Chinese Journal of Catalysis 34 (2013) 704–710

a v a i l a b l e a t w w w. s c i e n c e d i r e c t . c o m

j o u r n a l h o m e p a g e : w w w . e l s e v i e r. c o m / l o c a t e / c h n j c

Article
Combustion‐derived CuO nanoparticles: An effective and
environmentally benign catalyst in the synthesis of aromatic nitriles
from aromatic aldehydes
Belladamadu Siddappa ANANDAKUMAR a, Muthukur Bhojegowd Madhusudana REDDY a,
Chikka Nagaiah THARAMANI b, Mohamed Afzal PASHA a, Gujjarahalli Thimmanna CHANDRAPPA a,*
a Department of Chemistry, Bangalore University, Bangalore‐560001, India
b Department of Chemistry, Ruhr Universität Bochum, Bochum, Germany

A R T I C L E I N F O A B S T R A C T

Article history: CuO nanoparticles were synthesized using an energy‐efficient and rapid solution combustion tech‐
Received 31 August 2012 nique with malic acid employed as a fuel. The combustion‐derived CuO nanoparticles were used as
Accepted 3 December 2012 catalysts in a one‐pot synthesis of aromatic nitriles from aromatic aldehydes and hydroxylamine
Published 20 April 2013 hydrochloride. The catalyst was characterized by X‐ray diffraction, scanning electron microscopy,
energy‐dispersive X‐ray analysis, transmission electron microscopy, and Brunauer‐Emmett‐Teller
Keywords: surface area analysis. The catalytic activity of the CuO nanoparticles in the synthesis of aromatic
Copper oxide nitriles from aromatic aldehydes was evaluated. The present protocol offers the advantages of a
Nanoparticle clean reaction, simple methodology, short reaction duration (1–2 min), and high yield (85%–98%).
Solution combustion The catalytic activity of the CuO nanoparticles was found to be higher than that of bulk CuO powder
Nitrile under the same conditions. The catalyst can also be recovered and reused up to four times with no
Aldehyde significant loss of catalytic activity. The present approach is inexpensive and is a convenient tech‐
Hydroxyl amine nique suitable for industrial production of CuO nanoparticles and nitriles.
© 2013, Dalian Institute of Chemical Physics, Chinese Academy of Sciences.
Published by Elsevier B.V. All rights reserved.

1. Introduction catalysts for organic synthesis [2–5]. There have thus far been
numerous methods developed for the preparation of copper
The advanced properties of nanoscale metal oxide particles oxide NPs, including via solid‐state reactions [6]; sol‐gel [7],
have encouraged wide‐ranging research activity on their ap‐ sonochemical [8], solvothermal, alcohothermal [9], hydro‐
plication in electronics, optics, and catalysis [1]. Within the field thermal [10], and vapor deposition template methods [11]; wet
of green chemistry, nanometal oxide catalyzed reactions are chemistry routes [12]; and alkoxide‐based preparations [13].
recognized as being attractive and environmentally benign All of these methods require expensive precursors and high
methods of organic synthesis. Among the known varieties of temperatures, are time‐consuming, and consume significant
metal oxides, copper oxide nanoparticles (NPs) possess unique amounts of energy for completion. However, among the meth‐
physicochemical properties such as small particle size, large ods reported in the literature, solution combustion (SC) has
surface area, and unusual reactive morphology and surface proved one of the more successful methods for the synthesis of
active sites. In addition to their high thermal stability, strong metal oxide NPs and this method is relatively simple and envi‐
basic characteristics mean that copper oxide NPs are promising ronmentally benign. The advantages of this method over the

* Corresponding author. Tel: +91‐80‐22961350; E‐mail: [email protected]

