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 1 971

semiconductor material and having an extensive optical

1. Introduction bandgap, which is responsible for the fast recombination of
the photogenerated excitons, consequentially, it shows poor
In the present scenario, the contamination of the water photocatalytic activity [9]. To accomplish such problems,
stream is one of the critical problems of the world, mainly due recently, an organic metal-free moiety n-type g-C3N4 semi-
to the growing population and disposal of wastes from the conductor with a bandgap of 2.70 eV is a promising candidate
elaboration of textiles as well as chemical industries. A syn- because of its low cost, high performance, nontoxicity, and
thetic dying agent employed in these industries is a major spectacular optical properties. NiO and g-C3N4 give a potent
responsible for pollution of the environment because it is non- pen junction, which enhances the photocatalytic perfor-
biodegradable and having great toxicity towards both flora mance of the heterostructure. During this process, the inter-
and fauna. MG is a green-colored, tri-phenylmethane dye that nal electric field of the heterostructure helps to achieve the
is used in encompassing manner in food, leather, silk, textile proper bandgap, consequently, decrease the rate of recombi-
industries as an additive and as a dying agent because of its nation of photogenerated electroneholes. There is very few
disinfectant and antibacterial nature [1e3]. However, since reports on the photocatalytic applications of the hetero-
the 1990s, it is found that MG and leucomalachite green structured g-C3N4/NiO nanocomposite [25,26]. There are other
(reduced form of malachite green) has carcinogenic, muta- reports in which g-C3N4 used as a dopant with nickel based
genic, and genotoxic effects on living beings [4,5]. Henceforth materials that displays an efficient photocatalytic perfor-
it is required to evolve some emphatic techniques for the mance [27].
removal of such types of hazardous organic recalcitrants from In the present article, we synthesized novel hexagonal-
the water stream. Several methods are used for expulsion of shaped nano heterojunction of n-type g-C3N4 (10 wt %) with
toxic materials from wastewater like biological treatment [6], p-type semiconductor NiO through hydrothermal deposition
adsorption [7] process, and heterogeneous semiconductor route followed by the calcination process. The synthesized
photocatalysis [8e12]. Among these methods, semiconductor heterojunction, g-C3N4/NiO, displays efficient photocatalytic
heterogeneous photocatalysis is one of the efficient methods activity with much higher TOF than previous studies. As
for degradation of harmful organic wastes into CO2 and H2O, synthesized nanocomposites also facilitate efficient charge
and it may occur in the presence of sunlight, which is eco- separation between photogenerated excitons, which makes g-
friendly and renewable energy source [12,13]. From last C3N4/NiO a superior nanocomposite for MG dye degradation.
several decads, heterogeneous semiconductor photocatalyst The mechanism for the superiority of our synthesized catalyst
like TiO2, WO3, CuO, ZnO, Cu2S, SnO2, and NiO have drawn the could be endorsed with the proper optical bandgap and fine
researchers attention because of their higher photocatalytic internal transfer of charge carriers within the pen junction in
efficiency as well as stability, less toxicity, reusability, cost- the presence of UV light.
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 2. Materials and methods
remediation, NiO also has been used as a good adsorbent and
shows better adsorption efficiency in comparison to CuO, 2.1. Materials
Y-Al2O3, and several other metal oxides towards the adsorp-
tion of organic dyes [22e24]. All the required chemicals such as Nickel nitrate hexahydrate
The particle size and bandgaps of the synthesized photo- (Ni(NO3)2.6H2O) (Sigma Aldrich), sodium citrate tribasic dihy-
catalyst have a major role in their photocatalytic perfor- drate (Merck), ethyl alcohol (Merck), malachite green (Sigma
mance. Pure NiO displays the properties of p-type Aldrich), and melamine (Alfa Aesar) were acquired are of

Fig. 1 e The pictorial representation for the synthesis of SK-3 nanocomposite.

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analytical reagents (AR) grade and used without any further XRD) pattern using Rigaku Smart Lab 9 kW (with Cu Ka radi-
purification. ation, l ¼ 1.54

A). Fourier transformed infrared spectra (FT-IR)
were run in between 4000 and 400 cm1 for the functional
2.2. Synthesis of g-C3N4 group analysis. TEM (Tec. G2 20 TWIN) and FE-SEM (Nova N.
SEM 450) were used to analyzed particle size and the Surface
g-C3N4 (SK-1) was synthesized by the thermal condensation analysis of nanocomposites. Pore volume and Specific Surface
method by using melamine as a precursor. 10 g of melamine area of samples were determined by the Bru-
was placed in an alumina crucible and put it into a muffle nauereEmmetteTeller (BET) analysis. Elemental analysis was
furnace at 550  C temperature for 4 h with a ramp rate of 10  C performed by the X-ray photoelectron spectroscopy (XPS), and
per minute. The obtained yellow color material was further bandgap calculation of the synthesized sample was done by
washed numerous times with ethyl alcohol and double- ultravioletevisible diffuse reflectance spectroscopy (UVevis
distilled water to remove the impurities from the precipitate. DRS).
Finally, g-C3N4 was collected by the centrifugation method
and placed for drying into a vacuum oven at 60  C (Fig. 1). 3.1. Photocatalytic efficiency

