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STM JOURNALS
1. A One-Step Selective Oxidation of Benzene to Phenol over CuCr O Spinel Nanoparticles Catalyst 2 4
with Air as Oxidant Shankha Shubhra Acharyya, Shilpi Ghosh, Rajaram Bal 1
2. In Situ Synthesized Cu(OH) -Al O : A Novel and Highly Efficient Nano-Catalyst System for One pot 2 2 3
Synthesis of N-Substituted Triazole at Room Temperature Ravi Kant Shukla, Yogesh Somasundar, Radha Sawana, Babita Baruwati 8
3. Alcohol Oxidation in Ionic Liquids Catalysed by Recyclable Platinum Nanoparticles: A Green ApproachDeb Kumar Mukherjee, Arijit Mondal, Amit Das 15
4. H Production by Methanol Steam Reforming over Copper Impregnated Anodized Aluminum 2
Oxide (AAO)M. Jhansi L. Kishore, Dong Hyun Kim 23
5. Ru(III)-Catalyzed Oxidative Cleavage of Ritodrine Hydrochloride: A Kinetic and Mechanistic StudyPuttaswamy, S. Dakshayani, A. S. Manjunatha 29
6. Synthesis of Zeolite Y-Encapsulated Copper(II) Complexes with Aminobenzonitriles and Carbonitriles by Flexible Ligand MethodPoonam Ghansiala 41
7. Synthesis, Structural Studies and Catalytic activity of Copper(II) Complex Supported by N, N′-bis (2-Hydroxy-3-Methoxybenzaldehyde) 4-Methylbenzene-1, 2-DiamineAlekha Kumar Sutar, Yasobanta Das, Sasmita Pattnaik, Anita Routaray, Nibedita Nath, Prasanta Rath, Tungabidya Maharana 53
ContentsJournal of Catalyst & Catalysis
JoCC (2014) 1-7 © STM Journals 2014. All Rights Reserved Page 1
Journal of Catalyst and Catalysis Volume 1, Issue 1
www.stmjournals.com
A One-Step Selective Oxidation of Benzene to Phenol
over CuCr2O4 Spinel Nanoparticles Catalyst
with Air as Oxidant
Shankha Shubhra Acharyya, Shilpi Ghosh, Rajaram Bal* Catalyst Conversion & Process Division, CSIR-Indian Institute of Petroleum, Dehradun, India
Abstract CuCr2O4 spinel nanoparticles catalyst was prepared by hydrothermal synthesis method in presence of the cationic surfactant, cetyltrimethylammonium bromide and hydrazine.
Detailed characterization of the material was carried out by XRD, BET, ICP-AES, SEM and TEM. XRD revealed the exclusive formation of CuCr2O4 spinel phase and TEM
showed the formation of 30–50 nm particle size. The catalyst was highly active for
selective oxidation of benzene to phenol with air as oxidant. Influence of reaction parameters were investigated in detail. The advantages of the reaction lie behind its
simplicity, low-cost set up and less time consumption.
Keywords: CuCr2O4 spinel, selective hydroxylation, benzene, phenol, air
*Author for Correspondence E-mail: [email protected]
INTRODUCTION The Direct functionalization of C–H bonds has
been developed as a powerful strategy to form
new chemical bonds [1–3]. Among them,
transition-metal-catalyzed hydroxylation of C
has received considerable attention because of
the industrially important alcohol or phenol
products [4–6]. Hydroxylation of benzene is
one of the most important and economically
attractive reactions in industry as phenol is an
important intermediate in the production of
phenolic resins, nylon, polycarbonate resins as
well as used as antioxidants and stabilizers.
Currently, phenol is produced in industry
through the so-called cumene process in which
cumene (i.e., isopropyl benzene) is converted
to phenol via a multi-step peroxidation
reaction. First of all, such reaction requires a
large amount of added reagents such as
aluminum chloride or phosphoric acid and a
radical initiator. In addition to the problem of
disposal of large amounts of waste, this
process also employs the conditions that are
corrosive to the production equipment [7].
