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 Page 1 of 26 Catalysis Science & Technology
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Selective catalytic oxidation of olefins by novel oxovanadium(IV) complexes

having different donor ligands covalently anchored on SBA-15: a comparative
study

Catalysis Science & Technology Accepted Manuscript

Andrea Di Giuseppe,a Corrado Di Nicola,b Riccardo Pettinari,b Italo Ferino,c Daniela Meloni,c
Maurizio Passacantandod and Marcello Crucianelli*d
a
Instituto de Sntesis Qumica y Catlisis Homognea (ISQCH)-Departamento de Qumica Inrganica, CSIC-
Universidad de Zaragoza, Pl. S. Francisco S/N 50009 Zaragoza, Spain. bDipartimento di Scienze Chimiche, Universit
Published on 08 April 2013 on http://pubs.rsc.org | doi:10.1039/C3CY00126A

degli Studi di Camerino, Via S. Agostino 1, I-62032 Camerino (MC), Italy. cDipartimento di Scienze Chimiche e
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Geologiche, Universit di Cagliari, Complesso Universitario Monserrato, I- 09042 Monserrato (CA), Italy.
d
Dipartimento di Scienze Fisiche e Chimiche, Universit dellAquila, via Vetoio, I-67100 Coppito (AQ), Italy. E-mail:
[email protected]; Fax: +39 862 433033; Tel: +39 862 433308

Abstract:
Using a post-synthetic grafting method, mesoporous SBA-15 was functionalized firstly with
aminopropyl silane reagents such as (3-aminopropyl)trimethoxysilane (APTMS) or bis[3-
(trimethoxysilyl)propyl]amine (BTMSPA), and then with chlorinated ligands as 4-(2-chloroacetyl)-
3-methyl-1-phenyl-1H-pyrazol-5(4H)-one (H-AP) or 5-chloromethyl-8-quinolinol hydrochloride (H-
HQ). Vanadyl cations [(VO)2+] were then immobilized over functionalized silica samples in order
to prepare new oxovanadium(IV) based quasi-homogeneous catalysts, namely Ia (Ia'), Ib (Ib'),
and IIa. Alternatively, a preformed oxovanadium(IV) complex such as [VO(AP)2(H2O)] has been
immobilized over previously functionalized SBA-15-NH2 silica support, affording catalyst Ic.
Elemental analysis (C, H, N), N2 adsorption-desorption isotherms, FT-IR, 29Si and 13C CP-MAS
NMR, XPS, ICP-AES, SEM-EDX and TG-DTG techniques, have been used for the full
characterization of these materials. Their catalytic properties in the H2O2 promoted oxidation of
conjugated olefins like styrene, -methyl and -methylstyrene were investigated, in terms of
activity, selectivity and recyclability, and compared with that showed by more simple systems
prepared by the direct grafting of vanadyl cation onto SBA-15 (catalyst A) or SBA-15-NH2
(catalyst B). Generally, high activity, selectivity and recyclability (over the first three runs) were
showed by all anchored catalysts, with the only exception for A and B systems. A full account of
the obtained results, along with insights into the effects due to the different strategies employed for
the functionalization of SBA-15 on the properties of final anchored catalysts, are reported.

1 Introduction
Transition metal complexes showed to act as efficient homogeneous catalysts for a number of
liquid-phase reactions, but some drawbacks related to their use, such as low stability, high cost and
difficult recovery from the reaction medium, limited their use, especially from an industrial point of
view. Their immobilization onto solid supports has then become a potential strategy to overcome
these issues, giving rise to recyclable catalysts which received, recently, attention as green
catalysts.1 Different types of hybrid solid supports have been used, namely bulk supports such
as carbon materials, mesoporous silicas, clay based materials and metal-organic frameworks or
 Catalysis Science & Technology Page 2 of 26
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nanosupports such as carbon nanotubes, nanosilicas, magnetic iron oxide nanoparticles, etc.2
Ordered mesoporous silicas featuring high surface areas (> 600m2g1), narrow pore size distribution
and tuneable pores diameters (>2nm), have attracted a great deal of attention due to their promising
properties and applications in various areas including adsorption, separation, tailored delivery

Catalysis Science & Technology Accepted Manuscript

devices for bio-applications, chemical sensing and catalysis. Catalytic applications of such materials
have been extended to numerous processes and reactions, ranging from acid catalysis (alkylations,
acylations, esterifications, biodiesel production, etc.) to redox chemistries (oxidation of alcohols,
alkenes, sulfides and hydrogenations of acids, aldehydes and ketones and alkenes/alkynes),3 also
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including asymmetric applications.4 Two main strategies have been, so far, exploited for the
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preparation of mesoporous silica-based catalysts: i) introduction of organic groups during the

synthesis of the material, through the co-condensation of tetraethylorthosilicate (TEOS) and an
organotrialkoxysilane RSi(OR')3 in the presence of a structure-directing agent; ii) post-synthetic
grafting of an organotrialkoxysilane, RSi(OR')3, onto the pore surface of ordered previously
synthesized mesoporous silica. The latter way has allowed the anchoring of a large number of
functional groups5 and so, following this procedure, we focused our interest on the post-synthetic
functionalization of mesoporous SBA-15 supports. Introduced by Stucky and co-workers,6 SBA-15
exhibits a highly ordered 2D hexagonal structure, well-defined pore size and thicker walls (which
make it thermally and hydrothermally more stable) than other mesostructured silicas. Therefore, it
showed to be an ideal candidate for a strong confinement of different species of catalytically active
metals. In confirmation of this, even in the presence of a variety of possible alternatives,7 SBA-15
has been well explored for the heterogenization of oxovanadium based complexes, to be used as
efficient catalysts in the oxyfunctionalization of many different substrates.8 It has long since proven
that vanadium complexes are effective catalysts for the activation of peroxides in the selective
oxidation of organic and inorganic substrates such as bromides, sulfides, alcohols and alkenes, as
witnessed by several reviews on this topic.9 Besides their capability to form metalloperoxo species,
which effectively transfer oxygen atoms to the substrate, these systems are synthetically useful for
obtaining valuable oxidized molecules on a preparative scale, with a high degree of selectivity and
high turnover numbers (TONs). Furthermore, the use of environmentally friendly oxidants like O2
and H2O2 increases significantly their potential application at an industrial level. In fact, as known,
selective catalytic oxidation of alkenes into more valuable oxygen-containing compounds is one of
the most important synthetic reactions. We have recently described the preparation and
characterization of a series of new oxovanadium(IV) complexes containing 4-acyl-5-pyrazolone
donor ligands, aiming at studying their catalytic activity under mild conditions: we used these
catalysts in the oxidation of styrene derivatives, to produce versatile intermediates for perfumery,
 Page 3 of 26 Catalysis Science & Technology
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pharmaceutical, dyestuff and agrochemical industry.10 We also recently published a computational

study to provide further insights into the reaction mechanism operative during the catalytic
oxidation of simple and conjugated olefins in the presence of an oxovanadium(IV) model complex
like the [VO(acac)2]/H2O2 system.11 Following our ongoing interest in the selective oxidation

Catalysis Science & Technology Accepted Manuscript

processes catalyzed by oxovanadium complexes, also stimulated by the growing environmental
concerns which require the developing of more green and sustainable catalytic systems, in this
paper we report on the preparation of a series of novel quasi-homogeneous vanadium catalysts.
Our synthetic strategy was based either on the formation of anchored oxovanadium(IV) complexes
Published on 08 April 2013 on http://pubs.rsc.org | doi:10.1039/C3CY00126A

in the final synthetic step or, on the immobilization of a preformed oxovanadium(IV) complex like
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[VO(AP)2(H2O)] on SBA-15 supports, previously functionalized as will be described later on.

