Fine-tuning the local structure and catalytic activity of titanium-amine functionalized silica in oxidation of limonene by aqueous hydrogen peroxide

Article abstract of DOI:10.1016/j.catcom.2012.01.009

Titanium-amine functionalized silica was successfully prepared by a so-called one-pot approach by using 3-aminopropyltrimethoxysilane (APTMS), tetraethoxysilane (TEOS) and titanium(IV) sulfate as precursors. It is demonstrated that the TEOS/APTMS molar ratio in the synthesis of titanium-amine functionalized silica affected the local coordination of titanium and its corresponding positive impact on catalytic activity in oxidation of limonene by aqueous hydrogen peroxide.

Full text of DOI:10.1016/j.catcom.2012.01.009

Catalysis Communications 20 (2012) 85–88
Contents lists available at SciVerse ScienceDirect
Catalysis Communications
journal homepage: www.elsevier.com/locate/catcom
Short Communication
Fine-tuning the local structure and catalytic activity of titanium-amine functionalized
silica in oxidation of limonene by aqueous hydrogen peroxide
a
a,b
a
a,
Lai Sin Yuan , Jon Efendi , Nur Syafiqa Hazirah Razali , Hadi Nur ⁎
a
Ibnu Sina Institute for Fundamental Science Studies, Universiti Teknologi Malaysia, 81310 UTM Skudai, Johor, Malaysia
Department of Chemistry, Universitas Negeri Padang, Jl. Prof. Hamka, Air Tawar, Padang, West Sumatera, Indonesia
b
a r t i c l e i n f o
a b s t r a c t
Article history:
Titanium-amine functionalized silica was successfully prepared by a so-called one-pot approach by using
Received 15 November 2011
Received in revised form 8 January 2012
Accepted 12 January 2012
Available online 20 January 2012
3
-aminopropyltrimethoxysilane (APTMS), tetraethoxysilane (TEOS) and titanium(IV) sulfate as precursors.
It is demonstrated that the TEOS/APTMS molar ratio in the synthesis of titanium-amine functionalized silica
affected the local coordination of titanium and its corresponding positive impact on catalytic activity in
oxidation of limonene by aqueous hydrogen peroxide.
©
2012 Published by Elsevier B.V.
Keywords:
Local coordination of titanium
Titanium-amine functionalized silica
Limonene oxidation
1
. Introduction
our strategy is different from those previously reported because the
aim of this communication is to demonstrate fine-tuning of the local
structure of Ti in titanium-amine functionalized silica. To examine this
In nature, there are many minerals that contain titanium; unfortu-
nately not all structures of them are being known [1]. From local structure
point of view, titania has three types of structures: six-fold, five-fold and
four-fold coordinated titanium. Six-fold coordinated titanium(IV) is the
structure which is most likely to be found, as the oxygen octahedron
around the titanium. It is well known that rutile, anatase and brookite
phases of titanium dioxide contain six-fold coordinated structures. One
of the examples of minerals that contain five-fold coordinated titaniu-
m(IV) is fresnoite [2]. Four-fold coordinated titanium(IV) is present in
the framework position in TS-1 zeolite [3].
The coordination of titanium(IV) is intensively studied because
the tetrahedral (four-fold coordination) and octahedral (six-fold
coordination) titanium(IV) gives distinguishable effect to the reactivity
in heterogeneous catalysis. From the previous works, it showed that the
isolated tetrahedral Ti plays a significant role in the catalytic reactions
catalytic system, the oxidation of limonene by using aqueous H
was chosen as a model reaction.
