j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 1 ; 1 1 : 9 7 0 e9 8 1

Available online at www.sciencedirect.com

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

Original Article

Enhanced photocatalytic efficiency of

hydrothermally synthesized g-C3N4/NiO
heterostructure for mineralization of malachite
green dye

Suresh Kumar Pandey a, Manish Kumar Tripathi a, V. Ramanathan a,

Pradeep Kumar Mishra b, Dhanesh Tiwary a,*
a
Department of Chemistry, Indian Institute of Technology (Banaras Hindu University), Varanasi, 221005, India
b
Department of Chemical Engineering and Technology, Indian Institute of Technology (Banaras Hindu University),
Varanasi, 221005, India

article info abstract

Article history: In this article, the photocatalytic performance of the heterostructure g-C3N4/NiO for the
Received 29 July 2020 mineralization of the malachite green (MG) dye under the exposure of the UV light in an
Accepted 16 January 2021 aqueous medium was characterized. The first part of the study was devoted to the syn-
Available online 29 January 2021 thesis of the heterostructured nanocomposite by single-step hydrothermal process
accompanied by calcination. Physical and chemical behaviour of the synthesized photo-
Keywords: catalyst was examined by a high-resolution powder X-ray diffraction (XRD), Fourier
Photocatalysis transform infrared (FT-IR), Transmission electron microscope (TEM), Field emission scan-
Nanocomposite ning electron microscope (FESEM), BrunauereEmmetteTeller (BET), X-ray photoelectron
Heterojunction spectroscopy (XPS), and ultravioletevisible diffuse reflectance spectroscopy (UVevis DRS)
Mesoporous measurements. TEM and XRD measurements confirms the formation of the hetero-
Exciton structured hexagonal shaped g-C3N4/NiO. The structural stability of the nanocomposite
photocatalyst was analysed by XRD measurment after the recyclability test. XPS analysis
disclosed the oxidation state of the nickel (Niþ2) into the photocatalyst. The superiority of
our synthesized catalyst is that the better optical band gap matching and the fact that it
regulates internal charge transfer of excitons within the heterojunction. Second part of the
study focused on the degradation of the MG with nanocomposite g-C3N4/NiO. Scavenger
analysis revealed the existence of the superoxide radicals (O-
2 ) as the main active species,

which is the caretaker of mineralization of the MG with the nanocomposite that have one
of the highest turn over frequency (TOF) till date.
© 2021 The Authors. Published by Elsevier B.V. This is an open access article under the CC
BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

* Corresponding author.
E-mail address: dtiwari.apc@itbhu.ac.in (D. Tiwary).
https://doi.org/10.1016/j.jmrt.2021.01.059
2238-7854/© 2021 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://
creativecommons.org/licenses/by-nc-nd/4.0/).
 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 1 ; 1 1 : 9 7 0 e9 8 1
1. Introduction
In the present scenario, the contamination of the water
stream is one of the critical problems of the world, mainly due
to the growing population and disposal of wastes from the
elaboration of textiles as well as chemical industries. A syn-
thetic dying agent employed in these industries is a major
responsible for pollution of the environment because it is non-
biodegradable and having great toxicity towards both flora
and fauna. MG is a green-colored, tri-phenylmethane dye that
is used in encompassing manner in food, leather, silk, textile
industries as an additive and as a dying agent because of its
disinfectant and antibacterial nature [1e3]. However, since
the 1990s, it is found that MG and leucomalachite green
(reduced form of malachite green) has carcinogenic, muta-
genic, and genotoxic effects on living beings [4,5]. Henceforth
it is required to evolve some emphatic techniques for the
removal of such types of hazardous organic recalcitrants from
the water stream. Several methods are used for expulsion of
toxic materials from wastewater like biological treatment [6],
adsorption [7] process, and heterogeneous semiconductor
photocatalysis [8e12]. Among these methods, semiconductor
heterogeneous photocatalysis is one of the efficient methods
for degradation of harmful organic wastes into CO2 and H2O,
and it may occur in the presence of sunlight, which is eco-
friendly and renewable energy source [12,13]. From last
several decads, heterogeneous semiconductor photocatalyst
like TiO2, WO3, CuO, ZnO, Cu2S, SnO2, and NiO have drawn the
researchers attention because of their higher photocatalytic
efficiency as well as stability, less toxicity, reusability, cost-
effective and mainly, due to high capability towards the
degradation of toxic organic wastes into harmless com-
pounds, i.e., CO2, H2O [14e21]. In the process of wastewater
remediation, NiO also has been used as a good adsorbent and
shows better adsorption efficiency in comparison to CuO,
Y-Al2O3, and several other metal oxides towards the adsorp-
tion of organic dyes [22e24].
The particle size and bandgaps of the synthesized photo-
catalyst have a major role in their photocatalytic perfor-
mance. Pure NiO displays the properties of p-type
Fig. 1 e The pictorial representation for the synthesis of SK-3 nanocomposite.
971
semiconductor material and having an extensive optical
bandgap, which is responsible for the fast recombination of
the photogenerated excitons, consequentially, it shows poor
photocatalytic activity [9]. To accomplish such problems,
recently, an organic metal-free moiety n-type g-C3N4 semi-
conductor with a bandgap of 2.70 eV is a promising candidate
because of its low cost, high performance, nontoxicity, and
spectacular optical properties. NiO and g-C3N4 give a potent
pen junction, which enhances the photocatalytic perfor-
mance of the heterostructure. During this process, the inter-
nal electric field of the heterostructure helps to achieve the
proper bandgap, consequently, decrease the rate of recombi-
nation of photogenerated electroneholes. There is very few
reports on the photocatalytic applications of the hetero-
structured g-C3N4/NiO nanocomposite [25,26]. There are other
reports in which g-C3N4 used as a dopant with nickel based
materials that displays an efficient photocatalytic perfor-
mance [27].
In the present article, we synthesized novel hexagonal-
shaped nano heterojunction of n-type g-C3N4 (10 wt %) with
p-type semiconductor NiO through hydrothermal deposition
route followed by the calcination process. The synthesized
heterojunction, g-C3N4/NiO, displays efficient photocatalytic
activity with much higher TOF than previous studies. As
synthesized nanocomposites also facilitate efficient charge
separation between photogenerated excitons, which makes g-
C3N4/NiO a superior nanocomposite for MG dye degradation.
The mechanism for the superiority of our synthesized catalyst
could be endorsed with the proper optical bandgap and fine
internal transfer of charge carriers within the pen junction in
the presence of UV light.
2. Materials and methods
2.1. Materials
All the required chemicals such as Nickel nitrate hexahydrate
(Ni(NO3)2.6H2O) (Sigma Aldrich), sodium citrate tribasic dihy-
drate (Merck), ethyl alcohol (Merck), malachite green (Sigma
Aldrich), and melamine (Alfa Aesar) were acquired are of
972 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 1 ; 1 1 : 9 7 0 e9 8 1
analytical reagents (AR) grade and used without any further
purification.
2.2. Synthesis of g-C3N4
g-C3N4 (SK-1) was synthesized by the thermal condensation
method by using melamine as a precursor. 10 g of melamine
was placed in an alumina crucible and put it into a muffle
furnace at 550  C temperature for 4 h with a ramp rate of 10  C
per minute. The obtained yellow color material was further
washed numerous times with ethyl alcohol and double-
distilled water to remove the impurities from the precipitate.
Finally, g-C3N4 was collected by the centrifugation method
and placed for drying into a vacuum oven at 60  C (Fig. 1).
2.3. Synthesis protocol of g-C3N4/NiO composite
g-C3N4 (195 mg) was redispersed in 30 mL ethyl alcohol, fol-
lowed by sonication for 1 h. Hereafter, 0.22 M of Ni(NO3)2$6H2O
was mixed with vigorous stirring. At that time, a 0.4 M sodium
citrate solution was also added to the reaction mixture. Then,
the mixed solution was allowed to transfer into the autoclave
and placed into the oven for 12 h at 180  C. After that, the
autoclave was further cooled at room temperature. The ob-
tained sample was centrifuged and washed properly with
ethyl alcohol and double-distilled water to fixed the impurities
from the sample. The resulting nanocomposites were desic-
cated in a vacuum oven at 65  C. The nanocomposite was
further transferred into an uncovered crucible of alumina and
calcined in a muffle furnace at 500  C temperature for 3 h. The
found g-C3N4/NiO (SK-3) heterostructure nanocomposite was
grinding for 5 min. Similar protocols were followed for the
synthesis of pure NiO (SK-2) nanoparticle without using g-
C3N4 (Fig. 1).
3. Characterization
The crystalline faces of the synthesized samples were
analyzed by normalized high-resolution X-ray diffraction (HR-
Fig. 2 e (a) HR-XRD Pattern of SK1, SK2, and SK3 (b) FT-IR spectra of SK1, SK2, and SK3 samples.
XRD) pattern using Rigaku Smart Lab 9 kW (with Cu Ka radi-
ation, l ¼ 1.54

