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Bio-derived CuO nanoparticles for the photo-catalytic treatment of dyes
Chandan Tamuly, Moushumi Hazarika, Jadu-moni Das, Manobjyoti Bordoloi, Dipankar J.Borah, Manash R. Das
PII: S0167-577X(14)00348-6DOI: http://dx.doi.org/10.1016/j.matlet.2014.03.010Reference: MLBLUE16552
To appear in: Materials Letters
Received date: 27 September 2013Accepted date: 1 March 2014
Cite this article as: Chandan Tamuly, Moushumi Hazarika, Jadumoni Das,Manobjyoti Bordoloi, Dipankar J. Borah, Manash R. Das, Bio-derived CuOnanoparticles for the photocatalytic treatment of dyes, Materials Letters, http://dx.doi.org/10.1016/j.matlet.2014.03.010
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1
Bio-derived CuO nanoparticles for the photocatalytic treatment of dyes
Chandan Tamulya*, Moushumi Hazarikaa, Jadumoni Dasa, Manobjyoti Bordoloib, Dipankar J. Borahb and Manash R. Dasb
a CSIR-North East Institute of Science and Technology. Branch Itanagar Arunachal Pradesh-
791110, India b CSIR-North East Institute of Science and Technology. Jorhat, Assam-785006, India
Corresponding author: Telefax: +91360-2244220 e-mail: [email protected]
Abstract Eco-friendly synthesis of CuO nanoparticles and its utility as photocatalyst in degradation of
methyl red (MR) dye is reported. CuO nanoparticles were characterized by XRD, XPS, SEM
and TEM technique. In XRD analysis, 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. The SEM image indicated the formation of micro flower CuO nanoparticles.
The photocatalytic activity of CuO nanoparticles was evaluated by using MR dye.
Photocatalytic activity of CuO nanoparticles increased significantly in presence of Ag
nanoparticles under visible light. The result showed that Ag/CuO nanoparticles have suitable
photocatalytic activity in degradation of MR dye.
Keywords: Nanoparticles; Plant materials; XRD; Phtotocatalyst.
Introduction
Copper oxide (CuO) has received much attention for the applications in the fields ranging
from energy conversion and storage, electronics, sensors and environmental science [1-2]. It
is still a challenge to develop a simple, rapid, eco-friendly, easy to control and energy-
efficient method for a large scale preparation of CuO nanostructures with a designable
morphology. Gao et al. reported the green synthesis of CuO hollow microspheres for lithium
battery applications [3]. Green synthesis of CuO nanoparticles by using brown alga
(Bifurcaria bifurcata) [4], gum karaya [5] and its application in biological activity also is
reported.
2
Here we report a simple, efficient and eco-friendly method for synthesis of CuO
nanoparticles by using the peel of Musa balbisiana [6]. The photocatalytic activity of the
micro flower CuO nanoparticles was evaluated in presence/absence of Ag nanoparticles.
Materials and Methods
Synthesis of CuO nanoparticles: In this method, the peel of Musa balbisiana was dried then
burnt in muffle furnace at 500ºC to obtained ash of the peel. To the 1 g of the ash, 20 ml of
distilled water was added and filtered. 5 ml 1M CuSO4·5H2O solution was added to the
filtered and stirred for 10 min. Light green precipitate was obtained. After filtration, the
precipitate was heated for 2 h at 500ºC temperature for the formation of powder CuO
nanoparticles. It is the first report of eco-friendly bio-derived synthesis of CuO nanoparticles
by using peel of Musa balbisiana.
Characterization: Scanning electron microscopy (SEM) characterization was performed on
JEOL JSM - 6360 at 15 kV. X-ray diffraction (XRD) measurement was carried out by Rigaku
X-ray diffractometer (Model: ULTIMA IV, Rigaku, Japan). The X-ray photoelectron
spectroscopy (XPS) analysis was done on instrument ESCA-3000 (VG Scientific, UK). The
source used is AlKalpha having energy 1486.6 eV. The high resolution transmission electron
microscopy (HRTEM) images were recorded by a JEOL Model 2100 EX.