Furthermore, because an equimolar acetone is
produced concomitantly as the byproduct, the
cumene route to phenol has lower overall
efficiency than it would be without the
byproduct. The economical efficiency of the
cumene process is strongly dependent on the
market price of acetone. Therefore, many
efforts are in progress for the development of a
new route towards phenol synthesis by a one
step process through the direct oxidation of
benzene. Although there have been several
reports using different oxidizing agents like
N2O [8], H2O2 [9–11], NH3+ O2 [12], air+CO
[13], molecular oxygen [7,14,15] etc. but most
of the cases phenol yield is very low because
phenol is more reactive toward oxidation than
benzene, over oxidation products are usually
formed [16],
and rapid deactivation of the
catalyst by coke deposition during gas phase
reaction [17]. In the light of the green
chemistry, molecular oxygen is regarded as an
ideal oxidant because of its natural,
inexpensive, and environmental friendly
characteristics [18–20]. But activating C–H
bond and thereafter, reaction with molecular
oxygen is not an easy task [15], because C–H
bonds are thermodynamically strong and
kinetically inert [21,22] On the other hand, O2
in the triplet state is kinetically hindered to
undergo formation of highly reactive oxygen
radicals, hydroxyl radicals, hydroperoxides, or
peroxides. Selective oxidations can convert
relatively cheap hydrocarbons into valuable
oxyfunctionalized products as feedstock for
Selective Oxidation of Benzene to Phenol using Air Acharyya et al. __________________________________________________________________________________________
JoCC (2014) 1-7 © STM Journals 2014. All Rights Reserved Page 2
the chemical and pharmaceutical industries.
Therefore, the catalytic aerobic C–H oxidation
is one of the “dream reactions” from both a
laboratory and industrial perspective [15]. The
main challenges of selective functionalization
towards versatile organic building blocks
when employing molecular oxygen are: a)
activation of the C–H bond, b) activation of
the O2 molecule and c) control of selectivity of
the desired product. Although there are several
reports on direct oxidation of benzene to
phenol using molecular O2 as oxidant using
Cu-containing catalysts, yet, self-assembled
architectures (of catalyst) with designed
chemical components and tunable morphology
still remains a challenge in the field of
catalysis.
Copper chromium mixed oxides with a spinel
structure had been recognized as an important
class of bi- metallic oxides that act as a
versatile catalyst [23–25]. Copper chromium
mixed oxides can be prepared by a variety of
synthetic methods, involving the reduction of
Cu-Cr oxide prepared by Adkins’ route [26],
template method [27],
citric acid complex
method [28], sol-gel
method [29] etc. Among
these methods, the sol-gel process using metal
alkoxide shows promising potential for the
synthesis of mixed oxides, owing to its high
purity, good chemical homogeneity and low
calcinations temperature [29].
The major disadvantages of using the metal
alkoxides based sol-gel process are due to its
moisture sensitive nature and the
unavailability of suitable commercial
precursors especially for mixed metal oxides.
The sol-gel synthesis of mixed metal oxides
from alkoxide mixture usually suffers from the
different hydrolysis susceptibilities of the
individual components and the benefits of
improved homogeneity can be lost during the
hydrolysis of the alkoxides, which may
ultimately lead to component segregation and
mixed phases in the final materials. These
preparation methods are not good enough
largely because many of their metal alkoxides
are expensive, and still others are sensitive to
moisture, heat, and light making their use and
long-term storage difficult. In addition, some
metal alkoxide are not commercially available
or are difficult to obtain, thus precluding
detailed studies on the preparation and
application [30].
Here we report the preparation of CuCr2O4
spinel nanoparticles with size 30–50 nm,
promoted by cationic surfactant CTAB and
hydrazine. CuCr2O4 spinels are highly
effective due to the tetragonally distorted
normal structure, where higher higher active
Cu2+
possesses tetrahedral coordination.
Furthermore, spinel (which are considered to
be of single phase) nanoparticles prepared in
our process are devoid of leaching properties,
when they are employed as catalysts. So they
can be used several times, without hindrance
of the stable spinel phase.
The use of oxygen as oxidant is known in
literature and the references are already been
cited. But in maximum cases, the catalyst
cannot be reused due to the deposition of
carbon particles (coke) on the catalyst, or
much higher temperature is being employed to
activate molecular oxygen.
In our case, CuCr2O4 spinel nanoparticles
catalyst is highly effective to activate oxygen
(oxidant) at considerable lower temperature
and can be reused several times without any
significant activity loss. Furthermore, in our
case air is used as oxidant, which is attractive
from both environmental and industrial
viewpoint. So far, there is no report on
benzene oxidation using air (the greenest
oxidant) to date.