Despite the several cases reported in the literature for the immobilization of oxovanadium
complexes,8 the poor number of examples describing the use of acylpyrazolone derivatives as
proligands for the functionalization of SBA-1512a or alternative solid supports12b prompted us to
carry out this study. We used two different chlorinated compounds, namely 4-(2-chloroacetyl)-3-
methyl-1-phenyl-1H-pyrazol-5(4H)-one (H-AP) and 5-chloromethyl-8-quinolinol hydrochloride (H-
HQ), as potential ligands for the formation of anchored oxovanadium(IV) complexes. To this end,
SBA-15 support was firstly amino modified with 3-aminopropyl trimethoxysilane (APTMS) or
bis[3-(trimethoxysilyl)propyl]amine (BTMSPA), respectively, and then derivatized with one of the
above described H-AP or H-HQ chlorinated ligands, by exploiting the nucleophilic substitution of
amino moiety onto carbon atom of the chloromethylen group for the covalent C-N bond formation.
Furthermore, our goal was to evaluate the catalytic performance of such new supported complexes
in the H2O2 promoted oxidation of styrene and its derivatives and methyl styrene, under mild
conditions, and compare their behaviour with that of systems prepared by the direct grafting of the
vanadyl [(VO)2+] cation onto SBA-15 (catalyst A) or SBA-15-NH2 (catalyst B), in order to assess
which are the best catalytic systems in terms of activity, selectivity and recyclability.13 Additionally,
insights into the effects of the different strategies employed for the functionalization of SBA-15 on
the properties of final anchored catalysts, will be given.

2 Experimental
2.1 Materials
SBA-15 mesostructured silica was prepared according to a known procedure exploiting the
templating effect of a neutral triblock copolymer surfactant.6 Details can be found elsewhere.14 (3-
aminopropyl)trimethoxysilane (APTMS, 97%), bis[3-(trimethoxysilyl)propyl]amine (BTMSPA,
90%), vanadium(IV) oxide sulfate hydrate (97%), toluene (99.8%), diethyl ether (98%),
 Catalysis Science & Technology Page 4 of 26
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dichloromethane (99.5%) were purchased by Aldrich; vanadyl acetylacetonate (97%) and

absolute ethanol were purchased by Fluka. A 35% aqueous solution of hydrogen peroxide
was used as primary oxidant. The chlorinated ligands 4-(2-chloroacetyl)-3-methyl-1-phenyl-1H-
pyrazol-5(4H)-one (H-AP)15 and 5-chloromethyl-8-quinolinol hydrochloride (H-HQ)16 were

Catalysis Science & Technology Accepted Manuscript

synthesized in our laboratory, and their identity confirmed by NMR analyses. All the materials were
reagent grade. The samples for microanalyses were dried in vacuo to constant weight (20 C, ca. 0.1
Torr). Elemental analyses (EA) were performed with a Fisons Instruments 1108 CHNS-O
Elemental Analyzer. Gas chromatographymass spectrometry (GCMS) analyses of the catalytic
Published on 08 April 2013 on http://pubs.rsc.org | doi:10.1039/C3CY00126A

oxidation products were performed by means of a Varian 2000 GC-MAS instrument, using a
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30m0.32mm0.25m film thickness (crosslinked 5% phenylmethylsiloxane) column and

chromatography grade helium, as carrier gas. In GC calculations, all peaks amounting to at least
0.5% of the total products were taken into account. When necessary, 1H and 13C NMR analyses of
products were performed after flash chromatographic purification on columns packed with silica gel
(230400 mesh), and compared with authentic samples.

2.2 Catalysts preparation

2.2.1 Synthesis of hydrated oxovanadium(IV) complex [VO(AP)2(H2O)]:
a water solution (10 mL) of VOSO4 5H2O (0.253 g, 1.0 mmol) was added to a methanol solution
(20 mL) containing the chlorinated ligand H-AP (0.501 g, 2.0 mmol) and NaOCH3 (0.108 g, 2
mmol); the reaction mixture was then refluxed, under stirring, for 4 hours. A pale cerulean
precipitate slowly formed, which was then filtered off, washed with methanol (10 mL) and dried
under vacuum, affording the complex (82 % yield). It showed to be soluble in dimethylsulfoxide
(DMSO) and slightly soluble in MeOH. mp: 284287 C (dec.). Anal.Calc. for C24H22Cl2N4O6V: C
= 49.33%, H = 3.80%, N = 9.59%. Found: C = 49.55%, H = 3.75%, N = 9.51%. eff: 1.81 BM. IR
(cm1): 3293br (OH), 3105w, 3081w (CaromH), 1615sh (H2O), 1607s, 1591s, 1578s (CO),
1539m, 1494vs (CN + CC), 969s (V=O).

2.2.2 Functionalization of mesostructured silica SBA-15:

a) preparation of SBA-15-NH2 and (SBA-15)2-NH
0.500 g of activated SBA-15 (250 C, 12 hours) were added to a flask containing 20 mL of dry
toluene and the suspension allowed to stir, at r.t. and under nitrogen, for 15 minutes. After addition
of 1.0 mmol of the chosen silylating reagent (APTMS or BTMSPA, respectively), the mixture was
refluxed for 18 hours. The suspension was then centrifuged and the modified silica obtained was
sequentially washed with toluene (10 mL) and with diethyl ether (10 mL), then Soxhlet extracted
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with dichloromethane for 24 hours, and finally dried at 353 K, overnight. Found for SBA-15-NH2:
C = 6.42%, H = 1.67%, N = 1.80%. Found for (SBA-15)2-NH: C = 8.14%, H = 1.69, N = 1.00%.

b) preparation of SBA-15-NH-AP and (SBA-15)2N-AP

Catalysis Science & Technology Accepted Manuscript

0.500 g of activated (90 C, 5 hours) amino functionalized proper silica sample [SBA-15-NH2 or
(SBA-15)2-NH] were added to a flask containing 20 mL of dry toluene and the suspension allowed
to stir, at r.t. and under nitrogen, for 15 minutes. After one-pot addition of a slight excess (1.1
equiv. respect to the nitrogen molar content of silica) of the 4-(2-chloroacetyl)-3-methyl-1-phenyl-
Published on 08 April 2013 on http://pubs.rsc.org | doi:10.1039/C3CY00126A

1H-pyrazol-5(4H)-one (H-AP) ligand, the mixture was refluxed for 18 hours. The suspension was
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then centrifuged and the obtained modified silica washed with diethyl ether (10 mL), then Soxhlet
extracted with dry acetone for 24 hours, and finally dried overnight, at 303 K, affording a pale pink
powder. Found for SBA-15-NH-AP: C = 16.38%, H = 2.08%, N = 3.76%. Found for (SBA-15)2N-
AP: C = 12.06%, H = 1.91%, N = 1.99%.

