Materials Science in Semiconductor Processing 24 (2014) 68–73

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Materials Science in Semiconductor Processing

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

Synthesis, characterization and catalytic properties

of palladium–cupric oxide–aluminum oxide nanocomposites
Md Abdus Subhan a,b,n, Tanzir Ahmed b, M.R. Awal b, B.Moon Kim a
a
Department of Chemistry, Seoul National University, South Korea
b
Department of Chemistry, Shah Jalal University of Science and Technology, Sylhet, Bangladesh

a r t i c l e in f o abstract

Available online 25 March 2014 Cupric oxide–aluminum oxide (CuO–Al2O3) composites were prepared by co-precipitation of
Keywords: carbonates from aqueous solutions of metal nitrates followed by calcination. A novel palladium-
Metal oxide nanoparticle oxide (Pd
Cu1 þ xAl2 xO4) composite has been synthesized by heating Pd (acetylacetonate)3
Nanocomposite and CuO
Al2O3 in a mixture of oleic acid and oleyl amine. The sample was characterized by
Photoluminescence XRD, SEM, EDS, TEM and PL measurements. Both XRD and TEM indicate that the product is Pd
Catalysis dispersed in Cu1 þ xAl2 xO4 matrix. Emission spectra have been recorded at 220 to 470 nm
Semiconductor excitations. The sharp PL peak observed in each case in the UV region (360–371 nm) when
excited at 220, 250, 270 and 300 nm, respectively is due to the Near Band Edge Emission (NBE)
of Pd
Cu1 þ xAl2 xO4. It has been found that the PL behavior of Pd
Cu1 þ xAl2 xO4 depends on
the excitation wavelength. This kind of excitation wavelength dependent PL behavior is a
violation of Kasha's rule of excitation wavelength dependence of emission spectrum. The major
excitation peak was observed at 356 nm when monitored at 470 nm. Catalytic activity of
Pd
Cu1 þ xAl2 xO4 was tested for Suzuki-Coupling reactions.
& 2014 Elsevier Ltd. All rights reserved.

1. Introduction nanocrystals, exhibiting synergistic and enhanced properties

Oxide semiconductors contain metal atoms and have wide
band gap resulting in transmission of visible light [1]. Mixed
metal oxides comprise high carrier concentrations and high
mobilities, and various devices have been designed by using
these semiconductors [2,3]. There have been a number of
studies on multi-metal-oxide (MMO) nanoparticles to test
their suitability as luminescent [4], catalyst [5], adsorbent [6]
and wide-band-gap semiconducting oxide [7]. Recently,
various hybrid nanocrystals composed of two or more
different metals have been synthesized [8–12], for the pur-
pose of merging properties of the individual materials.
Scores of individual nanocrystals can be integrated in hybrid
n
Corresponding author at: Department of Chemistry, Shah Jalal
University of Science and Technology, Sylhet, Bangladesh.
E-mail addresses: subhan-che@sust.edu,
subhan_che@yahoo.com (M.A. Subhan).
[13–26]. Among them, heterometal nanocrystals composed of
metals and oxides have been synthesized and some of them
have been used for multifunctional biomedical applications
[26–28]. For example, Xu et al. synthesized Au–Fe3O4 hetero-
dimer nanocrystals and used them for dual imaging probes
for MRI and optical imaging [27]. In the present study we have
been interested in the excitation wavelength dependent
PL as well as catalytic properties of mixed metal oxide,
Pd
Cu1þ xAl2 xO4. The excitation wavelength dependent PL
behavior is a violation of Kasha's rule of excitation wavelength
dependence of emission spectrum. It has been reported that
the existence of a distribution of energetically different
molecules in the ground state coupled with a low rate of
the excited state relaxation processes is responsible for the
excitation wavelength dependent luminescence behavior of
the systems [29,30].
Catalyst used for each reaction has very specific char-
acteristics depending on the type of process involved.

