the vanadium
species on the support occurs via surface OH groups (see
Fig. S1 in the ESI†). The broad band between 1000 and
1100 cm−1 reflects the VvO stretch of vanadyl groups on the
Al2O3 sites. These groups possess a short terminal VvO bond
and three bridging V–O–Al bonds.16 The weaker broad band
between 850 and 900 cm−1 is characteristic of pyrovanadate
(V2O74−).16 Note that the IR spectrum of the catalyst C shows
two important bands at 830 cm−1 and 890 cm−1, respectively.
These bands are assigned to vanadate and pyrovanadate
species on the MgO surface.17–19 We suggest that the surface
vanadium species are attached to the alumina sites in catalysts
A and B, and to magnesia sites in catalyst C.
175 m2 −1, requiring 16 wt% V2O5 for monolayer coverage.
g
The XRD patterns of catalysts A–C (see also Fig. S2 in the ESI†)
after calcination at 500 °C are similar to that of the MgO–Al2O3
support. This suggests indeed that no crystalline V2O5 are
present, in agreement with the IR spectra. Note that the ICP
analysis shows that the vanadium loading is well below the
Fig. 2 Diffuse reflectance UV-Vis spectra for catalysts A–C.
Fig. 1 IR spectra of the plain support and catalysts A–C.
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monolayer coverage in all catalysts. BET surface areas of the
calcined catalysts at 500 °C are presented in Table 1. The BET
surface area for catalysts A and C is higher than that of the
support. These values are highly reproducible when using the
same catalyst sample or a catalyst sample coming from a
different synthesis performed in identical conditions. This
suggests that some pores are washed during the synthesis. B
has the lowest surface area. The BET values seem to decrease
with increasing vanadia loading (catalysts A and B), but
strongly depend on the active species at the support surface
(catalysts B and C).23
Polycrystalline vanadia can dissociate partially upon
heating.24 It loses oxygen, resulting in V4+ defects. Some
studies suggest that a specific reaction between the dispersed
V5+ ion and the matrix occurs upon calcination at elevated
temperatures. This results in the formation of V4+ even in the
presence of air.25,26 Clary et al. showed that the presence of
vanadyl units in octahedral surroundings occurs at coverage
below monolayer.27 This is also the case for catalysts A–C. We
therefore used electron paramagnetic resonance (EPR) for
estimating the presence of paramagnetic surface VO2+ species.
The VO2+ ion has a d1 electronic configuration. In the
presence of a magnetic field, the electron can orient parallel or
antiparallel to the magnetic field vector. This leads to two
energy levels with mS = 1/2. Because the nuclear spin of V4+ is
I = 7/2, a so-called hyperfine interaction between S and I can
arise. This leads to a further splitting of the two electronic states
into 2I + 1 sublevels. The spin Hamiltonian then takes the form:
Fig. 3 The X-band EPR spectra of the non-reduced catalyst B recorded at 70
and 30 K. The inset cartoon shows a possible structure of the V(O)2V dimer
wherein the two VvO double bonds are orthogonal, in agreement with the
ferromagnetic interaction indicated by the band at half-field.
intramolecular ferromagnetic interactions in the exchange-
coupled d1–d1 systems (VO2+–VO2+) and thus of a triplet
ground state. It also indicates the presence of dimers at the
catalyst surface. Lower temperatures give better hfs resolution,
albeit with a slight decrease in signal intensity. At 30 K, the
spectrum centered at 3300 G consists of the overlapping of
low- and high-field parallel and perpendicular components.
A qualitative interpretation of the magnetic interactions in
transition metal dimers is usually based on the interaction
between pairs of natural magnetic orbitals.28 The unpaired
electron in the oxovanadium(IV) unit resides in a metal-
centered orbital with dxy character, with the oxo group oriented
along the z-axis. The direct overlap pathway leads to an anti-
ferromagnetic interaction when the V(O)2V or V(O)V core is
planar and the V–V distance is short. In an anti-coplanar con-
figuration, the orthogonality depends on the structural para-
meters of the dimer core. Moreover, the direct overlap
between the two magnetic orbitals is expected to be rather
small. Conversely, in a ferromagnetically coupled system the
two magnetic orbitals are orthogonal. In our case such a con-
dition favors the observed ferromagnetic interaction. This
suggests that the VO2+ dimers formed at the alumina surface
have either an anti-coplanar configuration, or that the vanadyl
ions sit in two different geometrical surroundings.