c) preparation of SBA-15-NH-HQ
0.500 g of activated (90 C, 5 hours) silica SBA-15-NH2 were added to a flask containing 20 mL of
dry toluene and the suspension allowed to stir, at r.t. and under nitrogen, for 15 minutes. After
one-pot addition of a slight excess (1.1 equiv. respect to the nitrogen molar content of silica) of
the 5-chloromethyl-8-quinolinol (H-HQ) ligand (its hydrochloride precursor was formerly treated
with an equimolar amount of triethylamine, as scavenger of HCl), the mixture was refluxed for 18
hours. The suspension was then centrifuged and the obtained modified silica washed with diethyl
ether (10 mL), then Soxhlet extracted with dry acetone for 24 hours, and finally dried overnight, at
303 K, affording a light yellow powder. Found for SBA-15-NH-HQ: C = 14.01%, H = 2.61%, N =
2.66%.

2.2.3 Oxovanadium(IV) complex immobilization onto functionalized silica:

a) Preparation of catalysts Ia (Ia'), Ib (Ib') and IIa:
0.250 g of proper functionalized silica sample [SBA-15-NH-AP, or (SBA-15)2N-AP, or SBA-15-
NH-HQ, respectively] were added to a flask containing 12 mL of ethanol and the suspension
allowed to stir, at r.t. and under nitrogen, for 15 minutes. Then, a solution of 0.150 mmol of the
chosen vanadyl precursor [VOSO4 5H2O for Ia, IIa and Ib, or VO(acac)2 for Ia' and Ib',
respectively] in 8.0 mL of ethanol, was dropwise added to the suspension, and the mixture refluxed
for 3 hours, under nitrogen. The suspension was then centrifuged and the obtained catalyst Soxhlet
extracted with ethanol for 12 hours, and finally dried overnight, at 303 K, affording a brown
 Catalysis Science & Technology Page 6 of 26
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powder. Found for Ia: C = 15.56%, H = 2.27%, N = 3.74% (or Ia': C = 16.53%, H = 2.28%, N =
3.73%). Found for Ib: C = 13.93%, H = 2.28%, N = 2.65% (or Ib': C = 13.86%, H = 2.17%, N =
2.64%). Found for IIa: C = 10.11%, H = 1.91%, N = 1.98%.

Catalysis Science & Technology Accepted Manuscript

b) Preparation of catalyst Ic
0.250 g of activated (90 C, 5 hours) amino functionalized silica sample SBA-15-NH2 were added
to a flask containing 15 mL of dry toluene and the suspension allowed to stir, at r.t. and under
nitrogen, for 15 minutes. After one-pot addition of 0.135 mmol of oxovanadium(IV) complex
Published on 08 April 2013 on http://pubs.rsc.org | doi:10.1039/C3CY00126A

[VO(AP)2(H2O)] (0.5 equiv. respect to the nitrogen molar content of silica sample), the mixture was
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refluxed for 18 hours. The suspension was then centrifuged and the recovered solid catalyst
sequentially washed earlier with toluene (5 mL) and then with diethyl ether (5 mL), afterwards
Soxhlet extracted with acetone for 24 hours, and finally dried overnight, at 303 K, affording a
greenish yellow powder. Found for Ic: C = 18.58%, H = 2.36%, N = 3.41%.

2.2.4 Direct grafting of vanadyl [(VO)2+] cation onto SBA-15 (catalyst A) or SBA-15-NH2
(catalyst B):
a) Preparation of catalyst A (SBA-15/VO)
Catalytic system was obtained by direct loading of VOSO4 5H2O (0.03 mmol) onto 0.050 g of
previously activated SBA-15 (see above): both followed experimental and work-up procedures
were identical to those already described for the preparation of catalyst Ia.

b) Preparation of catalyst B (SBA-15-NH2/VO)

0. 072 g of activated (90 C, 5 hours) SBA-15-NH2 were added to a flask containing 6.0 mL of
ethanol and the suspension allowed to stir, at r.t. and under nitrogen, for 15 minutes. Then, a
solution of 0.039 mmol of VOSO4 5H2O in 4.0 mL of ethanol, was dropwise added to the
suspension, and the mixture refluxed for 3 hours, under nitrogen. The work-up procedure was
identical to that already described for catalyst Ia. Found for B: C = 9.92%, H = 2.64%, N = 1.77%.

2.3 Physicochemical characterization

Scanning Electron Microscopy (SEM) and Energy-Dispersive X-ray Spectroscopy (EDX) studies
were performed by using a SEM Philips XL30CP microscope, equipped with an OXFORD INCA
Energy 250-SDD x-act detector.
Inductively coupled plasma atomic emission spectrometry (ICP-AES) analyses were performed
with a Varian Liberty 200 spectrophotometer, to determine the vanadium content. Samples (50 mg)
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were treated with 12 mL of a nitric and hydrochloric acid mixture (molar ratio 1 : 3) for 3 hours at
353 K under stirring to extract the metal from the surface. After complete removal of the acid
solution by repeated washing and evaporating with doubly-distilled water, the samples were filtered
and the liquid was quantitatively recovered and diluted to 250 mL.

Catalysis Science & Technology Accepted Manuscript

Textural analyses were carried out on a Micromeritics ASAP 2020, by determining the nitrogen
adsorption/desorption isotherms at 77 K. Before analysis, the samples were pretreated overnight
under vacuum (103 Pa) at 298 K. The specific surface areas were determined by the BET method.
The total pore volume and the pore size distribution according to the BJH model were also assessed.
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Thermogravimetric analyses were performed on a Mettler Toledo TGA/SDTA 851 thermobalance,

under the following conditions: sample weight, 8 mg; heating rate (from 298 to 1073 K), 10 K/min;
O2 flow rate, 50 mL/min.
X-Ray Photoelectron Spectroscopy (XPS) measurements were performed with a ultra-high vacuum
(UHV) multipurpose surface analysis system (PHI 1257) operating at pressures <109 mbar using a
conventional X-ray source (Mg K, 1253.6 eV). Binding energies were referenced to the C 1s line
at 284.8 eV from adventitious carbon. The XPS data analysis was performed with the XPSPeak4.1
program17 and a Shirley function was used to subtract the background.
High resolution NMR spectra were collected using a Varian UNITY INOVA Spectrometer with a
9.39 T widebore Oxford magnet. Experiments were performed with a 4 mm probe and Si3N4 rotors
at a spinning rate of 7 kHz. 13C CP-MAS spectra were collected with a recycle time of 3 s and a
contact time of 4 ms. 29Si CP-MAS spectra were collected with a recycle time of 4 s and a contact
time of 4 ms. 29Si and 13C chemical shifts were referenced to that of tetramethylsilane.
FT-IR spectra were collected on a Bruker FTIR Equinox 55 instrument (resolution 2 cm1)
operating in transmission mode.

