Inorganic and Nano-Metal Chemistry

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Photocatalytic activity of Cu@Ag BNCs synthesized

by the green method: Photodegradation methyl
orange and indigo carmine

Zahra Kheibarian, Esmaiel Soleimani & Hamid Reza Mardani

To cite this article: Zahra Kheibarian, Esmaiel Soleimani & Hamid Reza Mardani (2022):
Photocatalytic activity of Cu@Ag BNCs synthesized by the green method: Photodegradation
methyl orange and indigo carmine, Inorganic and Nano-Metal Chemistry, DOI:
10.1080/24701556.2022.2068594

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Published online: 28 Apr 2022.

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INORGANIC AND NANO-METAL CHEMISTRY
https://doi.org/10.1080/24701556.2022.2068594

Photocatalytic activity of Cu@Ag BNCs synthesized by the green method:

Photodegradation methyl orange and indigo carmine
Zahra Kheibariana, Esmaiel Soleimania, and Hamid Reza Mardanib
a
Inorganic Chemistry Research Laboratory, Faculty of Chemistry, Shahrood University of Technology, Shahrood, Iran; bDepartment of
Chemistry, Payame Noor University (PNU), Tehran, Iran

ABSTRACT ARTICLE HISTORY

In this research, four bimetallic nanocomposites (BNCs) of copper and silver with weight ratios Received 8 January 2022
(0.9:0.10, 0.92:0.08, 0.94:0.06, 0.96:0.04) formulated and specified as ([email protected]), Accepted 27 March 2022
([email protected]), ([email protected]), and ([email protected]) were prepared via the green synthesis in
KEYWORDS
the presence of Citrus paradisi extract as a low cost, simple and environmentally friendly method.
Cu@Ag BNCs; photocatalytic
The as-prepared Cu@Ag BNCs were identified by FTIR, XRD, EDX, FE-SEM, and EDX mapping analy- activity; photodegradation
ses. The FTIR analysis was performed to determine the functional groups in Cu@Ag BNCs. EDX MO and IC; citrus paradisi
analysis confirms the existence of Cu and Ag in BNCs. These Cu@Ag BNCs were used as catalysts extract; green synthesis
for the photodegradation process of methyl orange (MO) and indigo carmine (IC) as the anionic
organic dye. The effect of parameters such as different weight percentages of BNCs constituent
metals, the amounts of photocatalyst and hydrogen peroxide on the degradation rate of MO and
IC under visible light was investigated and their optimal values were determined. The optimized
conditions for removal of the dyes in the natural pH and 0.005 g of photocatalyst [email protected]
BNCs reached for degradation dyes MO and IC to 90.0% and 100% respectively.

Introduction Researchers have proposed various methods for the effective

treatment of colored effluents.[11] So far, physical, chemical,
The increase in population and the development of urban
and biological methods such as adsorption, coagulation,
communities have led to the production of organic effluents
membrane filtration, and ion exchange have been used to
from various industries which are a threat to both human
remove dyes. Some of these methods do not lead to dye
life and aquatic life. For the past few decades, with the
degradation in one step but require more steps. Another
development of the paint industry, dye pollutants such as
way to remove dyes is the common oxidation process, which
effluents have been found in the sewage of various indus-
tries, including paints, textiles, etc., causing water and envir- takes place in the presence of oxidizing agents such as oxy-
onmental pollution. gen, hydrogen peroxide, ozone, and permanganate.
Due to the release of these effluents, many people around Nevertheless, these processes cannot completely oxidize sta-
the world do not have access to clean water, which causes ble chemical compounds. Also, by-products may be formed
millions of people the release contaminated water to die.[1,2] during the oxidation process which is even more toxic than
Most dyes are azo-based, which have one or more groups the main pollutants.[12]
-N ¼ N-. This group of dyes is very toxic and due to the low Given the high chemical stability and limitations in the
reactivity of azo bonds, they have high chemical and phys- biodegradation of most organic pollutants in water, an
ical stability and are resistant to degradation.[3–5] Methyl effective approach to the degradation of pollutants in the
orange (MO) is one of the azo group dyes which easily advanced oxidation process (AOP). In this process, a
penetrate soil and living systems in small amounts and hydroxyl radical (HO) is produced, which reacts rapidly
causes damage.[6] Another dye that pollutes sewage is Indigo due to its high oxidation potential, converting pollutants
Carmine, Acid Blue 74. Indigo Carmine (IC) is an indigo into harmless components of CO2, water, and to some
dye that is also used as a dye in the textile industry in add- extent harmless compounds. Photocatalysts transfer elec-
ition to being used for medical diagnostic purposes. trons from the capacitance band upon receiving energy and
Although indigo carmine is harmless at small contents, the creating a pair of electrons and holes, which react freely
presence of large amounts of this pollutant in wastewater is with the pollutant causing degradation of the pollutant com-
harmful to the environment and humans due to its toxicity pound.[13,14] Advanced oxidation processes, based on the
and carcinogenicity. Removal of these pollutants from waste- catalyst phase, are divided into two categories: homogeneous
water has been considered by many research groups.[7–10] and heterogeneous photocatalysts. Heterogeneous

