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School of Chemistry and Biochemistry, Thapar University, Patiala 147004, Punjab, India
Department of Chemistry, Maharishi Markandeshwar University, Mullana 133207, Haryana, India
g r a p h i c a l a b s t r a c t
This paper deals with the study of co-relation of surface structural and morphological properties of CuO anisotropic nanoparticles supported on
mesoporous SBA-15, as a function of increased Cu loading for selective hydrogenation of nitroaromatics.
a r t i c l e
i n f o
Article history:
Received 9 June 2015
Revised 30 August 2015
Accepted 1 September 2015
Available online 1 September 2015
Keywords:
Anisotropic CuO nanoparticles
CuO/SBA-15 nanocomposites
Hostguest systems
Selective nitroaromatic reduction
Zeolite analogues
Mesoporous SBA-15
Supported catalyst
CuO nanostructures
Heterogeneous catalysis
Post modification
Corresponding author.
E-mail address: bpal@thapar.edu (B. Pal).
http://dx.doi.org/10.1016/j.jcis.2015.09.002
0021-9797/ 2015 Elsevier Inc. All rights reserved.
a b s t r a c t
SBA-15 modified with APTMS (3-aminopropyl trimethoxysilane) having pore diameter (8 nm) has been
synthesized and impregnated with 110 wt.% Cu using Cu(NO3)2 as a metal source followed by calcination at 350 C. As-prepared CuO/ap-SBA-15 powder showed changes in the color from white for bare
SBA-15 to light green due to formation of anisotropic CuO nanoparticles that exhibited a characteristic
plasmon absorption band at 359 and 747 nm. TEM studies showed a change in the morphology of CuO
NPs as a function of increased Cu loading. Moreover, well dispersed CuO nanospheres (56 nm) and
nanorods (aspect ratio 1120 nm) having monoclinic crystal phase were observed within the mesoporous channels of SBA-15. Elemental mapping studies confirmed uniform distribution of CuO nanoparticles on the surface of SBA-15. An increase in surface area was also observed from 694 m2 g 1 for SBA-15
to 762 m2 g 1 for 10 wt.% Cu loading probably due to the deposition of excess of CuO nanoparticles on the
outer siliceous surface. The catalytic activity also increased with Cu loading and 10 wt.% CuO/ap-SBA-15
catalyst displayed the highest catalytic activity for the reduction of m-chloronitrobenzene and
m-nitrotoluene with 83% and 100% selectivity for m-chloroaniline and m-aminotoluene respectively.
2015 Elsevier Inc. All rights reserved.
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S. Sareen et al. / Journal of Colloid and Interface Science 461 (2016) 203210
1. Introduction
Synthesis of metal nanoparticles (NPs) of varying shapes and
sizes have received great attention in the last decade due to their
unique physico-chemical properties leading to vast applications
in the field of electronics [1], sensing [2] and catalysis [3,4] as compared to their bulk counterparts. Extensive work has been done in
the synthesis of noble metal NPs like Au [5], Ag and Pd [6] and Pt
[7]. Though these catalysts exhibit excellent catalytic activity, but
their high cost limits their applicability on a large scale, stimulating studies on non-precious metals. Compared with noble metals,
Cu and CuO being economically viable and easily available, offers
a promising material owing to its wide applications in the field
of optics, electronics and catalysis [8,9]. Cu and CuO NPs has been
used as a catalyst in many organic reactions like low temperature
CO oxidation [10], oxidation of alcohols [11], click synthesis [12]
and cross coupling reactions [13]. Most of the catalytic systems
being homogeneous suffer with the problem of separation of the
catalyst from the mixture. Moreover, the synthetic procedures rely
on elaborate processes utilizing hazardous chemicals, strong
reducing agents like NaBH4 [14] and capping agents like PVP [15]
with harsh experimental conditions. Though capping agents prevent aggregation, but also lead to inhibition of the molecular access
to the surface of the catalyst leading to decrease in the catalytic
efficiency. Hence, there is a need for the development of an ecofriendly, economical route for the synthesis of stabilized metallic
nanostructures. This can be achieved through heterogenisation of
homogeneous catalysts i.e., by immobilizing metal NPs on some
suitable support which is desirable for the stabilization and dispersion of metal NPs.