2.4 Catalytic studies

Catalytic experiments were carried out in a 5.0 mL two-necked glass flask, fitted with a water
condenser. In a typical experiment, 8.0 mg (0.167 mmol% of vanadium) of catalyst Ia were
suspended in 2.0 mL of acetonitrile. Then, 118 L (3.0 equiv.; 1.140 mmol) of an aqueous solution
of H2O2 (33% w/w) were added followed, after 2 min, by 0.380 mmol of selected olefin. The
mixture was allowed to stir at 50 C, for 6 hours. Then, after further addition of 79 L (2.0 equiv.;
0.760 mmol) of H2O2 the mixture was allowed to react for 4 extra hours. The reaction products
were monitored at periodic time intervals using GCMS analyses. At the end of reaction, after
centrifugation, the surnatant was quenched with 5.0 mg of MnO2 and, after 15 min, filtered and
evaporated under reduced pressure. The oxidation products were identified by comparison of their
 Catalysis Science & Technology Page 8 of 26
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GC retention times with those of authentic samples. The residual catalyst, recovered after the first
centrifugation, was carefully washed firstly with 1.0 mL of acetonitrile and then, for two times, with
1.0 mL of diethyl ether. The solid was then dried under argon and reused for successive catalytic
cycles.

Catalysis Science & Technology Accepted Manuscript

OMe O OH
O Si H
N
N
O
N
OH VOSO4
SBA-15-NH-AP
Published on 08 April 2013 on http://pubs.rsc.org | doi:10.1039/C3CY00126A

H-AP Ia [or Ia']

[or VO(acac)2]
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OMe
OH O Si NH2
APTMS H-HQ
OH O OH
Toluene OMe
OH OH O Si H
N
SBA-15-NH2 N
SBA-15 O

OH
[VO(AP)2(H2O)] SBA-15-NH-HQ
VOSO4

[or VO(acac)2]
OMe
O
Si
O NH O Ib [or Ib']
V O
OH O

N N
Ph
Ic
2

OMe
OMe O Si
O Si
O OH
OH O H-AP O
BTMSPA OH N
OH OH NH
OMe N
OMe
Toluene O Si
O Si
OH N
O
SBA-15 O
VOSO4
OH
OH
(SBA-15)2NH (SBA-15)2N-AP IIa

ClH2C
CH2Cl
O
N N O O N N
N OH O
N V
Type of ligands: N O O
OH HCl OH2
Cl Cl

H-AP H-HQ [VO(AP)2(H2O)]

Scheme 1. General procedure for the preparation of anchored catalysts Ia (Ia'), Ib (Ib'), Ic and IIa.

3 Results and Discussion

3.1 Structural characterization and chemical composition of catalytic systems
The N2 adsorption-desorption isotherms and the pore size distribution curves (inset) of SBA-15 and
of selected catalysts Ia, IIa, and Ic, are shown in Figure 1 (a-d). The pure siliceous support (Fig. 1a)
exhibits a type IV isotherm with an H1 hysteresis loop starting from P/P0 0.60, typical of the
 Page 9 of 26 Catalysis Science & Technology
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SBA-15 structure.14 A surface area (SBET) of 1152 m2g1 and a pore volume (Vp) of 1.67 cm3g1
were calculated from the BET equation. By applying the BJH method to the desorption branch of
the curve, a narrow pore size distribution, centred at 6.5 nm, was obtained. The steep N2 uptake
observed at low relative pressures indicates the presence of some microporosity in the SBA-15

Catalysis Science & Technology Accepted Manuscript

support. The corresponding volume (0.02 cm3g1, as assessed by Horvath-Kawazoe equation) stems
from the presence of intrawall micropores, resulting from the removal, during the calcination step,
of the templating molecules penetrated with their hydrophobic PEO tail in the silica walls.18 The
nitrogen adsorption-desorption isotherms for the selected grafted samples are shown in Fig. 1 (b-d).
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They are of type IV with a narrow H1-type hysteresis loop. This indicates that the mesoporous
structure with cylindrical mesopores of regular size and shape of SBA-15 is preserved after its
functionalization. The textural features of the functionalized samples are summarized in Table 1.
Compared to the SBA-15 support, the surface area, the pore volume, and the mean pore size are
lower. The observed large difference in surface area (as well as in, both, pore volume and mean
pore size) between the support SBA-15 and the functionalized catalysts (Ia, IIa and Ic) can be
ascribed to the anchoring of different ligand molecules on the internal surface of the SBA 15
mesopores.

Figure 1. Nitrogen adsorption (full symbols) and desorption (open symbols) isotherms at 77 K for
SBA-15 (a), Ia (b), IIa (c), and Ic (d).
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Catalysis Science & Technology Accepted Manuscript

Table 1. Textural features of SBA-15 and of selected
heterogeneous catalysts Ia, IIa and Ic
Sample SBET (m2/g) Vp (cm3/g) Mean pore
diameter (nm)
SBA-15 1152 1.67 6.5
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Ia 202 0.38 5.1

IIa 230 0.41 5.6
Ic 301 0.54 5.5

From a comparative analysis of SEM images of SBA-15 and of selected catalysts Ia and Ib' (Figure
2) it can be observed that, as expected, functionalization of silica and grafting of vanadyl
precursors, do not influence the original morphology of SBA-15, while preserving the surface
characteristics of the mesoporous siliceous support also in the final vanadium based catalysts Ia and
Ib'.

SBA-15 Ia Ib

Figure 2. SEM micrographs of as-synthesized SBA-15, Ia and Ib' at a magnification of 20000x.

The derivatization extent of the silica-based materials and the metal loading for the oxovanadium
complexes are listed in Table 2, where the abbreviations of each derivative refer to the hypothesized
structures depicted in Scheme 1. Selected chemical composition values of catalysts are reported in
Table 3. The initial amino functionalized SBA-15-NH2 and (SBA-15)2NH silica samples were
obtained by a post-synthetic modification of SBA-15. In order to evaluate the molar ratio between
the silylating reagent (APTMS or BTMSPA, respectively) and SBA-15, we assumed an average
concentration of silica surface hydroxyl groups of 4 OH unit/nm2 (being the silica phase previously
activated, see Experimental).19 Based on results obtained from CHN elemental analyses (EA), the
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nitrogen loading of SBA-15-NH2 was 1.29 mmol/g, corresponding to a derivatization efficiency of

76% (see Table 2, entry 1). It must be noticed that the presence of a little residual amount of
Pluronic surfactant, used in the preparation of the starting SBA-15, cannot be ruled out, as also
confirmed by the larger C amount obtained for SBA-15-NH2 by EA (C = 6.42 %) in comparison