This work was supported by University Grant Commission, India.
DOI: 10.1016/S1872‐2067(11)60503‐2 | http://www.sciencedirect.com/science/journal/18722067 | Chin. J. Catal., Vol. 34, No. 4, April 2013
 Belladamadu Siddappa ANANDAKUMAR et al. / Chinese Journal of Catalysis 34 (2013) 704–710

synthesis approaches mentioned vide supra are shorter reac‐ synthetic organic chemistry because of their rapid reaction rate
tion time (< 5 min), lower cost (with the potential to scale up), and ease of manipulation [54]. Simple experimental proce‐
and the possibility of using a one‐pot synthesis. In addition to dures, high yields, improved selectivity, and cleaner reactions
this, the SC method is useful for producing homogenous, po‐ of many microwave‐induced organic transformations offer
rous, and fine crystalline powders [14]. To the best of our additional advantages. Our ongoing research program is aimed
knowledge, the synthesis of CuO NPs using SC method has not at developing environmentally benign synthetic methodologies
been extensively reported [15]. suitable for organic compounds that are widely used [55,56].
In the present study, we focus on the synthesis of CuO NPs We were therefore inspired to attempt the microwave‐assisted
via an SC route using malic acid as a fuel. The combus‐ synthesis of aromatic nitriles from aromatic aldehydes under
tion‐derived CuO NPs possess a high surface area with high solvent‐free conditions using catalytic amounts of copper oxide
porosity. A large surface area results in the potential for more NPs. The catalytic activity of bulk CuO in comparison with the
active sites such as low‐coordinate oxide sites (edges and cor‐ combustion‐derived CuO NPs was also evaluated.
ners) and lattice defects (anions and cations) [16]. The porous
structure also facilitates the adsorption and diffusion of reac‐ 2. Experimental
tant molecules. Both the high surface area and high porosity
enhance the catalytic performance. Although homogeneous 2.1. Materials
organic basic catalysts are desirable because of their high activ‐
ity and selectivity, the separation of such catalysts from the Copper(II) nitrate trihydrate (98.8% purity) and DL‐malic
products of the reaction and/or catalyst recovery are inherent acid (99% purity) were purchased from Merck Chemicals (In‐
problems. dia) Pvt. Ltd. All organic chemicals used were of commercial
Use of heterogeneous basic catalysts has advantages related grade and procured from Merck Chemicals (India) Pvt. Ltd. All
to easy separation, efficient recycling, and only minimum traces solid aldehydes were used without further purification; liquid
of metal oxide remaining in the product. This is particularly aldehydes were distilled before use.
beneficial to industrial processes in the domain of green chem‐
istry. Thus, heterogeneous basic catalysts have been recognized 2.2. Synthesis of CuO nanoparticles
as potential alternatives to the more commonly used homoge‐
neous catalysts. An aqueous solution containing a mixture of copper(II) ni‐
The synthesis of nitriles from aldehydes is one of the most trate as an oxidizer (O) and malic acid as a fuel (F) (corre‐
important reactions in organic chemistry. The nitrile group is a sponding F/O ratio = 1:1) was placed in a petri dish [57,58].
useful functional group and is an important key intermediate in Excess water was allowed to evaporate by heating on a hot
organic synthesis [17]. Furthermore, nitrile functionality fre‐ plate until it decomposed with frothing as a result of formation
quently appears in pharmaceutical products. For example, the of viscous gel. The petri dish was then placed in a muffle fur‐
cyano group is present in HIV protease inhibitors, nace maintained at (450 ± 10) °C. Initially, the viscous gel un‐
5‐lipoxygenase inhibitors, and in many other bioactive mole‐ derwent dehydration and commenced smoldering combustion,
cules [18,19]. Nitriles also serve as useful precursors in the which appeared at one end and propagated through the mass
synthesis of carboxylic acids [20,21], ketenes [22], amines within 1 min. Voluminous and porous nanocrystalline
[23,24], amides [25], and heterocyclic compounds [26]. black‐colored product was obtained. This non‐carbonaceous
Over the years, methods have been developed for the syn‐ powder is hereafter referred to as CuO NPs.
thesis of nitriles, including the nucleophilic displacement of
groups such as halogens, aryl sulfonates, alcohols, esters, 2.3. General procedure
ethers, and of nitro, amino, and diazonium groups in substrates
with inorganic cyanide ions [27,28]. Alternative methods for A mixture of aldehyde (2 mmol), hydroxylamine hydrochlo‐
the synthesis of nitriles involve dehydration of amides [29,30] ride (3 mmol), and copper oxide NPs (5 mol%) was placed in a
and aldoximes [31–33]. Conversion of aldehydes [34–41], al‐ Pyrex cylindrical tube and then homogenized and irradiated at
cohols [42–44], and carboxylic acids [45–48] to nitriles using 250 W in a MILESTONE microwave reactor. After irradiation
various reagents and the direct conversion of amines [49–52] (1–2 min), the mixture was cooled to 25 °C and extracted with
are also documented in the literature. However, these methods dichloromethane (5 ml × 2). The solvent was filtered under
of synthesizing nitriles suffer from limitations such as pro‐ vacuum and the organic layer dried over fused calcium chlo‐
longed reaction time, low yield, the necessary use of toxic rea‐ ride. The crude product was then subjected to short‐column
gents and solvents, a requirement for excess rea‐ silica gel chromatography using light petrol as an eluent to
gents/catalysts, laborious work‐up procedures, or harsh reac‐ produce pure product.
tion conditions. Thus, the development of an alternate, milder, NMR spectra of the organic compounds were obtained on a
and cleaner procedure is highly desirable. 400 MHz Bruker AMX spectrometer in DMSO‐d6 using TMS as
Organic syntheses involving greener processes under sol‐ a standard. Gas chromatography‐mass spectroscopy (GC‐MS)
vent‐free conditions have been investigated as a consequence patterns were obtained using a Shimadzu GC‐MS QP 5050A
of stringent environmental and economic regulations [53]. In instrument equipped with a 30‐m long and 0.32‐mm diameter
this context, microwave‐assisted reactions are significant for BP‐5 column at temperatures from 80 to 250 °C with an inter‐
 Belladamadu Siddappa ANANDAKUMAR et al. / Chinese Journal of Catalysis 34 (2013) 704–710