A). Fourier transformed infrared spectra (FT-IR)
were run in between 4000 and 400 cm1 for the functional
group analysis. TEM (Tec. G2 20 TWIN) and FE-SEM (Nova N.
SEM 450) were used to analyzed particle size and the Surface
analysis of nanocomposites. Pore volume and Specific Surface
area of samples were determined by the Bru-
nauereEmmetteTeller (BET) analysis. Elemental analysis was
performed by the X-ray photoelectron spectroscopy (XPS), and
bandgap calculation of the synthesized sample was done by
ultravioletevisible diffuse reflectance spectroscopy (UVevis
DRS).
3.1. Photocatalytic efficiency
Photocatalytic efficiency of g-C3N4 (SK-1) pure NiO (SK-2) and
g-C3N4/NiO (SK-3) were explored through the photocatalytic
mineralization of MG under UV light irradiation (254 nm,
Phillips, 8 W). 10 mg of catalysts were redispersed in 100 mL
aqueous solution of MG (2.76  105 mol/L) dye, and then the
reaction mixture was further irradiated by UV light (light
source). The whole reaction was performed in a 1 cm path
length quartz cuvette and recorded by the UVeVis spectro-
photometer. The change of the absorbance MG dye with the
time indicates the degradation process of MG. The percentage
of degradation of MG was investigated by using [28].
A0  At C0  Ct
% Degradation ¼  100 ¼  100 (1)
A0 C0
In the above equation, A0 and At are the initial and final
absorbance of MG, respectively, while C0 represents the initial
concentration and Ct shows the MG concentration after the
degradation.
4. Results and discussion
4.1. HR-XRD
HR-XRD patterns of the prepared sample (SK-1, SK-2, and SK-
3) are shown in Fig. 2a. SK-1 recorded two broad peaks at 2q
 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 1 ; 1 1 : 9 7 0 e9 8 1
Fig. 3 e TEM images of (a) SK-2 (b) SK-3 and SAED (inset) (c) histogram of the average size of SK-2 (d) the average size of SK-3.
values 13.07 and 27.47 , which is indexed at [100] and [002]
plane, respectively (JCPDS no. 87-1526). Broad peaks are an
indicator of the poor crystallinity and small thickness of the
samples. SK-2 shows sharp peaks at 2q values 37.19 , 43.32 ,
62.84 , 75.31 , and 79.35 are obtained (JCPDS Card no. 04-0835)
corresponding to the plane [111], [200], [220], [311], and [222]
respectively. Here sharpness of peak visualizes the crystal-
linity of the sample. The formation of the heterostructure of
NiO with C3N4 (10 wt. %) is confirmed by the presence of the
peaks for both NiO and C3N4 in SK-3 nanocomposites.
4.2. FT-IR analysis
The samples were characterized through FT-IR for the func-
tional group analysis and the type of vibrations present in the
molecules, the result is displayed in Fig. 2b. In the case of the
SK1 appearance of intense band at 1200-1650 cm1 is mainly
due to the aromatic stretching of CeN and C]N heterocycles.
Apart from that, the vibration band at 816 cm1 is due to the
bending frequency of triazine rings [29,30]. In the case of the
SK-2 sample, at 425 cm1, a broad vibration band is recorded,
which is responsible for the stretching vibration between the
NieO bond [31]. All the band of SK-2 are also recorded in the
case of SK-3, but the absorption band appear at 425 cm1 in
SK-2 is slightly shift at 434 cm1, which shows the interaction
of the triazine ring of g-C3N4 with NiO by electrostatic inter-
action [31]. The absorption band around 1450 cm1 is due to
carbonate, and the band area at 3200-3500 cm1 is corre-
sponding to the vibrational stretching frequency of the OeH
973
bond, which comes out due to unavoidable moisture absor-
bed by the sample from the atmosphere [32].
4.3. Morphology measurements
4.3.1. TEM and FE-SEM
The morphological properties of the nanoparticles were
determined by TEM micrographs. Fig. 3a demonstrates that
most of the particles of SK-2 are spherical nanodiscs type with
an average size is approx 35-40 nm (Fig. 3c). The correspond-
ing SAED pattern shows the polycrystalline nature of SK-2,
inset in Fig. 3a. The TEM micrograph of SK-3 (Fig. 3b) dis-
plays the hexagonal nanostructure of NiO is decorated with a
g-C3N4 lamellar structure. For this, the SAED pattern is given
in the inset of Fig. 3b, which indicates the crystalline proper-
ties of the composite because of the higher amount of the NiO
component. The average diameter for heterostructure is
shown in the histogram of Fig. 3d, which is found to be
25e30 nm. HR-TEM image of SK-3 is also given in the Fig. SI-1,
which validate the formation of the heterostructured nano-
composite. The particle size of composites is in good agree-
ment with the XRD’s crystallite size, which was found with
the help of Scherer’s equation. The SAED and XRD result from
both of them having a good agreement, and they confirm the
formation of SK-3 heterostructure through our designed
scheme for its synthesis. Fig. 4a displays the FE-SEM image of
SK-2, which depicts that the particles are slightly spherical,
having small pores on its surface. The surface morphology
and EDS spectrum of SK-3 is displayed in Fig. 4b, c, from the
974 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 1 ; 1 1 : 9 7 0 e9 8 1

