Microporous and Mesoporous Materials 253 (2017) 64e70

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Microporous and Mesoporous Materials

journal homepage: www.elsevier.com/locate/micromeso

Cytosine-functionalized SBA-15 mesoporous nanomaterials:

Synthesis, characterization and catalytic applications
Fatemeh Rajabi a, *, Fatemeh Fayyaz a, Rafael Luque b
a
Department of Science, Payame Noor University, P. O. Box 19395-4697, Tehran, Iran
b
Departamento de Química Orga
nica, Universidad de Co
rdoba, Campus de Rabanales, Edificio Marie Curie (C-3), Ctra Nnal IV-A, Km 396, Cordoba 14014,
Spain

a r t i c l e i n f o a b s t r a c t

Article history: Periodic mesoporous silica functionalized by cytosine (Cyt@SBA-15) was prepared from Cytosine-
Received 14 November 2016 chloropropyltriethoxysilane and tetraethoxysilane as precursors by a sol-gel method. The surface area
Received in revised form and pore volume of Cyt@SBA-15 were 490 m2/g and 0.77 cm3/g. Due to their porous structure and active
6 June 2017
functional groups of cytosine on the pore of the hybrid material (Cyt@SBA-15), its catalytic performance
Accepted 20 June 2017
Available online 21 June 2017
was studied in the Knoevenagel condensation of aldehydes and ketones with malononitrile to a, b-un-
saturated dicyanides in the presence of ethanol as solvent. The catalyst exhibited an excellent activity
and selectivity toward the final condensation product under mild reaction conditions. Furthermore, the
Keywords:
Functionalized nanomaterials
catalyst could be recovered and reused several times without any significant loss in either activity or
Cytosine product selectivity.
SBA-15 © 2017 Published by Elsevier Inc.
Knoevenagel condensation

1. Introduction homogeneity of texture and modifiable surface chemistry via

Nanostructure mesoporous materials possess inherent me-
chanically and thermally stable structures and unique properties
including open and tunable periodic scaffold, high surface area,
controlled large pores and narrow size distributions. Recently,
these materials have attracted much attention in their potential
applicability for adsorption [1e3], sensing [4e9], catalysis [10e12],
gas storage [13,14], drug delivery [15e17], and separation processes
[18,19]. During the past two decades, various mesoporous materials
have often been functionalized by adding novel ligands and active
molecules on the surface or within the pores of mesoporous com-
pounds to extend their physical and chemical properties. Among
various nanomaterials, mesoporous silicas are promising inorganic
supports featuring abundant SieOH bonds on the surface. A
considerable progress has been made in the field of ordered mes-
oporous silicas (OMSs) and these compounds were the first choice
for the preparation of functionalized nanosensors. Mesoporous
silicas not only possess all the properties of mesoporous com-
pounds but also high physico-chemical stability, long-range
* Corresponding author.
E-mail addresses: f_rajabi@pnu.ac.ir (F. Rajabi), q62alsor@uco.es (R. Luque).
functionalization [20e24]. The development of modified meso-
porous silicas based on Mobile Composition of Matter (MCM-41)
[25,26], Santa Barbara Amorphous (SBA-15) [27,28], and Meso-
structured Cellular Foams (MCF) [29] because of their great ad-
vantages for adsorption applications such as removal and deter-
mination of metal ions, radio nuclides, dyes, organics, and anionic
complexes, has generated considerable interest [30e36].
The Knoevenagel condensation is of great importance in syn-
thetic chemistry in the construction of new CeC bonds. This reac-
tion proceeded between a C]O group and an activated methylene
group homogenously in the presence of strong basic catalysts,
followed by dehydration to yield a, b-unsaturated compounds.
These products find a wide range of useful applications as medical
intermediates in the pharmaceutical industry (e.g. anti-
hypertensive drugs) as well as in cosmetics, polymers, herbicides,
insecticides flavors, perfumes, and agrochemical industries
[37e43]. The Knoevenagel condensation is rarely catalysed by
Lewis acids [44] and traditionally by organic bases mainly nitrogen-
containing molecules such as aliphatic amines [45], urea [46], and
piperidine [47] under homogeneous conditions. However, in spite
of the high catalytic activity of these homogeneous catalysts, major
drawbacks of their utilization include difficulties associated with
separating and recovery of catalysts from products. The