2 2
O
2. Experiment
2.1. Synthesis of titanium-amine functionalized silica
Titanium-amine functionalized silica with the TEOS/APTMS molar
ratio of 1:1 was synthesized as follows. TEOS (5 mmol, 1.12 ml) was
added into the mixture containing HCl (0.01 M, 0.156 ml), H O
2
(0.75 ml), ethanol (4.98 ml) and hexane (30 ml). The mixture was
then stirred for 1 hour to produce silica sols. APTMS (5 mmol,
0.93 ml) in ethanol (25 ml) and hexane (25 ml) was reacted with
silica sols under reflux at 80 °C for 2 h and followed by stirring over-
night to produce amine functionalized silica particles. Titanium(IV)
sulfate (2.5 mmol, 0.54 ml) was added into the amine functionalized
silica particles, and the mixture was stirred overnight at room
temperature. Then the resulting powder was washed with water,
hexane and ethanol, respectively. The solid particles were dried at
100 °C overnight. A similar procedure was also carried out to prepare
titanium-amine functionalized silica with different composition of
TEOS/APTMS for the molar ratio 1:2, 1:3, and 1:4, respectively.
Hydrolyzed TEOS and APTMS were also prepared for comparison.
TEOS and APTMS were hydrolyzed under stirring with water. After
washing with ethanol, the solid particles were then dried at 100 °C
overnight.
[3–7]. In view that TS-1 zeolite is a very active catalyst in oxidation
reactions by using aqueous hydrogen peroxide, the synthesis of
materials with tetrahedral coordination of Ti has attracted a great deal
of attention. Several methods have been reported to prepare materials
containing Ti with tetrahedral coordination, such as incorporation of
titanium within zeolites cavity and framework [3], loading NaY zeolite
2 2 2
particles with TiO [6] and impregnation of TiO on ZrO [5]. However,
⁎
Corresponding author. Tel.: +60 7 5536162; fax: +60 7 5536080.
E-mail address: hadi@kimia.fs.utm.my (H. Nur).
URL: http://www.hadinur.com (H. Nur).
1566-7367/$ – see front matter © 2012 Published by Elsevier B.V.
doi:10.1016/j.catcom.2012.01.009

86
L.S. Yuan et al. / Catalysis Communications 20 (2012) 85–88
2
.2. Characterizations
(
(
a)
b)
The solid catalysts obtained were characterized by Fourier transform
infrared spectrometer (FTIR), diffuse reflectance ultraviolet–visible
29
spectrometer (DR UV–vis), and Si solid-state magic angle spinning
nuclear magnetic resonance (29Si MAS NMR) spectrometer.
Si-OH bending
The FTIR spectra of all samples were collected on a Perkin Elmer
Spectrum One spectrometer with 10 scans and resolution of
(695)
Ti-O
(
3445)
c)
Si-OH stretching
(
−
1
−1
4
cm , in the range of 4000–400 cm . By using these parameters,
3
a very clear spectrum and low noise absorption bands were obtained.
Potassium bromide (KBr) pellet technique was used to examine the
functional groups of titanium-amine functionalized silica particles,
where the samples were mixed with KBr in the weight ratio of
sp C-H
(
(
d)
e)
(
1644) (1599)
NH bending
stretch
1
:100. The samples were also recorded by Perkin Elmer Ultraviolet–
visible Spectrometer Lambda 900 and plotted using Kubelka–Munk
function, in the range of 200–800 nm. The 29Si MAS NMR experiments
were performed using Bruker Avance 400 MHz 9.4 T spectrometer.
The spectra were recorded at 79.44 MHz using 4 μs radio frequency
pulses, a recycle delay of 60 s and spinning rate of 7.0 kHz using a
(f)
(g)
4
mm zirconia sample rotor. 29Si MAS NMR chemical shifts were
referred to external TMS at 0 ppm.
(h)
2
.3. Catalytic activity of titanium-amine functionalized silica
All reactions were carried at 70 °C with limonene (0.83 ml), 30%
(
1624) (1508)
NH bending
H
(
2
O
2
(0.38 ml), and acetonitrile (2 ml) as solvent and catalyst
50 mg) with stirring for 22 h. The products of reaction were
(618)
Ti-N
(3435) (3105)
analyzed by Agilent Gas Chromatography model 68900N equipped
with Ultra-1 column and a Flame Ionization Detector (FID).