Catalysis Science & Technology Accepted Manuscript

with the expected value (C = 6.14 %). The amount of amino groups grafted onto SBA-15 was also
confirmed by means of potentiometric titration,20 being the matching between the two techniques
within 1-4 % range. The SBA-15 functionalization by the bis[3-(trimethoxysilyl)propyl]amine
(BTMSPA) reagent showed to be less efficient, affording the (SBA-15)2NH derivative with the
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lowest derivatization extent amongst all (ca. 50%, Table 2, entry 9). Probably, in this case, the
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occurrence of a partial self-polymerization of the more reactive BTMSPA reagent may not be
disregarded. The successive grafting of chlorinated ligands 4-(2-chloroacetyl)-3-methyl-1-phenyl-
1H-pyrazol-5(4H)-one H-AP and 5-chloromethyl-8-quinolinol hydrochloride H-HQ (Scheme 1)
occurred in a satisfactory way on SBA-15-NH2, with a high grafting extent (95% and 96%,
respectively, Table 2, entries 2 and 5), the second derivatization step of (SBA-15)2NH, with ligand
H-AP, being less efficient (76%, Table 2, entry 10) probably because of steric hindrance during
nucleophilic substitution.
Based on ICP-AES data, the efficiency of vanadium loading seems quite satisfactory, with values
ranging from 35% to 60% (Table 2, entries 3-4, 6-7 and 11), with a peak of 70% in the case of
complex Ic, where the direct grafting of oxovanadium(IV) complex [VO(AP)2(H2O)] was
performed (Table 2, entry 8). In the last steps of the synthetic sequence relative to the formation of
vanadium complexes Ia or Ia' and Ib or Ib' (Scheme 1), we chose two different reagents as carriers
of the vanadyl [VO]2+ cation, namely vanadyl sulfate hydrate and vanadyl acetylacetonate, in order
to detect, if any, some remarkable differences in terms of either, metal coordinating or metal
loading ability. However, as can be seen from Tables 2 (compare entries 3 and 6 vs entries 4 and 7,
respectively) and Table 5 (see onward), no relevant effects nor significant differences were found
between the two different types of vanadyl cation delivering reagents employed, in terms of either,
effective vanadium loading or catalytic efficiency.
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Table 2. Quantitative characterization of the silica-based materials

Entry Material % Silica % V loadingd

{(wt% N)a or [wt% V]b} Functionalizationc
1 SBA-15-NH2 (1.8) 76 (I step) -

Catalysis Science & Technology Accepted Manuscript

2 SBA-15-NH-AP (3.76) 95 (II step) -
3 Ia [1.06] - 40
4 Ia [0.98] - 35
5 SBA-15-NH-HQ (2.66) 96 (II step) -
6 Ib [1.49] - 50
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7 Ib [1.80] - 60
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8 Ic (3.41) [1.48] 98d 70

9 (SBA-15)2NH (1.0) 50 (I step) -
10 (SBA-15)2N-AP (1.99) 76 (II step) -
11 IIa [1.28] - 47
a
Calculated from EA. bCalculated from ICP-AES. cBased on (wt% N). dBased on [wt% V].

Table 3. Selected chemical composition of silica based catalysts

Catalyst wt% Na wt% Vb Catalyst wt% Na wt% Vb
Ia 3.74 1.06 Ic 3.41 1.48
Ia' 3.73 0.98 IIa 1.98 1.28
Ib 2.65 1.49 A - 1.80
Ib' 2.64 1.80 B 1.77 1.33
a
From EA. bFrom ICP-AES

The XPS spectra of the C 1s, N 1s, V 2p3/2 and O1s are shown in Figure 3, for selected catalysts Ia,
Ib and Ic; the core level binding energies (BE) and the atomic concentrations are reported in Table
4. The obtained results confirm the successful functionalization of SBA-15, in agreement with the
synthetic strategy depicted in Scheme 1. The spectra of the C 1s show, in fact, the presence of four
peaks originating from the different nature of the carbon bonds with the different elements (i.e. N,
O, H or, C) present in the matrix of each sample, due to the grafting of the APTMS fragment and to
the different ligands used (H-AP, H-HQ or the oxovanadium(IV) complex [VO(AP)2(H2O)] for Ia,
Ib or Ic, respectively). In the spectra of the N 1s are highlighted the peaks due to the presence of
free amine groups (about 399.0 eV) and the presence of protonated amine species (about 400.3 eV),
which can be likely formed by the partial interaction of free amino groups with surface silanol
groups, affording species like [Si-O+H3N-C3H6-Si].21 The SiO2 material is mainly composed
of oxygen and silicon in the expected O/Si ratio. In the O 1s and Si 2p3/2 XPS spectra are detected
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bands with BEs of 532.5 and 103.1 eV, respectively (Table 4), which are characteristic of oxygen
and silicon in a silica framework. The O1s peak was first curve fitted, and then the related X-ray-
induced satellite peaks were subtracted, leaving the V 2p3/2 and V 2p1/2 envelope. On all samples,
the binding energy of the V 2p3/2 peak was found to be about 516.2 eV (main contribution), which
is ascribed to V4+ in agreement with literature (516.2 eV).22 From the Figure 3, we can observe that

Catalysis Science & Technology Accepted Manuscript

for sample Ib, the maximum of the V 2p3/2 peak shifts toward lower binding energy (515.6 eV), so
confirming the occurring of a hetero (O-V-N) coordination of vanadium with O- and N-donor atoms
of the H-HQ ligand, in comparison with the homo (O-V-O) coordination for Ia (Ia') and Ic systems
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due to the interaction with O-donor atoms of the H-AP ligand. Therefore, we can claim that the
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shift towards lower binding energies, is due to the lower electronegativity of nitrogen compared to
that of oxygen, which produces a variation in the chemical bond of vanadium.

Table 4. Core level binding energies (BE) and atomic concentration (%) for selected catalysts Ia,
Ib and Ic, obtained by curve fitting of their XPS spectra.
C 1s N 1s V 2p3/2 O 1s Si 2p
Atomic Atomic Atomic Atomic Atomic
Sample BE (eV) BE (eV) BE (eV) BE(eV) BE(eV)
Conc. (%) Conc. (%) Conc. (%) Conc. (%) Conc. (%)
Ia 284.8 12.8 399.0 1.8 516.2 1.1 530.3 2.0 103.1 23.8
285.5 2.4 400.3 2.3 532.5 47.6
286.4 5.0
288.2 1.2
Ib 284.8 12.6 399.1 2.9 515.6 1.0 530.4 1.7 103.0 24.0
285.5 2.9 400.4 1.0 532.4 49.0
286.4 3.9
288.2 1.0
Ic 284.8 12.7 398.8 2.2 516.0 1.1 530.5 2.1 103.1 21.7
285.5 3.8 400.3 2.9 532.5 47.4
286.4 5.1
288.2 1.0
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Figure 3. XPS spectra of selected Ia, Ib and Ic catalysts.

3.2 Spectroscopic (FT-IR, NMR) and thermogravimetric analyses

Catalysis Science & Technology Accepted Manuscript

All new silica anchored catalytic systems Ia (Ia'), Ib (Ib'), Ic and IIa were characterized by FT-IR
spectroscopy as can be seen in Figure 4 for the sample Ia and its precursors.

