Journal of Solid State Chemistry 263 (2018) 79–83

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Journal of Solid State Chemistry

journal homepage: www.elsevier.com/locate/jssc

Eco-friendly synthesis of cuprous oxide (Cu2O) nanoparticles and MARK

improvement of their solar photocatalytic activities
⁎
A. Keroura, , S. Boudjadara, R. Bourzamib, B. Allouchec
a
Ceramics Laboratory, Department of Physics, Frères Mentouri University, Constantine 25000, Algeria
b
Emerging Materials Research unit, Ferhat Abbas University Setif 1, Sétif 19000, Algeria
c
Condensed Matter Physics Laboratory, Picardie Jules Verne University, Amiens Cedex 80039, France

A R T I C L E I N F O A BS T RAC T

Keywords: In this work, we have synthesized cuprous oxide (Cu2O) nanoparticles with octahedral and spherical like shapes
Nanoparticles by an ecofriendly, simple and coast effective method, by using the aqueous extract of Aloe vera and copper
Green synthesis sulfate as solvent and precursor respectively. The effect of Aloe vera aqueous extract concentration on the
Cuprous oxide morphological, structural and optical properties of as synthesized nanoparticles was studied by Scanning
Aloe vera extract
electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform (FT-IR) spectroscopy and UV–visible
Solar photocatalysis
diffuse reflectance. The SEM images showing octahedral and spherical agglomeration of nanoparticles. The
cubic structure of Cu2O was confirmed by XRD analysis, the crystallites size depends to the concentration of
Aloe vera aqueous extract with an average size ranged between 24 and 61 nm. The FT-IR vibration
measurements valid the presence of pure Cu2O in the samples. The UV–visible spectra show that the prepared
cuprous oxide (Cu2O) has a gap energy estimated from 2.5 to 2.62 eV. The photocatalytic activities of the as-
prepared material were highly improvement by the fast degradation of methylene blue in aqueous solution at
room temperature under solar simulator irradiation.

1. Introduction monoclinic crystalline structure [9], with a narrow band gap of

Recently, biosynthesis of nanoparticles via eco-friendly processes
has attracted more attention, this is due to the several advantages of
this approach, compared to the conventional chemical and physical
synthesis techniques, which habitually involved a crude, toxic and
expensive chemicals and complicated apparatuses. The green synthesis
of nanoparticles through biological entities such as plants, algae [1],
bacteria [2], fungi and viruses [3], are considered as a new simple,
rapid, inexpensive and eco-friendly alternative [4,5]. During the last
decades, metals and metallic oxides nanoparticles have attracted great
attention, due to their extraordinary properties. These unique proper-
ties, controlled by their size and shape, allowed these materials an
important impact on different nanotechnological fields such as: cata-
lysts, chemical sensors, electronic components, pharmaceutical pro-
ducts, bio-medical, antimicrobials, optical fibers, agricultural and so on
[6,7]. Among these metal oxide nanoparticles, copper oxide has
attracted more attention due to its properties such as non-toxicity,
low cost, easy availability, important optical absorptions in visible and
ultra-violet domain [8]. Copper oxides nanoparticles are p-type semi-
conductor, it exists in two different forms: Cupric oxide (CuO)
1.2 eV, and Cuprous oxide (Cu2O) cubic structure, with an average
band gap of 2.17 eV [10]. The electronic properties offer to copper
oxides a potential applications: in solar energy conversion [9], elec-
trode materials [11], magnetic storage devices [12], biosensor [13],
photocatalysis [14] and in antibacterial activities [15]. Therefore,
several routes have been used to synthesis cuprous oxide such as
electro chemical [16], sonochemical [17] and microwave irradiation
[18]. While, currently the green method synthesis of cuprous oxide is
attracting an increasing interest. Ramesh and al have used the Arachis
hypogaea L. leaf extract, they obtained spherical, and semi spherical
Cu2O nanoparticles [19]. Abboud and al reported the synthesis of
cuprous oxide using marine alga (Bifurcaria bifurcata), the synthesized
nanoparticles have a spherical shape with an average size ranged
between5 and 45 nm [12]. Gunalan Sangeetha reported the synthesis of
CuO using Aloe vera leaf aqueous extract [20].
The use of plant extracts has several advantages such as being easily
available, safe to handle. It enables the production of large quantities of
nanoparticles and can acts both as reducing and stabilizing agents
in the synthesis of nanoparticles [21,22]. The main naturally
organic chemicals water soluble and responsible for the synthesis of