N-H stretching
Si-O-Si
1200
4
000 3600 3200 2800 2400 2000
1600
800
400
3
. Results and discussion
Wavenumber / cm-1
Fig. 1 shows the infrared spectra of silica, 3-aminopropyltri-
Fig. 1. The FTIR spectra of (a) titanium dioxide, (b) hydrolyzed TEOS, (c) hydrolyzed
APTMS, (d) amine functionalized silica, and titanium-amine functionalized silica with
the following molar ratios of TEOS/APTMS: (e) 1:1, (f) 1:2, (g) 1:3, and (h) 1:4.
methoxysilane (APTMS), amine functionalized silica, and titanium-
amine functionalized silica with various molar ratios of TEOS/
APTMS. From all of the spectra, it is clear that the vibration bands of
−
1
Si–O–Si appear at ca. 1030 cm
with the previous reports [4–8]. The broad feature at 3445 cm
hydrolyzed TEOS was undoubtedly due to the Si–OH, while the two
in all samples which is in agreement
which are centered at ca. 250 and 300 nm, respectively [11]. The
decrease in peak area of deconvoluted tetrahedral to octahedral
coordination of titanium with a decrease in the TEOS/APTMS molar
ratio is clearly observed in titanium-amine functionalized silica. This
suggests that the amount of tetrahedral titanium in titanium-amine
functionalized silica from the molar ratio of TEOS/APTMS 1:1 to 1:4
has decreased by an increase the amount of the amine groups.
We have applied 29Si MAS NMR to obtain independent information
about the local structure of silicon in titanium-amine functionalized
silica. As shown in Fig. 3, each of 29Si spectrum of titanium-amine
functionalized silica consists of four peaks, which are denoted as
−
1
of
−
1
bands at 3435 and 3105 cm
in titanium-amine functionalized silica
are assigned to primary N–H vibration stretch. It has been generally
accepted that the two bands represent asymmetrical and symmetrical
N–H stretching vibrations [9]. This evidence reinforces our argument
that the primary amines are present in titanium-amine functionalized
−
1
silica. There is a peak absorption appearing at 2873 cm in hydrolyzed
APTMS and titanium-amine functionalized silica samples which is the
3
assignment of sp C–H stretch.
−
1
2
3
As shown in Fig. 1, a new band at 618 cm
has appeared in all
T =RSi(OH)(OSi)
2
(−57 ppm),3 T =RSi(OSi)
3
(−66 ppm),
2
titanium-amine functionalized silica samples suggesting the formation
of Ti―N bonding [10]. Since the amount of Ti(IV) in the entire variation
in experiment is the same, the intensity of the Ti–N (bending mode)
should also be similar. It is worth noting that the N–H bending bands
of the primary amine of titanium-amine functionalized silica, which
Q =(HO)
2
Si(OSi)
2
(−90 ppm), Q =HOSi(OSi)
3
(−110 ppm), and
4
Q =Si(OSi)
4
(−110 ppm) silicon species [12]. There are no peaks of
2
3
T
and T ; the characteristic peaks of the silane coupling agent are
observed in the NMR spectrum of hydrolyzed TEOS (Fig. 3a), since
TEOS is completely hydrolyzed into silica. It is also clearly observed
−
1
3
4
3
are presented at absorption bands at 1624 and 1508 cm , are shifting
to lower frequencies compared to APTMS at absorption bands at 1644
that intensity of the Q and Q peaks decreased, while that of the T
and T2 peaks increased when the molar ratio of TEOS/APTMS in the
synthesis of titanium-amine functionalized silica is decreased
(Fig. 1b, c and d). Thus, it has proven that the numbers of Si–O–Si
linkages are reduced with the increasing amount of APTMS. It is
suggested that the amine group induced the changing of the titanium
chemical environment from tetrahedral to octahedral with the
increase in the amount of amine groups. Based on the above results,
one expects that the change of titanium coordination in titanium-
amine functionalized silica affects its catalytic activity in oxidation of
limonene by using aqueous hydrogen peroxide.
