Ceramics International 47 (2021) 30572–30583

Contents lists available at ScienceDirect

Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

One-pot synthesis of multifunctional graphitic carbon-metal oxide

nanocomposite for photocatalytic water purification and
supercapacitor applications
Edugulla Girija Shankar b, c, Sanjeev Billa b, d, A.B.V. Kiran Kumar a, b, *, Jae Su Yu c, **
a
Vijaya Lab, Buchireddypalem, Nellore District, Andhra Pradesh, 524305, India
b
Amity Institute of Nanotechnology, Amity University, Noida, U.P, 201313, India
c
Department of Electronics and Information Convergence Engineering, Institute for Wearable Convergence Electronics, Kyung Hee University, Yongin-si, Gyeonggi-do,
17104, Republic of Korea
d
Institute for Micro Manufacturing, Louisiana Tech University, Ruston, LA, USA, 71270

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

Keywords: Multifunctional nanomaterials are emerging as potential materials with a wide variety of applications. Herein,
Multifunctional nanocomposite we reported the one-pot facile synthesis of multifunctional graphitic carbon (gC)-CuO-ZnO nanocomposite for
Photocatalyst various applications of photocatalytic water purification, water disinfection, and supercapacitor electrode. The
Water disinfectant
prepared gC-CuO-ZnO nanocomposite was characterized using microscopic and X-ray analysis techniques. Pri­
Supercapacitor
marily, the synchrotron soft X-ray absorption spectroscopy studies were performed to investigate the internal
environment of the nanocomposite using O K-edge, C K-edge, Zn L-edge, and Cu L-edge. The energy bandgap of
the gC-CuO-ZnO nanocomposite was estimated to be 2.97 eV from the Tauc plot using ultraviolet–visible ab­
sorption spectra. In this regard, the prepared nanocomposite revealed excellent photocatalytic degradation
against pharmaceutical compound amoxicillin and clavulanate potassium tablet, textile industrial effluent, and
methylene blue dye under direct sunlight, indicating the efficiencies of 49 %, 89 %, and 97 %, respectively. Anti-
microbial studies were performed against multidrug-resistant Escherichia fergusonii (MDR) strain using the gC-
CuO-ZnO nanocomposites with different weight% of 1 %, 2 %, and 3 % and the obtained inhibition values
were 16, 17.3, and 17.3 mm, respectively. Also, the gC-CuO-ZnO nanocomposite was employed as an electrode
material of supercapacitors in energy storage applications. The gC-CuO-ZnO nanocomposite electrode exhibited
excellent electrochemical properties, exhibiting the specific capacitance of 1102 F g-1 at 1 A g-1. Consequently,
the heterojunction nanocomposite via a facile one-pot synthesis was successfully employed for degradation of
industrial effluents, toxicity against MDR bacteria, and an efficient supercapacitor electrode.

1. Introduction carbon absorption [3], air stripping [4], centrifugation [5], and floccu­
lation [6]. However, these purification techniques can only convert the
Water pollution is a major concern across the world because of the pollutants from one phase to another one, causing generation of sec­
increasing demand for textile, pharmaceutical, and dye industries. Ef­ ondary pollutants [7]. Among these techniques, photocatalytic water
fluents releasing from these industries contain azo dyes and volatile toxic purification has emerged as a novel, economical, eco-friendly, and effi­
organic compounds (TOC). The releasing of the following toxins into the cient technique to purify the TOC into safe byproducts and can also be
water can affect biological oxygen demand, chemical oxygen demand, used for industrial effluent treatment as this technique uses the solar
alkalinity, total dissolved solids, pH, and total hardness of the water body energy which is the most economical and abundant source of energy [8].
[1]. The removal of these TOC is extremely difficult due to their high The photocatalytic water purification technique uses an advanced
stability and solubility in water. Up to now, various purification tech­ oxidation process to generate reactive oxygen species (ROS) of hydoxyl
niques have been developed such as reverse osmosis [2], activated radical (OH.) and superoxide radical (O-2⋅) to degrade the TOC into safe

* Corresponding author. Vijaya Lab, Buchireddypalem, Nellore District, Andhra Pradesh, 524305, India.
** Corresponding author.
E-mail addresses: [email protected] (A.B.V.K. Kumar), [email protected] (J.S. Yu).

https://doi.org/10.1016/j.ceramint.2021.07.235
Received 29 May 2021; Received in revised form 23 July 2021; Accepted 24 July 2021
Available online 27 July 2021
0272-8842/© 2021 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
E.G. Shankar et al. Ceramics International 47 (2021) 30572–30583

