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Separation and Purification Technology 191 (2018) 295–300

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Separation and Purification Technology


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

Melissa Officinalis L. leaf extract assisted green synthesis of CuO/ZnO T


nanocomposite for the reduction of 4-nitrophenol and Rhodamine B
⁎ ⁎
Maryam Bordbara,b, , Neda Negahdara, Mahmoud Nasrollahzadeha,b,
a
Department of Chemistry, Faculty of Science, University of Qom, Qom 37185-359, Iran
b
Center of Environmental Researches, University of Qom, Qom, Iran

A R T I C L E I N F O A B S T R A C T

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.

1. Introduction environmentally friendliness and highly versatile device fabrication


[7–10]. Thus, the development of a simple method for the synthesis of
Toxic dyes and nitroarene compounds are highly hazardous in the well dispersed, stable CuO NPs and their immobilization on an effective
environment and are potentially toxic toward humans, animals and plants. support is highly desirable.
Thus, the degradation of organic dyes is of great environmental and in- Bio-derived materials are alternative environmentally benign sup-
dustrial importance. Environmentally acceptable processes in the catalytic ports in this regard. The advantages of biological methods compared
reduction of colorless organic pollutants are becoming increasingly ne- with other methods are: (i) no costly and poisonous capping agents or
cessary [1]. A well-known example of such organic pollutants is 4-ni- stabilizers are required, (ii) high temperature calcinations are not ne-
trophenol (4-NP), which is a toxic and bio-refractory compound, damaging cessary for the preparation of the final product, (iii) no poisonous or-
the central nervous system, liver, kidney and blood of humans and animals ganic solvent or hazardous materials are required and (iv) the methods
and causing various diseases [2]. The high stability and low solubility of 4- can be easily scaled up. A metal NP preparation method using various
NP in water makes its degradation to non-dangerous products difficult. 4- plant extracts or tree gums has recently been reported [4,5,11–14].
Aminophenol (4-AP), the reduction product of 4-NP, is widely applied in However, the agglomeration of metal NPs during catalytic reactions is
the preparation of analgesic and antipyretic drugs as a photographic de- unavoidable [4,15,16].
veloper and corrosion inhibition [3], making the reduction of 4-NP to 4-AP Hence, in our experiment, Melissa Officinalis L. (lemon balm) leaf
greatly important both environmentally and industrially. Metal nano- extract has been used to synthesize CuO/ZnO nanocatalyst. Melissa
particles (MNPs) catalyze the reduction of 4-NP to 4-AP by facilitating Officinalis L. is a well-known medicinal plant from the family of la-
electron relay from the donor BH4 to the acceptor 4-NP to overcome the miaceae. The many pharmacological actions of Melissa Officinalis L.
kinetic barrier [4]. include purgation, antibacterial, antitumor, antimutagenicity curing
CuO NPs are MNPs catalysts, which play an important part in the mental and renal disorders. The bioactive components of Melissa offi-
overall catalytic performance [5]. Nevertheless, there are disadvantages cinalis L. leaf are anthraquinones, dianthrones, stilbenes, anthocyanins,
associated with CuO NPs such as difficulty of quantitative separation flavonoids, polyphenols, organic acids, and chromones. Melissa
from the reaction mixture, impossibility to recycle, excess use of Cu Officinalis L. is a well-known medicinal plant from the family of la-
reagents and agglomeration [5]. To overcome these problems, CuO NPs miaceae. The plant is high inflavonoid. Flavonoids of lemon balm such
have recently been supported on solid supports such as zeolites to form as rosmarinic acid and anthocyanin have an antiviral and antioxidant
composite catalysts [6]. ZnO NPs are inorganic compounds widely effect [17–19]. Thus, the plant can be used as an important source for
applied as efficient supports for the immobilization of the MNPs given bioreduction of metallic ions and production of nanoparticles con-
their exceptional opto-electronic properties, low synthesis cost, sidering the potent antioxidants contained in it.


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

We report an environmentally friendly approach for the preparation


of the CuO/ZnO nanocomposite using Melissa Officinalis L. leaf extract
as a reducing and stabilizing agent. Furthermore, the catalytic activity
and recyclability of CuO/ZnO nanocomposite in the reduction of 4-NP
and RhB in aqueous medium at ambient temperature using NaBH4 as
the hydrogen source have been investigated. The catalyst can be easily
recycled following the reaction completion. Melissa Officinalis L., how-
ever, has never been applied in the green synthesis of CuO/ZnO na-
nocomposite despite its natural abundance, non-toxicity and biological
relevance.

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.

