Bio-derived CuO nanocatalyst for oxidation of aldehyde: A greener approach

Article abstract of DOI:10.1039/c4ra01683a

Eco-friendly synthesis of hierarchical CuO nanoparticles using the peel of Musa balbisiana and its application as a nanocatalyst in oxidation of aldehyde to the corresponding carboxylic acid is reported here. CuO nanoparticles were characterized by using XRD, XPS, SEM, TEM and PL techniques. In XRD analysis, significant peaks appeared at 18.2, 24.6, 33.3, 34.9, 35.5, 38.6 and 42.3. The SEM images indicate the formation of a micro flower hierarchical CuO architecture. The hierarchical CuO architecture is found to be made up of 2D nanosheets as building blocks, which were self assembled to form micro flower like assemblies. The synthesized CuO nanoparticles are efficiently utilised in the oxidation of aldehyde to the corresponding carboxylic acid in the presence of 30% H₂O₂ with high yields. The utilization of the CuO nanocatalyst in the oxidation reaction in environmental friendly conditions is the novelty in this study. This journal is the Partner Organisations 2014.

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Bio-derived CuO nanocatalyst for oxidation of aldehyde: a greener approach
Chandan Tamulya*, Indranirekha Saikiaa, Moushumi Hazarikaa and Manash R Dasb
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
DOI: 10.1039/b000000x
5
Eco-friendly synthesis of hierarchical CuO nanoparticles synthesised by using peel of Musa balbisiana and its application as
nanocatalyst in oxidation of aldehyde to corresponding carboxylic acid is reported here. CuO nanoparticles were characterized by using
XRD, XPS, SEM, TEM and PL technique. In XRD analysis, significant peaks appeared at 18.2, 24.6, 33.3, 34.9, 35.5, 38.6 and 42.3
respectively. The SEM images indicate the formation of micro flower hierarchical CuO architecture. The hierarchical CuO architecture is
found to be made up of 2D nanosheets as building blocks, which were self assembled to form micro flower like assemblies. The
10 synthesized CuO nanoparticles are efficiently utilised in oxidation of aldehyde to corresponding carboxylic acid in presence of 30% H2O2
with high yields. The utilization of the CuO nanocatalyst in oxidation reaction in environmental friendly conditions is novelty in this
study.
and liquid–liquid interface techniques involving organic solvents
50 and harsh reducing agents.11 Therefore, there is a need to develop
newer eco friendly processes for the synthesis of CuO nano
Introduction
15
Cupric oxide (CuO) has received much attention for the
applications in the fields ranging from catalysis, batteries,
magnetic storage media, solar energy conversion, gas sensing,
field emission transistors, energy conversion and storage,
electronics, sensors and environmental science 1-4. The prospect
20 of potential applications of CuO nanostructures has led to
substantial research and development efforts to form various
types of nanostructures. So far, a variety of CuO nanostructures
including nanoparticles, nanoneedles, nanowhiskers, nanowires,
nanobelts and nanosheets have been obtained successfully by
particles and it is a challenging task to find a convenient, mild,
nontoxic, natural product to produce metal nanoparticles in an
aqueous environment. Several studies have been made in this
55 regard in recent years. The green synthesis of metallic
nanoparticles includes use of biological agents such as bacteria,
fungi, actinomycetes, yeast and plants.12 has been studied by
several research groups. The microorganism like Streptomyces
Sp.,13 Escherichia coli,14 fungi Penicillium aurantiogriseum,
60 Penicillium citrinum and Penicillium waksmanii,15 Morganella
17
sp.,16 Phormidium cyanobacterium etc was extensively used in
5
6
25 various methods namely alcothermal
,
hydrothermal
,
biosynthesis of CuO nanoparticles. Biosynthesis of CuO
nanoparticles by plants is currently in under development
process. Lee at al used Magnolia kobus leaf extract for the
65 synthesis of Cu nano particles.18 Gopalakrishnan reported the
synthesis of Cu nanoparticles from Fehling’s solution using
Tridax procumbens leaf extract.19 Vellora et al used gum karaya
as a biotemplate for the biosynthesis of CuO nano particles.20
Looking towards the unavailability of such methods, we were
70 intended to develop an alternative procedure for the biosynthesis
of CuO nanoparticles using the peel of Musa balbisiana. This
method is more valuable since production of nanoparticles by
chemical method may lead to absorption of harsh chemicals on
the surfaces of nanoparticles raising the toxicity issue. Our
75 procedure is environmentally benign technique for production of
well characterized nanoparticles without use of harsh, toxic and
expensive chemicals. Furthermore, Synthesis of metal nano
particles using plant materials is very cost effective and therefore
can be used as an economic and valuable alternative for the large
80 scale production of CuO nanoparticles. Again in our case the
waste materials i.e. the peel of Musa balbisiana was used which
is another advantage of this method.