by-products of CO2 and H2O [9]. Among many photocatalyst materials, 2. Experimental section
semiconducting metal oxides such as TiO2 and ZnO are the most studied
metal oxides due to their unique properties including thermodynamic 2.1. Materials and methods
stability, nontoxicity, tunable energy bandgap, and anti-microbial ac­ Polyvinyl pyrrolidone (PVP K30), zinc acetate dihydrate, urea, copper
tivity [10,11]. However, energy bandgap (3.32 eV) lies in the ultraviolet acetate monohydrate, absolute ethanol, and MB were purchased from
(UV) range which is 3–5% in the whole solar spectrum [12]. Thus, it is Sigma Aldrich Co. Beef extract, agar powder, sodium chloride, and
not suitable for visible light photocatalysis. To overcome this limitation, peptone were purchased from Thermo Fisher Scientific Co., India. Super-
researchers have focused on tuning the energy bandgap of ZnO by doping P, N-methyl-2-pyrrolidone (NMP), polyvinylidene fluoride (PVDF), and
using non-metals like C and N [13,14] and metals like Al, Cu, Fe, and Mn potassium hydroxide (KOH) were purchased from Daejung Chemicals
[15–18]. To enhance the sunlight photocatalytic efficiency, extensive Ltd., South Korea. TIF was collected from the Delhi NCR region, India,
research was focused on increasing the exciton lifetime by developing and the commercially available drug was used. Nickel (Ni) foam (thick­
nanocomposite materials [19]. Some of the reported nanocomposites are ness of 1.6 mm and porosity of 95 %) was purchased from MTI Korea,
ZnO/PMMA, RGO-ZnO, PANI-ZnO, g-C3N4-ZnO, N doped ZnO-graphitic South Korea. All the purchased reagents were of analytic grade and used
carbon (gC), CuO-ZnO, CuO-ZnO, and ZnO-CuO-RGO [20–28] which can without further purification for experiments. Further experiments were
be activated in solar light, but the heterojunction synthesis methods carried using distilled (DI) water.
include complicated synthesis process more than one step. In our present
study, we synthesized the gC-CuO-ZnO nanocomposite using a novel
2.2. Synthesis of gC-CuO-ZnO nanocomposites
facile one-pot pyrolysis synthesis method and studied the photocatalytic
The typical synthesis procedure was followed. Firstly, the 0.5 g, 12 g,
degradation against aqueous commercially available amoxicillin and
and 8 g of copper acetate monohydrate, urea, and zinc acetate dehy­
clavulanate potassium tablet (drug), textile industry effluent (TIF), and
drate, respectively were dissolved in 1:1 DI water and ethanol (100 ml
methylene blue (MB) under direct sunlight.
each) solution by sonication for 1 h. 1 g of PVP K30 was added to the
Besides TOC in dyes, textiles, and pharmaceutical industrial
obtained homogenously mixed solution, and the sonication was further
wastes, another cause of water pollution is the contamination of water
continued for next 30 min to make a concentrated slurry. The resulting
by microbes such as fungi, bacteria, viruses, and many more. The
slurry was ground for 30 min using a mortar pestle. Then, it was
presence of bacteria in drinking water causes dreadful diseases such as
transferred to an alumina crucible, heated at 100 ◦ C in an oven for
typhoid, cholera, and bacillary dysentery [29]. The generation of
overnight, and annealed at 500 ◦ C with a ramp rate of 5 C/min for 2 h in
◦

multidrug-resistant (MDR) strains is becoming a major problem due to

a muffle furnace. Finally, brown-colored material was obtained, named
the capability of attaining resistance to conventional synthetic water
as gC-CuO-ZnO nanocomposite, which was further utilized for charac­
disinfectants. In this regard, nano water disinfectants have emerged as
terizations and experiments.
novel antimicrobial agents due to their high surface-to-volume ratio
which increases the contact surface area of the bacteria with particle
and unique chemical and physical properties. From the past few years, 2.3. Characterization
copper and silver particles are known as antibacterial agents. In the
present scenario, particularly, ZnO nanoparticles are proven as good The crystallographic studies were done using Bruker Cu Kα (1.5405
antimicrobial agents due to their ability to release ROS causing the Å) at a scan rate of 3◦ per minute at 40 kV from 2θ = 20◦ to 80◦ . Surface
killing of bacteria [30]. Several reports showed that ZnO nanoparticles morphology and structures with elemental composition were studied
are efficient to inhibit the growth of Escherichia coli commonly found using a ZEISS scanning electron microscope (SEM) with Au coating at an
in urban wastewater, Staphylococcus aureus, and some of the MDR accelerating voltage of 10 kV and transmission electron microscope
strains [31–33]. Herein, the antimicrobial activity of the prepared (TEM, JEM 200CX, JEOL, Japan) equipped with energy dispersive X-ray
gC-CuO-ZnO nanocomposite has been studied against Escherichia fer­ (EDX) spectroscopy. Soft X-ray absorption spectroscopy (SXAS) studies
gusonii (MDR) strain which was collected from sewage water of the were performed in total electron yield (TEY) mode at Beamline 01,
Delhi NCR region. INDUS 2, RRCAT, India. X-ray photoelectron spectroscopy (XPS,
On the other hand, metal oxide-based supercapacitors have come to Thermo Multi-Lab 2000 system) was performed to study the chemical
light as the most promising energy storage devices [34]. Namely, composite. UV-2600 model Shimadzu UV–Vis–NIR spectrophotometer
supercapacitors are categorized as electric double-layer capacitor where was employed to perform UV-Vis diffusive reflectance studies from 200
energy is stored due to the electrostatic interaction between the elec­ to 800 nm. The electrochemical studies were performed using a three-
trode and electrolyte at the interface of double layer and pseudocapa­ electrode cell system with IviumStat electrochemical workstation
citor where charge storage occurs by redox chemical reactions at the (Ivium Technologies).
electrode surface [35–37]. Metal oxide electrode materials like ZnO,
Co3O4, Bi2O3, MnO2, etc., conducting polymers such as PANI (polyani­ 2.4. Photocatalytic activity
line) and polypyrrole, and carbon-based materials have emerged as the
most promising pseudocapacitor electrode materials [38–43]. However, The drug was extracted from the commercially available amoxicillin
slow redox reactions and specific surface area are some of the reported and clavulanate potassium tablet by Abbott Healthcare Pvt. Ltd. as
problems [44]. Here, efforts have been made to overcome the following discussed in our previous work [45]. The 2 ml of obtained 0.17 M drug
problems using heterojunction nanostructures. stock solution was added to 48 ml of DI water. TIF was collected from the
Multifunctional nanocomposites are emerging as potential materials textile industry in the Delhi NCR region, India, and used without further
for various applications due to their optical, electronic, and catalytic purification. 10 ppm MB solution was prepared. The above three solu­
properties. In this work, we prepared gC-CuO-ZnO nanocomposite and tions were used as a degradation solution.
its properties were investigated for applications in photocatalytic water The photocatalytic degradation efficiency of the prepared gC-CuO-
splitting for water purification by degrading dye and pharmaceutical ZnO nanocomposite was studied against the above-prepared drug, TIF,
industrial pollutants such as dye industrial effluent, MB, and drug. MB solutions under direct sunlight. 0.1 g of gC-CuO-ZnO nanocomposite
Escherichia fergusonii (MDR) bacterial strain inhibition for water disin­ was added to each solution. Initially, 3 ml of sample from each solution
fection and supercapacitor electrode material for energy storage were was collected before irradiating the sunlight and remaining samples
also studied. Moreover, the facile one-pot synthesis method and the were collected at the interval of 20 min from the next 100 min from each
proposed multifunctionality applications indicate the high commercial degradation solution. Next, UV–Vis spectrophotometer with a scan
ability of the prepared gC-CuO-ZnO nanocomposite. range of 200–800 nm was employed to analyze collect samples.