val of 15 °C. IR spectra were recorded using a Shimadzu

FT‐IR‐8400s spectrometer with KBr pellets used for solids and (a)
with thin films between NaCl plates in the case of liquids.

2.4. Characterization of catalysts

Powder X‐ray diffraction (PXRD) data were recorded on a

Philips X’pert PRO X‐ray diffractometer using graphite mono‐
chromatized Cu Kα radiation (λ = 0.1541 nm) operated at 40 kV
and 30 mA. The morphologies of the products were examined
using a Quanta‐200 scanning electron microscope equipped
(b)
with an energy‐dispersive X‐ray spectroscope. Samples were
gold‐coated prior to scanning electron microscopy (SEM) anal‐
ysis. The nano/microstructure of the products was observed by
transmission electron microscopy (TEM) and selected‐area
electron diffraction (SAED), which was performed using a Hi‐
tachi model H‐600 instrument operating at 100 kV. Surface
area measurements and pore size distribution analyses were
carried out after degassing the sample under high vacuum at
300 °C for 4 h, and nitrogen adsorption measurements were
Fig. 2. SEM image of bulk CuO powder (a) and the CuO nanoparticles
carried out at –196 °C using gas sorption analyzer (b).
(Quantachrome Corporation NOVA 1000).

3. Results and discussion the amount of gases that escaped during combustion. The pro‐
cess of agglomeration takes place because of an increase in the
3.1. Catalyst characterization results rate of nucleation of the particles at higher temperatures.
The elemental quantification and stoichiometric ratio of
Figure 1 shows the XRD pattern recorded for the CuO NPs, copper oxide NPs were confirmed by energy‐dispersive X‐ray
where all diffraction peaks have been indexed to the pure analysis (EDX), which showed the presence of a uniform dis‐
monoclinic crystalline phase of CuO. These values are con‐ tribution of copper to oxygen (atomic ratio of 1:1) in CuO NPs,
sistent with those reported in the literature and with the re‐ as shown in Fig. 3. This agrees well with the results obtained
spective JCPDS card No. 45‐0937. The broadness of the peaks via XRD.
indicates the nanocrystalline nature of the CuO NPs and the The TEM image in Fig. 4(a) shows a network of larger parti‐
particle size calculated from the Scherrer’s formula (D = cles that are of moderate size and that are irregularly shaped,
Κλ/βcosθ) is in the range of 20–30 nm. formed by the agglomeration of well‐dispersed NPs with aver‐
The morphologies of the bulk CuO powder and combus‐ age sizes of 20–30 nm. The sizes of these NPs are in good
tion‐derived CuO nanopowder were investigated by SEM. The agreement with the values obtained from XRD analysis. The
SEM image of bulk CuO powder (Fig. 2(a)) reveals that the phase purity, clear morphology, and crystallinity were con‐
powder has less porosity compared with the combus‐ firmed by SAED. SAED (inset) provides supporting evidence for
tion‐derived CuO nanopowder. The SEM micrograph (Fig. 2(b)) the polycrystalline structure of the CuO NPs.
reveals that the latter powder is porous and agglomerated with The surface area of the CuO NPs was measured using the
polycrystalline NPs. The pores and voids can be attributed to BET method. The CuO NPs have a larger surface area (52 m2/g)
compared with that of bulk CuO (10–12 m2/g). This can be
attributed to the liberation of gaseous products such as H2O,
(111)

Cu
(002)
Intensity

Cu
Intensity
(202)

(113)

(220)
(202)
(022)

(311)
(020)
(110)

30 40 50 60 70 0 4 8 12 16
2/( o ) Energy (keV)

Fig. 1. XRD pattern of the CuO nanoparticles synthesized in this work. Fig. 3. EDX spectrum of the CuO NPs.
 Belladamadu Siddappa ANANDAKUMAR et al. / Chinese Journal of Catalysis 34 (2013) 704–710