Fig. 4 e FE-SEM images of (a) SK-2 (b) SK-3 (c) EDS image of SK-3.

figure, it is seen that spherical nanoparticles of NiO with a
diameter between 25 and 35 nm are placed on the sheet-like
surface of g-C3N4. Just like pure NiO, many tiny pores are
also existing on the surface of SK-3, which provides space for
adsorption of MG. The EDS spectrum confirms the presence of
all the elements present in SK-3.
4.3.2. BET
The mesoporosity and specific surface area of the synthesized
samples SK-2 and SK-3 were analyzed by N2
adsorptionedesorption isotherm and BET. The results of N2
adsorptionedesorption in Fig. 5a and b clearly shows a hys-
teresis loop of type IV pattern, which confirms the meso-
porous nature of SK-2 and SK-3. The specific surface area was
calculated with the help of the BET equation, and it was 14 and
22 m2/g, respectively, for SK-2 and SK-3 nanocomposite. The
pore diameter of the synthesized sample SK-3 is obtained
approx 40-50 nm while in SK-2 sample the pore is of irregular
diameter, insert of Fig. 5a and b, which was determined by
Barret-Joyner-Halenda (BJH) plot.

Fig. 5 e N2 adsorptionedesorption isotherm and BJH plot (inset) for (a) SK-3 and (b) SK-2.
 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 1 ; 1 1 : 9 7 0 e9 8 1 975

Fig. 6 e XPS spectra of SK-3 sample for (a) Carbon 1s (b) Nitrogen 1s (c) Oxygen 1s and (d) Nickel 2p.

4.4. X-ray photoelectron spectroscopy (XPS) analysis interfacial interaction between p-n heterojunction. The
spectrum of XPS survey of SK-3 also confirms the presence of
The chemical composition and elemental states of the SK-3 all the above mentioned (i.e., C 1s, O 1s, N 1s, and Ni 2p) ele-
heterostructure are analyzed by utilizing the principle of ments (referred in Fig. SI-2). Here, the þ2 oxidation state of
XPS. Fig. 6 represents the XPS spectrum of the SK-3 sample. nickel helps in the modification of electron density corre-
The heterostructured nanocomposite contains the element sponding to pen junction and in the refinement of crystal-
like C 1s, N 1s, O 1s, and Ni 2p. As shown in Fig. 6a The peaks at linity of the nanocomposite. In order to this, it also facilitate
284.5 eV correspond to the CeC bond, whereas the peaks at the charge separation, which is remarkable in the enhance-
286.1 and 288.1 eV are because of the presence of sp2 and sp3 ment of photocatalytic activity.
carbon of CeN and C]N bond, respectively in the g-C3N4
[33,34]. Fig. 6b displays the 1s spectra of nitrogen for SK-3 in
which the peak at 398.7 eV attribute to sp2 N (aromatic)
attached with carbon (C]NeC) [35] and the peaks at 399.2 and
401.2 eV correspond to Ne(C)3 groups, and due to p excitations
respectively [36], The prominent peak at 528.6 and 529.1 eV are
appeared because of the NieO bond, whereas the abundant
peak at 531.7 eV attributed to the presence of the O species in
water adsorbed on the surface [37e39]. From Fig. 6d, the peak
at 853.7 eV is due to Ni in 2p3/2, and the peak appeared at
879.1 eV, represent the 2p1/2 state of Ni, which confirms that Ni
of NiO exists in þ2 oxidation state [39]. Other peaks present at
860.8 and 870.6 eV are satellite peaks that are induced by
shake-up [40]. The peak of Ni 2p3/2 at 855.4 eV and 1s peak of
the O at 533.3 eV suggests the presence of Ni2O3 (Fig. 6d.) [41].
Moreover, a slight variation in the binding energies of C 1s, O
1s, and Ni 2p are observed in the spectra of nanostructure
composite [42,43] because of shifting of binding energy mainly
due to variation in the electron concentration, which is
happened due to transfer of electron and because of the Fig. 7 e Tauc plot for SK-1, SK-2, and SK-3.
976 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 1 ; 1 1 : 9 7 0 e9 8 1

Fig. 8 e UVeVisible Absorption spectra of MG degradation by the photocatalyst (a) SK-3 (b) SK-2 (c) percentage degradation of
MG with catalysts (d) kinetic plot for Blank, SK-1, SK-2, and SK-3 photocatalyst.

