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Keywords: CuO/ZnO nanocomposite has been synthesized using Melissa Officinalis L. leaf extract as a mild, renewable and
CuO/ZnO nanocomposite non-toxic reducing agent and efficient stabilizer in the absence of hazardous and toxic materials. SEM, EDS,
NaBH4 elemental mapping, TEM and XRD have been used for the characterization of CuO/ZnO nanocomposite. CuO
Melissa Officinalis L. nanoparticles (NPs) with sizes in the 10–20 nm range have been formed, as shown by TEM micrograph.
4-Nitrophenol
Furthermore, excellent catalytic activity in the degradation of 4-nitrophenol (4-NP) and Rhodamine B (RhB) in
Rhodamine B
water at ambient temperature has been shown by CuO/ZnO nanocomposite.
⁎
Corresponding authors at: Department of Chemistry, Faculty of Science, University of Qom, Qom 37185-359, Iran.
E-mail addresses: m.bordbare@gmail.com (M. Bordbar), mahmoudnasr81@gmail.com (M. Nasrollahzadeh).
http://dx.doi.org/10.1016/j.seppur.2017.09.044
Received 9 May 2017; Received in revised form 18 August 2017; Accepted 20 September 2017
Available online 21 September 2017
1383-5866/ © 2017 Elsevier B.V. All rights reserved.
M. Bordbar et al. Separation and Purification Technology 191 (2018) 295–300
2. Experimental
Fig. 1. UV–Vis spectra of the aqueous extract of the leaves of Melissa Officinalis L. (A) and
2.1. Instruments and reagents
biosynthesized CuO NPs using aqueous extract of the leaves of Melissa Officinalis L. be-
tween 5 minand1 month (B).
Reagents were all obtained from Merck and Aldrich Chemical
Companies and used without further purification. A Varian model 640
spectrophotometer was used to record IR (KBr) spectra. A Philips model
X'PertPro diffractometer X-ray diffraction equipped with a graphite
monochromator crystal was used to perform X-ray diffraction (XRD)
measurements. The X-ray wavelength was 1.5405 A° and the diffraction
patterns were recorded in the 2θ range (10–80) with scanning speed of
2°/min. Scanning electron microscopy (SEM) (Cam scan MV2300) was
used to investigate the morphology and particle dispersion. EDS
(Energy Dispersive X-ray Spectroscopy) performed in SEM was used to
measure the chemical composition of the prepared nanostructures. The
chemical analysis of prepared nanostructures was carried out by EDS
(S3700N). A double beam Perkin Elmer Lambda 25 UV–Vis spectro-
photometer was used to record UV–Visible spectral analysis.
Transmission electron microscope (TEM) was used to identify the CuO/
ZnO nanocomposite shape and size using aPhilips-EM-2085 transmis-
sion electron microscope with an accelerating voltage of 100.0 kV. Fig. 2. FT-IR spectra of the aqueous extract of the leaves of Melissa Officinalis L. (A), Cu
NPs (B) and CuO NPs (C) synthesized using aqueous extract of the leaves of Melissa
Officinalis L.
2.3. Preparation of the CuO NPs using the aqueous extract of the leaves of
Melissa Officinalis L
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M. Bordbar et al. Separation and Purification Technology 191 (2018) 295–300
Table 1
Atomic and weight ratios of catalyst.
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M. Bordbar et al. Separation and Purification Technology 191 (2018) 295–300
Zn-Ka Cu-Ka
NPs in the presence of the aqueous extract of Melissa Officinalis L. 3500–3100, 1720, 1422, 1300 and 1000 cm−1 are associated with the
leaves. OH functional groups, carbonyl group (C]O), stretching C]C aromatic
In addition, FT-IR spectroscopy has been used to monitor the in- ring and CeOH stretching vibrations, respectively (Fig. 2B). Green
teraction between reactants and of phytochemical sites involved in synthesis and adsorption of phenolic groups on the nanosurface, pos-
order to show the phenolic effects on Cu NP formation. The peaks at sibly via interaction of π-electrons in the absence of other strong
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M. Bordbar et al. Separation and Purification Technology 191 (2018) 295–300
1.5 NaBH4 to 4-NP solution, the light yellow color changed to intense
yellow, indicating an absorption peak at about 400 nm due to the for-
1 1 min mation of 4-nitrophenolate ions in alkaline conditions caused by the
addition of NaBH4, which does not change with time. When CuO/ZnO
0.5
nanocomposite is added to the reaction system, the peak at 400 nm
0 decreases and a new peak appears at about 300 nm, corresponding to 4-
200 300 400 500 600 aminophenol (4-AP), as shown in Fig. 8. The whole peak at 400 nm
disappears after about 180 s and the yellow color of the solution
Wavelength (nm)
changes to white, showing the conversion of 4-NP 4 to 4-AP.
Fig. 9. UV–Visible spectra for catalytic degradation of RhB at several interval, conditions: Reduction of 4-NP to 4-AP using NaBH4 was investigated to study
[RhB] = 2 × 10−5 M, [NaBH4] = 2.6 × 10−3 M, Cu/ZnO nanocomposite = 5.0 mg.
the catalytic activity of various catalysts including ZnO NPs (Table 2).