⁎
Corresponding author.
E-mail address: kerour.a@gmail.com (A. Kerour).

https://doi.org/10.1016/j.jssc.2018.04.010
Received 15 February 2018; Received in revised form 12 April 2018; Accepted 13 April 2018
Available online 14 April 2018
0022-4596/ © 2018 Elsevier Inc. All rights reserved.
A. Kerour et al.
nanoparticles are terpenoids, flavonoids, alkaloids and phenolic com-
pounds [23].
To the best of our knowledge, the use of Aloe vera leaf aqueous
extract for the green synthesis of cuprous oxide Cu2O nanoparticles,
has not been reported. Herein, in the present work, we report the effect
of Aloe vera aqueous extract concentration on the morphological,
structural and optical properties of cuprous oxide. The solar photo-
catalytic activity of the as synthesized photocatalyst was evaluated by
photo degradation of methylene blue (MB) under simulated sunlight
irradiations.
2. Experimental
2.1. Synthesis
2.1.1. Preparation of Aloe vera leaves extract
Aloe vera leaves were collected from Constantine University garden
in month of October. Leaves were washed thoroughly with distilled
water, then cut into small pieces. These fine pieces were boiled in
distilled water for 10 min on medium flame, and finally were purified
and stored under 5 °C for used in biosynthesis of cuprous oxide
nanoparticles. Different concentrations of Aloe vera aqueous extracts
were prepared from 0.25 to3.5 g/ml.
2.1.2. Synthesis of cuprous oxide (Cu2O)
In this “bottom-up” biological procedure, the nanoparticles are
built from atoms and molecules to form the first nanostructures.
Cuprous oxide nanoparticles were synthesized by an eco-friendly
synthesis method. Fig. 1 shows a schematic synthesis of Cu2O
nanoparticles, in typical procedures, different solutions with several
concentrations of Aloe vera aqueous extract(0.25–3.5 g/ml) and fixed
amount of copper sulfate were prepared (0.5 g of CuSO4-5H2O +
100 ml of Aloe vera aqueous extract), then 40 ml of 2 M of NaOH
solution was added drop by drop to the solutions. The reactional
mixtures were kept under magnetic vigorous steering at 130 °C, after
25 min, brick red precipitates appear, indicating the formation of Cu2O.
The precipitates were collected and washed by water and ethanol
several times, then dried at 90 °C for 7 h. According to the concentra-
tion of Aloe vera extract, the as-obtained samples were labeled S1, S2,
S3 and S4 respectively.
2.2. Characterizations
The shape and size of the nanoparticles were characterized by
scanning electron microscopy (SEM) (Quanta 200 F). The crystalline
phase and crystallite orientation of the as-prepared Cu2O were
investigated by X-ray diffractometer (D8 Focus, Bruker) using Cu
Fig. 1. Green synthesis of cuprous oxide nanoparticles (Cu2O).
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Journal of Solid State Chemistry 263 (2018) 79–83
kαradiation. The chemical composition of the synthesized powder was
characterized, by Fourier transform infrared (FT-IR) (JASCO 7800) in
the range (400 – 4000 cm−1). The optical properties of nanoparticles
were measured by UV–visible spectrophotometer (JASCO 670-V) on
diffuse reflectance in the wavelength range from 250 nm to 800 nm.
2.3. Photocatalytic study
The photocatalytic activity of the photocatalyst was carried out