4.5. Optical property analysis
Bandgap calculation is essential to explain the photocatalytic
mechanism. The absorbance data obtained from UVevis DRS
are castoff to construct the Tauc plot for SK-1, SK-2, and SK-3
sample. Fig. 7 shows the tauc plots, which are drawn by using
[44e48].

Fig. 8c The photolysis of MG is almost negligible in a blank
1=n
ðahnÞ ¼ hn  Eg
where the symbol a denotes the molar absorption coefficient,
photonic energy is represented by hn, and n ¼ ½ value used for
the direct transition [44,45]. Eg, signifies the optical bandgap
energy of the materials. With the help of Eq. (2), the band gaps
of SK-1, SK-2, and SK-3 nanocomposites were calculated as
2.63, 3.30, and 2.89 eV, respectively.
617 nm, This was used as a signature to determine the
degradation of MG. This peak disappeared (96%) on irradiation
for 12 min. There was no substantive change in the result
beyond 12 min. So we have taken 12 min as a standard time for
all other samples. Fig. 8b displays the degradation of MG by
SK-2, which was 72% at a similar time of 12 min. The efficiency
of MG degradation by the different catalyst is displayed in
(2) experiment while SK-1 removes only 12% of MG dye (refer
Fig. SI-3 and SI-4). The porous surface of SK-3 adsorbs about
23% MG under the dark condition, as it is well known that
higher adsorption favors the photocatalysis. The photo-
degradation efficiency of MG over SK-3 achieves 96% in 12 min
under UV light irradiation, which is greater than the SK-2

4.6. Photocatalytic degradation measurements

The results of the photocatalytic removal of MG under UV light

over the porous surface of SK-3 nanocomposites are displayed
in Fig. 8a. The MG displays a characteristic absorption peak at

Table 1 e Representing the optical band gap, R2, and rate

constant (k) of SK-1, SK-2, and SK-3.
Samples Bandgap Degradation R2 The rate constant of
(eV) (%) MG (min1)
SK-1 2.63 12 0.988 1.14  102
SK-2 3.30 72 0.999 1.08  101
SK-3 2.89 96 0.996 2.66  101
Fig. 9 e Effect of the g-C3N4 content on MG degradation.
 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 1 ; 1 1 : 9 7 0 e9 8 1
Fig. 10 e Effect of trapping agent on MG degradation.
(72%) and SK-1 (12%). The reason for the higher photocatalytic
efficiency of SK-3 is the formation of a pen junction in be-
tween g-C3N4 and NiO, which facilitates the transfer of pho-
togenerated excitons (e/hþ) and avoid the charge
recombination process.
The rate constants for photocatalytic degradation were
calculated with the help of [49].
 
A0
ln ¼ kt
At
where k represents the rate constant for dye degradation and t
denotes the denotes irradiation time of UV light. The rate
constant of the reaction was determined by a slope that is
obtained by plotting a kinetic graph between concentration [ln
(A0/At)] and t (time in min) as displays in Fig. 8d. The linear
fitting of plots confirms the photocatalytic removal of MG is
according to pseudo 1st order kinetics. The rate constant (k)
Fig. 11 e Mechanism for the removal of MG by SK-3 under UV-light.
977
and linearity coefficient (R2) of SK-1, SK-2, and SK-3 obtained
from kinetic plots are given in Table 1.
Table 1 demonstrates that SK-3 has a higher degradation
rate constant (k) and percentage degradation than SK-1 and
SK-2, which validate that SK-3 is an efficient photocatalyst for
the degradation of MG. Based on the above results, we can say
that the loading of g-C3N4 (10 wt. %) with NiO performs the
higher photocatalytic efficiency because of the formation of a
p-n heterojunction, which delayed or avoid the recombination
of excitons (e/hþ). Simultaneously, low activity in SK-1 and
SK-2 may be attributed to poor charge transport and fast
recombination of charge carriers (e/hþ).
4.6.1. Effect of g-C3N4 content
In order to elucidate the impact of g-C3N4 content on the
photocatalytic efficiency of SK-3 nanocomposite photo-
catalysts, a series of parallel experiments run to check the
photocatalytic degradation of MG dye. The results of the MG
degradation with SK-2 and NiO with 5 wt% (SK-3ʹ), 10 wt% (SK-
3), and 15 wt% (SK-3ʺ) of g-C3N4 displayed in Fig. 9. It is clear
from Fig. 9 that the performance of the 10 wt% g-C3N4 is
significantly higher than 5 and 15 wt% of g-C3N4 while the
pure NiO has the lowest photocatalytic activity. The results
indicate that there is an improvement in the photocatalytic
performance in comparison with pure NiO. Fig. 9 also reveals
that when the g-C3N4 content is low, then the charge sepa-
(3) ration is insufficient; hence the photocatalytic activity of SK-3ʹ
is slower than that of SK-3. However, On increasing the con-
tent of the g-C3N4 from 10 wt%, we found that the photo-
catalytic performance of the nanocomposite decreased
because overloading of the g-C3N4 caused a shielding effect on
the NiO and inhibited the contact between NiO and reactant
MG.
978 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 1 ; 1 1 : 9 7 0 e9 8 1