electrodeposition 7, thermal oxidation 8, reverse micelle and
microwave synthesis 10. It is still a challenge to develop a simple,
rapid, eco-friendly, easy to control and energy-efficient method
for preparation of CuO nanostructures with suitable catalytic
30 activity.
9
Biosynthesis of metal oxide nanoparticles using natural
sources like plants and microorganism is becoming an emerging
area of research in nano-biotechnology due to its clean, nontoxic,
and environmentally friendly nature. Generally, the preparation
35 of CuO nanoparticles uses a variety of methods including sol-gel,
quick precipitation, sonochemical, electrochemical, solid state
reaction, alcohothermal synthesis, microwave irradiation,
a Natural Product Chemistry Section, CSIR-North East Institute of
40 Science and Technology. Branch Itanagar Arunachal Pradesh-
791110, India, e-mail: c.tamuly@gmail.com, Telefax:
+913602244220
bMaterial Science Division, CSIR-North East Institute of Science
and Technology. Jorhat, Assam-785006, India
45 † Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI:xxxxxxxx
The transformation of aldehydes to carboxylic acids is an
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important and most fundamental reaction in organic chemistry.
(221) and (202) indicates the formation of monoclinic crystallite
The oxidation of aldehydes is of interest owing to their potential 60 without having any peak due to the possible Cu2O and Cu(OH)2
in organic synthesis and industrial manufacturing.21 Most of the
oxidation reactions were carried out by the use of varieties of
oxidizing agent like potassium permanganate, chromic acid,
bromine, nitric acid, Jones reagent, H2O2 etc.22 However, H2O2 is
impurity and well arrange in specific orientation 27. The
significant 2θ values appeared at 18.2, 24.6, 33.3, 34.9, 35.5,
38.6, 42.3 corresponds to (020), (021), (002), (111), (042), (138)
and (131) planes respectively (Figure 1A). The corresponding d
5
regarded as environment friendly oxidant which can be used in 65 values are 4.87, 3.61, 2.68, 2.58, 2.52, 2.32 and 2.13 Aº
both laboratory and industrial scale. Since the only degradation
product of its use is water, and thus it has played a large role in
respectively. These are very close to those in the JCPDS File
No.5-0661.The result is similar as reported data 28
.
10 environmentally friendly methods in the chemical industry.23 The
aqueous H2O2 has been considered to have a weak ability to
oxidize aldehydes. There are numerous approaches described in
the literature for the synthesis of carboxylic acids24-25. These
protocols suffer from shortcomings such as large waste
15 production, higher reaction temperature, prolonged reaction time,
low yields, harsh conditions, undesirable by products, toxicity,
low recovery, and reusability of the catalyst. Therefore, to
overcome these drawbacks afford has been done for a convenient
protocol of synthesis carboxylic acid from corresponding
20 aldehyde.
110000
105000
100000
95000
90000
85000
60000
55000
50000
45000
40000
35000
30000
A
O1s
2P
B
3/2
2P
1/2
70
75
80
Shake up satellite
peak of 2P
3/2
930
940
950
960
970
534
536
538
540
542
544
Binding Energy (eV)
Binding Energy(eV)
Figure 2: XPS spectra of CuO nanaoparticles, (i) Cu 2P and (ii) O
1s
Here we reported eco friendly, simple, efficient method for
synthesis and characterization of hierarchical CuO nanoparticles
by using the peel of Musa balbisiana (alkaline precursors). In
order to demonstrate the application of our synthesized nano
25 particle in organic synthesis; we are reporting here the oxidation
of aldehydes to acids using H2O2 as oxidant in presence of CuO
The formation of CuO nanoparticles was further confirmed by
using FT-IR analysis. The FT-IR spectrum of CuO nano pellets is
shown (SI, Figure S1). Weak band at 2361 cm-1 assigned to
carboxylic group (COO-) vibration. Peak at 1629 cm-1 assigned to
amide (COO-) while the very intense peak positioned at 1112
nano particle. It is a convenient, very simple, efficient protocol of 85 cm-1 revealed the presence of (O-H) stretching for alkyl. These
synthesis carboxylic acid from corresponding aldehyde from the
green chemistry point of view which is suitable for medium and
30 large scale reactions in oxidation of aldehyde to corresponding
carboxylic acid.