2.2. Preparation of Melissa Officinalis L. leaf extract

10 g of Melissa Officinalis L. powdered dried leaves were added to


60 mL of double distillated water in a 250 mL flask and well stirred
using a magnetic heater stirrer at 100 °C for 440 min to obtain the ex-
tract. The extract was then centrifuged at 6000 rpm and filtered. The
filtrate was kept in a refrigerator for further use.
Cu(II) + Cu (I)

2.3. Preparation of the CuO NPs using the aqueous extract of the leaves of
Melissa Officinalis L

30 mL of aqueous extract of the plant was added to 10 mL of 5 mM


CuCl2⋅2H2O solution at 70 °C and vigorously shaken. The mixture be-
came dark after 1 min.; showing the formation of CuO NPs (as mon- 350 ºC
itored by UV and FT-IR techniques). The nanoparticle colloidal dis- CuO NPs Cu NPs +
persion was then filtered and centrifuged at 7000 rpm for 30 min. The
obtained precipitate was finally washed with absolute ethanol to re-
Scheme 1. Possible mechanism of the reduction of Cu2+ and formation of the CuO NPs.
move possible impurities and kept in Ar atmosphere to protect it from
deformation and decomposition.
2.5. RhB catalytic degradation in the presence of the CuO/ZnO
nanocomposite
2.4. Preparation of the CuO/ZnO nanocomposite using the aqueous extract
of the leaves of Melissa Officinalis L 5.0 mg of the CuO/ZnO nanocomposite were added to an aqueous
solution containing RhB (2.0 × 10−5 M, 25 mL) and freshly prepared
CuO/ZnO nanocomposite was prepared by the green method. 1.0 g aqueous NaBH4 solution (2.6 × 10−3 M, 25 mL) in a typical experi-
of ZnO NPs was mixed with 0.3 g of CuCl2⋅2H2O and 50 mL of the ment and stirred for 1 s at room temperature. The absorption peak
aqueous plant extract in a 100 mL conical flask and then heated at 75 °C change at the maximum wavelength (λmax = 551 nm) was recorded to
under vigorous stirring. The solid product was collected by cen- monitor the reduction of RhB. The catalyst was separated from the
trifugation approximately 2 h later and then washed several times with reaction mixture by centrifugation following reaction completion, wa-
water and ethanol. shed with double distilled water and then dried for the next cycle.

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M. Bordbar et al. Separation and Purification Technology 191 (2018) 295–300

Table 1
Atomic and weight ratios of catalyst.

Element Series Norm. C [wt%] Atom. C [at.%]

Carbon K series 31.41 51.49


Oxygen K series 29.88 36.77
Copper K series 9.80 3.03
Zinc K series 28.91 8.71

completion of the reaction, successively washed with deionized water


and dried at 80 °C.

3. Results and discussion


Fig. 3. XRD pattern of the CuO/ZnO Nanocomposite.

In this work, we report a low-cost, environmentally friendly and


easy method for the preparation of CuO/ZnO nanocomposite using
aqueous extract of Melissa Officinalis L. leaves as a reducing and capping
agent is reported in this work. SEM, EDS, elemental mapping, TEM and
XRD have been used in the characterization of the stable CuO/ZnO
nanocomposite. CuO NPs have been separately synthesized and char-
acterized using FT-IR and UV–Vis for further monitoring. As shown in
the UV–Vis spectrum of the plant extract (Fig. 1A), the fingerprint
signals appearing around 325 nm (bond A) and 275 nm (bond B) belong
to cinnamoyl of the rosmarinic acid and 220 nm (bond C) belong to
benzoyl systems of flavonoid nuclei [18,19] as indicated in Fig. 1A. The
UV spectrum of the plant shows characteristic signals of the transition
localized from the cinnamoyl and benzoyl systems due to the π → π∗
transitions of conjugated double bounds of the flavone nucleus and
matches well with the reported literature [20,21].
FT-IR spectroscopy has been used to monitor the phenolic content of
the plant extract and its effect on NP biosynthesis. The FT-IR spectrum
of the plant aqueous extract shows peaks at 3500–3100, 1720, 1605,
Fig. 4. SEM image of the CuO/ZnO nanocomposite. 1395 and 1100 cm−1, corresponding to the free OH in molecule and OH
group forming hydrogen bonds, carbonyl group (C]O), stretching
C]C aromatic ring and CeOH and CeH stretching vibrations, respec-
2.6. 4-NP catalytic degradation in the presence of the CuO/ZnO
tively (Fig. 2A). The presence of the phenolic structures in the extract is
nanocomposite
indicated by all the peaks.
Aqueous extract of the of Melissa Officinalis L. leaves has been used
In a typical experiment, 5.0 mg of catalyst were added to 4-NP
to synthesize CuO NPs. UV–Vis absorbance behavior of the biosynthe-
aqueous solution (2.5 × 10−3 M, 25 mL) in a beaker and constantly
sized CuO NPs is shown in Fig. 1B. Maximum absorbance of green
stirred for 1 min. 25 mL of freshly prepared aqueous NaBH4
synthesized CuO NPs occurs at 270 nm due to the surface absorption of
(2.5 × 10−2 M, 25 mL) were then added to the mixture. UV–Vis spec-
nanosized cupric oxide particles, as indicated by our results. UV–Vis
troscopy was used to monitor the concentration of 4-NP in the super-
spectra show that the synthetic nanoparticles are approximately stable
natant at wavelength of 400 nm. The mixture was centrifuged at certain
with relative variances in the shape, position and symmetry of the ab-
intervals; 1.0 mL of the solution was extracted and then diluted to
sorption peak after one month, indicating the time dependence and
25 mL for further UV–Vis absorption analysis. In the recycling experi-
relative stability of product. Scheme 1 shows the most possible general
ment, the catalyst was separated by centrifugation following the
mechanism involved in the reduction of Cu2+ and formation of the CuO