under solar simulator light irradiation (100 mW/cm2, model 16S-300-
002, with AM1.5 filter). As-prepared Cu2O nanoparticles were evalu-
ated by the degradation of methylene blue (MB) dye solution at room
temperature. The distance between the source and samples was
fixedat17 cm. The initial concentration of MB solution is C0 = 10 mg/
L, 0.4 mg of the photocatalyst (Cu2O) was added to the MB solution in
order to activate the degradation process. The variation in concentra-
tion of irradiated MB solution was measured after 3 min for every
1 min by the absorbance of the solution at 662 nm using UV–visible
spectrophotometer (JASCO 670-V).
3. Results and discussion
3.1. MEB analysis
The particles morphology was studied by means of FE-SEM. Fig.
.2(a,c,e) shows images of as-obtained samples S1, S2, S3 and S4 at
different magnifications. As can be seen, Particles have irregular shapes
and size. For the low concentration of ALE (S1), the Cu2O nanocrystals
have the truncated octahedral structure with small square facets and
the size of these particles is in the range of 1252 ± 12 nm, while ALE
extract concentration increasing up to 1.5 g/ml (S2), leads to particles
with octahedral shape. Sphere-like Cu2O particle was observed with
rough surface and an average size range of 500 nm at 3.5 g/ml of ALE
(S4). However, the spherical form was conserved with the increasing of
ALE (S4).
It is well-known that the nanoparticles contact each other to
minimize the surface energy of the planes and grow along different
directions with different growth rate. This will drive the grain
morphology evolution [24,25]. The morphological transformation
among the polyhedron, octahedron, and truncated octahedron depend
on the ratio, R(R is the ratio of growth rate along the 〈100〉 versus
〈111〉 direction) [26]. It is reported that a perfect octahedron is
achieved when the ratio (Roct) is 1.73. While, when R is within the
range 0.8–1.73, the truncated octahedron is formed. If the amount of
additive (ALE) increases, nanocrystals of Cu2O nucleated in all crystal-
lographic directions to form spherical structure [27]. Actually, nano-
particles aggregate together to form particles, this may explain the
A. Kerour et al.
Fig. 2. SEM images and magnified images of truncated octahedral Cu2O prepared with 0.25 g/ml of ALE (a, b), octahedral Cu2O prepared with1.5 g/ml of ALE (c, d), spherical like Cu2O
prepared with 3.5 g/ml of ALE (e, f, g).
measured large particles diameter between 200, 500 and 1000 nm.
3.2. DRX analysis
XRD patterns of cuprous oxide powders are shown in Fig. 3, it
exhibits six prominent peaks located at: 29.7, 36.6, 42.6, 52.73, 61.7
and 73.9°, they are assigned to (110), (111), (200), (220), (211), (311)
and (222) crystal planes respectively. The crystallinity of cuprous oxide
was confirmed by comparing the observed XRD pattern with (AMCSD
No. 99-100-8925) [28], the comparison confirms the cubic cuprite
structure of the produced powder. Furthermore, no other secondary
phases such as CuO and Cu are detected confirming that all the samples
exist as pure Cu2O phase.
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Journal of Solid State Chemistry 263 (2018) 79–83
The average crystallite sizes were estimated using Scherrer'sEq. (1).