Table 2 e Comparison table of TOF values obtained from MG degradation by various photocatalysts.
S. No. Photocatalysts Source of illumination Turn Over Frequency [mole g1min1] Reference
1. Mn/BiOCl Halogen lamp (500 W) 7.99  107 [10]
2. ZnO (flower-like) Mercury lamp (30 W) 2.54  105 [54]
3. SnO2/CuO UV-Light (15 W) 2.92  106 [55]
4. NiO0.8ZnO0.2/ZnO UV lamp (18 W) 7.53  107 [56]
5. a-Fe2O3/SnO2 Solar light 8.95  106 [57]
6. TiO2/ZnO UV-light (4  30 W) 1.11  106 [58]
7. Pt/In2O3/CdS Xenon lamp (300 W) 5.71  106 [59]
8. CNT/ZnO LED lamp (200 W) 1.08  104 [60]
9. Pt/ZnO Xenon lamp (300 W) 1.83  105 [61]
10. NiO UV- Laser 8.60  106 [62]
11. NiO/GO Mercury lamp (500 W) 6.05  105 [63]
12. WO3/C3N4 Tungsten lamp (500 W) 3.79  106 [64]
13. g-C3N4/NiO (SK-3) UV light (8 W) 7.30  103 Present work

Bold represents that our photocatalyst have higher turn over frequency (TOF) than the TOF of previous studies listed.

4.6.2. Observation of active species involved in MG
degradation
We have performed radical (active species) trapping experi-
ments with SK-3 photocatalyst to understand the chief reac-
tive species formed during the photocatalytic removal of MG.
The para-benzoquinone (PBQ) molecule used to trap O- 2 radi-
cals, iso-propyl alcohol (IPA) as OH radical scavenger, and
potassium iodide (KI) molecules used as hole (hþ) scavenger.
The results of the radical trapping experiments displayed in
Fig. 10 reveals that the photocatalytic removal of MG in the
presence of PBQ was greatly inhibited in comparison to other
scavengers. It confirms that superoxide radicals (O-2 ) are the
main active species produced in the photocatalysis. KI (hþ
scavenger) also affects MG degradation, but the effect is less
than PBQ and higher to IPA. So O- þ 
2 ˃ h ˃ OH is the priority
order of the active species generated during the photocatalytic
reaction.
4.6.3. Mechanism of photocatalytic degradation of MG
The reason for the higher photocatalytic activity of SK-3 can
be elucidated by a mechanism shown in Fig. 11, which
displays the mode of electron transfer and the alignment of
band positions of SK-3. Eqs. (4) and (5) was used to calculate
the value of the conduction band (CB) and valence band (VB)
edges, respectively [44e46].
ECB ¼ c  Ee  0:5Eg (4)
EVB ¼ c  Ee þ 0:5Eg (5)
In the above equations, c (Chi) denotes the electronega-
tivity; the energy of free electron on hydrogen scale repre-
sented by Ee and Eg shows the optical bandgap of
heterostructure material. The Ee value is Constant i.e.
(Ee ¼ 4.5 eV). Valance band (VB ¼ 1.55 eV) and conduction
band (CB ¼ 1.09 eV) of g-C3N4 is lying above than those of
NiO (VB ¼ 2.9 eV, CB ¼ 0.4 eV), which facilitate the transfer
of charge carrier (e and hþ). As shown from the band po-
sition of the SK-3 heterojunction nanocomposite behaves
like a typical type-II heterojunction photocatalyst. However,
if charge transfer takes place according to type-II, then the
transfer of electrons will take from CB of g-C3N4 to the CB of
NiO and holes from the VB of NiO to the VB of g-C3N4,