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2.5. Anti-microbial activity and the length was estimated as 14.2 μm. According to Sunaina et al., the
direct one-step thermal decomposition leads to the formation of mixed
The gram-negative bacteria, i.e., Escherichia fergusonii strain was structures. The thermal decomposition of zinc acetate releases the acetic
precultured by incubating it in Luria broth for overnight in a rotatory acid, leading to a decrease in the local pH at the reaction site, and at
shaker at 37 ◦ C. Then, nutrient agar media was poured into the three higher heating rates, released acetic acid evaporates fast due to almost
different Petri dishes under sterile conditions and allowed to solidify neutral pH maintained at the reaction site during calcination, which
them. The gC-CuO-ZnO nanocomposites with different concentrations of results in the formation of a mixture of structure [46]. In addition, TEM
1 %, 2 %, and 3 % were prepared in 1 ml of sterile DI water. Under sterile was performed to study the structural properties of the gC-CuO-ZnO
conditions, the 10 μl of 24 h culture of bacterial growth in Luria broth nanocomposite. Fig. 2(g) and (h) further verified the formation of
was spread on the solidified nutrient agar plate by a spread plate nanowires, nanoflakes, and nanoparticles. Fig. 2(i) depicts the selected
method. Wells were prepared in the solidified agar and the 25 μl of gC- area electron diffraction (SAED) pattern which shows the polycrystalline
CuO-ZnO nanocomposite of respective concentrations was poured in the nature of the prepared nanocomposite [47]. EDX elemental analysis was
respective wells of Escherichia fergusonii seeded plates. The assay anti­ performed to show the presence of constituting elements in the prepared
microbial plates were incubated at 37 ◦ C for 24 h. The diameters of nanocomposite. Fig. 2(j) depicts the EDX spectrum of gC-CuO-ZnO
inhibition zones of bacteria were measured in a millimeter range. nanocomposite which confirms the presence. The uniform distribution
of O, Cu, C, and Zn in the prepared nanocomposite can be observed from
Fig. 2(k)(i-iv) which further confirms the formation of the gC-CuO-ZnO
2.6. Electrochemical studies nanocomposite.
The phase purity and crystal structure of the as-prepared gC-CuO-
To prepare the working electrode, firstly, Ni foam pieces with 2 × 1 ZnO nanocomposite were analyzed using XRD studies. Fig. 3 shows the
cm2 were sonicated with the 1 M HCl solution to remove their oxide formation of hexagonal wurtzite phase ZnO. The XRD peaks of the gC-
layer. Then, the Ni foam was washed few times with DI water and dried CuO-ZnO nanocomposite were indexed according to the previous
with the N2 gas stream. The working electrode was fabricated by studies [48]. Furthermore, two significant peaks, i.e., (002) peak of
physically blending the 80 wt% of gC-CuO-ZnO nanocomposite material graphite at 26.5◦ with the d spacing of 0.3401 nm [49] and (200) peak of
with the 10 wt% of super P (conductive carbon black) and the 10 wt% of CuO at 38.75◦ [50], were observed in Fig. 3(d), indicating the presence
PVDF binder. This mixture was well ground using the mortar and pestle of gC and CuO in the synthesized nanocomposite. In some reports, urea
for about 30 min by adding appropriate volume of NMP solvent to make was used as a carbon source, leading to the formation of graphitic carbon
a homogenous slurry. Afterwards, the prepared mixture was coated on nitride (g-C3N4) while increasing the calcination temperature to 500 ◦ C
the cleaned Ni foam with an area of 1 × 1 cm2 and kept in a hot air oven and a peak for this can be observed around 27.3◦ in the XRD pattern
at 100 ◦ C for 3 h. The gC-CuO-ZnO nanocomposite material-coated Ni [51]. However, as shown in Fig. 3(d), a peak at 26.4◦ with the d spacing
foam electrode with a mass of 2.1 mg was considered as a working value of 0.3401 nm was exactly matched with the graphitic peak value.
electrode. Furthermore, the electrochemical properties such as cyclic This confirms the formation of a crystalline graphitic carbon structure.
voltammetry (CV), galvanostatic charge-discharge (GCD), and electro­ According to the well-known Bragg’s law (nλ = 2d sinθ), the lattice
chemical impedance spectroscopy (EIS) of the gC-CuO-ZnO nano­ parameters of a and c and the volume of the unit cell (V) were calculated
composite were measured in the three-electrode system using 1 M using the following formulae [52]:
aqueous KOH electrolyte at normal atmospheric conditions. For the
electrochemical measurements, the Ag/AgCl and Pt wire were used as a = λ /√3sinθ, c = λ /sinθ, V = 0.8660 x a2c (1)
reference and counter electrodes, respectively in the traditional three-
and the crystallite size (D) was calculated using the well-established
electrode beaker-type system.
Scherer’s formula (D = Kλ/(βhkl cosθ)), as listed in Table 1. From
Table 1, we can observe an increase in the d spacing for the prepared
3. Results and discussion
nanocomposite compared to the pure ZnO. This may be due to either
substitution or interstitial spacing of carbon atom into ZnO lattice,
Fig. 1 shows the schematic representation of the synthesis of the gC-
which causes lattice expansion. The increase in lattice constant “a” and
CuO-ZnO nanocomposite. The present investigation was designed to
“c” values when compared with the pure ZnO is ascribed to the substi­
synthesize the in-situ gC-CuO-ZnO nanocomposite using copper acetate
tution of carbon atoms by replacing the oxygen atoms in the ZnO crystal
monohydrate, zinc acetate dihydrate, urea, and PVP K30 by a facile py­
structure without disturbing the host because the ionic radius of C4−
rolysis method. The metal salts act as a source for the formation of metals
(0.260 nm) is considerably larger than that of O2− (0.140 nm) [53]. In
oxides, whereas the urea acts as a precursor for the formation of gC.
Fig. 3(c), a slight peak shift towards the lower values of 2θ for the
Fig. 2 shows the SEM images for the formation of nanostructures. The
gC-CuO-ZnO nanocomposite was observed when compared to the pure
SEM images clearly revealed the formation of three morphologies, i.e.,
ZnO nanoparticles, which indicates the substitutional doping of Cu in
nanowires, nanoflakes, and nanoparticles. The nanoparticles were
ZnO lattice. The ionic radius of Cu2+ (0.57 Å) is relatively lower than
spherical with the 50–100 nm size distribution. As shown in Fig. 2(e)
that of Zn2+ (0.60 Å), which is attributed to compressive strain, causing
and (f), the radius of the obtained nanowires was approximately 50 nm
a lowering of 2θ. This shows that Cu successfully replaced Zn without
changing the ZnO crystal structure. As shown in Fig. 3(c), the full width
at half maximum (FWHM) of peak increased with respect to the pure
ZnO nanoparticles, which is a clear evidence of the decrease in crys­
tallinity. The new phase in the XRD pattern at 2θ = 38.75◦ is ascribed to
the formation of CuO (111) clusters in the crystal lattice [50,54].
The K-edge SXAS is very sensitive to chemical bonding around the
ligand element. The electronic structure of O can be influenced by Zn, C,
and Cu content around the ligand environment. Fig. 3(e) displays the O
K-edge SXAS spectra of the pure ZnO and gC-CuO-ZnO nanocomposite.
So, the normalized O K-edge SXAS spectral variation can provide the
evidence regarding the electronic structure of O and the bonding nature
Fig. 1. Schematic representation for the synthesis of the gC-CuO-ZnO of O with Zn. The energy ranging from 530 to 550 eV is related to the
nanocomposite.