characteristic peaks indicated the presence of very small amount
of protein/amino acid molecules along with CuO nanoparticles.
The characteristic peaks of CuO positioned from 984 cm-1 to 450
cm-1. The peaks positioned at around 640, 606 cm-1 and 530 cm-1
90 corresponding to the characteristic stretching vibrations of Cu–O
bond in the monoclinic CuO . The peak observed at 530 and 606
cm-1 due to Cu-O stretching along the [-202] direction and 450
cm-1 from Cu-O stretching along the [202] direction in CuO
Results and Discussion
In the present investigation, an eco-friendly, cost effective, green,
simple approach in synthesis of hierarchical CuO nanoparticles
35 by using peel of Musa balbisiana is demonstrated. The peel of the
plant burnt in muffle at 500ºC for 1 h and the ash was filtered. 1
kg of the ash contained 233.60 g of K+, 2.00 g of Na+, 161.40 g of
crystal 27
.
95
The Figure 2A-B shows the XPS spectra of CuO
nanoparticles. The spectrum obtained was calibrated binding
energy (BE) at 284.5 eV for a C1s electron. The XPS BE at 941
and 961 eV corresponds to Cu 2p3/2 and Cu 2p1/2 respectively
which is in agreement with reported data 29. In addition to these
2-
CO3 and 6.62 g of Cl-, when prepared from peel of Musa
balbisiana 26. CuSO45H2O react with the alkaline precursors like
40 K+, Na+, CO32- etc to formed Cu(OH)2 which further calcinations
at temperature 500ºC for 1 h to formed CuO nanoparticles. These
ions may be responsible for formation of Cu(OH)2, which further
undergo in formation of CuO nanoparticles by thermal process
[supporting information(SI), scheme 1].
100 peaks, there is observation of other peak at 951 eV correspond to
the shake-up satellite peaks of Cu (2p3/2
30. The BE at 538 eV
)
corresponds to O1s of CuO nanoparticles. It is strongly supported
by reported data 31. The XPS analysis reveal that no Cu2O and
Cu(OH)2 impurities are present within the sample.
45
5000
(020)
105
(021)
(111)
4000
3000
2000
1000
0
(002)
(042) (131)
(130)
(110)
(200)
(152)
(221)
(151)
(150)
50
(113)
(202)
10
20
30
40
50
60
70
80
2 theta (degree)
Figure1: (A) XRD spectrum of CuO nanoparticles
55
The formation of CuO nanoparticles was confirmed by using
XRD analysis. In XRD analysis, the planes (020), (021), (110),
(002), (111), (042), (130), (131), (150), (151),(113), (200), (152),
2
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Entry
Solvent
Time (hr)a
Yield(%)b
75
95
80
72
83
85
84
1
2
3
4
5
6
7
8
Ethyl acetate
Acetonitrile
Toluene
Chloroform
Methanol
Ethanol
THF
DMSO
DMF
2
1
3
11
10
11
10
12
13
77
79
Figure 3: SEM image (A-B) and TEM image (C-D) of CuO
nanoparticles
9
a
Reactions performed at 60ºC and monitored using TLC until all the
45 aldehyde was found to have been consumed.