http://dx.doi.org/10.1016/j.mssp.2014.02.053
1369-8001/& 2014 Elsevier Ltd. All rights reserved.
 M.A. Subhan et al. / Materials Science in Semiconductor Processing 24 (2014) 68–73
When products are to be obtained from catalytic reaction,
the suitable catalyst must be identified and compounds
that can poison the catalysts should be eliminated or
reduced significantly. The selection of catalysts that have
long life span will reduce the cost of buying fresh catalysts
and decrease the time for replacing the catalyst [31,32].
Catalyst that has high resistance toward poisoning sub-
stance indicates long life span and high activation energy.
The catalyst should be able to be regenerated with ease
without affecting its activity. Large scale production is
possible, as basically every industry requires catalyst
in huge amount [33]. Pd catalysis of C–C cross coupling
reactions continued to appear. The related coupling of aryl
halides and alkynes rather than alkenes was improved by
Sonogashira et al. using copper and Pd catalysts [34]. Pd(0)
catalyzed C–C, C–C, C–S, and C–N cross coupling reactions
are among the most powerful organometallic transforma-
tions employed in organic synthesis [35,36].
Most of the reported syntheses of heterometal nano-
crystals have involved several complex steps. We herein
reported on the simple synthesis of Pd
Cu1 þ xAl2  xO4
nanocomposites. These synthesized nanocrystals exhibit
excitation wavelength dependent PL properties as well as
catalytic activity for Suzuki coupling reactions.
2. Materials and methods
2.1. Synthesis of Pd
Cu1 þ xAl2  xO4
The composite CuO
Al2O3 metal oxide was prepared by
co-precipitation of carbonates from the aqueous solution of
metal nitrates. Solutions of 0.25 M Cu (NO3)3
6H2O, Al
(NO3)3
9H2O and a solution of 1 M Na2CO3 in distilled
water were prepared. First of all, Al(NO3)3
9H2O and Cu
(NO3)3
6H2O solutions were mixed together in a beaker in
the ratio 1:1 with stirring vigorously at room temperature for
5 min. Then the solution of Na2CO3 was added to the mixture
of metal solutions slowly with agitation, until precipitation
was completed. The resultant mixtures were stirred for
further 1 h at 45 1C with constant stirring to convert the
metal salts into metal carbonates. After terminating the
reaction, white metal carbonate precipitates were separated
from the solution by centrifugation, washed several times
with deionized water and finally dried at 120 1C in an oven.
The obtained white precipitate was crushed in a mortar to
make it amorphous. Then the amorphous powder sample was
calcined in a muffle furnace at 600 1C for 2 h. The calcination
converted carbonates of the sample into their oxides. For the
preparation of Pd
Cu1 þ xAl2 xO4, Pd(acac)3 (100 mg) and
CuO
Al2O3 (300 mg), samples were heated slowly in a
mixture of oleic acid and oleyl amine (4 ml and 6 ml) up to
200 1C and aged at this temperature for 30 min. The tem-
perature was raised to 300 1C and aged for another 30 min at
this temperature. Then the sample was precipitated by adding
ethanol. The black crystalline product was then dispersed in
hexane and dried in vacuum using a rotary evaporator.
2.2. Characterization
In order to obtain compositional and structural infor-
mation about multi metal oxide, XRD measurements were
69
performed by a Bruker-AXD advance laboratory diffract-
ometer, using Cu-Kα X-ray radiation. They were recorded
in the step scan mode at 0.05 steps and at a measurement
rate of 10 s/step. The diffraction patterns were registered
within the 2θ angle range from 31 to 951.
The morphology of the multi metal oxide particle was
investigated with a scanning electron microscope (SEM)
(Hitachi S-4800 Scanning Electron Microscope). Samples
for the SEM were prepared by dispersing the multi-metal
oxide on a carbon tape. SEM images of the sample with
different magnification were taken with 5 mm and
15.3 mm working distances by applying an accelerating
voltage of 20 kV and current of 20 mA. Thermo Electron
Corporation –NORAN System SIX microanalysis system
was used to perform the qualitative chemical analysis of
the sample. Point-and-shoot analyses were employed to
determine the presence and distribution of elements in
the sample.
The TEM micrographs were recorded on a JEOL JSM-
1200 II microscope at an operating voltage of 100 kV.
The particles were dispersed in ethanol by ultrasoni-
cation, loaded on a carbon-coated copper grid and then
allowed to dry at room temperature before recording the
micrographs.
The optical properties of particles were measured by a
spectroflurophotometer (Shimadzu Corp., model RF-5301)
in acetone.
Gas chromatographic mass spectroscopy (GCMS) data
were collected on a HP 6890 series GC system coupled
with a 5973 Mass Selective Detector. 1H NMR and 13C NMR
spectra were taken in OXFORD NMR AS 500.
3. Results and discussion
3.1. XRD of Pd
Cu1 þ xAl2  xO4
The XRD spectrum of Pd
Cu1 þ xAl2  xO4 is depicted in
Fig. 1. The diffraction peaks at 2θ of 38.49, 42.4, 64.8, 82,
and 85.9 are assigned to Pd diffractions. All peaks of the
X-ray diffraction (XRD) pattern (Fig. 1) of Pd can be
assigned to the (1 1 1), (2 0 0), (2 2 0), (3 1 1), and (2 2 2)
lattice planes (from left to right) of a face-centered cubic
(fcc) Pd crystal structure (JPCDS 46-1043) [35]. The dif-
fraction angles, 2θ of 33.781, 36.881, 58.961, 65.621 and
78.541 are due to the diffraction of crystalline CuAl2O4
(ICDD PDF-2 WIN 00-033-0448). The particle size was
calculated using Scherrer’s formula, d¼kλ/βcosθ, where d
Fig. 1. XRD spectrum of Pd
Cu1 þ xAl2  xO4 where Pd (ο) and CuAl2O4( ).
70 M.A. Subhan et al. / Materials Science in Semiconductor Processing 24 (2014) 68–73