Fig. 12 e (a) Recyclability of SK-3 photocatalyst (b) HR-XRD pattern of SK-3 after recyclability.
 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 1 ; 1 1 : 9 7 0 e9 8 1
which may not have high reduction potential (only 0.40 eV
for CB of NiO) and oxidation potential (only 1.55 eV for VB of
g-C3N4) for generating O- 2 radicals (0.33 eV) and OH
(2.40 eV). From the staggered band structure of the nano-
composite SK-3 and other experimental results, the most
appropriate photocatalytic mechanism of charge transfer in
SK-3 photocatalyst follows the step scheme (S-scheme)
mechanism [50,51]. In this work, a novel heterojunction
nanocomposite following S-scheme was formed due to the
interaction of chemical bonds between the interfaces of the
nanocomposite. The electrons from the CB of NiO and holes
from the VB of g-C3N4, which are relatively useless, are now
recombined with each other due to the effect of the internal
electric field and band bending interaction, while the useful
electrons and holes in the CB of g-C3N4 and VB of NiO
having higher redox potential are retained. The electrons on
the CB of g-C3N4 could reduce O2 to O-2 and holes on the VB
of NiO could oxidize OH to OH, which are the major active
species generated during the photocatalytic degradation
experiment.
4.6.4. Turn over frequency (TOF) and recyclability
TOF of the SK-3 catalyst is calculated by using [52,53].
Number of moles of reactant
Number of gram of catalyst
 Yield
Turn Over Frequency ðTOFÞ ¼
time ðminÞ
(6)
The calculated TOF of SK-3 was compared with the TOF
of other photocatalysts, which are used for the degradation
of MG from different works of literature, the data is shown
in Table 2. From the table, we can see that SK-3 has a much
higher TOF than previously reported literature. To check the
reusability and stability of the SK-3 photocatalyst, we per-
formed the recyclability experiment and characterized the
SK-3 photocatalyst through, HR-XRD, HR-TEM, and XPS after
the 3rd cycle. The results of recyclability (Fig. 12a.), XRD
(Fig. 12b), HR-TEM, and XPS are referred to in Fig. SI-5and 6,
respectively, displays that our synthesized catalyst degrades
almost the same amount of MG up to the 3rd cycle, and
only a 5% decrement was observed in the 4th cycle. It shows
that the SK-3 photocatalyst is stable with good photo-
catalytic degradation efficiency. From the XRD, HR-TEM, and
XPS results after recyclability, it is clear that there is no
significant change is observed in the crystal structure and
oxidation states of SK-3, which confirms the stability of the
synthesized photocatalyst.
5. Summary
From the above results and discussion, we can conclude our
work in the following points given below-
 Our synthesized catalyst is a mesoporous and hexagonal
shape in the range of 25e35 nm, which is very close to the
crystallite size.
979
 Higher rate of adsorption of dye on the surface of nano-
composite SK-3, because of larger surface area (22 m2/g)
and pore diameter (40-50 nm).
 g-C3N4 plays a vital role in the separation of the photo-
generated excitons (e/hþ).
 A novel pen junction formed between g-C3N4 and NiO,
responsible for the higher photocatalytic activity of the SK-
3 nanocomposite.
 The primary reactive species formed in the photocatalytic
experiment is O-2 radical.
 For the mineralization of MG (2.76  105 moL/L), the
optimized amount of the catalyst (0.1 mg/mL) degrades
96% of the dye with good recyclability.
 The synthesized SK-3 nanocomposite has much higher
TOF (7.30  103 mol g1min1) than other reported pho-
tocatalysts for MG degradation.
 Photocatalyst SK-3 is an efficient candidate for the miner-
alization of the pollutant without photocorrosion.
Declaration of Competing Interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgements
Suresh Kumar Pandey, Manish Kumar Tripathi acknowledge
financial support (SRF) received from IIT (BHU). Authors also
thanks central instrumental facility IIT (BHU) for availing
instrumental facilities.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.jmrt.2021.01.059.
references
[1] Sarmah S, Kumar A. Photocatalytic activity of polyaniline-
TiO 2 nanocomposites. Indian J Phys 2011;85:713.
[2] Crini G, Peindy HN, Gimbert F, Robert C. Removal of CI Basic
Green 4 (Malachite Green) from aqueous solutions by
adsorption using cyclodextrin-based adsorbent: kinetic and
equilibrium studies. Sep. and purif. Tech. 2007;53:97e110.
[3] Cheng W, Wang SG, Lu L, Gong WX, Liu XW, Gao BY, et al.
Removal of malachite green (MG) from aqueous solutions by
native and heat-treated anaerobic granular sludge. Biochem
Eng J 2008;39:538e46.
[4] Rao KV. Inhibition of DNA synthesis in primary rat
hepatocyte cultures by malachite green: a new liver tumor
promoter. Toxicol Lett (Shannon) 1995;81:107e13.
980 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 1 ; 1 1 : 9 7 0 e9 8 1
[5] Alderman DJ, Clifton-Hadley RS. Malachite green: a
pharmacokinetic study in rainbow trout, Oncorhynchus
mykiss (Walbaum). J Fish Dis 1993;16:297e311.
[6] Qiao M, Wei K, Ding J, Liu Z, Zhang KQ, Huang X. Decolorizing
activity of malachite green and its mechanisms involved in
dye biodegradation by Achromobacter xylosoxidans MG1. J
Mol Microbiol Biotechnol 2011;20:220e7.
[7] Mittal A. Adsorption kinetics of removal of a toxic dye,
Malachite Green, from wastewater by using hen feathers. J.
of hazar. Mater. 2006;33:196e202.
[8] Sayılkan F, Asiltürk M, Tatar P, Kiraz N, Arpac E, Sayılkan H.
Preparation of re-useable photocatalytic filter for
degradation of Malachite Green dye under UV and vis-
irradiation. J. of hazar. Mater. 2007;148:735e44.