Mesoporous silica materials (MSM) such as SBA-15 are preferred to be an ideal host for the deposition of metal NPs as they
possess a high surface area and pore volume, greater hydrothermal
stability, hexagonal structure with tunable pore diameter (5
30 nm) with minimum hindrance, thus allowing easy diffusion
[1619] of the reactants. It is accepted that the unique architecture
of SBA-15 can contain NPs within mesopores with improved dispersal leading to the enhancement of their catalytic efficiency
[2022]. A great deal of research has been dedicated to the incorporation of various precious metals like Pt [23], Ag [24], Au and
Pd [25] on SBA-15 by different chemical approaches and their
use as catalyst for catalyzing various oxidationreduction reactions. In recent decades, Cu modified molecular sieves have shown
to be a good catalyst for different reactions. Ghosh et al. [26] synthesized Cu/SBA-15 nanocomposites by post modification in the
presence of NaBH4 as reducing agent for reduction of dyes. Zhang
et al. [27] prepared a series of Cu/SBA-15 nanocomposites by
evaporation induced self assembly route for hydroxylation of
phenol. Gu et al. [28] developed well dispersed Cu nanospecies
within SBA-15 channels by post modified method for cyclohexane
oxidation. However, there are a few reports on the synthesis of
supported CuO nanocomposites for catalyzing different oxidationreduction reactions. Zhong et al. [29] optimized the preparation of CuO/SBA-15 nanocomposites by varying the metal loading
and autoclaving temperature for catalyzing wet peroxide oxidation
of phenol and found that nanocomposite with lower metal loading
(4 wt.%) exhibited higher catalytic activity while higher loading
(10 wt.%) resulted in CuO aggregates within the mesopores of the
host. Chen et al. [30] compared the synthesis of CuO/SBA-15
nanocomposites by different post modified methods such as incipient wetness impregnation (IWI), deposition precipitation (DP),
grafting and homogeneous deposition precipitation (HDP), and
found that Cu/SBA-15 prepared by HDP method exhibited the
highest catalytic activity for the hydrogenolysis of dimethyl maleate to 1,4 butanediol. In contrast, the impregnation method
formed larger CuO NPs (size >90 nm) aggregated on the outer
2. Experimental section
2.1. Chemicals
Pluronic (M.W. 5800, EO20PO70EO20), tetraethoxysilane (TEOS),
copper nitrate Cu(NO3)23H2O, sodium borohydride (NaBH4) and
3-aminopropyltrimethoxysilane (APTMS) were obtained from
Sigma Aldrich. Aniline, m-chloronitrobenzene, m-chloronitroaniline, m-nitrotoluene, m-aminotoluene and other reagents were
obtained from Loba Chemie, India and were used as received without further purification. De-ionized water with ultra-pure filtration
system (Milli-Q, Millipore) was used throughout the experiments.
S. Sareen et al. / Journal of Colloid and Interface Science 461 (2016) 203210
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S. Sareen et al. / Journal of Colloid and Interface Science 461 (2016) 203210
(a)
(b) SiO2
10 wt. %
(110)
(111)
(200)
10 wt.%
5 wt. %
5 wt.%
(202)
Intensity (a.u.)
Intensity (a.u.)
4 wt. %
3 wt. %
2 wt. %
4 wt.%
(113)
3 wt.%
2 wt.%
1 wt. % CuO/ap-SBA-15
(100)
1.0
1 wt.% CuO/ap-SBA-15
2.0
2.5
2 (degree)
10
20
30
40
50
60
70
80
2 (degree)
Fig. 1. (a) Low angle and (b) wide angle XRD patterns of bare SBA-15 and various wt.% CuO/ap-SBA-15 catalysts.
Moreover, the effect of increase in calcination (S.I Fig. 1) temperature up to 550 C on the dispersion and size of 4 wt.% and 10 wt.%
CuO/ap-SBA-15 nanocomposites was also studied. It showed an
increase in the intensities and sharpness of all the peaks, indicating
the formation of large sized CuO NPs within the mesoporous
matrix.
TEM micrographs (Fig. 2a) displayed regular hexagonal
mesoporous SBA-15 structure with cylindrical channels exhibiting
narrow pore size distribution. Although, no disruption of mesoporous channels was observed yet large differences in morphology
of CuO NPs were observed as a function of increased Cu loading.