ZnO NPs do not function as catalysts in this reaction, as shown by the
Table 3
Comparison of results for the degradation of 4-NP and RhB by NaBH4 in the presence of various catalysts.
4-NP Cu Microspheres, (0.5 mL, 1000 mg/L) 4-NP (30 mL, 0.2 mM), NaBH4 (10.0 mL, 25.0 mM,), r.t. 18 min [22]
Cu NPs (12.5 mg) 4-NP (25 mL, 0.12 mM), NaBH4 (25.0 mL, 20.0 mM,), r.t. 50 min [23]
Cu NPs (0.1 mmol) 4-NP (1.0 mmol), NaBH4 (3.0 mmol), THF/H2O (1:2) (20 mL), 50 °C 60 min [24]
Resin-Au NPs (100 mg) 4-NP (0.5 mmol), NaBH4 (5.0 mmol), MeOH/H2O (1:1) (20 mL), 40 °C 20 min [11]
Ni NPs (3 mg) 4-NP (3 mL, 0.1 mM), NaBH4 (0.3 mL, 0.2 M), 20 °C 10 min [12]
Cu3Ni2 nanocrystals (4.0 mg) 4-NP (1 × 10−4 M), NaBH4 (0.02 M), r.t. 6 min [25]
FeNi2 alloy nanostructure (1.0 mL, 100 mg/L) 4-NP (1.0 mL, 1 × 10−4 M), NaBH4 (1.0 mL, 6 × 10−2 M), 20 °C 60 min [26]
CuO/ZnO (5.0 mg) 4-NP (25.0 mL, 2.5 mM), NaBH4 (25.0 mL, 0.25 M), r.t. 3 min This work
RhB Cu/Fe3O4 NPs (10.0 mg) RhB (25.0 mL, 2.09 × 10−5 M), NaBH4 (25.0 mL, 5.3 × 10−3 M), r.t. 450 s [4]
SiNWAs-Cu NPs (1 × 1 cm2) RhB (25.0 mL, 5 × 10−5 M), NaBH4 (0.01 g), r.t. 14 min [27]
Fe3O4@PANI@Au, [Au]0 = 2.5 × 10−5 M RhB (2.0 × 10−5 M), NaBH4 (1.0 × 10−2 M), r.t. 18 min [28]
12.5Cu@SBA-15 (9.0 × 10−2 g/L) RhB (1.0 × 10−5 M), NaBH4 (0.025 M), r.t. 5 min [29]
Cu/eggshell nanocomposite (10.0 mg) RhB (25.0 mL, 2.09 × 10−5 M), NaBH4 (25.0 mL, 5.3 × 10−3 M), r.t. 90 s [16]
Fe3O4/Ag (20.0 mg) RhB (25.0 mL, 5.0 mg/L), NaBH4 (2.0 mL, 0.05 M), r.t. 15 min [13]
CuO/ZnO (5.0 mg) RhB (25.0 mL, 2.0 × 10−5 M), NaBH4 (25.0 mL, 2.6 × 10−3 M) 1 min This work
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M. Bordbar et al. Separation and Purification Technology 191 (2018) 295–300
results. The results also show that pure CuO NPs can catalyze 4-NP preparation of CuO/ZnO nanocomposite using aqueous extract of
reduction to 4-AP, but with at slower reaction rates compared with Melissa Officinalis L. leaves as a reducing and stabilizing agent in the
CuO/ZnO nanocomposite. Complete reduction of 4-NP to 4-AP by absence of any harmful reducing or surfactant template.
NaBH4 using pure CuO NPs takes 22 min longer, as shown in Table 2. Environmentally benign plant starting materials provide enormous
CuO/ZnO nanocomposite showed the best catalytic performance of benefits such as environmentally friendliness and compatibility with
all catalysts investigated (Table 2). Therefore, CuO/ZnO nanocomposite biomedical and pharmaceutical applications. FT-IR spectroscopy has
has a higher catalytic activity in 4-NP reduction to 4-AP than CuO NPs, confirmed that flavonoid and other phenolic constituents of the extract
which may be attributed to the active part of ZnO support in the cat- are responsible for the reduction of the CuCl2 and function as capping
alysis, leading to a synergistic effect. The evidences for synergistically ligands to the surfaces of the CuO NPs. NPs synthesized by this method
enhanced catalytic activity are: (1) CuO NPs show a high catalytic ac- are quite stable for as long as a month. Strong catalytic activity is shown
tivity; (2) ZnO NPs provide a high surface area and a relatively high by CuO/ZnO nanocomposite in 4-NP and RhB degradation at ambient
concentration of reactant molecules closer to the CuO NPs on ZnO, temperature. The catalyst was recovered and reused several times with
leading to highly efficient contact between the reacting species. CuO no loss in the catalytic activity.
NPs can transfer electrons from BH4− to 4-NP, which are both absorbed
on the catalyst, leading to the production of 4-AP when CuO/ZnO na- Acknowledgements
nocomposite is used in 4-NP catalytic reduction. BH4− can donate
electrons to CuO NPs as a nucleophile. In addition, 4-NP can capture The author is thankful to Iran National Science Foundation (INSF)
electrons from the CuO NPs as an electrophile. Eventually, 4-AP desorbs for supporting this project numbered 95823609.
from the supports to create a free surface and the catalytic cycle starts
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