Here, we also report a benzene conversion of
38% with a phenol selectivity of 22% over the
so prepared CuCr2O4 spinel nanoparticles
catalyst using air (molecular O2) as oxidant.
To the best of our knowledge, there is no
report for benzene hydroxylation reaction with
air (the greenest oxidant) as oxidant, with
CuCr2O4 spinel nanoparticles catalyst (~35 nm
size).
MATERIALS AND METHODS Materials
Cu(NO3)2.3H2O, Cr(NO3)3.9H2O, cetyltri-
methylammonium bromide and hydrazine
(80% aqueous solution), benzene were bought
from Sigma Aldrich. All chemicals were of
analytical grade and were used without further
purification.
Journal of Catalyst and Catalysis
Volume 1, Issue 1
__________________________________________________________________________________________
JoCC (2014) 1-7 © STM Journals 2014. All Rights Reserved Page 3
Preparation of the Catalyst
The CuCr2O4 spinel nanoparticles were
prepared by modifying our own preparation
method taking nitrate precursors of copper and
chromium [31]. In a typical synthesis, an
aqueous solution of 4.5 g Cu(NO3)2.3H2O was
added with vigorous stirring to 14.4 g
Cr(NO3)3.9H2O (from Sigma Aldrich)
dissolved in 65 g deionized water. By gradual
addition of few drop ammonia solution, the pH
of the solution was made 8. An ethanolic
solution (10%) of 6 g CTAB was added drop
wise to the reaction mixture.
After that few drops of hydrazine hydrate was
added dropwise to it to get a creamy fluffy
solution. The reagents were added maintaining
the molar ratio: Cu: Cr: CTAB: H2O:
hydrazine = 1: 2: 0.9: 200:1. After stirring, the
so obtained solution was hydrothermally
treated at 180°C for 24 h in a Teflon-lined
autoclave vessel under autogenous pressure.
The solid product was collected by means of
centrifugation at 18,000 rpm and dried at
120°C, for 10 h, followed by calcination at
750°C for 6 h in air. For the reusability test,
the catalyst was repeatedly washed with
acetonitrile and acetone and dried overnight at
130°C and used as such, without regeneration.
Characterization Techniques Powder X-ray diffraction patterns were
collected on a Bruker D8 advance X-ray
diffractometer fitted with a Lynx eye high-
speed strip detector and a Cu K radiation
source. Diffraction patterns in the 5–80°
region were recorded at a rate of 0.5 degrees
(2q) per minute. Scanning electron microscopy
(SEM) images were taken on a FEI Quanta
200 F, using tungsten filament doped with
lanthanum hexaboride (LaB6) as an X-ray
source, fitted with an ETD detector with high
vacuum mode using secondary electrons and
an acceleration tension of 10 or 30 kV.
Samples were analyzed by spreading them on
a carbon tape. Energy dispersive X-ray
spectroscopy (EDX) was used in connection
with SEM for the elemental analysis. The
elemental mapping was also collected with the
same spectrophotometer. Transmission
Electron Microscopy images (TEM) were
collected using a JEOL JEM 2100 microscope,
and samples were prepared by mounting an
ethanol-dispersed sample on a lacey carbon
Formvar coated Cu grid. Chemical analyses of
the metallic constituents were carried out by
Inductively Coupled Plasma Atomic Emission
Spectrometer; model: PS 3000 uv, (DRE),
Leeman Labs, Inc, (USA).
Catalytic Evaluation
The vapour phase benzene hydroxylation
reaction was performed in a 100 ml stainless
steel autoclave reactor (batch reactor)
(Autoclave Engineers, a division of snaptite,
INC., USA) with mechanical stirrer and an
electric temperature controller, operated under
pressure (maintained by air) of 30 bar at
350°C and 750 rpm for 6 h. Prior to reaction,
the obtained Cu-Cr oxides were activated by
Ar with a flow rate of 100 cm/min at 300°C
for 2 h in a fluidized bed reactor. 15 ml
benzene, and about 7 wt % catalyst (based on
benzene) were charged into the autoclave
under Air atmosphere. The reactor was sealed
and pressurized to the required air pressure,
and then heated to the desired temperature.