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Fig. 2. gC-CuO-ZnO nanocomposite: (a-f) SEM images at different magnifications, (g,h) TEM images, (i) SAED pattern, (j) EDX spectrum, and (k)(i-iv) elemental
mapping images of O, Cu, C, and Zn. Inset of (g,h) shows the magnified TEM images.

electronic transition of O from 1s to 2p. Peak A around 533 eV is states in gC-CuO-ZnO nanocomposite was less than that of pure ZnO.
attributed to the O 2p hybridization with Zn 3d4s/Cu 3d states, while The broadening of peak A was observed when compared with pure ZnO
the peak B at 537 eV corresponds to the non-dispersive O 2p states. The due to the oxygen defects. In other words, the peak was broader with a
peaks from 537 to 550 eV are ascribed to the O 2p hybridized with Zn higher concentration of the point defects in gC-CuO-ZnO [55]. Fig. 3(f)
4p/Cu 4sp states. From the O-K edge spectrum of the gC-CuO-ZnO shows the Zn L-edge SXAS spectra of the pure ZnO and gC-CuO-ZnO
nanocomposite, it is observable that the significant edge peak at 537 nanocomposite. Zn has a completely filled d-orbital, so the Zn SXAS
eV was slightly shifted by 0.44 eV towards the higher energy when spectrum between 1015 and 1035 eV is attributed to the electron tran­
compared with the pure ZnO, which is attributed to the replacement of O sition from O 2p to Zn 4s and 4d unoccupied levels [56]. The change in
with C [48]. The intensity variation can arise due to the structural the peak intensity is associated with the unoccupied density of states.
distortion of the ZnO structure caused by doping. The O K-edge spectral The Zn and O peak intensity variations clearly indicate that the peak
intensity of the gC-CuO-ZnO nanocomposite was reduced in comparison intensity of Zn corresponds to the covalent bonding of Zn-O and Zn-C.
with the pure ZnO. This means that the number of O 2p unoccupied This indicates the increase in the electron transfer from O 2p, C 2p,

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Fig. 3. Crystal phase study of both pure ZnO and gC-CuO-ZnO nanocomposite assessed by XRD patterns: (a) XRD pattern of the gC-CuO-ZnO nanocomposite, (b)
comparison of pure ZnO and gC-CuO-ZnO nanocomposite, (c) magnified (100), (002), and (101) peaks of pure ZnO and gC-CuO-ZnO nanocomposite, and (d)
magnified CuO and gC peaks of the gC-CuO-ZnO nanocomposite. SXAS spectra of the pure ZnO and gC-CuO-ZnO nanocomposite to study the chemical environment:
(e) O K-Edge, (f) Zn L-Edge, (g) C K-Edge, and (h) Cu L2,3-Edge. (i) UV–Vis absorbance spectrum. Inset in (i) shows the Tauc plot of the gC-CuO-ZnO nanocomposite.