Fig. 5. EDS spectrum of the CuO/ZnO nanocomposite.

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M. Bordbar et al. Separation and Purification Technology 191 (2018) 295–300

Fig. 6. EDS elemental mapping of the CuO/ZnO nano-


composite, Zn (Green) and Cu (Red). (For interpretation of
the references to colour in this figure legend, the reader is
referred to the web version of this article.)

Zn-Ka Cu-Ka

Fig. 7. TEM images of the CuO/ZnO nanocomposite.

Scheme 2. Mechanism of the catalytic reduction and


degradation of 4-NP and RhB dye with CuO/ZnO na-
nocomposite at room temperature.

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

ligating agents is confirmed by the FT-IR spectra of the obtained Cu


NPs. CuO NPs were prepared by calcinations at 350 °C for 2 h. Fur-
thermore, FT-IR spectrum of CuO NPs is shown in Fig. 2C. The peak
appearing at 400–600 cm−1 can be related to the CuO NPs.
Fig. 3 shows the XRD pattern and crystallinity of the CuO/ZnO
nanocomposite synthesized by the green method. XRD peaks at 47.7°
(2 0 0) and 72.9° (2 2 0) correspond to CuO NPs (JPCDS 80-1916). The
other diffraction peaks are also similar to those of pure ZnO and are
associated with the hexagonal phase of ZnO (JPCDS 36-1451).
SEM analysis was used to study the CuO/ZnO nanocomposite sur-
face morphology. Formation of narrow sized spherical CuO NPs is in-
dicated by SEM images (Fig. 4). EDS analysis was used to determine the
elemental composition of the CuO/ZnO nanocomposite (Fig. 5). EDS
spectroscopy confirmed the presence of Cu, Zn and O. The atomic and
Fig. 8. UV–Vis spectra for reduction of 4-NP catalyzed by CuO/ZnO nanocomposite. weight ratios are listed in Table 1. As observed in the FT-IR spectra, the
Conditions: [4-NP] = 2.5 mM; [NaBH4] = 0.25 M; catalyst = 5.0 mg. green synthesis and absorption of phenolics on the nanosurface, pos-
sibly via the interaction of π-electrons in the absence of other strong
Table 2
ligating agents, is confirmed by presence of carbon peak. Further, the
Effect of various catalysts for reduction of 4-NP; Conditions: [4-NP] = 2.5 mM; presence of Cu was approved using the elemental mapping images
[NaBH4] = 0.25 M; catalyst = 5.0 mg. (Fig. 6).
The morphology of the CuO/ZnO nanocomposite was studied by
Time (min)
TEM analysis. Spherical, narrow sized (nearly 10–20 nm) CuO NPs are
Catalyst RhB 4-NP attached to ZnO NPs, as Fig. 7 clearly shows.
CuO/ZnO nanocomposite catalytic activity was studied in the re-
CuO/ZnO 1 3 duction of aqueous solutions of 4-NP and RhB dye in the presence of
CuO 10 22
NaBH4 at ambient temperature (Scheme 2). UV–Visible spectroscopy,
ZnO 30a 30a
carried out at regular time intervals, was used to monitor the reaction
a
Not completed. progress.
4-NP has a maximum absorption at 317 nm in aqueous medium
(Fig. 8). In the absence of catalyst, the peak at 317 nm remains un-
3 changed even after a couple of days. In order to evaluate the CuO/ZnO
nanocomposite catalytic activity, 25.0 mL of 4-NP (2.5 mM) were
2.5
mixed with a freshly prepared aqueous solution of 25.0 mL of NaBH4
2 (0.25 M) at ambient temperature. 5.0 mg of CuO/ZnO nanocomposite
0 min
were then mixed with the above reaction mixture. Upon addition of
Absorbance

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.

Substrate Catalyst Reaction conditions Time Ref.

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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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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