After the reaction, the autoclave was cooled to
ambient temperature, and then brought to
atmospheric pressure. It was then opened to
allow the reaction mass to be discharged and
centrifuged for removal of catalyst. The
products were analyzed with an analysed by
Gas Chromatograph (GC, Agilent 7890)
equipped with flame ionisation detector (FID)
and TCD detector (for the detection of CO2
and CO). An n-butanol solution with a known
amount was used as internal standard for
analysis.
RESULTS AND DISCUSSION Catalyst Characterization
The X-ray diffraction patterns of the Cu-Cr
catalysts presented in Figure 1 showed the
typical diffraction lines of the bulk, single
phased CuCr2O4 spinel exclusively (Figure
1(f)) with the maximum intensity peak at 2θ
value of 35.16° (JCPDS. 05-0657). By using
the Scherrer equation the average crystallite
size (based on 35.16°) was found ~ 28 nm,
which possessed consistency with that
obtained from TEM analysis. Interestingly,
XRD diffractogram (Figure 1 (f)) also predicts
that, the catalyst retains its spinel phase even
after 6 consecutive runs, only negligible
decrement in the intensity was observed,
Selective Oxidation of Benzene to Phenol using Air Acharyya et al. __________________________________________________________________________________________
JoCC (2014) 1-7 © STM Journals 2014. All Rights Reserved Page 4
which was furthermore supported by ICP-AES
analyses. SEM images of the catalyst (Figure
2a, b) showed the formation of almost
homogeneously distributed uniform particles
with size 30–50 nm and devoid of any
agglomeration. From TEM images (Figure
2c,d) revealed that the particles were well
distributed and are seen to be roughly
hexagonal. The lattice fringe with a d-spacing
of 0.30 nm corresponding to [220] plane of
CuCr2O4 spinel [32] with diffraction angle (2θ)
of 29.57° has also been presented (Figure 2d).
20 40 60 80
g
f
e
d
c
b
a
2Theta/ Degree
Inte
nsi
ty(a
mu
)
Fig. 1: XRD Diffractogram of the (a) CuO, (b)
Cu2O, (c) CrO3, (d) Cr2O3, (e) Cu/Cr2O3imp
(imp: impregnation method), (f) CuCr2O4
(prepared catalyst) and (g) CuCr2O4 (spent
catalyst, after consecutive 6 runs).
Fig. 2: SEM (a,b) and TEM Diagram (c,d) of
the CuCr2O4 Spinel Nanoparticles Catalyst.
Catalytic Activity
The results of catalytic hydroxylation of
benzene with air as oxidant have been given in
Table 1. Formation of phenol was detected
using CuCr2O4 spinel nanoparticles (as
confirmed by GC analyses). Apart from
phenol and CO2, a little amount of biphenyl
was detected as side product; additionally, no
product was detected when the reaction was
carried out under a nitrogen atmosphere
(maintaining 30 bar pressure), which
ascertains the fact that, the reaction proceeds
through radical-formation mechanism.
Molecular oxygen (in air) is effectively
activated by Cu2+
(present in CuCr2O4 spinel)
and compels the so generated oxygen species
(probably peroxide) to react with benzene
moiety. 30 bar pressure (air) and 350°C was
proved to be the optimum one.
With the increment of either temperature or
pressure, the selectivity to phenol decreases
owing to the formation of CO2 and over-
oxidation of phenol. Blank experiment was
performed in absence of catalyst maintaining
all the optimum conditions (Entry 15, Table
1), no product was detected in the absence of
catalyst, which indicated its necessity. This
result suggested that a catalytic hydroxylation
of benzene, featuring CuCr2O4 spinel
nanoparticles catalyst and air as oxidant in a
batch reactor.
To further elucidate the role of NPs in this
reaction, we studied the reaction under
identical conditions using different
commercial and conventional catalyst, with
average size ~ 2 µm. The selectivity towards
phenol changed drastically. These
observations substantiated that the success of
the reaction is largely dependent on the NPs
ability to activate oxygen. Maintaining all the
optimum conditions, when the reaction was
allowed to run for hours (Figure 3), it was
noticed that with time, increment in benzene
conversion, with decrement towards the
selectivity of phenol, presumably because of
the formation of CO2 and over-oxidized
products of phenol (quinol/hydroquinone),
including bi-phenyls.