H ¼ βSgB0 þ SAI ꢁ gNβNIB0
ð4Þ
where β is the Bohr magneton, S the electron spin operator
and B0 the magnetic field vector. The g tensor is determined
by the interaction of the S with B0 and by the orbital angular
momentum which leads to the spin–orbit coupling. Depend-
ing on the symmetry of the VO2+ ion, the tensors g and A may
be anisotropic. For an axial symmetry, there are two g com-
ponents (gzz = g|| and gxx = gyy = g⊥). The same applies for the
hyperfine tensor. Therefore, the EPR spectra of isolated VO2+
ions have well resolved lines corresponding to g|| and g⊥.
These lines are split by the interaction with the vanadium
nucleus into eight partially superimposed hyperfine structure
lines. However, spin–spin dipolar or exchange interactions
often occur between neighboring VO2+ ions. In such cases, the
EPR spectra consist of single Lorentzian lines that are broad-
ened due to spin–spin exchange interactions. Therefore, the
hyperfine structure is not well-resolved.
The EPR spectra of A and B (Fig. 3 and Fig. S3–S4 in the
ESI†) at room temperature display a line centered at ca.
3300 G. This indicates the presence of VO2+ sites connected by
oxygen bridges, forming polymeric species. The broadening is
due to the effective spin–spin exchange interactions between
neighboring VO2+ centres within the structure. For the same
reason, the anisotropic g and hyperfine structures (hfs) are
The absorption band due to the d–d transition ion in the
range 500–800 nm (Fig. 2) is absent for catalyst A and weak
for B and C. This indicates that the amount of V4+ is small.
Thus, UV-Vis and EPR techniques are complementary for our
studies. For catalysts A and B, we performed the spectroscopic
analysis for both hydrated samples and non-hydrated ones
(the latter were treated at 200 °C for 4 h). However, we did not
observe any change in the spectra.
3.3 Characterization of the reduced catalyst
not well resolved. The band at half-field from the forbidden We further used temperature programmed reduction (TPR) to
ΔMS
=
2 transitions occurs at 1650 G. This indicates investigate the reducibility of the supported vanadium oxide.29
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Fig. 4 shows the hydrogen TPR profiles of catalysts A–C. The
profiles of pure V2O5 and the support are also shown for com-
parison. Pure V2O5 shows two reduction peaks at 937 K and
968 K, plus a broad peak at 1000 K. These three peaks corres-
pond to the V5+ → V4+ → V3+ stepwise reduction,21 progres-
sing through V2O5 → V6O13 → V2O4 → V2O3.10,21,30 Conversely,
the support reduces at temperatures above 1000 K. The TPR
profiles of catalysts A–C reveal an intense peak at 870 K, 885 K,
and 880 K respectively. The sharpness indicates a uniform dis-
tribution of the surface vanadia species. Table 2 lists the
formal average oxidation states (AOS).
Table 2 Total hydrogen consumption, H2/V ratios and Tmax values for catalysts
A–C
Total H2 consumption H2/V
Tmax
AOS of Vb (K)
Catalysta (μmol gcat
)
(mol mol−1
)
−1
A
B
C
576
1263
1801
1.04
1.14
1.09
2.9
2.7
2.8
870
885
880
The formal average oxidation state of vanadium upon reduction was
estimated assuming that the reduction of V5+ to V4+ corresponds to a
consumption of 0.5 H2/V. a In all cases, the support was 40 : 60 Al2O3–
MgO, as 5 mm extrudates. b Average oxidation state of vanadium.