The obtained values are varied between 24 and 61 nm for different
samples.
Kλ
Φ=
Bcosθ (1)
where Φ is the mean crystallite size of the powder, λ the wavelength of
Cu-Kα (λ = 1.54178 Å), B the full width at half maximum (FWHM)
intensity of the peak in radian, θ is the Bragg's diffraction angle and k is
a constant usually equal to ∼ 0.9. However, when the concentration of
ALE extract increases the crystallite size decreases, as can be deduced
from Fig. 4.
A. Kerour et al.
Fig. 3. XRD patterns of cuprous oxide nanoparticles.
Fig. 4. Variation of grain size with concentration of Aloe vera extract.
3.3. FT-IR analysis
The FT-IR patterns of all samples are shown in Fig. 5, all spectra
exhibit characteristic band at 616 cm−1 which corresponds to the
stretching vibration of pure Cu2O [29]. The bands in 2915, 2852 due
to C-H stretching vibration [8]. The band at 1596 cm−1 is assigned to
C˭O stretching vibration while bands of C–O and C–C stretching
vibrations are observed in the region 1413 and 1051 cm−1. The bands
at 878 cm−1 represent C–O out of plane bending vibrations [30]. The
Fig. 5. FT-IR spectra of Cu2O nanoparticles.
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Journal of Solid State Chemistry 263 (2018) 79–83
Fig. 6. UV–Vis spectra of Cu2O nanoparticles with different concentration of ALE (a)
and variation of band gap with the grain size (b).
existence of organic bands is attributed to the adsorption of Aloe vera
molecules on the cuprous oxide.
3.4. UV–Vis analysis
Fig. 6a shows the UV–Vis spectra of the as-obtained nanoparticles.
Cu2O band gap energies were calculated using the Eq. (2) [31]:
1240
Eg(eV) =
λ max(nm) (2)
The variation of gap energy with grain size is shown in Fig. 6b. The
estimated band gap energies of Cu2O nanoparticles increases from
2.50 eV to 2.62 eV with decrease in particle size. The relative large band
gap values, by comparison to Cu2O bulk (2.17 eV), is attributed to the
quantum confinement effects due to the crystallite small sizes [32].
3.5. Photocatalytic properties
Photocatalytic activity of Cu2O obtained was evaluated by the
degradation of MB in aqueous solution under visible-light using Xe
lamp irradiation. Fig. 7. shows the photo degradation of MB as a
function of irradiation time. The intensity of the characteristic absorp-
tion peak at about 662 nm of methyl blue (MB) decreases slowly in the
absence of Cu2O Fig. 7b, only 10% of MB is degraded after 3 min.
However, in the presence of the catalysis (Cu2O), about 70% of MB is
degraded after 3 min to disappear totally after 10 min of light exposure,
as shown in Fig. 7c. This result indicates the fast photo degradation of
MB solution in the presence of Cu2O nanoparticles.
A. Kerour et al.
Fig. 7. Photo degradation of MB in the presence of the photocatalyst (Cu2O) (a), without photocatalyst (b), degradation rate of MB with and without Cu2O (c).
4. Conclusion
In summary, cuprous oxide (Cu2O) nanoparticles were successfully
synthesized through eco-friendly method using Aloe vera leaves plants
extract with different concentrations. The average size of these
nanoparticles ranged between 24 and 61 nm proved by XRD analysis.
The solvent (ALE) concentrations have a significant effect on the
particles size and shape of as prepared material. The high photocata-