Journal of Catalyst and Catalysis
Volume 1, Issue 1
__________________________________________________________________________________________
JoCC (2014) 1-7 © STM Journals 2014. All Rights Reserved Page 5
Table 1: Reaction Conditions of Catalytic Hydroxylation of Benzenea.
Entry Catalyst Temperature (°C) Pressure
(Bar)
CB (%)b SP (%)
c
1 CuOCOM
350 30 5 -
2 Cu2OCOM
350 30 4 -
3 Cr2O3COM
350 30 6 -
4 CuCr2O4COM
350 30 12 0.8
5 CuCr2O4IMP
350 30 10.5 1.0
6 CuCr2O4NP
350 30 38 22
7d CuCr2O4
NP 350 30 30.5 16.5
8 CuCr2O4NP
350 20 14 18
9 CuCr2O4NP
350 40 44 12
10 CuCr2O4NP
200 30 18 8
11 CuCr2O4NP
300 30 32 15
12 CuCr2O4NP
400 30 47 6.5
13e CuCr2O4
NP 350 30 8 55
14f CuCr2O4
NP 350 30 42.5 10.5
15g - 350 30 2 -
aReaction conditions: benzene = 15 ml, CuCr2O4 nanoparticles catalyst= 1.0 g, time = 6 h.
bCB: Conversion of
benzene = [Moles of benzene reacted/initial moles of benzene used] x 100. cSP: Selectivity to phenol=
[phenol]/([phenol] + 1/6[CO2] + 1/6[CO]) x 100. dPrepared CuCr2O4 catalyst after consecutive 6 runs.
eReaction time= 1h.
fReaction time = 12 h.
gNeat reaction. COM: Commercial. IMP: catalyst prepared by
impregnation method.[] is the number of moles produced. The obtained carbon balances were usually more
than 90%.
0 5 10 15 20 25
0
25
50
75
100
Conversion/Selectivity(%)
Time
Fig. 3: Effect of Time on Benzene Hydroxylation Reaction.
[ ■ ] Conversion of Benzene; [●] Selectivity to Phenol; [▲] Selectivity to CO2;
[▼]Selectivity to CO; [♦] Selectivity to other by-products.
Reaction Condition: Benzene =15 ml; Catalyst = 1g; Pressure (air) =30 bar; Temperature = 350°C.
Selective Oxidation of Benzene to Phenol using Air Acharyya et al. __________________________________________________________________________________________
JoCC (2014) 1-7 © STM Journals 2014. All Rights Reserved Page 6
Benzene Hydroxylation Mechanism
The benzene hydroxylation reaction
mechanism can be explained on the basis of
C6H6+•
formation in presence of oxygen and
Cu(II) present in the CuCr2O4 spinel
(Figure 4). 15
Cu(II) in presence of high
temperature produces Cu(II)O2–
species, which
further react with C6H6+•
species to form an
intermediate A, which further generates
phenol moiety over CuCr2O4 spinel surface.
The intermediate A is then converted to the
species Cu(II)O•
species, which enters the
catalytic cycle and takes part in the benzene
hydroxylation reaction. Furthermore,
molecular oxygen is plays the important role
in the generation of C6H6+•
species. At
optimum conditions, when air was substituted
by nitrogen, benzene remained as such in the
reactor; even formation of biphenyl was not
discovered in the medium, emphasizing the
consistency with the suggested mechanistic
path.
H
O O O-O-H +
O O H-O-O-H
H-O-O-H OH
C6H6 O-O-H C6H6
Cu(II)
O O
Cu(II) O2
Cu(II) O O
H
Cu(I) O O
H
+
O-H
OH Cu(II)-O-O-H
C6H6
+
+ + +
Biphenyl2
+
C6H6
Cu(II)-O
+
O-O-H
O2
A B
H H
Fig. 4: Mechanism of Benzene Hydroxylation
Reaction.
CONCLUSION To summarize, we have successfully prepared
CuCr2O4 spinel nanoparticles (with size
~35 nm) in hydrothermal method using
cetyltrimethylammonium bromide as
surfactant. The catalyst is effective enough to
convert benzene to phenol in a single step,
with air as oxidant; it eliminates the use of
precious metal catalyst and of H2 gas. The use
of inexpensive Cu/Cr precursors, simplicity of
the preparation method, use of the cheapest
(and greenest) oxidizing agent air and overall,
recyclability of the catalyst etc. can make this
process valuable both on laboratory scale, but
also on an industrial scale.