CONTACT Esmaiel Soleimani [email protected] Inorganic Chemistry Research Laboratory, Faculty of Chemistry, Shahrood University of
Technology, Shahrood, Iran
ß 2022 Taylor & Francis Group, LLC
2 Z. KHEIBARIAN ET AL.

photocatalysts have received much attention due to their

environmental applications and easy separation from the
reaction medium.[15]
In recent years, metal nanoparticles (NPs) have been con-
sidered by many researchers due to their wide range of
applications.[16–19] Bimetallic nanocomposites (BNCs) are a
new type of metal NPs that are composed of two separate
metals. According to the methods of preparation and distri-
bution of elements, they are divided into two categories:
alloy and core-shell. Bimetallic NPs show not only a com-
bination of properties related to two metals but also show
new properties that do not exist in single metal NPs, such
as electrical, optical, catalytic properties due to the synergy
of the two metals. For this reason, these compounds can
also be used in photocatalytic processes.[20,21]
Among NPs, Cu NPs are widely used in the photocata-
lytic process due to their high abundance and high electron
conductivity. Noble metals such as silver can absorb visible
light due to their local surface plasmon resonance (LSPR)
and can act as electron donors to transfer electrons from the
metal surface while also preventing electron and hole recom-
bination and enhancing photocatalytic activity.[22] In gen-
eral, NPs are produced by various chemical and physical
routes, which are usually costly and lead to the formation of
harmful by-products which are dangerous to the environ-
ment. For this reason, the synthesis of NPs by the green
method has been considered by researchers. The green
method is a nontoxic method that uses biological resources
such as plants, fungi, algae, and microorganisms. This
method has several advantages over conventional methods
such as availability, efficiency, and environmental friendli-
ness.[23,24] Thus, one of the ways to synthesize NPs is to use
plants.[25] Plant extracts included compounds such as flavo-
Scheme 1. The molecular structures of MO (a) and IC (b).
noids, polyphenols, alkaloids, and other active species that
these compounds are accountable for reducing metal ions
and forming metal NPs.[26]
Various plants have been used to synthesize NPs. Citrus percentage of silver and copper in the removal of
fruits, such as oranges, lemons, etc. are among the plants organic pollutants.
that have been used in this regard. Citrus paradisi is also a
member of the citrus family, which first grew in Southeast Experimental
Asia and is now cultivated in the northern hemisphere.
Citrus paradisi peel contains compounds such as polyphe- Chemicals and measurements
nols, flavonoids, ascorbic acid, etc. which can all be respon- Copper sulfate pentahydrate (CuSO4.5H2O), silver nitrate
sible for stabilizing and reducing the preparation of (AgNO3), methyl orange (C14H14N3NaO3S), Indigo Carmine
metal NPs.[27–30] (C16H8N2S2O8Na2), 30% hydrogen peroxide, and sodium
In this project, we aim to produce bimetallic nanocompo- hydroxide (NaOH) were prepared from Merck. Double dis-
sites (BNCs) by green method to increase photocatalytic tillation water was used to prepare all solutions.
activity. Therefore Cu@Ag BNCs was synthesized and The phase-detection of NPs was performed using an X-
studied as photodegradation catalyst to two anionic: azo and ray diffraction device (PHILIPS, PW1730, Netherlands) with
non-azo dyes. We prepare Cu@Ag BNCs with different a voltage of 40 kV and Cu-Ka (1.54 Å) radiation. FT-IR
ratios of copper and silver (with a ratio of 0.90:0.10, spectrum was prepared in the range of 400-4000 cm1 by
0.92:0.08, 0.94:0.06, 0.96:0.04) through the green method AVATAR, Thermo, USA. Raman spectra were prepared by
with aqueous extract of Citrus paradisi and to evaluate its a Raman scattering microscope (TakRam N1-541, Teksan,
behavior in the photocatalytic degradation process of MO Iran) with laser power of 100-10 mW at 532 nm. The
and IC dyes under visible light. morphology of the nanoparticle structure was investigated
Scheme 1 shows the structures of MO and IC. In other using FE-SEM (TESCAN, MIRA III, Czech). Analysis and
words, we intend to explore the effect of changing the size characterization of the elements were performed by
 INORGANIC AND NANO-METAL CHEMISTRY 3