5
The SEM images indicate the formation of micro flower like
hierarchical CuO nanoparticles. Figure 3A-B shows the SEM
images of CuO products synthesized using peel of Musa
balbisiana (alkaline precursor). It can be observed that the peel of
Musa balbisiana have substantial impact on the growth of CuO
b
Isolated yield after column chromatography of the crude product with
2% standard deviation
Initial attempts to optimize the reaction conditions for the
50 oxidation of aldehyde to the corresponding carboxylic acid were
done using 4-nitrobenzaldehyde as the substrate in presence of
different solvents and 2 mol% of CuO catalyst (Table 1). The
reaction was observed by using different solvent like acetonitrile,
ethyl acetate, chloroform, DMF, toluene, ethanol, methanol and
55 DMSO. From the Table 1, it was observed that acetonitrile was
best solvent in oxidation of 4-nitro bezylaldehyde to 4-
nitrocarboxylic acid when 2 mol% CuO nanocatalyst and 10
equiv. 30% H2O2 use as oxidant at 60ºC temperature. In
acetonitrile, 95% yield was found within 1 h of reaction time. In
60 case of other solvent the product was formed in longer period of
time with comparatively low yield.
10 nanostructures. SEM images of sample synthesized using peel of
Musa balbisiana as alkaline precursor showed the formation of
3D flower-like hierarchical CuO architecture with an average
diameter of about 200-400 nm. Higher magnification shows that
the flower-like hierarchical micro flowers are composed of 2D
15 nanosheet subunits as building blocks, which were self-organized
to form micro flower assemblies. The HR-TEM analysis results
showed the formation of micro flower like cluster of CuO
nanostructure. The nanoparticles overlap each other which
strongly support the formation of flower like nanostructure along
20 with spherical and oval shape (Figure 3C-D). The size of CuO
nanoparticles was found in the range of 10.0±0.2–40.0±1.3 nm.
The average size of the particles is 23.5±0.8 nm. The difference
between the two atomic layers is 0.16 nm. Further, the EDX
spectra clearly indicated the formation of CuO nanoparticles [SI,
25 Figure S2]. The element C, O, K, Cl etc may be due to presence
of minerals with the extract of Musa balbisiana.
Table 2: CuO catalyzed oxidation of aldehyde to carboxylic acid
O
i) 10 equiv 30% H2O2
O
65
ii) 2 mol % CuO catalyst
iii) Acetonitrile
R
H
R
OH
iv) 60ºC temperature
Ent
ry
Aldehyde
Acid
Time Yiel
TOF
(h-1)c
(h)a
d
(%)b
(398 nm)
500
(470 nm)
400
1
2
1.00 95
2.00 87
475.0
217.5
O2
N
CHO
O2N
COOH
300
200
COOH
CHO
30
O2N
100
O2N
3
4
5
2.50 85
5.00 82
3.50 75
170.0
82.0
CHO
O2N
COOH
O2
N
0
300
350
400
450
500
Wavelength(nm)
Cl
Cl
Figure 4: Photoluminescence spectrum of CuO nanoparticles
Cl
COOH
Cl
Cl
CHO
O2
N
O2N
O2N
In photoluminescence spectra, two emission peaks are observed
at 398 nm (violet), 470 nm (blue) was observed (Figure 4). The
35 first one corresponds to the band-edge emission and second one is
due to artefact 32
O2N
107.1
Cl
COOH
CHO
O2N
O2N
.
a
Reactions performed at 60ºC and monitored using TLC until all the
aldehyde was found to have been consumed.
Table 1. Optimization of the reaction conditions for the
conversion of 4-nitrobenzaldehyde to 4-nitrobenzoic acid with
different solvents, 1 equiv. 30% H2O2 and 2 mol% CuO catalyst.
70 b Isolated yield after column chromatography of the crude product with
2% standard deviation.
c TOF: Turn Over frequency
40
30% H2O2/CuO
CHO
O2N
COOH
O2N
The catalytic application of the synthesized CuO nanoparticles
75 towards the oxidation of aldehyde has been investigated. A
Solvent
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variety of aldehydes are smoothly oxidized to their corresponding
carboxylic acids with high yields. During the reaction, other
functional groups such as nitro, dinitro and chloro remain intact
(Table 2).
This is the first report on synthesis of bio-derived CuO
nanoparticles by using peel of Musa balbisiana which is a waste
materials having suitable catalytic activity. Moreover, this waste
26
material is easily available and has also some medicinal value
.