is average particle size, β is full width at half maxima

(FWHM), θ is the Bragg angle, and λ is the wavelength of
Cu-Kα in radians. According to XRD results, the particle
size was calculated to be in the range of 6–90 nm.

3.2. SEM and EDS of Pd
Cu1 þ xAl2  xO4

The morphology of Pd
Cu1 þ xAl2  xO4 mixed oxide

nanoparticle was studied by SEM as shown in Fig. 2. SEM
images of prepared Pd
Cu1 þ xAl2  xO4 have revealed the
typical texture and morphology.
Energy dispersive X-ray spectroscopy (EDS) analysis
was approved for the qualitative analysis of the as synthe-
size sample. Point-and-shoot analyses were employed to
determine the presence and distribution of elements in
the sample. All four points gave the identical EDS spectra
which proved the homogeneity of the as-synthesized
mixed metal oxide (Fig. 3). The major component of the
different spots of the samples in the EDS spectra, shown in
Fig. 3, revealed the presence of palladium (Pd), copper
(Cu), aluminum (Al) and oxygen (O). The presence of
carbon in the spectrum comes from carbon tape which
was used as a support for the sample measurement.

3.3. TEM of Pd
Cu1 þ xAl2  xO4

TEM image of the sample was obtained to have further

morphological information. As shown in Fig. 4, TEM shows
spherical morphology of nanoparticles with particle size
approximately 2–10 nm. The TEM image also demon-
strates highly dispersed homogeneity of particles in
Pd
Cu1 þ xAl2  xO4

3.4. Photoluminescence (PL) spectra of the

Pd
Cu1 þ xAl2  xO4

PL spectra of Pd
Cu1 þ xAl2  xO4 were measured in

acetone at different excitation wavelengths at room tem-
Fig. 3. EDS of Pd
Cu1 þ xAl2  xO4 at four different shoot points of the
perature. Pd
Cu1 þ xAl2  xO4 shows characteristic PL spec-
sample.
tra as shown in Figs. 5 and 6 and Table 1. Emission spectra
have been recorded at 220, 250, 270, 300, 360, 380, 405,
411, 433, 450 and 470 nm excitations in acetone at room
temperature. Sharp peaks in the UV region (at 360–
371 nm) were observed when excited at 220, 250, 270
and 300 nm, respectively (Fig. 5). The sharp peak in each
case may be due to the Near Band Edge Emission (NBE) of

Fig. 4. TEM image of Pd
Cu1 þ xAl2  xO4.