EDS attached to SEM. UV-vis spectrum was prepared using

the Lambda-UV-25 spectrophotometer. (Perkin Elmer, USA)
within the range of 200-800 nm.

Preparation of extract
Citrus paradisi extract was prepared according to the follow-
ing method. Initially, citrus paradise was prepared from
northern Iran. After cleaning and washing, its skin was
dried and ground in the shade. To prepare the extract,
20.0 g of powder was blended with 100.0 mL of water-etha-
nol (1:1 ratio) and put on a shaker for 48 hours at room
temperature to obtain the extract. This mixture was filtered
and placed in a hot water bath (Ben Marie) at 50  C for
7 hours to concentrate. The obtained extract was kept for
direct use at 4  C away from direct light. Figure 1. The FT-IR spectra: Citrus paradisi extract (a), [email protected] BNCs (b).

Preparation of Cu@Ag BNCs

Cu@Ag BNCs were prepared in two steps using citrus para-
disi extract. First, 70.0 mL of 10 ppm extract was added to
35.0 mL of 0.08 M copper sulfate solution while being stirred
on the stirrer. The mixture was stirred for 6 hours at 50  C.
Next, the solution color turns from green to brown, reflect-
ing the formation of Cu NPs. The mixture was then centri-
fuged and the synthesized Cu NPs were dried at 50  C in
an oven.
To prepare Cu@Ag BNCs, initially, 50.0 mL of deionized
water was added to 0.90 g of pre-prepared Cu NPs with
ultrasonic performed for 60 minutes. Then, 25.0 mL of
10 ppm citrus paradisi peel extract was added to the magnet-
ically stirring copper solution at 50  C. After stirring for a
few minutes, 0.100 g of silver nitrate salt was added to the
solution with the pH of the solution adjusted by sodium
hydroxide to 10.0, which formed Agþ by galvanic replace-
ment on the surface of Cu NPs. The mixture was refluxed
for 24 hours at 80  C. After the reaction, the obtained pre- Figure 2. XRD Patterns: Ag NPs (a), Cu NPs (b), [email protected] BNCs (c).
cipitate was washed with ethanol and deionized water sev-
eral times. It was then dried for 12 hours in an oven at C0 (mg/L) and C (mg/L) are the initial and final concen-
50  C. Other Cu@Ag BNCs at different Ag/Cu ratios were trations of each dye before and after photo-irradiation,
prepared under similar conditions with proportional respectively.
weight ratios.