50 This is the novelty in our study. This is one of the steps of
utilization of waste material for value addition. Preparation of 3D
flower-like hierarchical CuO architecture by with controlling the
size (<40 nm) by using very simple eco-friendly method is
another unique nature in our study
5
The progress of the oxidation reaction was monitored by
silica-gel TLC. Upon completion of the reaction, the product was
separated by silica-gel column chromatography using an
appropriate eluent system. The isolated compounds were purified
1
by H NMR, 13C NMR, FT-IR, GC-MS analysis. These data of
55
Therefore it can be concluded that we have achieved a
remarkable method for the oxidation of various aldehydes to their
corresponding carboxylic acids using CuO nano catalyst,
prepared from the peel of Musa balbisiana. This reaction is a
room temperature reaction which gives a very good yield with a
10 all the products were comparable with the commercialized
compounds. As shown in Table 2, all of the aldehyde afforded
their corresponding carboxylic acid in excellent yields. The
spectroscopic data of all isolated compounds is reported (SI,
Scheme 2). The effect of electron donating group and electron
15 withdrawing group on the benzaldehyde substrates cannot be
generalized with respect to reaction time 33-34. It has been
observed that the more substituted phenyl groups took longer
time for completion of reaction 35. Our protocol provides a milder
and facile methodology for oxidation reaction that is useful for
20 organic synthesis.
Since, we have tested the reusability of CuO catalyst in the
oxidation of 4-nitrobenzyldehyde. It is believed that CuO catalyst
can be reused for this oxidation reaction as well. In oxidation of
4-nitrobenzyldehyde to 4-nitrobenzoic acid, the activity of
25 catalyst was observed five times.
60 reasonable time period. The use of H2O2 is also promising for
environmental perspectives.
The reaction is anticipated to follow an electron transfer
mechanism where Cu(II) is reduced to Cu(I), accompanying the
oxidation of aldehyde. The reduced Cu(I) is again oxidized to
65 Cu(II) by the oxidant. Aqueous H2O2 is a eco-friendly, safe
oxidant which produces no hazardous by product. Although its
ability to oxidize aldehyde has been ignored, it is very useful for
this purpose and found significant yield in mild reaction
condition. Changing current practices to a process using this
70 environmentally friendly, green oxidant is highly desirable.
Conclusions
100
80
60
40
20
0
It is very simple eco-friendly process of synthesis of CuO
75 nanoparticles by using peel of Musa balbisiana. CuO flower-
shaped hierarchical architectures were obtained by using the peel
of Musa balbisiana (alkaline precursors). Owing to its great
chemical flexibility and synthetic tenability, the present route
provides a simple and green pathway of synthesizing 3D CuO
80 nanostructures. Moreover, we have developed a simple, efficient,
chemo selective and inexpensive catalytic method for the
oxidation of aldehyde to carboxylic acid using CuO nanocatalyst
and 30% H2O2 with high yield product. The CuO nanocatalyst
was found to be highly active and could be recycled for five
85 consecutive runs without significant loss of catalytic activity.
1
2
3
4
5
Nos. of Runs
Figure 5: Recycling of the catalyst after oxidation of 4-
nitrobenzyldehyde to 4-nitrobenzoic acid
Acknowledgement
30 The CuO catalyst was recovered by simple filtration and was
washed with hot water/ethanol to remove any absorbed products.
The catalyst was reused without obvious loss of their catalytic
activity, up to five cycles. Recyclability of the catalyst is shown
in Figure 5. It was confirmed that efficiency remain almost same
35 after five times recycle of catalyst (1st recycle 95%, 2nd recycle
94% and 3rd recycle 92%, 4th recycle 91% and 5th recycle 90% 4-
nitrobenzoic acid was obtained). It was further confirmed by
using XRD and TEM analysis after 5th recycle [Figure S3-S4].
The authors thank Director, CSIR-North East Institute of Science
& Technology, Jorhat, Assam for valuable advice. The authors
90 also thank to SAIF, Shillong for TEM & SEM analysis and Dr.
K. R. Patil, NCL Pune for XPS analysis.
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DOI: 10.1039/C4RA01683A
CHO
CuSO45H2O
R
30% H2O2
COOH
Peel of Musa balbisiana
Flower like CuO nanoparticles
R