Pd
Cu1 þ xAl2  xO4 [28]. The strongest and sharp emission

at 367 was observed when excited at 220 nm. Three
emission peaks for Pd
Cu1 þ xAl2  xO4 were observed at
380, 405 and 440 nm when excited at 360 nm. Three
Fig. 2. SEM image of Pd
Cu1 þ xAl2  xO4. emission peaks were also observed at 403, 428 and
 M.A. Subhan et al. / Materials Science in Semiconductor Processing 24 (2014) 68–73 71

Fig. 5. PL spectra of Pd
Cu1 þ xAl2  xO4 in acetone (blue ) at 220 nm, Fig. 7. Excitation spectra of Pd
Cu1 þ xAl2  xO4 in acetone monitored
(violet ) at 250 nm, (red ) at 270 nm and (green ) at 300 nm at 470 nm.
excitations. (For interpretation of the references to color in this figure
legend, the reader is referred to the web version of this article.)
can be observed because of their high transition energies.
They have zero-phonon emission line at shorter wavelength
and large phonon energy. As excitation wavelength
increases, large size or Cu rich particles are observed. They
emit zero-phonon line at longer wavelength and smaller
phonon energy. It has been observed that PL behavior of
Pd
Cu1 þ xAl2 xO4 depends on excitation wavelength (Fig. 6
and Table 1). This kind of excitation wavelength dependent
PL behavior is contrary to the well-known Kasha's rule of
excitation wavelength dependence of emission spectrum.
Kasha’s rule is true in molecules. The sample Pd
Cu1 þ x
Al2  xO4 is not molecule but nanoparticles of semiconduc-
tors. It is not surprising that Kasha’s rule is violated in our
present case. The excitation wavelength dependent PL
Fig. 6. PL spectra of Pd
Cu1 þ xAl2  xO4 in acetone (red ) at 360 nm, property of Pd
Cu1 þ xAl2 xO4 may be due to the existence
(green ) at 380 nm, (violet ) at 405 nm and (blue ) at 450 nm
of a distribution of energetically different molecules in the
excitations. (For interpretation of the references to color in this figure
legend, the reader is referred to the web version of this article.)
ground state coupled with a low rate of the excited state
relaxation processes. The solvation and energy transfer are
responsible for the excitation wavelength dependent PL
Table 1 behavior of the systems [29,30]. This observation may be a
Excitation wavelength dependent emissions of Pd
Cu1 þ xAl2  xO4. consequence of nano-dimension.
The sharp band-edge emission peak is found in violet
Excitation wavelength (nm) Emissions observed (nm)
region and broad emission peaks are observed in blue
220 367, 463 region. Excitations of Pd
Cu1 þ xAl2  xO4 in the shorter
250 371, 461 wavelength region provided UV and blue emissions. How-
270 363, 460
ever, excitations in the longer wavelength region (450 and
300 361, 410, 460
360 380, 405 and 440
470 nm) provided green emissions.
380 403, 428 and 452 Fig. 7 shows the excitation spectra of Pd
Cu1 þ xAl2 xO4 in
405 460 (with a shoulder at 434 nm) acetone at room temperature. Excitation peaks were observed
411 466 at 342, 358, 411 and 433 nm when monitored at 470 nm. The
433 463 and 495
excitation spectrum is different from that observed for CuO
450 501 and 541
470 503 and 543 nanoparticles [37]. This may be due to the mixing of dissimilar
oxides to form new stable compounds with different energy
levels [28]. The result may be fascinating in view of sensitiza-
452 nm when excited at 380 nm. Excitation at 405 nm tion of rare-earth elements (Eu, Tb, Nd, Er) in many com-
gave a sharp peak at 460 nm with a shoulder at 434 nm. pounds for their luminescence.
Two emissions peaking at 501 and 541 nm have been
observed corresponding to 450 nm excitation (Fig. 6). We 4. Catalytic properties of Pd . Cu1 þ xAl2  xO4