indicates the formation of dual mesopores, with the peak at 45

nm due to the mesopore opening leading into the main cavity
and a large number of mesopores uniformly distributed in the
CuO NPs at 48 nm. The pore size distribution, with reference to
the average pore diameter range and pore volume range calcu‐
lated via the Barrett‐Joyner‐Halenda method, were found to be
44.82–48.36 nm and 0.431–0.441 cm3/g, respectively. These
values are in good agreement with the values obtained from
the pore size distribution plot (Fig. 5).

3.2. Catalytic activity

In the course of the reaction it was found that, under mi‐

crowave heating, the reaction of an araldehyde with hydrox‐
ylamine hydrochloride in the presence of CuO NPs is rapid,
clean, and high yielding. To optimize the reaction conditions,
Fig. 4. TEM image of the CuO nanoparticles and SAED pattern of CuO we studied the reaction of 4‐methoxybenzaldehyde (2 mmol)
(inset). with hydroxylamine hydrochloride (3 mmol) in the presence of
CuO NPs (5 mol%) under microwave irradiation. The starting
CO2, and N2 during combustion, whereby the agglomerates material completely reacted within 60 s, as indicated by TLC
disintegrate and most of the heat is carried away from the sys‐ analysis. After isolation and purification by silica gel column
tem, thus hindering particle growth. This larger surface area is chromatography, 4‐methoxybenzonitrile was isolated with a
important for catalytic/adsorbent applications because the 98% yield.
small size of the particles maximizes the surface area that is The effect of catalyst load on the reaction time and yield was
exposed to the reactant, allowing more reactions to occur. Fig‐ studied. The best result was obtained with 5 mol% of the cata‐
ure 5 shows a representative adsorption‐desorption isotherm lyst which gave 98% yield within 60 s. The use of a lesser
of nitrogen obtained at the temperature of liquid nitrogen. This, amount of catalyst (< 5 mol%) resulted in lower yields, but a
according to the IUPAC classification, is a type IV isotherm with higher amount of catalyst (> 5 mol%) did not affect the reaction
type H1 hysteresis. Type H1 hysteresis indicates that, for with respect to either duration or yield. However, in the ab‐
spherical pores, the pore opening is smaller than the diameter sence of the catalyst, the yield of the nitrile was low (< 5%) and
of the main cavity. As the desorption portion of the isotherm oxime was a major product (> 90%) after 2 min of irradiation
moves from higher partial pressure to lower partial pressure, a at 250 W. Choosing an appropriate solvent is of critical im‐
gradual decrease in pore volume is observed. As with the ad‐ portance for successful microwave‐assisted synthesis. To
sorption portion of the isotherm, this is an indication of the search for the optimal solvent, the reaction of
broad distribution of mesopores in the CuO NPs. The type IV 4‐methoxybenzaldehyde (2 mmol), hydroxylamine hydrochlo‐
isotherm suggests the presence of mesopores in the CuO NPs ride (3 mmol), and CuO NPs (5 mol%) was examined using
and this was confirmed by the results of pore size distribution water, methanol, ethanol, MeCN, DMF, THF, ethyl acetate, di‐
measurements. The pore size distribution profile exhibits two ethyl ether, and hexane as solvents, at 100 °C under microwave
peaks for the CuO NPs centered at 45 and 48 nm. This result irradiation conditions. All of the reactions were carried out at
the maximum power of 250 W. The yields of the nitrile as a
minor product were 0, 5%, 3%, 8%, 7%, 6%, 4%, 8%, and 5%
Pore volume (cm3/(gnm))