in the energy range of 284–291 eV. The absorption peaks were assigned
Table 1
as A, B, C, and D at 284, 286, 287, and 291 eV, respectively. The ab­
XRD analysis of the pure ZnO and gC-CuO-ZnO nanocomposite.
sorption peaks A-C arise from the carbon π* transitions whereas the peak
Sample d (nm) FWHM, βhkl D (nm) a (Å) c (Å) V (Å3) D occurs from the σ* transitions. The peak A signifies the π* transitions.
(degree)
The peak B signifies the presence of a C=C ring structure corresponding
Pure ZnO 0.250 0.157 40.02 3.24 5.18 52.21 to the 1s-π* transition of aromatic/olefinic carbon. This attributes to the
gC-CuO- 0.251 0.447 21.32 3.25 5.20 52.94 transition of an electron from C 1s to unoccupied states of C=C π* [58].
ZnO
This further confirms the presence of gC in the prepared gC-CuO-ZnO
nanocomposite, as seen in the XRD pattern [58]. The peak C corre­
and Cu d states to Zn 4d states. It is theoretically proven that the O sponds to the 1s-π* transition of vinyl-keto (C = C-C = O). The peak D
K-edge and Zn L-edge SXAS spectra of ZnO are angle-dependent due to corresponds to the σ* C-C transition [48]. The as-prepared gC-CuO-ZnO
the existence of the bilayer σ bond and c-axis oriented π bond. The peak nanocomposite was brown in color. This preliminary color observation
A is attributed to the electron transition from the O 2p to Zn 3d level. is due to the formation of CuO and gC. Further XRD and SXAS studies
That is why it is very less sensitive. For the gC-CuO-ZnO nanocomposite, also confirmed the formation of CuO and gC. To verify the oxidation of
the energy shift of peaks A and B compared to the pure ZnO towards the Cu in the gC-CuO-ZnO nanocomposite, we performed the SXAS studies.
higher energy states indicates the increase in the energy of Zn valence Fig. 3(h) shows the Cu L3,2-edge SXAS spectrum corresponding to the
states, which contributes to the increase in the bond strength of Zn-O dipole transitions of Cu 2p 3/2 and Cu 2p1/2 electrons into the empty
with an increase in the C content [57] because O is more electronega­ d-states. The strong peaks at 933.2 and 953.3 eV correspond to CuO L3
tive than C. This also implies the substitution of C in the O sites. Fig. 3(g) and L2 edges, respectively which are due to the electronic transitions
shows the C K-edge SXAS spectrum of the gC-CuO-ZnO nanocomposite from Cu 2p3/2 (L3) and 2p1/2 (L2) into the empty d-states, respectively.
which provides the elemental mapping of C. The peaks in the spectrum Similar peaks may be observed whenever the core electron is excited to
emerge from the unoccupied π* and σ* states corresponding to the sp2 narrow d or f orbitals. The energy separation between L3 and L2 was
hybridized C orbitals. The SXAS spectrum exhibits four main absorptions 19.9 eV for the synthesized gC-CuO-ZnO nanocomposite, further con­
firming the formation of CuO phase (Cu: +2 valence state) in the

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gC-CuO-ZnO nanocomposite [59]. In addition, the XPS was performed of 529.58 eV corresponds to the Zn-O/Cu-O (M− O) bonds. The inter­
to study the electronic and chemical composition of the prepared mediate peak at 530.51 eV is attributed to the O2− ions that are oxygen
gC-CuO-ZnO nanocomposite and the resulting spectra are shown in deficient state. The peak at a higher binding energy of 531.78 eV cor­
Figure. S1. Figure S1(a) depicts the XPS survey scan spectrum of the responds to the OH- species present on the surface [60]. Thermal
prepared nanocomposite. The obtained spectra were gaussian fitted and decomposition of the urea acted as an N source, causing the doping of N
deconvoluted. Figure S1(b) shows the O 1s spectrum of the prepared in the prepared nanocomposite. Furthermore, Figure S1(c) shows the N
nanocomposite. Primarily, three peaks were obtained after deconvolu­ 1s spectrum which confirms the N doping in the nanocomposite. After
tion at 531.78, 530.51, and 529.58 eV. The peak at a low binding energy deconvolution, two peaks were mainly observed at 402.78 and 398.03

Fig. 4. UV–Vis degradation absorption spectra of (a) drug, (b) TIF, and (c) MB as a function of sunlight irradiation time (interval: 20 min). Photocatalytic efficiency
of the gC-CuO-ZnO nanocomposite: (d) Degradation percentage, (e) catalyst efficiency, and (f) pseudo-first-order kinetics of drug, TIF, and MB. (g) Proposed
photocatalytic degradation mechanism.