http://dx.doi.org/10.1016/j.micromeso.2017.06.043
1387-1811/© 2017 Published by Elsevier Inc.
 F. Rajabi et al. / Microporous and Mesoporous Materials 253 (2017) 64e70
heterogenization of homogeneous catalysts is a promising route to
circumvent these problems. Easier handing, simple workup and
recyclability of heterogeneous catalyst are other important ad-
vantages of these heterogenous systems.
In this regard, several alternative heterogeneous catalysts have
been successfully employed to promote the Knoevenagel conden-
sation including graphene oxide (GO) [48], metal oxides/GO [49],
ionic liquids [50], alkali modified metal oxides [51], zeolites [52],
nitrogen containing carbons [53], organically functionalized mes-
oporous silica [54e56], polymers [57], and metal organic frame-
work (MOF) [58]. However, despite considerable progress in this
area, some of them suffer from high catalyst loading, high reaction
temperature, the formation of undesired by-products, the use of
hazardous and toxic solvents and low yield of the desired products.
The development of new type of immobilized catalysts combining
both the advantages of homogeneous and heterogeneous catalysis
with high atom efficiency is still a challenge in immobilized catalyst
design.
SBA-15, one of the family members of periodic mesoporous
materials, has inspired dominant research interest to enhance the
potential applicability of silica materials. SBA-15 materials with
unique properties including large surface areas, tunable pore sizes,
controllable thick walls and high thermal and mechanical stability
have found perfect interest in science and technology, particularly
in catalysis. SBA-15 materials are promising candidates for the
immobilization of organocatalysts [59e61]. Organic functionaliza-
tion of mesoporous silicas is a route to introduce or modulate
important surface properties, such as hydrophilicity or hydropho-
bicity and reactivity. Organic-inorganic hybrid materials were
prepared by incorporating different functional groups onto SBA-15.
One of the general approaches to covalently attach organic groups
to mesoporous materials is the functionalization of mesoporous
silicas with amino-organosilanes. After the first reports on the
synthesis of amino-functional mesoporous silica [62e64], signifi-
cant progress has been made in view of their applications by
different research groups [65e68].
Because of the efficiency of amino-functionalized groups on
SBA-15, supported Fe/SBA-15 [69e71] and Co/SBA-15 [72e74] were
synthesized using amino-functional mesoporous silica and effi-
ciently utilised in a range of different organic reactions by our
research group. Along these lines, the present work was aimed to
synthesize and characterize immobilized cytosine SBA-15 materials
as base-functionalized catalysts.
2. Experimental
2.1. Materials and characterization
Unless otherwise stated, all reagents and chemicals in this study
were used as received and were not further purified (from Mreck).
Solid-state 13C CP-MAS NMR (5 ms contact time, 3 recycle delay,
1200 scans) and 29Si CP-MAS NMR (6 ms contact time, 4 recycle
delay, 8000 scans) spectra were recorded with Bruker Avance
300 MHz NMR Ultrashield spectrometer. Nitrogen adsorption
measurements were carried out at 77 K using an ASAP 2000
volumetric adsorption analyzer from Micromeritics (Micromeritics,
Norcross, GA, USA). The samples were outgassed for 24 h at 100
C
under vacuum (102 Pa) and subsequently analyzed. Powder X-ray
diffraction patterns were recorded on a Bruker-AXS diffractometer
using a Cu Ka radiation (l ¼ 1.5409 Å). Thermogravimetric analysis
(TGA) was performed at a rate of 10
C min1 in a temperature
range of 25e800
C under N2 atmosphere using a Netzsch-
Gera€tebau GmbH - STA 409 PC Luxx Simultaneous thermal analyzer
65
instrument. FT-IR spectra were obtained using a Shimadzu 4300
FTIR spectrometer in the region 400e4000 cm1 using spectra
quality KBr powder. XPS measurements were performed in an ultra
high vacuum (UHV) multipurpose surface analysis system
(SpecsTM model, Germany) operating at pressures <1010 mbar
using a conventional X-Ray source (XR-50, Specs, Mg-Ka,
1253.6 eV) in a “stop-and-go” mode to reduce potential damage
due to sample irradiation. The survey and detailed metal high-
resolution spectra (pass energy 25 and 10 eV, step size 1 and
0.1 eV, respectively) were recorded at room temperature with a
Phoibos 150-MCD energy analyzer. Powdered samples were
deposited on a sample holder using double-sided adhesive tape
and subsequently evacuated under vacuum (<106 Torr) overnight.
Eventually, the sample holder containing the degassed sample was
transferred to the analysis chamber for XPS studies. Binding en-