Photocatalytic activity: To evaluate the photocatalytic activity of CuO nanoparticles,
degradation of MR in aqueous solution was considered as a model system [7]. The 0.1 mol %
CuO nanoparticles were added to 10 ml of 1×10-4M MR solution. A control setup was also
maintained without CuO nanoparticles. The dispersion was put under the visible light. The
absorbance of the solution was measured using at wavelength 523 nm. Similar photocatalytic
degradation of 10 ml of 1×10-4M MR was observed in presence of 0.1-0.5 mol% CuO
nanoparticles along with 100 µl of Ag nanoparticles as above.
Results and discussion
3
In the present investigation, an eco-friendly approach in synthesis of CuO nanoparticles by
using peel of Musa balbisiana is demonstrated. The peel of the plant burnt in muffle furnace.
1 kg of the ash contained 233.60 g of K+, 2.00 g of Na+, 161.40 g of CO32- and 6.62 g of Cl-,
when prepared from peel of Musa balbisiana [6]. CuSO45H2O react with the ions like 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 [supporting information(SI), scheme 1]. In
XRD analysis of CuO (Figure 1A), the planes (020), (021), (110), (002), (111), (042), (130),
(131), (150), (151), (113), (200), (152), (221) and (202) indicates the formation of monoclinic
crystallite without having any peak due to the possible Cu2O and Cu(OH)2 impurity [SI,
figure S1] [8]. Lattice parameters are a = 4.84 Å, b = 3.47 Å, c = 5.33 Å. 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. The corresponding d values are 4.87, 3.61,
2.68, 2.58, 2.52, 2.32 and 2.13 Aº respectively. These are very close to those in the JCPDS
File No.5-0661. The EDX spectra supported the formation of CuO nanoparticles [SI, figure
S2]. The figure 1B(i-ii) shows XPS spectra of CuO nanoparticles. The spectrum was
calibrated with binding energy (BE) 284.5 eV for C1s electron. The BE 941 and 961 eV
corresponds to Cu 2p3/2 and Cu 2p1/2 respectively which is in agreement with reported data
[9]. The splitting between these two states is about 20 eV. This is due to the formation CuO
nanostructures. In addition to these peaks, there is observation of other peak at 951 eV
correspond to the shake-up satellite peaks of Cu (2p3/2) [10]. The BE at 538 eV corresponds
to O1s of CuO nanoparticles. It is strongly support by reported data [9]. The XPS analysis
strongly indicates the absence of Cu2O and Cu(OH)2 impurities within the sample. In
photoluminescence spectra, two emission peaks are observed at 398 nm (violet), 470 nm
(blue) was observed (Figure 1C). The first one corresponds to the band-edge emission and
4
second one is due to artefact [11]. The SEM images indicate the formation of micro flower
like morphology of CuO nanoparticles. The size of petal of CuO microflower is ranged 200-
400 nm (Figure 2A-B). The microflower like morphology consists of petal like small
nanosheets. The HR-TEM analysis results showed the formation of flower like cluster of
CuO nanostructure. The nanoparticles overlap each other which strongly support the
formation of flower like nanostructure along with spherical and oval shape (Figure 2C-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 nanoparticles is 23.5±0.8 nm. The difference between the two atomic layers is
0.16 nm. The FT-IR spectra showed the characteristic peaks of Cu-O vibration at 984 cm-1 to
430 cm-1 which indicate the formation of CuO nanoparticles [SI, figure S3]. The peaks
observed at 530 and 605 cm-1 correspond to characteristic stretching vibrations of Cu–O bond
in the CuO nanoparticles [10].