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eV. The peak at 398.03 eV is attributed to the anionic N in the N-Zn-O -ln(C/Co) = kt (5)
linkage bond. The peak at 402.7 eV corresponds to the surface species of
N-N and N-C [55]. Figure S1(d) shows the C spectrum. After deconvo­ where k is the rate constant (min-1), C0 represents initial concentration,
lution, three peaks were obtained at 284.3, 286.03, and 288.01 eV and C represents the concentration of the drug, TIF, and MB at different
which correspond to the sp2 carbon, epoxide, and carboxyl functional time intervals. The rate constant, k, was equal to the slope of the fitting
groups, respectively [56]. Figure S1(e) shows the Cu 2p spectrum which line. The k values for degradation of the drug, TIF, and MB were
indicates the existence of Cu in the two oxidation states of Cu2+ and determined to be 0.004, 0.022, and 0.035 min-1, respectively which are
Cu1+ in the prepared nanocomposite. After deconvolution, the six peaks comparable with literature values. These results suggest that the gC-
were observed. The four peaks at 932.30, 939.78, 952.504, and 960.67 CuO-ZnO nanocomposite can effectively degrade not only the MB in
eV correspond to Cu 2p1/2 and Cu 2p3/2 in CuO and the two peaks at lab conditions but also the complex structured commercially available
931.08 and 951.12 eV correspond to Cu 2p1/2 and Cu 2p3/2 in Cu2O amoxicillin and clavulanate potassium drug and TOC molecules present
[57]. Figure S1(f) depicts the Zn 2p spectrum and two peaks were mainly in TIF. The developed technology can be readily transferred to the in­
observed at 1043.72 and 1020.69 eV which correspond to Zn 2p1/2 and dustry for the degradation of TOC in pharmaceutical and textile indus­
Zn 2p3/2, respectively [58]. Following results confirm the presence of O, trial effluents. Doping and formation of the composite is the best method
N, C, Cu, and Zn in the prepared gC-CuO-ZnO nanocomposite. Fig. 3(i) to increase the efficiency of the photocatalyst under sunlight. The
shows the absorbance spectrum of the gC-CuO-ZnO nanocomposite. incorporation of C and Cu energy levels in the crystal lattice of ZnO
Primarily, three peaks were observed at 208, 254, and 367 nm corre­ occurs in two ways that are either substitutional or interstitial spaces. In
sponding to the gC, CuO, and ZnO, respectively [48,61,62]. This con­ substitutional doping, the C replaces the O atom and also occupies the O
firms the presence of gC, CuO, and ZnO in the prepared nanocomposite, vacancies. At the same time, the Cu atom can replace the Zn2+ ions in the
which also coincides with the XRD and SXAS results. The energy lattice. However, the interstitial doping process was also possible by the
bandgap (Eg) of the gC-CuO-ZnO nanocomposite was calculated using formation of clusters. Fig. 4(g) shows the proposed photocatalytic
the Tauc plot. It is well known that ZnO is a proven direct bandgap degradation mechanism of the gC-CuO-ZnO nanocomposite. According
semiconductor [63]. Using UV–visible absorbance spectrum of the to molecular orbital theory, the interaction of 2p orbitals of O with 4s
gC-CuO-ZnO nanocomposite, the Tauc plot can be illustrated using the and 3d orbitals of Zn forms Zn-O bonding. In the case of substitutional
following equation: doping, the C will replace the O atom in the ZnO lattice structure which
(αhν)2 = c(hν- Eg) (2) leads to the interaction of the 2p orbitals of the C with Zn 4s and 3d
orbitals. In other words, the doping of Cu and C in the ZnO structure
where α represents the absorption coefficient, h is Planck’s constant, and leads to the generation of the new energy levels, so these introduced sub-
ν is the frequency of light. The inset of Fig. 3(i) shows the Tauc plot energy levels will activate material in sunlight. This was also confirmed
graph, plotted between (αhυ)2 and hν(eV) using the above-mentioned from bandgap calculations [48]. The doping of Cu will induce a new
equation. The extrapolation of the linear part in the graph gives the energy level below the conduction band and the C doping introduces a
energy bandgap value. The calculated energy bandgap value for the gC- new sub energy level above the valence band of pure ZnO. These new
CuO-ZnO nanocomposite was 2.97 eV. As expected, the energy bandgap sub-energy levels cause an increase in the charge separation efficiency
of gC-CuO-ZnO nanocomposite shifted towards the lower values by transferring photoexcited electrons from the valence band to the
compared to pure ZnO (3.13 eV), which further confirms the doping of C conduction band to metastable states that occurred due to the incor­
and Cu in the ZnO structure [64]. Further decrease in the energy porated impurities. This increases the charge separation efficiency. In
bandgap enhances the sunlight activation of the gC-CuO-ZnO nano­ addition, the Schottky barrier was formed at the interface of the
composite for photocatalytic activity. ZnO/gC. As ZnO is an n-type semiconductor, the photoexcited electron
Fig. 4(a), (b), and (c) shows the UV–Vis degradation absorption in the conduction band will move freely to the gC which acts as an
spectra of the gC-CuO-ZnO nanocomposite for drug, TIF, and MB, electron scavenger [66]. Electron-hole pair is generated when direct
respectively. The absorption peaks at 227 nm and 664 nm correspond to sunlight is irradiated on the compound in the water, leading to the
the drug and MB, respectively [45,65]. From all the absorbance spectra, diffusion of the electrons to the surface of the catalyst. The diffused
it can be observed that the absorbance intensity gradually decreased electrons react with dissolved oxygen molecules in the water to yield
with the increase of sunlight irradiation time. Furthermore, the absor­ superoxide radical ions. Simultaneously, the generated holes at the
bance peak position remains unchanged, implying that the prepared valence band diffuse onto the surface of the catalyst, thus resulting in the
gC-CuO-ZnO nanocomposite efficiently degraded the drug, TIF, and MB formation of OH. radicals from H2O. The highly reactive nature of the
under direct sunlight. The degradation percentage, catalyst efficiency, hydroxyl radical results in the degradation of the TOC in an aqueous
and rate of reaction were calculated from absorption intensity (con­ solution of the drug, TIF, and MB upon reacting. When the sunlight of
centration vs. time) using Eqs. (3)–(5), respectively, where C0 is the the required intensity is irradiated on the gC-CuO-ZnO nanocomposite,
initial concentration and Ct is the concentration at time t. Fig. 4(d) electron-hole pairs are generated. Holes in the valence band break down
shows the degradation percentage trend by the prepared gC-CuO-ZnO the H2O molecule into H+ and OH.. The OH. radicals have an oxidation
nanocomposite. The 49 % for drug, 89 % for TIF, and 97 % of MB potential of 2.80 V, which leads to the oxidation of TOC in the aqueous
were degraded in 100 min under direct sunlight. A comparison of tar­ medium into safe by-products of CO2 and H2O. Further O2 atom near
geted pollutants, pollutant concentration, light source, catalyst loading, conduction band is reduced to O-2⋅ by accepting electron in the con­
and degradation efficiency is shown in Table S1. The catalyst efficiency duction band which additionally enhances the exciton lifetime [28,45].
of the gC-CuO-ZnO nanocomposite is shown in Fig. 4(e). From the graph,
we can clearly observe that the function of time efficiency of the catalyst gC-CuO-ZnO + hν→e- (CB) + h+ (VB) (6)
tends to increase. e −
+ O2 →O−2 ⋅ (7)
Degradation percentage % = (C/Co) x 100 (3)
h+ + H2O→OH⋅+ H+ (8)
Degradation efficiency % (etha) =(1- (C/Co)) x 100 (4)
O−2 ⋅ +H +
→HO⋅2 (9)
As shown in Fig. 4(f), to understand the degradation efficiency of gC-
CuO-ZnO nanocomposite, the degradation results were fitted to a
⋅
OHad + Toxic organic compunds→Degradation(CO2 + H2 O) (10)
pseudo-first-order kinetics equation:
HO⋅2 + Toxic organic compunds→Degradation(CO2 + H2 O) (11)