[9] Chen CC, Lu CS, Chung YC, Jan JL. UV light induced
photodegradation of malachite green on TiO2 nanoparticles.
J. of hazar. Mater. 2007;141:520e8.
[10] Pare B, Sarwan B, Jonnalagadda SB. Photocatalytic
mineralization study of malachite green on the surface of
Mn-doped BiOCl activated by visible light under ambient
condition. Appl Surf Sci 2011;258:247e53.
[11] Liu Y, Ohko Y, Zhang R, Yang Y, Zhang Z. Degradation of
malachite green on Pd/WO3 photocatalysts under simulated
solar light. J. of hazar. Mater. 2010;184:386e91.
[12] Prado AG, Costa LL. Photocatalytic decouloration of
malachite green dye by application of TiO2 nanotubes. J. of
hazar. Mater. 2009;169:297e301.
[13] Lee WW, Chung WH, Lu CS, Lin WY, Chen CC. A study on the
degradation efficiency and mechanisms of ethyl violet by
HPLCePDAeESIeMS and GCeMS. Sep. and purif. tech.
2012;98:488e96.
_ So
[14] Altın I, € kmen M. Preparation of TiO2-polystyrene
photocatalyst from waste material and its usability for
removal of various pollutants. Appl Catal B Environ
2014;144:694e701.
[15] Zhang S, Li H, Yang Z. Controllable synthesis of WO3 with
different crystalline phases and its applications on
methylene blue removal from aqueous solution. J Alloys
Compd 2017;722:555e63.
[16] Saravanan R, Karthikeyan S, Gupta VK, Sekaran G,
Narayanan V, Stephen AJ. Enhanced photocatalytic activity
of ZnO/CuO nanocomposite for the degradation of textile dye
on visible light illumination. Mater Sci Eng C 2013;33:91e8.
[17] Saravanan R, Sacari E, Gracia F, Khan MM, Mosquera E,
Gupta VK. Conducting PANI stimulated ZnO system for
visible light photocatalytic degradation of coloured dyes. J. of
mole. liq. 2016;221:1029e33.
[18] Cui W, An W, Liu L, Hu J, Liang Y. Synthesis of CdS/BiOBr
composite and its enhanced photocatalytic degradation for
Rhodamine B. App. surface sci. 2014;319:298e305.
[19] Elango G, Roopan SM. Efficacy of SnO2 nanoparticles toward
photocatalytic degradation of methylene blue dye. J
Photochem Photobiol B Biol 2016;155:34e8.
[20] Malwal D, Gopinath P. Fabrication and characterization of
poly (ethylene oxide) templated nickel oxide nanofibers for
dye degradation. Env. Science: Nano 2015;2:78e85.
[21] Zhou L, Liu Z, Guan Z, Tian B, Wang L, Zhou Y, et al. 0D/2D
plasmonic Cu2-xS/g-C3N4 nanosheets harnessing UV-vis-
NIR broad spectrum for photocatalytic degradation of
antibiotic pollutant. Appl Catal B Environ 2020;263:118326.
[22] Wei A, Liu B, Zhao H, Chen Y, Wang W, Ma Y, et al. Synthesis
and formation mechanism of flowerlike architectures
assembled from ultrathin NiO nanoflakes and their
adsorption to malachite green and acid red in water. Chem
Eng J 2014;239:141e8.
[23] Darwish AA, Rashad M, AL-Aoh HA. Methyl orange
adsorption comparison on nanoparticles: isotherm, kinetics,
and thermodynamic studies. Dyes Pigments
2019;160:563e71.
[24] Ai L, Zeng Y. Hierarchical porous NiO architectures as highly
recyclable adsorbents for effective removal of organic dye
from aqueous solution. Chem Eng J 2013;215:269e78.
[25] Fu Y, Zhu C, Wang H, Dou Y, Shi W, Shao M, et al. High-
performance NiO/gC 3 N 4 composites for visible-light-driven
photocatalytic overall water splitting. Inorg. Chemistry Fron
2018;5:1646e52.
[26] Baig U, Khan A, Gondal MA, Dastageer MA, Falath WS. Laser
induced anchoring of nickel oxide nanoparticles on
polymeric graphitic carbon nitride sheets using pulsed laser
ablation for efficient water splitting under visible light.
Nanomaterials 2020;10:1098.
[27] Peng Y, Zhou L, Wang L, Lei J, Liu Y, Daniele S, et al.
Preparation of NiCoP-decorated g-C3N4 as an efficient
photocatalyst for H2O2 production. Res on Chem Intermed
2019;45:5907e17.
[28] Zhang Z, Liu H, Zhang H, Dong H, Liu X, Jia H, et al. Synthesis
of spindle-like Ag/ZnO heterostructure composites with
enhanced photocatalytic performance. Superlattice Microst
2014;65:134e45.
[29] Shi W, Guo F, Chen J, Che G, Lin X. Hydrothermal synthesis of
InVO4/Graphitic carbon nitride heterojunctions and
excellent visible-light-driven photocatalytic performance for
rhodamine B. J. of alloys and comp 2014;612:143e8.
[30] Lin X, Wei B, Zhang X, Song M, Yu S, Gao Z, et al.
Construction of heterostructured g-C3N4/Ag/Bi3. 64Mo0.
36O6. 55 nanospheres with enhanced visible-light
photocatalytic activity. Separ Purif Technol 2016;169:9e16.
[31] Selvarajan S, Suganthi A, Rajarajan M. Fabrication of g-C3N4/
NiO heterostructured nanocomposite modified glassy carbon
electrode for quercetin biosensor. Ultrason Sonochem
2018;41:651e60.
[32] Baig U, Uddin MK, Gondal MA. Removal of hazardous azo dye
from water using synthetic nano adsorbent: facile synthesis,
characterization, adsorption, regeneration and design of
experiments. Colloids Surf, A: Physicochemical and Engg.
Aspects 2020;584:124031.
[33] Li X, Zhang J, Shen L, Ma Y, Lei W, Cui Q, et al. Preparation
and characterization of graphitic carbon nitride through
pyrolysis of melamine. Appl Phys A 2009;94:387e92.
[34] Wei Z, Zhou L, Deng H. Ag modified g-C3N4 composites with
enhanced visible-light photocatalytic activity for diclofenac
degradation. J. of Mole. Cat. A: Chemicals 2016;423:270e6.
[35] Zhang C, Hao R, Liao H, Hou Y. Synthesis of amino-
functionalized graphene as metal-free catalyst and
exploration of the roles of various nitrogen states in
oxygen reduction reaction. Nanomater Energy
2013;2:88e97.
[36] Thaweesak S, Lyu M, Peerakiatkhajohn P, Butburee T, Luo B,
Chen H, et al. Two-dimensional g-C3N4/Ca2Nb2TaO10
nanosheet composites for efficient visible light
photocatalytic hydrogen evolution. Appl Catal B Environ
2017;202:184e90.
[37]  a
Santos VP, Pereira MF, Orf ~ o JJ, Figueiredo JL. The role of