2.3. Synthesis protocol of g-C3N4/NiO composite Photocatalytic efficiency of g-C3N4 (SK-1) pure NiO (SK-2) and
g-C3N4/NiO (SK-3) were explored through the photocatalytic
g-C3N4 (195 mg) was redispersed in 30 mL ethyl alcohol, fol- mineralization of MG under UV light irradiation (254 nm,
lowed by sonication for 1 h. Hereafter, 0.22 M of Ni(NO3)2$6H2O Phillips, 8 W). 10 mg of catalysts were redispersed in 100 mL
was mixed with vigorous stirring. At that time, a 0.4 M sodium aqueous solution of MG (2.76  105 mol/L) dye, and then the
citrate solution was also added to the reaction mixture. Then, reaction mixture was further irradiated by UV light (light
the mixed solution was allowed to transfer into the autoclave source). The whole reaction was performed in a 1 cm path
and placed into the oven for 12 h at 180  C. After that, the length quartz cuvette and recorded by the UVeVis spectro-
autoclave was further cooled at room temperature. The ob- photometer. The change of the absorbance MG dye with the
tained sample was centrifuged and washed properly with time indicates the degradation process of MG. The percentage
ethyl alcohol and double-distilled water to fixed the impurities of degradation of MG was investigated by using [28].
from the sample. The resulting nanocomposites were desic-
A0  At C0  Ct
cated in a vacuum oven at 65  C. The nanocomposite was % Degradation ¼  100 ¼  100 (1)
A0 C0
further transferred into an uncovered crucible of alumina and
calcined in a muffle furnace at 500  C temperature for 3 h. The In the above equation, A0 and At are the initial and final
found g-C3N4/NiO (SK-3) heterostructure nanocomposite was absorbance of MG, respectively, while C0 represents the initial
grinding for 5 min. Similar protocols were followed for the concentration and Ct shows the MG concentration after the
synthesis of pure NiO (SK-2) nanoparticle without using g- degradation.
C3N4 (Fig. 1).

4. Results and discussion

3. Characterization
4.1. HR-XRD
The crystalline faces of the synthesized samples were
analyzed by normalized high-resolution X-ray diffraction (HR- 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

Fig. 2 e (a) HR-XRD Pattern of SK1, SK2, and SK3 (b) FT-IR spectra of SK1, SK2, and SK3 samples.
 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 1 973

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] bond, which comes out due to unavoidable moisture absor-
plane, respectively (JCPDS no. 87-1526). Broad peaks are an bed by the sample from the atmosphere [32].
indicator of the poor crystallinity and small thickness of the
samples. SK-2 shows sharp peaks at 2q values 37.19 , 43.32 , 4.3. Morphology measurements
62.84 , 75.31 , and 79.35 are obtained (JCPDS Card no. 04-0835)
corresponding to the plane [111], [200], [220], [311], and [222] 4.3.1. TEM and FE-SEM
respectively. Here sharpness of peak visualizes the crystal- The morphological properties of the nanoparticles were
linity of the sample. The formation of the heterostructure of determined by TEM micrographs. Fig. 3a demonstrates that
NiO with C3N4 (10 wt. %) is confirmed by the presence of the most of the particles of SK-2 are spherical nanodiscs type with
peaks for both NiO and C3N4 in SK-3 nanocomposites. an average size is approx 35-40 nm (Fig. 3c). The correspond-
ing SAED pattern shows the polycrystalline nature of SK-2,
4.2. FT-IR analysis inset in Fig. 3a. The TEM micrograph of SK-3 (Fig. 3b) dis-
plays the hexagonal nanostructure of NiO is decorated with a
The samples were characterized through FT-IR for the func- g-C3N4 lamellar structure. For this, the SAED pattern is given
tional group analysis and the type of vibrations present in the in the inset of Fig. 3b, which indicates the crystalline proper-
molecules, the result is displayed in Fig. 2b. In the case of the ties of the composite because of the higher amount of the NiO
SK1 appearance of intense band at 1200-1650 cm1 is mainly component. The average diameter for heterostructure is
due to the aromatic stretching of CeN and C]N heterocycles. shown in the histogram of Fig. 3d, which is found to be
Apart from that, the vibration band at 816 cm1 is due to the 25e30 nm. HR-TEM image of SK-3 is also given in the Fig. SI-1,
bending frequency of triazine rings [29,30]. In the case of the which validate the formation of the heterostructured nano-
SK-2 sample, at 425 cm1, a broad vibration band is recorded, composite. The particle size of composites is in good agree-
which is responsible for the stretching vibration between the ment with the XRD’s crystallite size, which was found with
NieO bond [31]. All the band of SK-2 are also recorded in the the help of Scherer’s equation. The SAED and XRD result from
case of SK-3, but the absorption band appear at 425 cm1 in both of them having a good agreement, and they confirm the
SK-2 is slightly shift at 434 cm1, which shows the interaction formation of SK-3 heterostructure through our designed
of the triazine ring of g-C3N4 with NiO by electrostatic inter- scheme for its synthesis. Fig. 4a displays the FE-SEM image of
action [31]. The absorption band around 1450 cm1 is due to SK-2, which depicts that the particles are slightly spherical,
carbonate, and the band area at 3200-3500 cm1 is corre- having small pores on its surface. The surface morphology
sponding to the vibrational stretching frequency of the OeH 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 adsorptionedesorption isotherm and BET. The results of N2
diameter between 25 and 35 nm are placed on the sheet-like adsorptionedesorption in Fig. 5a and b clearly shows a hys-
surface of g-C3N4. Just like pure NiO, many tiny pores are teresis loop of type IV pattern, which confirms the meso-
also existing on the surface of SK-3, which provides space for porous nature of SK-2 and SK-3. The specific surface area was
adsorption of MG. The EDS spectrum confirms the presence of calculated with the help of the BET equation, and it was 14 and
all the elements present in SK-3. 22 m2/g, respectively, for SK-2 and SK-3 nanocomposite. The
pore diameter of the synthesized sample SK-3 is obtained
4.3.2. BET approx 40-50 nm while in SK-2 sample the pore is of irregular
The mesoporosity and specific surface area of the synthesized diameter, insert of Fig. 5a and b, which was determined by
samples SK-2 and SK-3 were analyzed by N2 Barret-Joyner-Halenda (BJH) plot.