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Agar well diffusion method with different load percentages (W/V) Table 2
of the gC-CuO-ZnO nanocomposite was carried out to analyze the Different load percentages of inhibition zone shown by the gC-CuO-ZnO nano­
resistance pattern of the prepared sample (gC-CuO-ZnO nano­ composite against Escherichia fergusonii strain.
composite) against Escherichia fergusonii strain; rod-shaped gram- Loading percentage Well 1 (mm) Well 2 (mm) Well 3 (mm) Average
negative bacterium commonly found in human blood samples. Fig. 5 1% 17 15 16 16
(a), (b), and (c) shows the inhibition zone against Escherichia fergus 2% 17 17 18 17.3
onii strain using different percentages (1 %, 2 %, and 3 %) of gC-CuO- 3% 17 17 18 17.3
ZnO nanocomposite loaded in different plates, respectively. Three
wells were made for each percentage and the average was calculated.
pathways are as follows. First, the direct physical contact of
Table 2 shows the growth inhibition zone for different load percent­
gC-CuO-ZnO nanocomposite with bacterial disrupts the lipid bilayer
ages of the gC-CuO-ZnO nanocomposite. From Table 2, we can clearly
cell membrane of the bacteria [69]. Second, the release of Zn2+ and
observe that there was an increase in the growth inhibition zone by
Cu2+ affects the metabolism of the amino acids, causing a disturbance
1.33 mm on increasing the gC-CuO-ZnO nanocomposite percentage
to enzyme action in bacterial cells [70,71]. Furthermore, gC enhances
from 1 % to 2 %. However, no change in the growth inhibition zone
the adsorption of the bacteria on the nanocomposite surface, leading to
was observed with increasing the prepared nanocomposite concen­
an increase in the prepared nanocomposite-bacteria contact [72].
tration from 2 % to 3 %. This may be due to the use of nearby con­
Third, ZnO and CuO-generated ROS is a major cause of gC-CuO-ZnO
centration values of the prepared nanocomposite for the experiment.
toxicity against bacteria. The generation of ROS species is directly
The following results confirm that the gC-CuO-ZnO nanocomposite
proportional to surface defects [68]. The release of ROS such as hy­
successfully inhibited the growth of Escherichia fergusonii bacterial
droxyl ions, O-2⋅, and H2O2 damages DNA, proteins, and lipids in bac­
strain experimentally. According to the previously published reports,
terial cells, which causes the killing of bacteria [73–81]. The bacterial
the anti-microbial activity of the nanomaterial is dependent on factors
inhibition efficiency of the prepared gC-CuO-ZnO nanocomposite is
like ROS species generation, particle size, shape, crystallinity, shape,
compared with the previous publication, as shown in Table S2. The
surface charge, soluble ions generation, and defects [67,68]. The above
surface reactions are followed as:
XRD and SXAS results confirm the presence of CuO, ZnO, and gC in the
prepared nanocomposite concerning that Fig. 5(d) shows the possible gC-CuO-ZnO + hν→e- (CB) + h+ (VB) (12)
anti-microbial activity mechanism against Escherichia fergusonii strain
for the prepared gC-CuO-ZnO nanocomposite. The possible three e −
+ O2 →O−2 ⋅ (13)

Fig. 5. Inhibition of Escherichia fergusonii strain with different percentages of the gC-CuO-ZnO nanocomposite: (a) 1 %, (b) 2 %, and (c) 3 %. (d) Proposed anti-
microbial activity mechanism of the prepared gC-CuO-ZnO nanocomposite against Escherichia fergusonii strain.