300 0.004 for the respective solvents listed above, and oxime as a major
250 0.003 product was produced in yields of 65%, 70%, 73%, 78%, 69%,
Volume adsorbed (cm3/g)

74%, 66%, 71%, and 77%, respectively. Contrastingly, for‐

0.002
200 mation of the corresponding nitrile (93%) as a major product
0.001 was observed when the same reaction was carried out under
150
solvent‐free conditions. This study clearly shows that micro‐
0.000
100 0 40 80 120 160 200 wave irradiation in conjunction with CuO NPs (5 mol%) as a
Pore diameter (nm) catalyst results in high yields of nitriles under solvent‐free con‐
50 ditions. Therefore, no solvent was used for the remaining mi‐
crowave‐assisted reactions to be discussed because it is envi‐
0
ronmentally friendly and the use of toxic organic reagents can
0.0 0.2 0.4 0.6 0.8 1.0 be avoided.
Relative pressure (p/p0) We have compared the catalytic activity of CuO NPs with
Fig. 5. Nitrogen adsorption‐desorption isotherm of the CuO nanopar‐ that of bulk copper oxide. When the model reactions between
ticles and pore size distribution curve (inset) determined from the 4‐methoxybenzaldehyde (2 mmol) and hydroxylamine hydro‐
N2‐desorption isotherm. chloride (3 mmol) with either CuO NPs (5 mol%) or bulk CuO
 Belladamadu Siddappa ANANDAKUMAR et al. / Chinese Journal of Catalysis 34 (2013) 704–710

(5 mol%) were conducted under the optimized conditions, were found to give the corresponding nitriles with excellent
yields of 98% and 39%, respectively, were obtained after 60 s. yield (85%–98%).
This clearly indicates that CuO NPs enhance the catalytic activ‐ We further explored the effect of increasing the power and
ity in the synthesis of aromatic nitriles from aromatic alde‐ reaction time in the conversion of 4‐methoxybenzaldehyde to
hydes. 4‐methoxybenzonitrile, but no change in product ratios was
The generality of the above reactions was tested by carrying observed. The identity of the synthesized compounds was con‐
out the reactions with various substituted araldehydes. It was firmed by IR analysis. In the IR spectra, the characteristic CN
consequently found that the reactions proceed smoothly irre‐ stretching mode was observed at 2220–2245 cm−1. The molec‐
spective of the substituent (see Table 1). Araldehydes pos‐ ular ion peaks (M+) observed in the mass spectra were in
sessing electron donating groups, e.g., –OMe, –OH or –N, agreement with the expected molecular weights. The melting
N(Me)2, electron withdrawing groups such as –NO2, or halides or boiling points of the compounds, as given in Table 1, also