ACKNOWLEDGMENTS S.S.A. thanks CSIR and S.G. thanks UGC,
India for the fellowship. The Director, CSIR-
IIP, is acknowledged for his help and
encouragement. The authors thank Analytical
Science Division, Indian Institute of Petroleum
for analytical services.
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JoCC (2014) © STM Journals 2014. All Rights Reserved
Journal of Catalyst and Catalysis
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In Situ Synthesized Cu(OH)2-Al2O3: A Novel and Highly
Efficient Nano-Catalyst System for One pot Synthesis of
N-Substituted Triazole at Room Temperature
Ravi Kant Shukla, Yogesh Somasundar, Radha Sawana, Babita Baruwati* Unilever R&D, Whitefield, Bangalore, Karnataka, India
Keywords: Copper hydroxide, Triazole, One pot, Room temperature, Reuse
Abstract One pot room temperature synthesis of N- substituted
Triazoles has been demonstrated using a novel catalyst
system Cu(OH)2-Al2O3. The catalyst has been synthesized by a very simple one step chemical process. The catalyst
is highly efficient and reusable with isolated yield as high as 87% even at the 4
th reuse. The catalyst could also be
used with water as a solvent with a little longer reaction
time.
Graphical Abstract: One pot room temperature
synthesis of N- substituted Triazoles using Cu(OH)2-
Al2O3 novel catalyst system.
JoCC (2014) © STM Journals 2014. All Rights Reserved
Journal of Catalyst & Catalysis
Volume 1, Issue 1
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Alcohol Oxidation in Ionic Liquids Catalysed by
Recyclable Platinum Nanoparticles: A Green Approach
Deb Kumar Mukherjee*, Arijit Mondal, Amit Das Ramsaday College, Amta Howrah, West Bengal, India
Abstract The effect of particle size on the catalytic performance of materials in organic reactions is of scientific and industrial importance. In the present case we demonstrate the use of
room temperature ionic liquids as effective agents of dispersion of platinum nanoparticles prepared from potassium tetrachloroplatinate. The platinum nanoparticles
in the range 2.5±0.5 nm are recyclable catalysts for aerobic oxidation of alcohols under
mild conditions. The particles suspended in ionic liquids show no metal agglomeration or
loss of catalytic activity even on prolonged use. The protocol followed supports green
chemistry as uses of hazardous, flammable organic chemicals have been limited.
Keywords: Platinum, nanoparticles, oxidation, agglomeration, ionic liquid
JoCC (2014)© STM Journals 2014. All Rights Reserved
Journal of Catalyst and Catalysis
Volume 1 Issue 1
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H2 Production by Methanol Steam Reforming over
Copper Impregnated Anodized Aluminum Oxide (AAO)
M. Jhansi L. Kishore1*, Dong Hyun Kim
2
1Department of Chemical Engineering and Technology, Birla Institute of technology Mesra, India
2Department of Chemical Engineering, Kyungpook National University, Daegu, South Korea
Abstract Hydrogen production by methanol steam reforming (MSR) is easy and simple as compared to other reforming methods using fossil fuels such as methane steam reforming.
The catalysts for MSR are well developed and available commercially. When constructing
a small or micro reformer, the catalyst often needs to be coated on the wall of the metal substrate. In this case, the bonding between the metal surface and the catalyst layer must
be strong enough to avoid peeling of the layer. Simple catalyst slurry coating on the metal
surface has not been successful due to the inherent weak bonding between the metal and the metal oxide layer. In this study, to develop a robust catalyst layer, we first formed a
strongly bonded porous aluminum oxide layer on an aluminum metal surface and then impregnated it with an active metal, Cu. Copper metal is incorporated into the pores of
alumina by impregnation using different concentrations of copper nitrate solution (Cu-
AAO). The surface morphology of the catalysts has been monitored by FE-SEM at various stages of synthesis and the amount of Cu metal incorporated has been analyzed
by SEM-EDX. This paper discusses the development of Cu-AAO catalyst for methanol
steam reforming.