ergies were referenced to the C1s line at 284.6 eV from adventitious
carbon.
2.2. Preparation of (Cyt-CPTES)
A mixture of cytosine (0.55 g, 5 mmol) and 3-chloropropyl-tri-
methoxysilane (1.01 g, 5.1 mmol) was stirred under nitrogen at-
mosphere at 110
C for 10 h. The volatiles were removed under
vacuum and the residue was thoroughly washed with anhydrous
pentane to afford 6-(3 (trimethoxysilyl) propylamino)-pyrimidin-
2(1H)-one as a solid.
2.3. Preparation of cytosine-functionalized SBA-15 mesoporous
materials (Cyt@SBA-15)
In a typical sol-gel synthesis procedure, co-condensed Cyt@SBA-
15 was synthesized according to a one-pot synthetic methodology
following a similar approach to previous work [27]. Pluronic 123
(4 g) (P123, Mn ¼ 5800, EO20PO70EO20), was dissolved in 125 g of
2.0 M HCl solution at room temperature. After TEOS was added, the
resultant solution was equilibrated at 40
C for prehydrolysis, and
then Cyt-CPTES was slowly added into the solution. The molar
composition of the mixture was 0.9 TEOS: 0.1 Cyt-CPTES: 6.1 HCl:
0.017 P123:165 H2O. The resulting mixture was stirred at 40
C for
20 h and then reacted at 90
C under static condition for 24 h. The
solid product was recovered by filtration and dried at room-
temperature overnight. The template was removed from the ma-
terial removed through solvent extraction: 1.0 g of the as-
synthesized sample was stirred in a solution of 1.0 mL 37% HCl
and 100 mL ethanol at reflux temperature for 12 h and then by
refluxing in excess ethanol for 24 h. Finally, the material was
filtered, washed several times with water and ethanol, and dried at
50
C for 20 h.
2.4. General procedure for knoevenagel reaction
A 50 mL round-bottomed flask equipped with a magnetic stir-
ring bar was charged with 1 mmol aldehyde and 1 mmol malo-
nonitrile in 5 mL ethanol. Then, 10 mg (Cyt@SBA-15) catalyst was
added in it and the reaction mixture was stirred at room temper-
ature for 2 h. Then, reaction mixture was filtered and the solid was
washed with the ethanol and dried. The solvent was removed by a
rotary evaporator to obtain the solid product residue. Then it was
crystallized from absolute ethanol. Upon completion of the first
reaction, the catalyst was recovered by filtration, washed with
ethanol and finally dried at 70
C. A new reaction was then per-
formed with fresh solvent and reactants under identical conditions.
66 F. Rajabi et al. / Microporous and Mesoporous Materials 253 (2017) 64e70
Fig. 1. Low angle XRD pattern of (Cyt@SBA-15).
3. Results and discussion
3.1. Morphology and characterization of immobilized cytosine on
SBA-15 materials
Following recent efforts from our group in the immobilization of
homogeneous catalysts and their application in various organic
Fig. 2. N2 adsorption-desorption isotherm of (Cyt@SBA-15). Inset corresponds to BJH average pore diameter diagram of Cyt@SBA-15.
reactions (i.e. oxidation reactions, protection and deprotection of
organic functional groups, CeC bond formation, etc.), an efficient
immobilized catalyst (Cyt@SBA-15) was designed for the first time
based on a one pot sol-gel method. The resulting hybrid material
was characterized by a series of techniques including XRD, nitrogen
adsorption/desorption, FT-IR, 29Si CP-MAS NMR, 13C CP-MAS NMR,
and TGA/DTGA. After fully characterization of the material, it was
applied as a catalyst for the synthesis of a, b-unsaturated com-
pounds from aldehydes and ketones and malononitrile by Knoe-
venagel condensation reaction (see Scheme 1).
Low-angle XRD pattern of (Cyt@SBA-15) in (Fig. 1) revealed a
single strong peak (100) followed by two additional peaks (110,
200) which can be indexed to a hexagonal lattice, characteristic of
the SBA-15 structure. This evidently indicates that the mesoporous
compound possess a 2D-hexagonal ordered structure and thus
retains their P6mm space group ordering in the final functionalized
material.
The surface properties of the material were investigated by N2
physisorption and the isotherm is shown in (Fig. 2). A hysteresis
loop between (0.6e0.7) P/P0 indicated the characteristic meso-
porosity of the sample with the bottle neck geometry (Type IV
isotherm), featuring a type H1 hysteresis according to the IUPAC
classification27. The BET surface area and pore volume of Cyt@SBA-
15 are 490 m2/g and 0.77 cm3/g, with 3.55 nm mean pore diameter.
A typical surface area of a purely siliceous SBA-15 is in the
800e900 m2/g range, with pore volume of ca. 1.2e1.7 cm3/g and a
mean pore diameter of 6e8 nm. The obtained values for our
Cyt@SBA-15, particularly pore volume and diameter support a
partial pore blocking in the SBA-15 material (significant reduction
 F. Rajabi et al. / Microporous and Mesoporous Materials 253 (2017) 64e70 67