−
1
and 1599 cm . This shifting is due to the weakening of the N―H
bond by the formation of Ti―N bond. The comparison between the
2
FTIR spectra of pure TiO (Fig. 1a) and titanium-amine functionalized
silica (Fig. 1e, f, g and h) clearly demonstrated the absence of a peak
−
1
of Ti―O bond at 695 cm
in titanium-amine functionalized silica.
This evidence reinforced our argument that the Ti―N bond existed in
titanium-amine functionalized silica.
Fig. 2 showed DR UV–vis spectra of titanium-amine functionalized
silica in different molar ratio of TEOS/APTMS. Deconvolution of the
broad peak at around 260–330 nm of the spectra showed the
existence of titanium with tetrahedral and octahedral coordinations,
Fig. 4 showed the effect of coordination of titanium on the catalytic
activity in oxidation of limonene. Gas chromatography analyses indicated

L.S. Yuan et al. / Catalysis Communications 20 (2012) 85–88
87
3
Tetrahedral Ti
Q
4
Q
Octahedral Ti
2
Q
(
(
a)
b)
3
T
(
a)
2
T
(c)
(
b)
(
(
d)
e)
(
c)
-40
-60
-80
-100
-120
-140
-160
ppm
Fig. 3. The 29Si solid state MAS NMR spectra of (a) hydrolyzed TEOS, and titanium-amine
functionalized silica with various molar ratios of TEOS/APTMS (b) 1:1, (c) 1:2, (d) 1:3, and
(e) 1:4.
was functionalized by 3-aminopropyltriethoxy silane (APTMS). It is
expected that all the –OH groups reacted with APTMS. So, the addition
of Ti(SO ) in the next step makes Ti coordinate to amine and not to –
4 2
(
d)
OH group.
200
250
300
350
400
450
100
0
Wavelength / nm
TEOS:APTMS = 1:1
Fig. 2. The DR UV–vis spectra of titanium-amine functionalized silica with various
molar ratios of TEOS/APTMS: (a) 1:1, (b) 1:2, (c) 1:3, and (d) 1:4.
8
0
0
0
0
0
20
40
60
80
100
6
4
2
that 1,2-epoxylimonene, carveol and carvone were the products. It can be
observed that titanium-amine functionalized silica with the TEOS/APTMS
molar ratio of 1:1 has the highest turnover number (TON). TON is the
number of moles of a limonene substrate consumed to yield given
products and is normalized to the number of moles of titanium. It has
shown that the increasing the environment of octahedral titanium is
causing the ineffectiveness in the conversion of limonene. This argument
is also supported by the fact that the catalytic activity of TEOS/APTMS
complex, without the titanium addition, showed only 2% of limonene
conversion. This result confirmed the catalytic action of Ti active site in
of titanium-amine functionalized silica.
TEOS:APTMS = 1:2
TEOS:APTMS = 1:3
TEOS:APTMS = 1:4
0
10
20
30
40
50
60
TON for Ti
Fig. 4. The effect of tetrahedral and octahedral coordination of Ti on turnover number
TON) in oxidation of limonene by aqueous hydrogen peroxide by using titanium-amine
functionalized silica as a catalyst. TON is the number of moles of a limonene substrate
consumed to yield a given product and is normalized to the number of moles of titanium.