Keywords: Anodized Aluminum Oxide, Methanol Reforming, H2 Production
JoCC (2014)© STM Journals 2014. All Rights Reserved
Journal of Catalyst & Catalysis
Volume 1, Issue 1
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Ru(III)-Catalyzed Oxidative Cleavage of Ritodrine
Hydrochloride: A Kinetic and Mechanistic Study
Puttaswamy*, S. Dakshayani, A. S. Manjunatha Department of Chemistry, Bangalore University, Central College Campus, Bangalore, India
Abstract A systematic kinetic and mechanistic study of the oxidation of ritodrine hydrochloride (RTH) with chloramine-T (CAT) in both HClO4 and NaOH media has been carried out at
303 K. In acid medium, the reaction rate is very sluggish to be measured kinetically. Ruthenium (III) chloride ([Ru(III)]) was found to be an efficient catalyst. The reaction
rate exhibits a first-order dependence on [CAT]0 in both media. It shows a fractional-
order on [RTH]0 in alkaline medium whilst zero-order dependence in presence of HClO4. The order with respect to [NaOH] and [HClO4] is negative-fractional. The order with
respect to [Ru(III)] is fractional. Dielectric effect is negative. Activation parameters have been evaluated. Oxidation products have been identified by LC-MS analysis. Further, it
was found that these oxidation reactions are about five-times faster in alkaline medium in
comparison to acid medium. It was also observed that Ru(III) was an efficient catalyst for
the oxidation of RTH by CAT in acid medium. Nearly a four-fold acceleration in the rate
relative to an uncatalyzed reaction is observed. The observed results have been explained
by plausible mechanisms and the related rate laws.
Keywords: Ritodrine hydrochloride, Chloramine-T, Oxidation-kinetics, Ru(III)
catalysis, Mechanism
JoCC (2014)© STM Journals 2014. All Rights Reserved
Journal of Catalyst and Catalysis
Volume 1 Issue 1
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Synthesis of Zeolite Y-Encapsulated Copper(II)
Complexes with Aminobenzonitriles and Carbonitriles
by Flexible Ligand Method
Poonam Ghansiala*
Department of Chemistry, M K P (PG) College, Dehradun, Uttarakhand, India
Abstract Zeolite Y encapsulated copper(II) sulphate complexes with 2-, 3- and 4- aminobenzonitrile and carbonitrile have been prepared by flexible ligand synthesis method. Complexes are characterized
by magnetic susceptibility, infra-red and electronic spectral techniques. The data clearly suggests
the presence of metal complexes in zeolite matrix.
Keywords: Zeolite Y, Copper(II) complexes, Encapsulation
JoCC (2014) © STM Journals 2014. All Rights Reserved
Journal of Catalyst and Catalysis
Volume 1 Issue 1
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Synthesis, Structural Studies and Catalytic activity of
Copper(II) Complex Supported by N, N′-bis (2-Hydroxy-
3-Methoxybenzaldehyde) 4-Methylbenzene-1, 2-Diamine
Alekha Kumar Sutar1*
, Yasobanta Das1, 2
, Sasmita Pattnaik1, Anita Routaray
1,
Nibedita Nath1, Prasanta Rath
2, Tungabidya Maharana
3*
1Catalysis Research Lab, Department of Chemistry, Ravenshaw University, Cuttack, Odisha, India
2School of Applied Sciences (Chemistry), KIIT University, Bhubaneswar, Odisha, India
3 Department of Chemistry, National Institute of Technology, Raipur, India
Abstract A novel robust method for synthesis of 3-MOBdMBn-Cu complex, supported by -
ONNO-tetradentate Schiff-base ligand is presented. This copper complex is prepared
by the reactions of metal solution with one molar equivalent of 3-MOBdMBn (N, N’-bis (2-hydroxy-3-methoxybenzaldehyde) 4-Methylbenzene-1, 2-diamine) Schiff-base ligand
in methanol under nitrogen atmosphere. In contrast to other catalysts, the main advantage of this catalyst system was that the cost of the catalyst was remarkably low
and it can be recycled up to eight times, due to its easily accessible materials and the
simple synthetic route. The higher efficiency of complexation of copper ion on the 3-MOBdMBn Schiff base was another advantage of this catalyst system. The structural
study reveals that copper(II) complex is of square planar geometry. The catalytic
activity of copper complex toward the oxidation of phenol is investigated. Experimental results indicate that the rate of phenol conversion was 6.055 x 10
-6 moledm
-3s
-1 with
turnover number 49.632 g mol-1
Cu hr-1 at 30 min.
Keywords: Schiff base, catalysis, organometallic catalyst, copper, phenol oxidation
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