2.7
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Ia

1.8
Intensity, a.u.

SBA-15-NH-AP

SBA-15-NH2

0.9

SBA-15

0.0

4000 3500 3000 2500 2000 1500 1000 500

-1
Frequency, cm

Figure 4. FT-IR spectra of Ia and its precursors (see Scheme 1)

The spectrum of SBA-15 sample shows the characteristic bands of the silica framework, for
example, at 1082 cm1 (SiOSi asymmetric stretching, with a shoulder around 1213 cm1), 951
cm1 (SiO stretching of SiOH groups), 804 cm1 (SiOSi symmetric stretching) and 461 cm1
(SiOSi bending vibrations). Further bands, at 1634 and 3448 cm1 are associated with HOH
bending vibrations of water (physically adsorbed) and with OH stretching vibrations of both
hydrogen-bonded surface silanol groups and adsorbed water, respectively. The effective binding of
APTMS onto SiO2 seems confirmed by the appearance of new bands (from medium to low
intensity) in the regions 2980-2885 cm1 and 1485-1385 cm1 of the SBA-15-NH2 spectrum, due to
C-H stretching and bending vibrations, respectively, as well as by the presence of new bands in the
interval 1598-1537 cm1 and at 698 cm1, caused by N-H bending vibrations of introduced amino
group. A comparison between SBA-15 and SBA-15-NH2 spectra show a clear reduction of the
intensity of the OH stretching and bending vibrations bands (3350 and 1630 cm1, respectively)
and of the peak due to SiOH stretching (at 948 cm1), which confirms the occurrence of grafting
by the mechanism showed in Scheme 1. The moderate absorption bands observed in the region
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1600-1500 cm1 of the spectrum of SBA-15-NH-AP, typical for the stretching vibrations of C-C, C-
N and C-O bonds of pyrazolone ring, confirm the grafting of ligand H-AP on the amino
functionalized siliceous support SBA-15-NH2. The typical IR bands of the V=O and V-O stretching
modes (at about 980 cm1 and in the range 500-470 cm1, respectively) are very low in the spectrum

Catalysis Science & Technology Accepted Manuscript

of catalyst Ia, due to the very low vanadium amount proportionally to the support, and partially
overlapped by stronger broad signals of SBA-15 at 1082 cm1 (SiOSi asymmetric stretching) and
461 cm1 (SiOSi bending vibration), respectively (see Figure 4).
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Figure 5. 29Si (a) and 13C (b) CP-MAS NMR spectra of SBA-15-NH2 sample.

Further evidence for the occurrence of functionalization of the starting SBA-15 by the reagent
AMPTS was provided by solid state CP-MAS 29Si and 13C NMR analyses of the corresponding
derivative SBA-15-NH2 (Figure 5, a and b). The 29Si NMR spectrum of SBA-15-NH2 showed three
partially overlapping signals in the range from 80 to 120 ppm (Figure 5a). In agreement with
literature the high field peaks were assigned to Q2 [(Si(OH)2(OSi)2), 91.1 ppm], Q3
[(Si(OH)(OSi)3), 100.4 ppm] and Q4 [(Si(OSi)4), 109.5 ppm] groups.13b,23 Besides these high
field signals, the functionalized sample showed peaks at low field in the range from 50 to 75
ppm, which can be assigned to T2 [(Si(OH)R(OSi)2), 57.7 ppm] and T3 [(SiR(OSi)3), 66.1 ppm]
groups i.e. to the silane organic moieties incorporated as a part of the silica wall structure. The
presence of the latter signals demonstrates the successful incorporation of the functional groups into
the silica framework. The inclusion of amino-propyl groups into the silica network is also
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confirmed by the 13C NMR spectrum of SBA-15-NH2, which showed the presence of three main
peaks at 8.5, 21.5 and 42.1 ppm ascribed to carbon atoms C1, C2 and C3 (Figure 5b), respectively.

Catalysis Science & Technology Accepted Manuscript

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Figure 6. TG (dotted line) and DTG (solid line) curves for SBA-15-NH2 (a), SBA-15-NH-AP (b)
and Ia (c) samples.

In Figure 6, the TG and DTG curves obtained from the thermogravimetric analyses of catalyst Ia
and of its precursors are reported. The thermogram for SBA-15-NH2 (Figure 6a) shows two regions
of weight loss, with peaks centred at about 85 C (ca. 5% of weight loss) and 330 C (ca. 15% of
total weight loss). The first peak can be assigned to the release of water physically adsorbed on the
silica surface, and the second one to the combustion of the aminopropyl fragment, as also reported
in literature.8a As expected, the curves for the SBA-15-NH-AP sample (Figure 6b), shows a
pronounced peak, centred at about 530 C (ca. 28% of total weight loss), assigned to the complete
decomposition of the more complex organic ligand (that is, the aminopropyl tethered fragment and
the chlorinated H-AP ligand).12a By comparing the thermograms for Ia and SBA-15-NH-AP
(Figure 6c vs Figure 6b) in terms of total weight loss, a vanadium content of 1.50 wt % is estimated
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for Ia, which is in a reasonable agreement with the value of 1.06 wt % obtained from the ICP
analysis (see Table 3).

3.3 Catalytic olefin oxidation

Table 5 shows the results of the oxidation of styrene with H2O2, in acetonitrile, by the silica-

Catalysis Science & Technology Accepted Manuscript

anchored catalysts Ia or Ia', Ib or Ib', Ic, IIa and the directly grafted catalysts A (SBA-15/VO) and
B (SBA-15-NH2/VO), under mild optimized heterogeneous conditions (see experimental). Blank
reaction performed over the pure support SBA-15 showed only negligible conversion (not shown).
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The stability and recyclability of anchored catalysts, were evaluated for three successive runs,
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recovering the catalyst from the reaction mixture, washing it several times with acetonitrile and then
diethyl ether and reusing it for a new run by adding fresh reagents (see experimental). The amount
of H2O2 we have used, strictly comparable to similar reactions catalyzed by oxovanadium
complexes, under heterogeneous conditions, was added in two successive steps, in order to increase
the conversion of substrates, preventing the excessive decomposition of the oxidant, if present in
large excess.

Table 5. Oxidation of styrene catalyzed by new silica-anchored catalystsa

CO2H
H2O2
Entry Catalyst TONb O
+
O
+
50 C, CH3CN 1 2 3

1st Run 2nd Run 3rd Run

conv.(%) (yield % [prod.]) conv.(%) (yield % [prod.]) conv.(%) (yield % [prod].)
1 Ia 228 >98 95[1]; 3[2]; 2[3] 96 92[1]; 4[2]; 4[3] 95 90[1]; 4[2]; 6[3]
2 Ia' 234 95 95[1]; 4[2]; 1[3] 90 91[1]; 5[2]; 4[3] 88 88[1]; 4[2]; 8[3]
3 Ib 156 96 93[1]; 3[2]; 4[3] 96 94[1]; 3[2]; 3[3] 92 91[1]; 4[2]; 5[3]
4 Ib' 134 >98 92[1]; 3[2]; 5[3] >98 93[1]; 4[2]; 3[3] 96 90[1]; 4[2]; 6[3]
5 Ic 147 90 92[1]; 4[2]; 4[3] 88 90[1]; 4[2]; 6[3] 88 88[1]; 5[2]; 7[3]
c
6 IIa 163 86 75[1]; 6[2]; 9[3] 65 76[1]; 7[2]; 7[3] 48 74[1]; 4[2]; 4[3]
d
7 A 116 86 60[1]; 3[2]; 9[3] 74 51[1]; 2[2]; 6[3] 20 20[1]; tr.[2]; tr.[3]
8 B 49 27 97[1]; 3[3] 3 83[1]; 17[3] 0 -
a
Reactions were performed in CH3CN (2.0 mL), (3+2) equiv. of H2O2, (0.15-0.28) mmol% V, 0.38 mmol of styrene, (6 + 4)
hours, 50 C. bTON (turnover number): (mol s.m. converted/mol metal ion) are calculated on 1st run. cThe formation of
unidentified by-products was also observed. dA discrete amount (5-10%) of glycol derived by opening of corresponding
styrene oxide, was also observed