Photocatalytic activity: The Langmuir and Hinshelwood model [12] can be used to describe
the relationship between the rate of the photocatalytic degradation of MR dye in presence of
CuO nanoparticles by using the following equation-
Ln(C0/C) = k Kt = kt (1) Where, K is the adsorption coefficient of the reactant on CuO, k is the reaction rate constant
and C is the concentration of the reactant at time t, C0 is initial concentration, k = kK is the
pseudo first order reaction rate constant.
The absorption of aqueous solution of MR dye tested at different time interval in presence
of CuO nanoparticles. The main absorption peak at 523 nm decreased with the extension of
the exposure time, indicating the photocatalytic degradation of MR dye [Figure: 3A].
Simultaneously, the absorption peak at 415 nm increased gradually due to formation of MR
monomer [12-13].
Plotting Ln(C0/C) versus the corresponding irradiation time (min) yields linear
relationship [Figure 3B]. Therefore the photocatalytic degradation reaction of MR by CuO
5
nanoparticles belongs to the pseudo first order reaction. The rate of reaction was studied by
using- i) commercial available CuO powder, ii) synthesized CuO nanoparticles by Musa
balbisiana and iii) Ag/CuO nanoparticles. The rate constant ranged 0.0030-0.0092 min-1
respectively in presence of commercial available CuO (0.1-0.5 mol%) as photocatalyst (Table
1). The rate of photocatalytic degradation of MR was also observed in presence CuO
nanoparticles synthesized by Musa balbisiana. The rate constant ranged 0.0150-0.0272 min-1
respectively when synthesized CuO nanoparticles were used. The rate of the reaction also
evaluated in presence of Ag nanoparticles along with synthesized CuO nanoparticles. The Ag
nanoparticles were synthesized by using Piper pedicellatum [14] [SI figure S4-S6]. It is
interesting to note that the rate of photocatalytic degradation of MR was found significantly
high after addition of 100 µl Ag colloids along with 0.1-0.5 mol% of CuO nanoparticles. The
rate constant found maximum 0.0775 min-1 in case of Ag/CuO when 0.5 mol % CuO
nanoparticles were used. In the photocatalytic system, a photon could be absorbed by the
metallic CuO nanoparticles under the visible light which would be then efficiently
decomposed into an electron and hole [13]. So, it may act as an efficient photocatalyst to
promote the reaction along with Ag nanoparticles. As the result, the electron can more easily
move from valence band to conduction band. The Ag/CuO nanoparticles play a major role in
photocatalytic degradation of MR dye. Moreover, addition of Ag nanoparticles, the
photocatalyst surface can enhance the activity due to lower crystal size, higher surface area,
higher efficiency for the electron hole regeneration and charge trapping [15].
Conclusion
It is very simple eco-friendly process of synthesis of CuO nanoparticles by using peel of
Musa balbisiana. The ions like K+, Na+, CO32- etc may responsible for synthesis of CuO
nanoparticles. It formed micro flower like nanostructure. The CuO exhibit suitable
photocatalytic activity in presence of Ag nanoparticles and rate of the reaction increase with
6
increasing the concentration of CuO nanoparticles. The rate constant was found significantly
high when Ag/CuO nanoparticles used as photocatalyst. Further investigation is required to
use the model for waste management and other industrial application.
Acknowledgement: The authors thank Director, CSIR-North East Institute of Science &
Technology, Jorhat, Assam for valuable advice.
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[2] Kumar RV, Diamant Y, Gedanken A. Chem Mater 2000; 12: 2301-5.
[3] Gao S, Yang S, Shu J, Zhang S, Li Z, Jiang K. J. Phys. Chem. C 2008;112:19324
[4] Abboud Y, Saffaj T, Chagraoui A, El Bouari A, Brouzi K, Tanane O, Ihssane B. Appl
Nanosci. 2013: DOI 10.1007/s13204-013-0233-x
[5] Thekkae Padil VV, Černík M. Int. J. Nanomedicine. 2013:8(1); 889-98.