Fig. 3. FT-IR spectrum of Cyt@SBA-15. The inset corresponds to the spectrum of pure P-123.

from 6 to 8 to 3.55 nm), indicative of the presence of Cyt within the extracted from the thermogravimetric (TG-DTG) analysis data
pores of the final material. (Fig. 5). Analysis was conducted from room temperature to 800
C.
FTIR was used to identify the incorporation of cytosine group A relatively constant weight decrease (2.5%, up to 180
C) relates to
within the silicate framework (Fig. 3). The FTIR spectrum of the loss of physisorbed water and organic solvent residues from the
Cyt@SBA-15 is shown in Fig. 4. SieOeSi bands approximately at pore channels. The weight loss (ca. 6.5%) between 300 and 400
C,
550, 750 and 1100 cm1 can be attributed to SBA-15. The particularly visible in the DTG curve, could be attributed to thermal
condensed silica network was reported to exhibit a wide absorption decomposition of the organic moieties. The total weight loss of
band at about 3433 cm1, attributed to the eOH stretching vibra- material amounts to 9.5%. This result indicates that Cyt@SBA-15 has
tions of silanol groups. The carbonyl group band in the cytosine a thermal stability up to 380
C after which the loss of organic
structure was detected at 1690 cm1 and the sharp stretching moieties from cytosine may influence its catalytic activity. Ac-
bands at ~2870 cm1 and 1750 cm1 can be attributed to asym- cording to the TG-DTG analysis, cytosine loading on SBA-15 was
metric and symmetric CeH stretching in the propyl chain. The 0.43 mmol/g.
1540 cm1 vibration seems to be characteristic of cytosine and,
more precisely, NH groups in cytosine as clearly visualized in the
spectrum of Cyt@SBA-15 in comparison to that of pure P-123 (Fig. 3,
inset). These findings confirmed the successful functionalization of
SBA-15 with Cyt-CPTES.
The organic-inorganic moiety as the basic structural unit in the
mesoporous materials was further confirmed by magic angle
spinning nuclear magnetic resonance (MAS NMR) experiments. 29Si
CP-MAS NMR spectrum of Cyt@SBA-15 showed both Tn and Qn
signal series (Fig. 4a). The signals at 105, 98, and 89 ppm
corresponded to framework silica sites Si(OSi)4 (Q4), HOSi(OSi)3
(Q3), and (HO)2Si(OSi)2 (Q2). The signals that originate from silicon
atoms attached to the cytosine appeared at 44, 52,
and 61 ppm, which can be assigned to ReSi(R’O)2(OSi) (T1),
ReSi(R’O) (OSi)2 (T2), and ReSi(OSi)3 (T3) organosiloxane sites. 13C
CP-MAS NMR spectrum of the sample exhibited 7 various signals of
carbon (C]O and ¼ CeN at 172 and 152 ppm, CeH groups in
cytosine at 115 and 123 ppm, CH2 groups in the propyl chain at 18,
45 and 58 ppm respectively) (Fig. 4b), further confirming the
presence of cytosine within the silicate framework. Additionally,
XPS recorded on the sample (results not shown) did not show any
N1s bands (typically around 400 eV) from the presence of cytosine
on the surface, while showing in both survey and detailed spectra
the typical contributions of residual C1s (285 eV)-from traces of
structure directing agent unremoved upon template extraction-
and O1s (532 eV) from mesoporous silica materials [75]. More in-
formation about the thermal stability of the (Cyt@SBA-15) could be Fig. 4. a) 29Si CP-MAS NMR spectrum of the Cyt@SBA-15. b) 13C MAS NMR spectrum of
Cyt@SBA-15.
68 F. Rajabi et al. / Microporous and Mesoporous Materials 253 (2017) 64e70