Based on the FTIR measurements, it is confirmed the formation of
Ti―N bonding in titanium-amine functionalized silica. The formation
of Ti―N bonding is possible since in the first step, the silica surface
(

88
L.S. Yuan et al. / Catalysis Communications 20 (2012) 85–88
4
+
2-
FTIR, and 29Si MAS NMR, and catalytic activity results indicated
strongly that Ti is in tetrahedral and octahedral environments of
nitrogen. The results of limonene oxidation by using aqueous hydrogen
peroxide showed that titanium-amine functionalized silica with the
highest amount of tetrahedral Ti has the highest TON in oxidation of
limonene by using aqueous hydrogen peroxide as an oxidant. Thus,
local structure of tetrahedral Ti as the nitrogen tetrahedron around
the titanium in titanium-amine functionalized silica is a potential active
site that can be further explored in the future.
(
-NH
2
)
n
+ Ti(SO
4
)
2
[Ti(-NH
2
n
) ]
+ 2SO
4
silica
NH
2
NH
2
NH
NH
NH
NH
2
2-
2
SO
4
2-
4+SO
4
NH
NH
2
4+
2
Ti
2-
Ti
SO
NH
4
2
2-
2
SO
4
Si
NH
2
NH
2
2
Acknowledgements
Low surface coverage of Ti-
amine functionalized silica
High surface coverage of Ti-
amine functionalized silica
The authors acknowledge the Ministry of Science, Technology and
Innovation, Malaysia for financial support through ScienceFund funding,
Ministry of Higher Education Malaysia through Fundamental Research
Grant Scheme and Universiti Teknologi Malaysia through Research
University Grant.
Fig. 5. The possible local structure of Ti in titanium-amine functionalized silica.
2 n
)
]4+ complex in
One suggests the formation of [Ti(−NH
titanium-amine functionalized silica. Because the amine group
NH ) has an electron pair, this group can act as a ligand, and Ti(IV)
can be coordinated to NH . As a result, a cation complex is formed
References
(
2
[
1] P.B. Moore, J. Louisnathan, Science 156 (1967) 1361.
[2] A.M. Valentine, Encyclopedia of Inorganic Chemistry, Wiley, New York, 2006.
3] B. Notari, Catalysis Today 18 (1993) 163.
[4] H. Nur, S. Ikeda, B. Ohtani, Journal of Catalysis 204 (2001) 402.
2
2−
and neutralized by SO
4
in order to maintain electrical neutrality.
[
This reaction is written as follows:
[
5] H. Nur, N.Y. Hau, I.I. Misnon, H. Hamdan, M.N.M. Muhid, Materials Letters 60
(2006) 2274.
Â
Ã
4þ
2−
ð−NH Þ þ TiðSO Þ → Tið−NH Þ
þ 2SO4
2
n
4
2
2
n
[
[
6] H. Nur, Materials Science and Engineering B 133 (2006) 49.
7] H. Nur, D. Prasetyoko, Z. Ramli, S. Endud, Catalysis Communications 5 (2004) 725.
On the basis of these results, a model of the possible local structure
of Ti in titanium-amine functionalized silica is proposed (see Fig. 5).
In summary, the Ti coordination could be fine-tuned by varying
the molar ratio of tetraethoxysilane (TEOS), 3-aminopropyltri-
methoxysilane (APTMS) and titanium(IV) sulfate as precursors in
the synthesis of titanium-amine functionalized silica by a so-called
one-pot approach. The spectroscopic analysis by using DR UV–vis,
[8] V.A. Zeitler, C.A. Brown, Journal of Physical Chemistry 61 (1957) 1174.
[
9] R.M. Silverstein, G.C. Bassler, T.C. Morrill, Spectrometric Identification of Organic
Compounds, 5th ed. Wiley, New York, 1991.
[
10] G.P. Pez, P. Apgar, R.K. Crissey, Journal of the American Chemical Society 104
(1982) 482.
[
[
11] E. Astorino, J.B. Peri, R.J. Willey, G. Busca, Journal of Catalysis 157 (1996) 482.
12] R.H. Glaser, G.L. Wilkes, C.E. Bronnimann, Journal of Non-Crystalline Solids 113
(1989) 73.