Photocatalytic activity Photodegradation of MO and IC

The photodegradation of MO and IC dyes was investigated Initially, 0.005 g of photocatalyst (Cux@Agy BNCs) with
using as-prepared Cu@Ag BNCs. Experiments were carried 0.5 mL of hydrogen peroxide (H2O2) was added to 10.0 mL
out in a cabinet photoreactor using a 400 W metal halide of MO solution at a concentration of 10 ppm at natural pH.
lamp as a light source. The reactions were performed at Before irradiating the light, the mixture was stirred in the
ambient temperature also the reaction mixture was cooled dark for 30 minutes using a magnetic stirrer to establish the
with continuous water circulation.
equilibrium of adsorption and desorption, after which the
The percentage of photodegradation (R %) of dyes was
reaction mixture was irradiated with visible light. At regular
calculated according to Eq. (1).
  intervals, 2.0 mL of the mixture was withdrawn and after
C0  C centrifugation, the dye adsorption rate was recorded by UV-
R% ¼  100 (1)
C0 Vis. spectra. A similar method was utilized for the IC dye.
4 Z. KHEIBARIAN ET AL.

Figure 3. FE-SEM images of Cu@Ag BNCs at different magnifications.

 INORGANIC AND NANO-METAL CHEMISTRY 5

Figure 4. (a) EDX and (b) EDX-mapping pictures of Cu@Ag BNCs.

Results and discussions phenolic compounds in the extract, respectively. The stretch-
ing vibration at 1370 cm1 is attributed to the amide I
Nanocomposites prepared by the green method were identi-
group. As shown in Figure 1b, the peak at about 3438 cm1
fied by various techniques, presented, and discussed in the
appears smaller and narrower after the formation of Cu@Ag
following sections.
BNCs. This alter indicates that H bonds between amide
groups break and are adsorbed onto the surface of the
FT-IR analysis BNCs and create stronger bonds with BNCs that lead to sta-
bility of the BNCs.[31,32]
The FT-IR spectra were utilized to identify the functional
group on the surface of as-synthesized Cu@Ag BNCs by the
extract. Figure 1 displays the FT-IR spectra of Cu0.90@Ag0.
XRD patterns
10 BNCs and Citrus paradisi peel extract. According to
Figure 1a, the peaks of about 3440 and 1636 cm1 are The phase structure and crystalline properties of the BNCs
related to stretching of the O-H and C ¼ C groups of the were examined by X-ray diffraction. Figure 2 depicts the
6 Z. KHEIBARIAN ET AL.

Figure 4. Continued.

XRD patterns of a combination of Cu@Ag as well as cop- FE-SEM images

per and silver NPs alone. The three lines appearing at posi-
The surface morphology of Cu@Ag BNCs was recorded by
tions 43.4, 50.4, and 74.1 , corresponded to the planes
FE-SEM analysis. As observed in Figure 3, the prepared
(111), (200), and (220), that corresponding to the face-cen-
tered cubic structure of copper (JCPDS-71-4610).[33] As Cu@Ag BNCs are spherical in shape and the particle size lay
observed, the four lines appearing at the positions 38.4, 44, within 21-27 nm.
64.7, and 77.6 corresponded to the planes (111), (200),
(220), and (311) with the FCC structure of silver (JCPDS- EDX spectra
04-0783).[34] Therefore, the X-ray diffraction patterns are
revealed that the Cu@Ag BNCs formed by the reduction of The results of EDX and EDX-mapping analysis for Cu@Ag
Cu2þ and Agþ ions to their lowest oxidation states. Thus, BNCs are shown in Figure 4. As shown in Figure 4a, the peak
XRD results confirmed the two-metal composite of copper at 3.0 KeV and the intense peak at 1.0 KeV are attributed to
and silver. silver and copper. The results of this analysis confirm the
 INORGANIC AND NANO-METAL CHEMISTRY 7

Figure 5. Photocatalytic activity of Cu@Ag BNCs at different ratios of Cu and Figure 6. Effect of the dosage Cu@Ag BNCs on photodegradation: MO (a) and
Ag for MO (a) and IC (b). IC (b).