As can be seen from Table 5, all the new heterogeneous catalysts showed high activity in the
oxidation of styrene with high conversion values in the first run (from 86% to >98%), affording
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with high yields (ranging from 75% to 95%) and selectivities (up to 95%) benzaldehyde 1 as main
product, besides trace amounts of acetophenone 2 and acetic acid 3, the latter being derived from
the over-oxidation of benzaldehyde 1 (Table 5, entries 1-6).
In the first run, no significant differences in terms of activity were found among the catalytic

Catalysis Science & Technology Accepted Manuscript

systems, irrespective to either the type of ligand used for anchoring the metal (see Scheme 1 and
compare complexes Ia, Ib, Ic and IIa of Table 5, entries 1, 3, 5 and 6, respectively) or the different
vanadyl-delivering reagents employed (Table 5, entries 1 and 3, vs entries 2 and 4), the complex IIa
being the less efficient of the series (Table 5, entry 6). The observed TON values, ranging from 134
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to 234 (Table 5, entry 4 and entry 2, respectively), showed to be quite good and comparable with
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those previously observed on similar heterogeneous catalytic systems.8c,24 Such results confirm the
higher selectivity toward benzaldehyde 1, in comparison with analogous homogeneous systems,10
observed when H2O2 is used as primary oxidant, for styrene oxidation.8a,8c Indeed, as already seen,
under kinetic (irreversible) control the double bond oxidative cleavage, promoted by the in situ
formed oxovanadium(V)monoperoxo complex (not shown), is always the favoured path with
respect to the epoxidation of double bond, especially in the case of conjugated olefins like styrene
and its derivatives and methylstyrene.10,11
In order to evaluate changes in the products distribution of styrene oxidation, a kinetic study was
carried out over six hours, with the complex Ia (Figure 7). After a rapid and quantitative initial
formation of benzaldehyde 1, a little amount of epoxide formed within the first two hours, which
successively converted into benzaldehyde 1 and acetophenone 2 and benzoic acid 3, while the
conversion of starting material increased. While acetophenone 2 seems to reach a stationary
concentration, benzoic acid 3, as expected, increases its concentration for prolonged reaction times,
totally in agreement with results previously obtained in the oxidation of styrene, promoted by
oxovanadium complexes with H2O2.9c,10
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Catalysis Science & Technology Accepted Manuscript

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Figure 7. Kinetic data obtained during the styrene oxidation reaction, by catalyst Ia. Reaction
conditions: styrene (0.38 mmol), Ia (8.0 mg), H2O2 (3.0 equiv.), acetonitrile (2.0 mL), 50 C, 6
hours.

Concerning recyclability (Table 5, entries 1-6, 2nd and 3rd run), the high stability of all studied
heterogeneous catalysts is manifest, Ia and Ib' being the best ones, with a slightly better
performance of Ib' (Table 5, entry 1 vs entry 4). Further experiments (not shown) aiming at
evaluating the leaching of the metal during the reaction, were carried out on catalyst Ib'. After the
first run, the catalyst was recovered by filtration and the filtrate thus obtained was charged with
fresh reagents and the oxidative reaction was repeated, under similar experimental conditions. No
oxidation occurred even after reaction times as long as 5 hours, confirming the absence of metal
leaching during the reaction and the truly heterogeneous nature of the process. Noteworthy, the
stability of the same selected catalyst Ib', recovered after the first run, was checked by means of
elemental CHN and ICP-AES analyses: the obtained values (C = 13.83%, H = 2.14%, N = 2.63%
and 1.78 wt% V, respectively) confirmed the substantial integrity of this catalytic system (see also
Table 3). From data reported on Table 5, we can say that the catalysts Ib and Ib', based on
coordination of vanadyl cation with the ligand H-HQ, seem somewhat more stable when compared
with catalysts Ia and Ia' containing the H-AP ligand, even if the latters are more active, showing
higher TON values (compare, in Table 5, entries 3 and 4 vs entries 1 and 2). The catalyst Ic,
characterized by the anchoring of preformed oxovanadium(IV) complex [VO(AP)2(H2O)] onto
SBA-15-NH2, showed high stability and recyclability. The catalytic system IIa (Table 5, entry 6)
showed some decrease in s.m. conversion upon recycling, which is indicative of partial leaching of
the metal.
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Another goal of this work was to compare the catalytic activity of our anchored coordinated
systems (Ia-Ia', Ib-Ib', Ic and IIa) with that shown by systems where the vanadyl (VO2+) cation
was directly grafted onto either, the as-synthesized siliceous support (SBA-15, for catalyst A) or the
aminopropyl-functionalized material (SBA-15-NH2, for catalyst B). In principle, these systems

Catalysis Science & Technology Accepted Manuscript

should exhibit a reduced catalytic efficiency, especially in terms of recyclability, due to a lower
effectiveness on the coordination of vanadium by the siliceous support. Indeed, as known, many
factors like the pore geometry and textural features of the support surface, along with the presence
of ligands with proven coordinating ability toward the vanadyl cation, may exert considerable
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influence on the metal complexation processes which, in turn, influence the catalytic activity and
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stability of the final materials.13

As expected, the performance of catalyst A was good as to s.m. conversion for the first two runs,
though with reduced yield and selectivity toward benzaldehyde 1 (compare in Table 5, entry 7 vs
entries 1-5), but a rapid reduction of activity was observed in the 3rd run; the catalyst B was
significantly less active and not recyclable, under our experimental conditions (Table 5, entry 8).
The drastic reduction of activity for the catalysts A and B, confirms the occurrence of metal
leaching as confirmed by ICP-AES analyses on selected filtrate samples during the recycling
experiments (not shown).
Further investigation on the possible causes underlying the different behavior of the two catalytic
systems A and B, is beyond the scope of the present study. We simply cite here, among the many
factors that may play a role, the active metal site isolation, as well as spatial restrictions imparted
from the different supports. On the other hand, systems analogous to catalyst B, showed a certain
catalytic activity and stability in the course of catalytic oxidations of various substrates,13b which
reveals that the matter is rather complex.
Among the different catalysts, the best ones (namely Ia and Ib) were selected for investigating the
oxidation of methyl- and cis-methylstyrene, with the aim of comparing these results with those
previously showed by their homogeneous complex analogues.10 The outcome of this study is shown
in Table 6.