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(F g-1) values of the prepared electrode material were 1102, 915, 842,
h+ + H2O→OH⋅ + H+ (14)
700, 532, and 452 F g-1 at current densities of 1, 1.5, 2, 3, 5, and 7 A g-1,
⋅
O2 + H + →OH2⋅ (15) respectively. Here, the specific capacitance values decreased somewhat
with increasing the current density, revealing the good rate capability of
OH2⋅ + H + + e− →H2 O2 (16) the gC-CuO-ZnO material. The EIS analysis was used to observe the
electrochemical impedance behavior of the synthesized gC-CuO-ZnO
Moreover, Cu is a known and proven antimicrobial agent used from the electrode material. After that, the charge-transfer kinetic of the pre­
past few decades. Cu nanoparticle increases the surface contact of pared material was further revealed by the Nyquist plot. Fig. 6(d) shows
bacteria with particles. The presence of the Cu nanoparticle in the the Nyquist plot of the electrode material in the frequency range of 0.01
prepared composite further enhanced the antimicrobial properties of Hz–100 kHz. The observed Rct value of 1.16 Ω revealed the low charge
the gC-CuO-ZnO nanocomposite [82]. resistance and excellent electrochemical conductivity of the gC-CuO-
The prepared gC-CuO-ZnO nanocomposite was also tested for ZnO electrode material. The specific capacitance value of the prepared
electrochemical properties as an electrode of supercapacitors in energy nanocomposite was compared with previous publications, as shown in
storage applications. Fig. 6(a) depicts the CV curves of gC-CuO-ZnO Table S3. The gC-CuO-ZnO nanocomposite is expected to be a good
nanocomposite electrode at different scan rates from 5 to 80 mV s-1 electrode material for supercapacitors applications. Consequently, the
in the potential range of 0–0.48 V. With increasing the scan rate, the above results suggest that the prepared gC-CuO-ZnO nanocomposite is a
redox peak behavior steadily increased, revealing the good reversibility multifunctional nanomaterial having potential applications in photo­
of the electrode material and excellent rate capability. These observed catalytic water purification, water disinfection, and supercapacitor
oxidation states in the CV curves exhibit the utilization of various electrode.
oxidation states of the elements in the electrode material. Furthermore,
at high scan rates, peak shift was observed in the CV curves, which may 4. Conclusions
be due to sluggish charge transfer reaction and solution resistance [83].
The outline of the CV curves purely indicates a pseudocapacitive The one-pot multifunctional gC-CuO-ZnO nanocomposite was suc­
behavior due to the electrochemical reactions. Fig. 6(b) reveals the GCD cessfully synthesized via a pyrolysis method. The prepared gC-CuO-ZnO
curves of the prepared electrode material at different current densities nanocomposite was investigated for photocatalytic water purification,
with a potential range of 0–0.48 V. It is clear that the shapes of GCD water disinfection, and supercapacitor electrode applications. PVP K30
curves were non-linear at different current density values. The specific acted as a soft template for forming various morphologies such as
capacitance (Cs) values of the electrode material can be calculated nanoparticles, nanowires, and nanoflakes. XRD and SXAS studies clearly
using the following equation [84]: explained the crystal structure of the gC-CuO-ZnO nanocomposite. By
incorporating the extra energy levels in ZnO by doping C and Cu, the
Cs= (I x Δt)/(m x ΔV) (17)
energy bandgap of gC-CuO-ZnO nanocomposite was reduced to 2.97 eV.
In the above equation, I is the discharge current (A), Δt is the discharge The prepared gC-CuO-ZnO nanocomposite exhibited outstanding pho­
time (s), and m and ΔV indicate the mass (g) and potential range (V) of tocatalytic degradation efficiency for 49 % of the drug, 89 % of TIF, and
the electrode material, respectively. The corresponding specific capac­ 97 % of MB under direct solar light. The nanocomposite gave a com­
itance values are shown in Fig. 6(c). The delivered specific capacitance parable inhibition zone against Escherichia fergusonii strain for different

Fig. 6. Electrochemical results of the prepared gC-CuO-ZnO nanocomposite: (a) CV curves at various scan rates from 5 to 80 mV s-1. (b) GCD curves at different
current densities from 1 to 7 A g-1 under the fixed potential window of 0–0.48 V. (c) Specific capacitance at different current densities and (d) Nyquist plot in the
frequency range of 0.01 Hz–100 kHz. Inset of (d) shows the photographic image of electrochemical working cell setup.

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E.G. Shankar et al. Ceramics International 47 (2021) 30572–30583

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[18] R. Saleh, N.F. Djaja, UV light photocatalytic degradation of organic dyes with Fe-
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interests or personal relationships that could have appeared to influence [19] Z. Zeng, X. Quan, H. Yu, S. Chen, Y. Zhang, H. Zhao, S. Zhang, Carbon nitride with
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synthesis of rGO-ZnO nanocomposite for demonstration of sunlight driven
This work was supported by the UGC-DAE Consortium for Scien­ enhanced photocatalytic and self-cleaning of organic dyes and tea stains of cotton
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tific research project with reference number CSR-IC-BL-48/CRS-165/
jhazmat.2018.07.103.
2016-17/829 & 2017-18/786 and National Research Foundation of [21] V. Eskizeybek, F. Sari, H. Gülce, A. Gülce, A. Avci, Preparation of the new
Korea (NRF) grant funded by the Korean government (MSIP) (No. polyaniline/ZnO nanocomposite and its photocatalytic activity for degradation of
2018R1A6A1A03025708 and No.2020R1A2B5B01002318). methylene blue and malachite green dyes under UV and natural sun lights
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Babu, K. Sethurman, K. Ramamurthi, Investigation on the g-C3N4 encapsulated
ZnO nanorods heterojunction coupled with GO for effective photocatalytic activity
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