Effect of Cu to Ag NPs ratios

presence of silver and copper elements in Cu@Ag BNCs with-
The evaluated for best photocatalytic loading with ratios of
out the presence of impurities. The atomic ratio percentages
(Cu0.90Ag0.10), (Cu0.92Ag0.08), (Cu0.94Ag0.06), and
of copper and silver are 88.45 and 11.55, respectively, repre-
(Cu0.96Ag0.04) were carried out. In photodegradation experi-
senting an approximately 9:1 ratio of copper and silver. As
ments for each of the dyes, 0.005 g of BNCs, an initial pH of
shown in the EDX-mapping image, a uniform distribution of
dye solution, room temperature, the dye of concentration of
copper and silver is observed in the BNCs.
10.0 mg/L, and 0.50 mL of hydrogen peroxide were utilized.
According to Figure 5, the photocatalytic activity varies as
Photocatalytic activity the percentage of silver and copper in the Cu@Ag BNCs
changes. The order of action of BNCs in the optical decom-
In this experiment, various parameters such as the percent-
position of both dyes is as follows:
age of copper/silver, the content of catalyst, and hydrogen
peroxide were optimized. Degradation of MO and IC dyes ðCu0:90 Ag0:10 Þ > ðCu0:96 Ag0:04 Þ < ðCu0:94 Ag0:06 Þ
under optimal conditions was then investigated. The solu-
< ðCu0:92 Ag0:08 Þ
tion of IC and MO in presence of H2O2 was decolorized for
about 180 min while dyes solution was decolorized in pres- As observed, Cu0.90Ag0. BNCs had the best performance
ence of H2O2 and catalyst after irradiation by visible light compared to other BNCs. In other words, a higher content
for about 40 min. of silver leads to higher photocatalytic performance, which
8 Z. KHEIBARIAN ET AL.

is by a study in this regard.[22] With the presence of silver

atoms in photocatalytic processes due to better electrical
conductivity and inhibition of electron-hole recombination,
silver causes better photocatalyst performance.

Effect of the amount of photocatalyst

After determining the appropriate photocatalyst, the next
parameter is to determine the dosage of the photocatalyst.
For this purpose, different values (0.0010, 0.0025, 0.0050 g)
were selected for the photocatalysts under the previous reac-
tion conditions. As displayed in Figure 6, by increasing the
dosage of catalyst from 0.0010 g to 0.0025 g, the degradation
percentage rose from 60.0% to 85.0% for MO and from
72.0% to 90.0% for IC. Also, upon increasing the dosage of
catalyst from 0.0025 g to 0.0050 g, the percentage of degrad-
ation in MO grew from 85.0% to 90.0% and in IC from
90.0% to 100.0%, with the degradation occurring completely.
Therefore, increasing the dosage of Cu@Ag BNCs are pro-
vided more active sites for the degradation. Thus, 0.0050 g
was selected as the optimal value.

Effect of H2O2 addition

Impact of hydrogen peroxide in the degradation of dyes
process, the content of hydrogen peroxide was varied from
0.10 mL to 0.50 mL while other parameters were kept con-
stant at optimum conditions (initial pH; 0.0050 g of
Cu@Ag BNCs).
According to Figure 7, the percent degradation of dyes
was increased with increasing the content of hydrogen per-
oxide from 0.10 mL to 0.50 mL. The highest percentage of
degradation was obtained at 0.50 mL of hydrogen peroxide.
The high degradation efficiency in the presence of hydrogen
peroxide molecules has acted as an electron trap due to the
presence of oxygenated water molecules. As a result, they
would react with electrons produced in the environment to Figure 7. Effect of the hydrogen peroxide content from 0.10- 0.50 mL on the
produce hydroxyl radicals. These radicals would react with degradation of MO (a) and IC (b).
the organic dye. Finally, the dyes are oxidized. Thus, they
enhance the percentage of dye degradation.[35]
The results obtained from this work have been compared Table 1. Comparison of different photocatalysts for dyes.
with other research reports and are shown in Table 1. Photocatalyst Dye Time (min) Degradation Ref.
In this study, Cu@Ag BNCs perform photocatalytic deg- Fe/Pd nanoparticles MO 6h 98.00% [4]
radation of dyes in less time and with a higher percentage. Fe-doped In2O3 MO 210 min 93.77% [36]
Fe3O4@SiO2@TiO2@Nd MO 90 min 79.2% [37]
ZnFe2-xLaxO4 MO 60 min 85 % [38]
Fe3O4 /RGO IC 60 min 100.00% [39]
Kinetics of degradation Cu@Ag BNCs IC 40 min 100.00% This work
Cu@Ag BNCs MO 40 min 90.00% This work
Generally, for determination of the photocatalytic degrad-
ation reaction rate on the concentration of organic pollu-
tants is used the Langmuir  Hinshelwood model.[10] Which relationship of Log (C=C0 Þ versus t that the correlation coef-
can be expressed as simplified into a pseudo-first-order ficient is 0.8809 in MO dye and 0.9852 in IC. The data
equation show that there is a better linear relationship for IC dye
than MO.
Log ðC=C0 Þ ¼  kt (2)
Where C0 (mg/L) is the initial concentrations of each dye
Proposed mechanism of photodegradation of dyes
before and C (mg/L) is the residual concentration of the dye
at time t (min). k (l/min) is the apparent rate constant in a Under the irradiation of light, the electrons are excited from
pseudo-first-order reaction. Figure 8 displays a linear the valence band of Cu to its conduction band, leaving holes
 INORGANIC AND NANO-METAL CHEMISTRY 9