lattice oxygen on the activity of manganese oxides towards
the oxidation of volatile organic compounds. Appl Catal B
Environ 2010;99:353e63.
[38] Guo J, Fu W, Yang H, Yu Q, Zhao W, Zhou X, et al. A NiO/TiO2
junction electrode constructed using self-organized TiO2
nanotube arrays for highly efficient photoelectrocatalytic
visible light activations. J Phys D Appl Phys 2010;43:245202.
[39] Zhang Y, Wang J, Wan P, Ye J, Hussain S, Wei H, et al. Ag2O
loaded NiO ball-flowers for high performance
supercapacitors. Mater Lett 2016;177:71e5.
[40] Dai W, Pan X, Chen S, Chen C, Wen Z, Zhang H, et al.
Honeycomb-like NiO/ZnO heterostructured nanorods:
 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 1 ; 1 1 : 9 7 0 e9 8 1
photochemical synthesis, characterization, and enhanced
UV detection performance. J of Mater Chem C
2014;2:4606e14.
[41] Kim KS, Davis R1. Electron spectroscopy of the nickel-oxygen
system. J Electron Spectrosc Relat Phenom 1972;1:251e8.
[42] Ze’ai HU, Sun Q, Lv K, Zhang Z, Li M, Li B. Effect of contact
interface between TiO2 and g-C3N4 on the photoreactivity of
g-C3N4. App. cat. B, Env. 2015;164:420e7.
[43] Lu M, Pei Z, Weng S, Feng W, Fang Z, Zheng Z, et al.
Constructing atomic layer gC 3 N 4eCdS
nanoheterojunctions with efficiently enhanced visible light
photocatalytic activity. Phys Chem Chem Phys
2014;16:21280e8.
[44] Zhang Z, Jiang D, Xing C, Chen L, Chen M, He M. Novel AgI-
decorated b-Bi 2 O 3 nanosheet heterostructured Z-scheme
photocatalysts for efficient degradation of organic pollutants
with enhanced performance. Dalton Trans
2015;44:11582e91.
[45] Islam MJ, Reddy DA, Choi J, Kim TK. Surface oxygen vacancy
assisted electron transfer and shuttling for enhanced
photocatalytic activity of a Z-scheme CeO 2eAgI
nanocomposite. RSC Adv 2016;6:19341e50.
[46] Yang Q, Chen F, Li X, Wang D, Zhong Y, Zeng G. Self-
assembly Z-scheme heterostructured photocatalyst of Ag 2
O@ Ag-modified bismuth vanadate for efficient
photocatalytic degradation of single and dual organic
pollutants under visible light irradiation. RSC Adv
2016;6:60291e307.
[47] Wang Y, Niu CG, Zhang L, Wang Y, Zhang H, Huang DW,
et al. High-efficiency visible-light AgI/Ag/Bi 2 MoO 6 as a Z-
scheme photocatalyst for environmental applications. RSC
Adv 2016;6:10221e8.
[48] Xu Y, Schoonen MA. The absolute energy positions of
conduction and valence bands of selected semiconducting
minerals. Am Mineral 2000;85:543e56.
[49] Ma S, Li R, Lv C, Xu W, Gou X. Facile synthesis of ZnO
nanorod arrays and hierarchical nanostructures for
photocatalysis and gas sensor applications. J. of hazar.
Mater. 2011;192:730e40.
[50] Xu Q, Zhang L, Cheng B, Fan J, Yu J. S-scheme heterojunction
photocatalyst. Inside Chem 2020;6:1543e59.
[51] Fu J, Xu Q, Low J, Jiang C, Yu J. Ultrathin 2D/2D WO3/g-C3N4
step-scheme H2-production photocatalyst. Appl Catal B
Environ 2019;243:556e65.
[52] Devi LG, Kumar SG, Reddy KM, Munikrishnappa C. Photo
degradation of Methyl Orange an azo dye by Advanced
Fenton Process using zero valent metallic iron: influence of
various reaction parameters and its degradation mechanism.
J. of hazar. mater. 2009;164:459e67.
981
[53] Zyoud A, Zu’bi A, Helal MH, Park D, Campet G, Hilal HS.
Optimizing photo-mineralization of aqueous methyl orange
by nano-ZnO catalyst under simulated natural conditions. J.
of env. health sci. and Engg. 2015;13:46.
[54] Saikia L, Bhuyan D, Saikia M, Malakar B, Dutta DK,
Sengupta P. Photocatalytic performance of ZnO
nanomaterials for self sensitized degradation of malachite
green dye under solar light. Appl Catal Gen 2015;490:42e9.
[55] Kumar A, Rout L, Achary LS, Mohanty A, Marpally J,
Chand PK, et al. Design of binary SnO2-CuO nanocomposite
for efficient photocatalytic degradation of malachite green
dye. AIP Conf. Proceedings 2016;1724:020027.
[56] Milenova KI, Zaharieva KL, Vassilev SV, Dimova SS,
Stambolova ID, Blaskov VN. Synthesis and investigation of
composite photocatalysts on the base of nickel and zinc
oxides. Bulgarian Chem. Com 2018;50:130e4.
[57] Pradhan GK, Reddy KH, Parida KM. Facile fabrication of
mesoporous a-Fe2O3/SnO2 nanoheterostructure for
photocatalytic degradation of malachite green. Cat. Today
Off 2014;224:171e9.
[58] Bansal P, Bhullar N, Sud D. Studies on photodegradation of
malachite green using TiO2/ZnO photocatalyst. Desalin. and
Water Treat. 2009;12:108e13.
[59] Qusti AH, Malkhasian AY, Salam MA. Enhancement of CdS
nanoparticles photocatalytic activity by Pt and In2O3 doping
for the degradation of malachite green dye in water. J Mol Liq
2018;255:364e9.
[60] Arsalani N, Bazazi S, Abuali M, Jodeyri S. A new method
for preparing ZnO/CNT nanocomposites with enhanced
photocatalytic degradation of malachite green under
visible light. J Photochem Photobiol Chem
2020;389:112207.
[61] Mohamed RM, McKinney D, Kadi MW, Mkhalid IA,
Sigmund W. Platinum/zinc oxide nanoparticles: enhanced
photocatalysts degrade malachite green dye under visible
light conditions. Ceram Int 2016;42:9375e81.
[62] Hayat K, Gondal MA, Khaled MM, Ahmed S. Effect of
operational key parameters on photocatalytic degradation of
phenol using nano nickel oxide synthesized by solegel
method. J. of Mole. Cat. A: Chemicals 2011;336:64e71.
[63] Ahmad J, Majid K, Dar MA. Controlled synthesis of p-type
NiO/n-type GO nanocomposite with enhanced
photocatalytic activity and study of temperature effect on
the photocatalytic activity of the nanocomposite. Appl Surf
Sci 2018;457:417e26.
[64] Zhaoa J, Jia Z, Shen X, Zhou H, Ma L. Facile synthesis of WO3
nanorods/g-C3N4 composites with enhanced photocatalytic
activity. Ceram Int 2015;41:5600e6.