Fine CuO NPs (size 5 nm, S.I Fig. 2) were depicted as black dots
well dispersed within the light background of mesoporous support
for 1 wt.% Cu loading (Fig. 2b). With increased metal loading to
2 wt.% (Fig. 2c), uniformly distributed CuO NS (size 6 nm, S.I
Fig. 2) were noticed within mesochannels. These results are in
accordance with wide angle XRD studies. However, with increase
in Cu loading to 4 wt.%, instead of aggregation, anisotropic CuO
NPs (Fig. 2d) were observed as trapped within as well as on the
surface of siliceous host. Both spherical and rod like CuO NPs were
observed with diameter 8 nm (in consistency with a pore diameter of SBA-15) and length 80150 nm. Due to strong metalsupport interaction and restriction from channel walls, excessive
CuO NPs (with increased Cu loading) were forced to align one after
another resulting in change in morphology from spherical to rod
shape (marked in Fig. 2d). Similar changes in particle morphology
with increased metal loading have been reported elsewhere
[40,44]. Moreover, Chamber et al. [45] also reported that due to
strong metal-support interaction, Ni NPs supported on carbon
nanofibres adopt different morphologies. For 5 wt.% Cu loading,
small NR (aspect ratio 11 nm, S.I. Fig. 2) along with nanobundles (Fig. 2e) formed by the growth of some nanorods in adjacent
mesopores were also observed. However, larger CuO NR (aspect
ratio 20 nm, S.I. Fig. 2) were seen homogeneously dispersed
and extending throughout the entire mesochannels for 10 wt.%
Cu loading (Fig. 2f) due to the perfect alignment of CuO NPs forming rod like morphology. Furthermore, the lattice distance
(0.25 nm) measured from HR-TEM (S.I. Fig. 3a and b) was found
to be in agreement with (1 1 1) plane of crystalline CuO (JCPDS
card no. 48-1548). Moreover, the selective area electron diffraction
(SAED) pattern (S.I. Fig. 3c) confirmed (1 1 1), (1 1 1) and (2 0 2)
planes corresponding to the presence of CuO nanospecies. Its
corresponding EDX spectra (S.I. Fig. 3d) further established the
S. Sareen et al. / Journal of Colloid and Interface Science 461 (2016) 203210
207
Fig. 2. TEM images of (a) SBA-15, (b) 1 wt.% CuO/ap-SBA-15, (c) 2 wt.% CuO/ap-SBA-15, (d) 4 wt.% CuO/ap-SBA-15, (e) 5 wt.% CuO/ap-SBA-15 and (f) 10 wt.% CuO/ap-SBA-15
catalyst.
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S. Sareen et al. / Journal of Colloid and Interface Science 461 (2016) 203210
desorption branch at p/po 0.6 was noticed. This results from the
cavitation phenomenon [56] that occurs due to the partial blockage
of SBA-15 pore openings with the increased amount of Cu impregnation and has been further supported by the increase in the surface area (more than that of SBA-15) for both 4 and 10 wt.% Cu
loaded materials possibly due to the deposition of excess of CuO
NPs (as shown in TEM studies) to the outer silica surface due to
the partial blockage of SBA-15 mesopores. Patel et al. [57] also
found that at higher Cu loading (10 wt.%) deposition of excess of
CuO NPs on the external surface resulted in an increase in the surface area for CuO/SBA-15 nanocomposites.
2.5.5. Catalytic activity
The catalytic activity of prepared CuO/ap-SBA-15 nanocomposites was evaluated for the reduction of m-substituted nitroaromatics such as CNB (Scheme 1) and NT (Scheme 2) to their respective
amines. It was observed that in the absence of CuO/ap-SBA-15 catalysts, reduction of nitroaromatics with NaBH4 and with bare SBA15 did not took place, implying that metal oxide NPs were the real
active sites. Moreover, the reaction was initiated by the addition of
CuO/ap-SBA-15 catalyst suggesting adsorption of electron donor
Counts/s
934 eV
943.3 eV
930
935
940
945
950
Fig. 5. Solid state UVVisible absorption spectra of (a) bare SBA-15, (b) 1 wt.% CuO/
ap-SBA-15, (c) 4 wt.% CuO/ap-SBA-15 and (d) 10 wt.% CuO/ap-SBA-15 catalysts
[Inset shows the color change in SBA-15 with increase in metal loading].
S. Sareen et al. / Journal of Colloid and Interface Science 461 (2016) 203210
100
SBA-15
4 wt. % CuO/ap-SBA-15
10 wt. % CuO/ap-SBA-15
Zone 1
% Weight loss
209
90
80
Zone 2
Zone 3
70
60
100
Temperature (C)
Fig. 6. TGA of SBA-15 and various wt.% CuO/ap-SBA-15 catalysts.
(S.I. Fig. 11). Moreover, the recycled catalysts retained same color
(light green) as that of the fresh catalyst illustrating no change in
the chemical composition of the catalyst. These results suggests
the high stability and reusability of the catalyst.
3. Conclusion
In conclusion, it was demonstrated that metal loading had a significant effect upon the size, morphology, dispersion ability and
catalytic activity of the metal oxide NPs present within the mesoporous host. The high surface area of the 10 wt.% CuO/ap-SBA-15
also contributed to the efficient adsorption of nitro groups on the
active sites of the CuO/ap-SBA-15 resulting in enhanced catalytic
activity. The reaction rate showed dependence on the electron
withdrawing ability of the substituents present on nitrobenzene
and was found to be maximum for m-CNB. The easy preparation
method, use of economical catalyst, benign reaction conditions,
greater selectivity of products and high recyclability of the catalyst
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