Table 1
Solvent‐free synthesis of nitriles from aldehydes under microwave irradiation at 250 W.
Isolated yield (%) m.p. or b.p.*(oC)
Entry Aldehyde Product Time (s)
CuO NPs Bulk CuO Found Reported
O CN
1 65 95 34 185* 190* [59]
H

O CN
2 60 98 39 55−56 57−59 [37]
H
MeO
MeO
O CN
3 45 97 35 60 63 [60]
H
MeO
MeO OMe
OMe
O MeO CN
4 55 96 34 90 92−94 [60]
MeO
H
MeO
MeO OMe
OMe
O
5 CN 45 93 32 110 110 [59]
H
HO
HO
O
6 CN 70 98 38 83 83 [60]
H
HO
HO
OMe
OMe
O
7 CN 85 90 30 71 73−75 [59]
H
N
N

O CN
8 80 94 33 92 94 [59]
H
Cl
Cl
O
9 CN 95 95 34 38 37−39 [59]
H

Cl
Cl
O
10 CN 75 96 35 40 43−46 [59]
H
Cl
Cl
O
11 CN 90 92 32 112 115 [59]
H

NO2
NO2
O
12 CN 100 95 33 104−106 107 [59]
H
NO2
NO2
Other conditions: aldehyde 2 mmol, hydroxylamine hydrochloride 3 mmol, CuO NPs 5 mol%.
 Belladamadu Siddappa ANANDAKUMAR et al. / Chinese Journal of Catalysis 34 (2013) 704–710

aldehydes and hydroxylamine hydrochloride has been devel‐

no-CuO
Nano-CuO Nano-CuO Nano-CuO
Nano-CuO oped. A wide range of nitriles have been synthesized under
O H OHOH
solvent‐free conditions in a short reaction time. This protocol
O O N N N
could prove to be a practical alternative for the synthesis of
-_H2O _HO
- H2O
h PhH (i)H (i)(i) Ph H H2O Ph Ph H H 2
Ph nitriles, especially in difficult cases wherein low nucleophilicity
N (iii)
.. ..
NH2OH
NH2OH
H OH (iii) (iv) of the aldehydes inhibits the reaction. The proposed method for
(ii)
(ii) obtaining aromatic nitriles is an inexpensive, convenient, and
Scheme 1. Proposed mechanism for the catalytic synthesis of aro‐ environmentally friendly technique that is suitable for indus‐
matic nitriles from aromatic aldehydes. trial production.

agree with the literature values. As can be seen from Table 1,

Acknowledgements
CuO NPs can serve as an efficient catalyst in the formation of
4‐methoxybenzonitriles with high yields in short reaction
G.T.C. gratefully acknowledges the financial support of the
times. The size of the CuO plays an important role in terms of
University Grants Commission, New Delhi. Authors are thankful
yield and reaction time. Changing the size of the particles from
to Prof. Sarala Upadhya, Department of Mechanical Engineer‐
nanoparticles to bulk resulted in a drop in the catalytic activity
ing, UVCE, Bangalore University, for recording the SEM images.
(entry 2 of Table 1). It is interesting to note that the CuO nano‐
particles catalyze the present reaction in high yield and within
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Graphical Abstract
Chin. J. Catal., 2013, 34: 704–710 doi: 10.1016/S1872‐2067(11)60503‐2
Combustion‐derived CuO nanoparticles: An effective and environmentally benign catalyst in the synthesis of aromatic nitriles
from aromatic aldehydes
Belladamadu Siddappa ANANDAKUMAR, Muthukur Bhojegowd Madhusudana REDDY, Chikka Nagaiah THARAMANI,
Mohamed Afzal PASHA, Gujjarahalli Thimmanna CHANDRAPPA *
Bangalore University, India; Ruhr Universität Bochum, Germany

CuO nanoparticles show excellent catalytic activity in the synthesis of aromatic nitriles from aromatic aldehydes. The present approach
offers the advantages of a clean reaction, simple methodology, short reaction duration, and high product yield.

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