in the valence band of Cu. The electron-hole pair can be BNCs were separated and washed after every cycle and dried
generated. The e- in the CB of Cu transfer to Ag NPs, the at 80  C for 5 h. The photodegradation time was found to be
Fermi level of the Ag NPs (E ¼ 0.8 eV). As shown in Figure increased slightly after each cycle that indicating the amount
9, the Ag NPs prevent the recombination of electron-hole of photocatalysts was lost during each cycle. Also, the active
pairs. Holes (hþ) can interact with water molecules and oxy- sites on the Cu@Ag BNCs after the reaction decreased. This
gen, hydroxyl radicals (OH), and anion superoxide radicals. exhibits that Cu@Ag BNCs are recyclable. Figure 11 shows
During this degradation, these reactive species react with the ability of the nanocomposite in the four cycles.
organic molecules and produce CO2 and water. The mech-
anism of photodegradation is shown in Figure 9.
Based on the obtained optimal conditions, the degradation of Conclusions
these two dyes was examined, with the results shown in Figure 10.
The Cu@Ag BNCs with different ratios of these two ele-
ments were prepared via the green method using citrus
Recyclability study paradisi peel extract as reducing and stabilizing agents. As-
synthesis Cu@Ag BNCs were identified by FTIR, XRD, FE-
Finally, the recycling stability of Cu@Ag BNCs in the photo- SEM, EDX, and EDX mapping analysis. FTIR confirmed the
degradation of dyes was investigated in four cycles. Cu@Ag functional groups of capping agents on the surface of
Cu@Ag BNCs. FE-SEM was indicated spherical shape BNCs.
In addition, the particle size estimated from the SEM images
was found to be in the range of 21 to 27 nm. Cu@Ag BNCs
performance was investigated in the degradation process of
MO and IC dyes under visible light irradiation. The percent-
age of copper/silver, the content of catalyst, and hydrogen
peroxide are the main factors that influence degradation
rates. Among the synthesized Cu@Ag BNCs with different
ratios of silver and copper, [email protected] BNCs revealed a
higher percentage of dye degradation. The optimized condi-
tions for removal of the dyes in the natural pH and 0.005 g
of photocatalyst [email protected] BNCs reached for degrad-
ation dyes MO and IC to 90.0% and 100% respectively. The
dyes degradation using [email protected] BNCs follows a
pseudo-first-order kinetic model and the rate of the degrad-
ation of IC is faster than MO. Therefore, the Cu@Ag BNCs
Figure 8. Relationships between Log ðC0 =CÞ and degradation time for kinetic synthesized from greener routes have been found to exhibit
data of MO and IC. excellent photocatalytic potential.

Figure 9. Diagram of the proposed mechanism of Cu@Ag BNCs.

10 Z. KHEIBARIAN ET AL.

Acknowledgments
We gratefully acknowledge financial and spiritual support from the
Shahrood University of Technology.

Conflict of interest
The authors declare that they have no conflict of interest.

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