Fig. 5. TG and DTG thermograms of Cyt@SBA-15.

Scheme 1. Synthesis of Cyt@SBA-15.

Scheme 3. Cyt@SBA-15 catalysed reaction of aromatic aldehydes and ketones with

Scheme 2. Knoevenagel condensation by Cyt@SBA-15. malonitrile.

Table 2
Table 1 Cyt@SBA-15 catalysed the Knoevenagel condensation of aldehydes and ketones with
Effect of catalyst loading and solvent on the Knoevenagel condensation of benzal- malononoitrile.
dehyde (1 mmol) and malononitrile (1 mmol) at room temperature.
Entry Aldehyde/Ketone Yield (%)a M.P. (
C)
Entry Catalyst (mol%) Solvent Yield (%)a
1 PhCHO 99 82e83
1 e e N.R.b 2 4-Cl-PhCHO 97 160e162
2 0.1 e 15 3 4-Br-PhCHO 95 153e154
3 0.2 e 47 4 4-NO2-PhCHO 99 159e160
4 0.3 e 68 5 3-NO2-PhCHO 96 102e104
5 0.4 e 82 6 4-Me-PhCHO 90 131e133
6 0.4 H2O 88 7 4-MeO-PhCHO 90 113e115
7 0.4 EtOH 99 8 4-OH-PhCHO 90 186e188
8 0.4 MeOH 71 9 PheCOeMe 88 90e92
a 10 MeeCOeMe 92 169e171
Isolated yield.
b a
Time reaction was 2 h. Isolated yield.
 F. Rajabi et al. / Microporous and Mesoporous Materials 253 (2017) 64e70 69

Table 3
Comparison of catalytic activity of Cyt@SBA-15 in Knoevenagel condensation with other reported systems.

Reaction Catalyst Reaction conditions Run times Ref.