Using EPR, we gained further information about the nature
of the reduced vanadium species. Catalysts A and B were
reduced in hydrogen using the same conditions employed for
TPR studies. The reduced A does not show EPR in ambient
conditions. Fig. 5 shows the EPR spectra of reduced A and B
recorded at 70 K and 298 K, respectively. These indicate the
presence of V4+ ions. In both cases, the unpaired electron
associated with V4+ (d1) interacts with the nuclear magnetic
moment of 51V (I = 7/2) to give a complicated hyperfine struc-
ture. For A, the absence of the EPR spectrum at 298 K indicates
the presence of V4+ in an axial ligand field. This may arise
from a distorted octahedron or tetrahedron of oxygen ions sur-
rounding a V4+ ion. In both octahedral and tetrahedral ligand
fields, V4+(d1) has excited states close to the ground state,
giving short spin–lattice relaxation times. Therefore, the EPR
spectra are not detectable at room temperature. A tetragonal
distortion of V4+ in B may be responsible for the EPR activity at
298 K. The perpendicular components of the EPR spectrum
indicate the presence of two chemically distinct V4+ species.
This may arise from a different interaction of the V4+ with the
surface oxygen atoms of Al2O3 support. We suggest that the V4+
is stabilized on alumina by removing oxygen from the V–O–V
linkage in a dimeric surface vanadia species. After exposure to
Fig. 5 EPR spectra of the reduced catalysts A at 70 K (grey line) and B at 298 K
(black line).
superposition of at least two signals. Both EPR and TPR data
strongly indicate the coexistence of different surface vanadium
species.
3.4 Catalytic dehydrogenation of n-butane
air, reduced catalyst A is EPR active at 298 K (see Fig. S5 in the Following the characterization studies, we tested catalysts A–C
ESI†) while the spectrum of reduced B remains unchanged. in the oxidative dehydrogenation of n-butane (see the results
All these spectra are complex and can be interpreted as a in Fig. 6). The n-butane conversion for catalysts A, B and C are
Fig. 6 Product distribution (columns) and TOF (dots) using different catalysts in
Fig. 4 Temperature programmed reduction plots for catalysts A–C, using
the dehydrogenation of n-butane. Reactions were run in a flow reactor at
hydrogen as the reducing agent. For completeness, the TPR profile of pure V2O5
500 °C and 1 atm pressure.
is included in the ESI (Fig. S6†).
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3.8, 7.9 and 4.7% respectively. There is no straight correlation
between the conversion values and the loadings. This is due to
the different types of vanadium species. To make this compari-
son loading independent, we represented in Fig. 6 the TOF for
all the catalysts. Samples A and B perform similarly in terms
of TOF. However, catalyst C has a significant lower activity
than catalyst B. This concurs with our characterization studies.
The vanadium species are placed on top of the alumina sites
for catalysts A and B whilst they are located on the magnesia
site in catalyst C. The lower TOF value for catalyst C can be
explained taking into account two different factors: (a) for cata-
lyst C the metal loading is close to the theoretical limit to form
a monolayer. This suggests that not all the vanadium atoms
are available for reaction and hence the TOF is underestimated
and (b) V atoms which are in close proximity to MgO (or even
forming vanadate) have less intrinsic activity due to the weaker
adsorption of the hydrocarbon in this system.31,32 The highest
selectivity for ODH products was achieved with catalyst C,
which has the highest vanadium content. The difference in
butenes and butadienes selectivity is mainly related to CO2
formation. Similar results were reported previously.33,34 It is
well known that the incipient carbonaceous species formed in
ODH reactions are rapidly oxidized to CO and CO2 in the pres-
ence of vanadium-based catalysts.33,34 Accordingly, deactiva-
tion by coke formation does not occur in our conditions.
Generally, high selectivity is obtained for highly dispersed
isolated and polymerized species in close proximity to the
basic sites (magnesia).35 Note that coke formation was not
found, and the conversion and selectivities were stable for at
least 24 h on stream.