Table 6. Oxidation of -methylstyrene and cis--methylstyrene by selected catalysts Ia and Ib'

OH
OH
Entrya Catalyst H2O2 O
+
50 C, CH3CN 2 4
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1st Run 2nd Run 3rd Run

conv.(%) (yield % [prod.]) conv.(%) (yield % [prod.]) conv.(%) (yield % [prod].)
1 Ia >98 98[2]; 2[4] 95 >98[2]; tr.[4] 94 >98[2]; tr.[4]
2 Ib' >98 98[2]; 2[4] 97 98[2]; 2[4] 97 >98[2]; tr.[4]

O OH

Catalysis Science & Technology Accepted Manuscript

H2O2 CO2H OH
O O
50 C, CH3CN + + + +
1 3 5 6 7

90[1]; 1[5]; 3[3]; 92[1]; tr.[5]; 89[1]; tr.[5]; 5[3];

3 Ia >98 4[6]; 1[7] 95 3[3]; 2[6]; 2[7] 92 tr.[6]; 3[7]
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92[1]; 1[5]; 1[3]; 90[1]; tr.[5]; 89[1]; tr.[5]; 5[3];

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4 Ib' >98 4[6]; 1[7] 96 3[3]; 4[6]; 2[7] 96 tr.[6]; 5[7]

a
Reactions were performed in CH3CN (2.0 mL), (3+2) equiv. of H2O2, (0.15-0.28) mmol% V, 0.38 mmol of olefin, (6 + 4)
hours, 50 C.

It can be seen that also in the case of -methylstyrene and cis--methylstyrene oxidation, catalysts
Ia and Ib' showed high activity and high stability over three reaction runs, catalyst Ib' being again
the best system (Table 6, entries 2 and 4, vs. entries 1 and 3). The heterogeneous catalysts Ia and
Ib' showed an increase in selectivity towards the formation of acetophenone 2 or benzaldehyde 1,
starting from -methylstyrene or cis--methylstyrene, respectively, if compared with their
homogeneous analogues,10 thus confirming what observed in the oxidation of styrene (Table 5).
In conclusion, this study confirms that, as far as the catalytic oxidation of conjugated olefins
promoted by oxovanadium(IV) complexes with H2O2 as primary oxidant is concerned, a high
selectivity towards the formation of aldehyde (or ketone) derivatives, with respect to the
corresponding epoxide, is observed. Indeed, under kinetic control, the double bond oxidative
cleavage is always the favoured path.11 Anyway, it must be observed that, the results we have
obtained under milder conditions are characterized by a very high selectivity towards the formation
of the corresponding benzaldehyde (or acetophenone), even greater than that previously obtained on
similar substrates, under both homogeneous and heterogeneous conditions.10,8c

4 Conclusions
Aminopropyl functionalized SBA-15 was used as mesoporous support for the anchoring of two
different chlorinated compounds, namely 4-(2-chloroacetyl)-3-methyl-1-phenyl-1H-pyrazol-5(4H)-
one (H-AP) and 5-chloromethyl-8-quinolinol hydrochloride (H-HQ), to be used as potential
proligands for the preparation of new anchored oxovanadium(IV) complexes such as Ia (Ia'), Ib
(Ib') and IIa. Besides, aminopropyl functionalized SBA-15 was also used for the anchoring of a
 Catalysis Science & Technology Page 22 of 26
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preformed oxovanadium(IV) complex as [VO(AP)2(H2O)], affording the catalyst Ic. All complexes
thus obtained, have been fully characterized by means of N2 adsorption-desorption isotherms, FT-
IR, 29Si and 13C CP-MAS NMR, XPS, ICP-AES, SEM-EDX and TG-DTG analyses, besides to
elemental analysis. Physicochemical characterizations confirmed the incorporation of
oxovanadium(IV) complexes into modified SBA-15 supports, where the metal retains the V4+

Catalysis Science & Technology Accepted Manuscript

oxidation state, as confirmed by XPS spectra. Textural studies and SEM results indicated that
functionalization of silica and grafting of vanadyl precursors, do not influence the original
morphology of SBA-15, while preserving the surface characteristics of the mesoporous support also
Published on 08 April 2013 on http://pubs.rsc.org | doi:10.1039/C3CY00126A

in the final catalysts. All Ia (Ia'), Ib (Ib'), Ic and IIa catalytic systems were employed in the
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hydrogen peroxide promoted oxidation of styrene and of its derivatives and methyl styrene,
under mild conditions. In addition, the catalytic behaviour showed by them was compared with that
showed by different catalysts, prepared through the direct grafting of the vanadyl [(VO)2+] cation
onto SBA-15 (catalyst A) or SBA-15-NH2 (catalyst B), aiming to assess which are the best catalytic
systems in terms of activity, selectivity and recyclability. The results obtained showed a high
catalytic activity with high conversion values of substrates, and excellent selectivity towards the
formation of benzaldehyde 1 (starting from styrene and methyl styrene) or acetophenone 2
(starting from methyl styrene), even working under milder experimental conditions with respect
to similar reactions.8c Noteworthy, the selectivity here observed by heterogeneous catalysts, was
even higher than that showed by their homogeneous analogues, previously studied by us,10 thus
confirming that the mesostructured matrix exerts an active role in affecting the selectivity of the
oxidative reaction. In terms of recyclability, the high stability over three reaction runs of all studied
heterogeneous catalysts is evident, Ia and Ib' being the best ones, with a slightly better performance
of Ib'. No relevant effects nor significant differences in terms of either, effective vanadium loading
or catalytic efficiency, were found between the two different types of vanadyl cation delivering
reagents employed, namely vanadyl sulfate hydrate (for Ia, Ib and IIa) and vanadyl acetylacetonate
(for Ia' and Ib'). Anyway, the catalyst IIa prepared by means of a different synthetic route for
SBA-15 functionalization, even if giving more than satisfactory results, showed the less efficiency
among all the other catalysts, particularly in terms of recyclability. Finally, under our experimental
conditions, poor results in terms of both catalytic activity and recyclability were obtained from
catalysts A and B, being the latter significantly less active and not recyclable, due to the occurrence
of severe metal leaching processes.

Acknowledgements
 Page 23 of 26 Catalysis Science & Technology
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The authors are thankful to Prof. Mariano Casu (University of Cagliari) for 29Si and 13C CP-MAS
NMR analyses on SBA-15-NH2 sample. M.C. gratefully acknowledges all members of Prof. Italo
Ferinos Laboratory, University of Cagliari, for the provided support during his research internship.

Catalysis Science & Technology Accepted Manuscript

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Catalysis Science & Technology Accepted Manuscript

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 Catalysis Science & Technology Page 26 of 26
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Selective catalytic oxidation of olefins by

novel oxovanadium(IV) complexes having
different donor ligands covalently anchored
on SBA-15: a comparative study

Andrea Di Giuseppe, Corrado Di Nicola,

Catalysis Science & Technology Accepted Manuscript

Riccardo Pettinari, Italo Ferino, Daniela
Meloni, Maurizio Passacantando and Marcello
Crucianelli*

Aminopropyl functionalized SBA-15 was used as

mesoporous support for the anchoring of a series of
Published on 08 April 2013 on http://pubs.rsc.org | doi:10.1039/C3CY00126A

new oxovanadium(IV) complexes behaving as

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selective and stable catalysts for the oxidation of

olefins