Bio-derived CuO nanoparticles for the photocatalytic treatment of dyes

Author's Accepted Manuscript

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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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.

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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

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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

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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

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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

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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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[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

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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)

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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)

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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.