Table 3 Conversions and selectivity in the limonene epoxidation catalyzed by
B and C
Selectivitya (%)
1,2-
8,9-
Conversiona Limonene Limonene
Entry Catalyst
(%)
oxide 2
oxide 3
Others
1
2
3
Noneb
Nonec
Support
onlyd
B
1.7
4
8.5
43.9
51.3
55.5
45.8
37.9
36.8
10.3
10.8
7.8
4
5
13.7
18.3
69.3
74.4
26.4
20.1
4.3
5.5
C
Reaction conditions: 1.2 ml (6.2 mmol) limonene 1, 6.0 ml H2O2
(molar ratio 8 : 1 H2O2 : limonene), 1.3 ml (12.4 mmol) benzonitrile;
0.025 g catalyst; 40 ml acetone : 2-butanol (ratio 2 : 8), 65 °C, 6 h.
a Quantitative GC-analysis using an external standard (anisole)
calibration. b Blank experiment (no catalyst or benzonitrile). c Blank
experiment, no catalyst. d Al2O3–MgO (40%–60%).
small amounts of the epoxide hydrolysis product, (1S,2S,4R)-
limonene-1,2-diol, as well as traces of other diols, carvone, and
carveol.36–38 These minor by-products were quantified together
and denoted as “Others” in Table 3. To avoid any effect of
hydrogen peroxide concentration changes on the reaction rate,
an 8 : 1 H2O2–limonene molar excess was used.39
In agreement with the results of Aramendia et al.,40 we
observed that the presence of benzonitrile is a must for the
reaction to proceed. A possible pathway for this reaction is
described by eqn (6) and (7). In the first step, the catalytic reac-
tion of benzonitrile and hydrogen peroxide gives a peroxy-
carboximidic acid. Subsequently, one oxygen atom of the acid
is inserted in the olefin, giving the corresponding amide and
the epoxide. Indeed, we identified the amide formation.
A series of control experiments showed that benzonitrile is
essential. Our studies show that the selectivity towards the
epoxide 2 increases when V2O5 is added on the Al2O3–MgO
surface. This suggests that the limonene oxidation takes place
on both the support and on the vanadium site.
3.5 Catalytic epoxidation of limonene with hydrogen
peroxide
We also tested catalysts B and C in the epoxidation of (R)-
limonene using hydrogen peroxide as an oxidant (eqn (5)).
ð6Þ
ð5Þ
ð7Þ
These liquid-phase reactions were run in stainless steel
autoclaves, using methanol as the solvent at 65 °C. Product
yields were monitored by GC. The main product was the (R)-
1,2-epoxide 2, with some epoxidation of the exocyclic double
The main oxidation products are the epoxides 2 and 3. In
bond, giving the (R)-8,9-epoxide 3. Additionally, we observed the aqueous medium they can easily hydrolyse to the
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corresponding diols. However, only traces of limonene glycol
were observed. We believe that this is due to the basic charac-
Funding sources
ter of the support and the catalysts. Limonene glycol is likely This research has been performed within the framework of the
to form by acid catalysed hydration of limonene oxide. In fact, CatchBio program. The authors gratefully acknowledge the
limonene epoxidation catalysed by V2O5 on acidic supports support of the Smart Mix Program of the Netherlands Ministry
gives polymers as the main reaction products.41 For catalyst B, of Economic Affairs and the Netherlands Ministry of
vanadia is supported on the alumina sites and it has a high Education, Culture and Science.
dispersion. Alumina has surface Lewis acid sites with high
relative strength. A decrease of the Lewis acidic sites occurs
when vanadia is highly dispersed. This is because the former
aluminium uncoordinated cations will bind VOx units. There-
Acknowledgements
fore, the free basic sites of the magnesia prevent the formation We thank Prof. E. Bouwman (UL) for access to the UV-Vis, EPR
of limonene glycol in this case.
and XRD facilities and Dr M. C. Mittelmeijer-Hazeleger (UvA)
We also tested our reaction conditions for catalyst leaching. for technical support.
Leaching tests were performed in duplicate experiments using
catalyst B. First, we ran our reactions under standard con-
ditions (see the Experimental part) for 1 h with catalyst B.
Notes and references
Then, we stopped the reaction, filtered out the catalyst and re-
started the reaction without the catalyst. Three samples were
collected in total: the first sample after 1 h with the catalyst,
the second one after 3 h reaction without the catalyst and
the third sampling at the end of the 6 h reaction, always
without the catalyst. The first sampling, with the catalyst in
the reaction mixture, reached a 4.5% conversion. The second
sampling, after filtration of the catalyst, showed an increase of
conversion up to 7.3%. The same conversion was measured at
the end of the 6 h reaction (see Fig. S7 in the ESI†).
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