ZIF8@SiO2@Fe3O4 (1e15 wt%) catalyst, 25
C, 4 h, toluene 5th [43]

Graphene oxide (GO) 0.5 mL catalyst (1.5 mg/mL), 25
C, 8 h, solvent free 5th [48]
{[Lu(BTC) (H2O)]$DMF}n 100 mg catalyst, (100e130)
C, 8 h, p-xylene 3th [58]
þ Ethylenediamine/(GO) 100 mg catalyst, 40
C, 4 h, n-decane and CH3CN 6th [49]
KOH/SnO2/(GO) 50 mg catalyst, 25
C, 15 min, DMF 5th [51]
Fe3O4@Cu3 20 mg catalyst, 80
C, 2 h, various organic solvents 2e3rd [53]
(BTC)2-NH2
Cyt@SBA-15 (0.004 mmol) 10 mg catalyst, 25
C, 1 h, ethanol 8th This work

To evaluate the catalytic activity of the Cyt@SBA-15, the Knoe-
venagel reaction of benzaldehyde and malononitrile was examined
as a model reaction to form the corresponding a, b-unsaturated
compounds (Scheme 2). In order to optimise the reaction condi-
tions, the effect of solvent and catalyst loading was studied at room
temperature. As shown in Table 1, blank runs (in the absence of
catalyst) gave no product yields even after 2 h reaction times at
room temperature (Table 1, entry 1). The reaction was conducted
with different catalyst loadings at room temperature. Cyt@SBA-15
exhibited a good catalytic activity due to its high reactivity even
at room temperature. In comparison, an excellent yield was ob-
tained employing 0.4 mol% catalyst and ethanol as solvent (Table 1,
entry 7).
Under optimized reaction conditions, the scope and generality
of the process was further investigated using a variety of aromatic
aldehydes bearing electron donating and withdrawing groups with
malononitrile (Scheme 3, Table 2). Good to excellent yields were
obtained to target products in all reactions. Reactions with
electron-withdrawing substituents on aldehydes provided the
desired products in excellent yields due to the higher reactivity of
the carbonyl group (Table 2, entries 2e5). Furthermore, the catalyst
also exhibited an excellent performance for less reactive ketones-as
compared to aldehydes-to give the corresponding condensation
products in up to 92% yield (Table 2, entries 9e10). All isolated
compounds were characterized using spectroscopic and physical
methods and compared to those in literature.
Reusability is an important feature that determines the appli-
cability of heterogeneous catalysts. The recyclability of Cyt@ SBA-15
was examined after the first run of the Knoevenagel reaction by
separating it from the reaction mixture (filtration, washing with
ethanol and drying). Under optimized reaction conditions, the
immobilized catalyst not only showed excellent activity but also
reusability. Leaching tests were carried out to determine whether
the reaction was truly heterogeneous. No further reaction occurs
after the catalyst was filtrated which suggests that cytosine
immobilized on the support is providing the high activity in the
systems. Owing to the tight covalent anchoring and the spatial
separation of the organic functional groups, Cyt@SBA-15 showed
consistent catalytic activity and almost no loss in activity in eight
subsequent reactions for the condensation reaction between
benzaldehyde and malononitrile under optimized reaction condi-
tions. Table 3 provides a comparison of the results obtained for our
present catalytic system with those reported in the literature. Cyt@
SBA-15 exhibited higher run times, low catalyst loading and the
possibility to use green solvents with respect to other reported
systems.
4. Conclusions
A new highly-ordered mesoporous Cyt@SBA-15 was prepared as
an organic-inorganic hybrid material. The structure and
physicochemical properties of Cyt@SBA-15 were characterized by
various analytical techniques. This cytosine-functionalized SBA-15
exhibited an excelling catalytic performance in the Knoevenagel
reaction of various aldehydes and ketones with malononitrile to
form a,b-unsaturated compounds in ethanol. High efficiency and
low catalytic amount of Cyt@SBA-15 in this studied condensation
reaction, along with easily catalyst recoverability for eight run
times, the use of green solvents and the mild reaction conditions
are among most important advantages of this organic-inorganic
hybrid material. This approach may find potential applications in
other types of organocatalysed reaction. Further applications of this
catalytic system in other chemical processes are currently ongoing
in our laboratories and will be reported in due course.
Acknowledgements
The authors gratefully acknowledge the support from the
Research Council of the Payame Noor University and both re-
viewers of the manuscript for their useful and insightful sugges-
tions to improve the quality of this work during peer review.
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.micromeso.2017.06.043.
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