[6] Deka DC, Talukdar NN. Ind J Trad Knowledge. 2007:6(10):72-8.
[7] Gardea-Torresdey JL, Parsons JG, Gomez JGE, Peralata-Videa J, Troinai HE, Santiago P,
Yacaman MJ. Nano Lett 2002:2:397-401.
[8] Suramwar NV, Thakare SR, Khaty NT Int J Nano Dimens. 2012: 3(1):75-80.
[9] Yoo CH and Kim TW. J Ceramic Processing Res. 2011:12(5):606-9.
[10] Krishnamoorthy K, Kim S.J. Mat. Res. Bull. 2013:48;3136-39.
[11] Ningthoujam RS, Sudarsan V, Kulshreshtha SK. J. Lumin. 2007:127;747-56.
[12] Mahmouda MA, Poncheri A, Badr Y, Abd El Wahe MG. South African J Sci 2009:105: 299-303.
[13] Comparelli R, Fanizza E, Curri ML, Cozzoli PD, Mascolo G. and Agostiano A. Appl. Catal. B:
Environ. 2005:60:1-11..
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[15] Lin Y, Zhang Z, Tang Z, Yuan F, Li J. Adv. Mater. Opt. Electron 1999:9:205-9
7
10 20 30 40 50 60 70 800
1000
2000
3000
4000
5000
Inte
nsity
(a.u
.)
2 theta (degree)
(020)
(021)
(110)
(002)
(111)
(042)(130)
(131)
(150)(151) (200)
(152)(221) (202)
(113)
A
Figure 1: XRD spectrum B) XPS spectrum of (i) Cu 2P and (ii) O 1s (C) Photoluminescence spectrum of CuO nanoparticles
534 536 538 540 542 54430000
35000
40000
45000
50000
55000
60000
Cou
nts
/s
Binding Energy(eV)
O1sB(ii)
930 940 950 960 97085000
90000
95000
100000
105000
110000
Cou
nts/
s
Binding Energy (eV)
2P3/22P1/2
B(i)
Shake up satellite peak of 2P3/2
300 350 400 450 5000
100
200
300
400
500
Inte
nsity
(a.u
.)
Wavelength(nm)
(C)
(398 nm)
(470 nm)
8
Figure 2: SEM image (A-B) and TEM image (C-D) of CuO nanoparticles
2 4 6 8 10
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
0.1mol% 0.2mol% 0.3mol% 0.4mol% 0.5mol%
Ln(C
0/C
)
Time(min)
B
Figure 3: A) The absorption spectra of Methyl red tested at different time in the presence of Ag/CuO (100µl: 0.1mol%) nanoparticles. B) The logarithm of the ratio between the original concentration of dye and the concentration after photocatalytic degradation versus corresponding irradiation time (min) for Ag/CuO nanoparticles.
Table 1: The rate constant of photocatalytic degradation of Methyl red dye in presence CuO and Ag/CuO nanoparticles
Rate constant(min-1)
CuO (mol%) Commercial CuO Powder
CuO nanoparticles
Ag/CuO nanoparticles
0.1 0.0030 0.0150 0.0589 0.2 0.0038 0.0196 0.0631 0.3 0.0061 0.0219 0.0689 0.4 0.0079 0.0233 0.0721 0.5 0.0092 0.0272 0.0775
300 400 500 600
0.0
0.1
0.2
0.3
0.4
0.5
0.6
Abs
orba
nce(
a.u.
)
Wavelength(nm)
0min 0min 4min 8min 12min 16min 20min
(A)
9
Highlights
Eco-friendly, simple synthesis of CuO nanoparticles by using Musa balbisiana
The K+, CO32-, Na+, Cl- ions may responsible for synthesis of CuO nanoparticles.
CuO nanoparticles is a efficient catalyst for oxidation of aldehyde.
Rate of photocatalytic reaction depend on the concentration of CuO nanoparticles.