have also measured the PL spectra corresponding to 411,
433 and 470 nm excitations. Excitation at 411 nm gave a PL Preliminary test of catalytic activity of Pd
Cu1 þ xAl2 xO4
peak at 466 nm; excitation at 433 nm gave two PL peaks at was performed for Suzuki C–C coupling reactions as shown
463 and 495 nm and excitation at 470 nm provided emis- in Scheme 1. General procedure for catalytic test using
sions at 503 and 543 nm (Table 1 and Figs S1–S3). the nanocrystals is as follows [35]. Degassed solvent
As shown in Figs. 5 and 6, if sample, Pd
Cu1 þ xAl2  xO4 is (1, 2-dimethoxyethane (DME):5 ml), aryl halide (1.0 mmol),
excited by shorter wavelength, small size or Al rich particles aryl boronic acid (1.2 mmol), Na2CO3 (1.3 mmol), and
72 M.A. Subhan et al. / Materials Science in Semiconductor Processing 24 (2014) 68–73
B(OH) 2
X
+
Scheme 1.
nanocrystal catalyst (50 mg) were added to a round-bottom
flask, which was backfilled with nitrogen. The reaction
mixture was refluxed for 24 h with vigorous stirring. After-
wards, the reaction mixture was cooled to room temperature
and the catalyst was separated by centrifugation. The pro-
duct was precipitated by adding water from mixture and
centrifuged again. The separated white product was dis-
solved in methylene chloride and then purified by column
chromatography using hexane and ethyl acetate as eluents.
For iodobenzene and bromobenzene, yields obtained were
90% and 60%, respectively. Products were characterized by
GC–MS, 1H and 13C NMR. The separated nanocrystal catalyst
was washed several times with hexane, methylene chloride,
methanol and water and then dried for recycling experiment.
5. Conclusion
The CuO
Al2O3 metal oxide composite was prepared by
co-precipitation of carbonates from the aqueous solution
ofmetal nitrates followed by calcination. A novel com-
pound Pd
Cu1 þ xAl2  xO4 was synthesized from Pd (acac)3
and CuO
Al2O3 by heat-up process in a mixture of oleic
acid and oleyl amine. XRD showed characteristics Pd
diffractions as well as crystalline CuAl2O4 diffractions.
TEM demonstrates spherical morphology of the nano-
particles with particle size approximately 2–10 nm in
a uniformly and highly dispersed arrangement. XRD and
TEM indicate that the product is Pd dispersed on
Cu1 þ xAl2  xO4. Sharp peaks observed in the UV region (at
360–371 nm) when excited at 220, 250, 270 and 300 nm,
respectively may be due to the Near Band Edge Emission
(NBE) of Pd
Cu1 þ xAl2  xO4. Excitations in the shorter
wavelength region provided UV and blue emissions. How-
ever, excitations in the longer wavelength region (450,
470 nm) provided green emissions. The Pd
Cu1 þ xAl2  xO4
nanocomposite exhibited excitation wavelength depen-
dent PL properties in violation of well-known Kasha's rule
of excitation wavelength dependence of emission spec-
trum. The observed PL behavior indicates that the com-
pound may have important applications in electronic
devices. Major excitation peak was observed at 356 nm
when monitored at 470 nm. Primary test of catalysis of
Pd
Cu1 þ xAl2  xO4 confirmed that it is a beneficial catalyst
for Suzuki coupling reactions.
Acknowledgment
Md Abdus Subhan acknowledged BK 21, Division
of Chemistry, Seoul National University for postdoctoral
fellowship. Professor Tuula Pakkanen and Professor Mika
Suvanto of University of Eastern Finland are acknowledged
for XRD, SEM and EDS data.
Appendix A. Supporting information
Supplementary data associated with this article can be
found in the online version at http://dx.doi.org/10.1016/j.mssp.
2014.02.053.
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