lytic activity of the obtained Cu2O nanoparticles has demonstrated by
degradation of MB with cuprous oxide. The MB pollutant has been
completed degraded after 10 min exposure under visible light irradia-
tion.
Acknowledgments
The authors would like to thank Pr. Mohammed Salah Aida of the
Department of Physics, King Abdulaziz University,Jeddah, Saudi
Arabia for his cooperation, that led us to improve the work.
References
[1] K. Govindaraju, S. KhaleelBasha, V. Ganesh Kumar, G. Singaravelu, Mater. Sci. 43
(2008) 5115–5122.
[2] M.F. Lengke, M.E. Fleet, G. Southam, Langmuir 23 (2007) 2694–2699.
[3] D. Rautaray, A. Ahmad, M. Sastry, Am. Chem. Soc. 125 (2003) 14656–14657.
[4] A. Saxena, R.M. Tripathi, R.P. Singh, Digest J. Nanomater. Biostruct. 5 (2010)
427–432.
[5] Amit Kumar Mittal, Yusuf Chisti, Uttam Chand Banerjee, Biotechnol. Adv. 31
(2013) 346–356.
[6] Iravani Siavash, Green Chem. 13 (2011) 2638.
83
Journal of Solid State Chemistry 263 (2018) 79–83
[7] Tianjie Hong, Feifei Tao, Jiudong Lin, Wei Ding, Mingxuan Lan, J. Solid State
Chem. 228 (2015) 174–182.
[8] Asar Ahmed, Namdeo, S. Gajbhiye, Amish, G. Joshi, J. Solid State Chem. 184
(2011) 2209–2214.
[9] A.A. Ogwu, T.H. Darma, E. Bouquerel, J. Achiev. Mater. Manuf. Eng. 24 (2007)
172–177.
[10] C.H.B. Ng, W.Y. Fan, J. Phys. Chem. B 110 (2006) 20801.
[11] A. Lamberti, M. Destro, S. Bianco, M. Quaglio, A. Chiodoni, C.F. Pirri, C. Gerbaldi,
Electrochim. Acta 70 (2012) 62–68.
[12] Y. Abboud, T. Saffaj, A. Chagraoui, A. El Bouari, K. Brouzi, O. Tanane, Appl.
Nanosci. 4 (2014) 571–576.
[13] M.M. Rahman, aJ.Saleh Ahammad, J.-.H. Jin, S.J. Ahn, J.-.J. Lee, Switzerland
4855–4886, 2010.
[14] Jing Ouyang, Huaming Yang, Aidong Tang, Mater. Des. 92 (2016) 261–267.
[15] Binjie Li, Yuanyuan Li, Yanbao Zhao, Lei Sun, J. Phys. Chem. Solids 74 (2013)
1842–1847.
[16] W. Zhao, W. Fu, H. Yang, C. Tian, R. Ge, C. Wang, et al., Appl. Surf. Sci. 256 (2010)
2269–2275.
[17] R.V. Kumar, Y. Diamant, A. Gedanken, Chem. Mater. 12 (2000) 2301–2305.
[18] P. He, X. Shen, H. Gao, Colloid Interf. Sci. 284 (2005) 510–515.
[19] C. Ramesh, M. HariPrasad, Ragunathan, Curr. Nanosci. 7 (2011) 995–999.
[20] Sangeetha Gunalan, Rajeshwari Sivaraj, Rajendran Venckatesh, Spectrochim. Acta
Part A 97 (2012) 1140–1144.
[21] S.P. Chandran, M. Chaudhary, Biotechnol. Prog. 2 (2006) 577–583.
[22] J.Y. Song, B.S. Kim, Bioprocess Biosyst. 32 (2009) 79–84.
[23] K.S. Kavitha, Syed Baker, D. Rakshith, H.U. Kavitha, H.C. Yashwantha Rao,
B.P. Harini, S. Satish, Int. Res. J. Biol. Sci. 2 (6) (2013) 66–76.
[24] Haolan Xu, Wenzhong Wang, Wei Zhu, Phys. Chem. 110 (2006) 13830.
[25] Deli Jiang, Chaosheng Xing, Ximeng Liang, Leqiang Shao, Min Chen, Colloid
Interface Sci. 461 (2016) 25–31.
[26] Hui Yang, Zhi-Hong Liu, Am. Chem. Soc. 10 (2010) 2064–2065.
[27] Yongming Sui, Wuyou Fu, Haibin Yang, Yi Zeng, Yanyan Zhang, Qiang Zhao, Am.
Chem. Soc. 10 (2009) 99–108.
[28] R.T. Downs, M. Hall-Wallace, Am. Mineral. 88 (2003) 247–250.
[29] J.A. Gadsden, Betterworths (1975) 44.
[30] Madiha A. Shoeib, Omar E. Abdelsalam, Monazah G. Khafagi, Rania E. Hammam,
Adv. Powder Technol. 23 (2012) 298–304.
[31] Z. Yang, C.-K. Chiang, H.-T. Chang, Nanotechnology 19 (2008) 025604.
[32] C.H. Kuo, M.H. Huang, Phys. Chem. 12 (2008) 18355.