Fig. 5 e N2 adsorptionedesorption isotherm and BJH plot (inset) for (a) SK-3 and (b) SK-2.
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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 617 nm, This was used as a signature to determine the
degradation of MG. This peak disappeared (96%) on irradiation
Bandgap calculation is essential to explain the photocatalytic for 12 min. There was no substantive change in the result
mechanism. The absorbance data obtained from UVevis DRS beyond 12 min. So we have taken 12 min as a standard time for
are castoff to construct the Tauc plot for SK-1, SK-2, and SK-3 all other samples. Fig. 8b displays the degradation of MG by
sample. Fig. 7 shows the tauc plots, which are drawn by using SK-2, which was 72% at a similar time of 12 min. The efficiency
[44e48]. of MG degradation by the different catalyst is displayed in

Fig. 8c The photolysis of MG is almost negligible in a blank
1=n
ðahnÞ ¼ hn  Eg (2) experiment while SK-1 removes only 12% of MG dye (refer
where the symbol a denotes the molar absorption coefficient, Fig. SI-3 and SI-4). The porous surface of SK-3 adsorbs about
photonic energy is represented by hn, and n ¼ ½ value used for 23% MG under the dark condition, as it is well known that
the direct transition [44,45]. Eg, signifies the optical bandgap higher adsorption favors the photocatalysis. The photo-
energy of the materials. With the help of Eq. (2), the band gaps degradation efficiency of MG over SK-3 achieves 96% in 12 min
of SK-1, SK-2, and SK-3 nanocomposites were calculated as under UV light irradiation, which is greater than the SK-2
2.63, 3.30, and 2.89 eV, respectively.

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.
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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
Fig. 10 e Effect of trapping agent on MG degradation. 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
(72%) and SK-1 (12%). The reason for the higher photocatalytic degradation with SK-2 and NiO with 5 wt% (SK-3ʹ), 10 wt% (SK-
efficiency of SK-3 is the formation of a pen junction in be- 3), and 15 wt% (SK-3ʺ) of g-C3N4 displayed in Fig. 9. It is clear
tween g-C3N4 and NiO, which facilitates the transfer of pho- from Fig. 9 that the performance of the 10 wt% g-C3N4 is
togenerated excitons (e/hþ) and avoid the charge significantly higher than 5 and 15 wt% of g-C3N4 while the
recombination process. pure NiO has the lowest photocatalytic activity. The results
The rate constants for photocatalytic degradation were indicate that there is an improvement in the photocatalytic
calculated with the help of [49]. performance in comparison with pure NiO. Fig. 9 also reveals
  that when the g-C3N4 content is low, then the charge sepa-
A0
ln ¼ kt (3) ration is insufficient; hence the photocatalytic activity of SK-3ʹ
At
is slower than that of SK-3. However, On increasing the con-
where k represents the rate constant for dye degradation and t tent of the g-C3N4 from 10 wt%, we found that the photo-
denotes the denotes irradiation time of UV light. The rate catalytic performance of the nanocomposite decreased
constant of the reaction was determined by a slope that is because overloading of the g-C3N4 caused a shielding effect on
obtained by plotting a kinetic graph between concentration [ln the NiO and inhibited the contact between NiO and reactant
(A0/At)] and t (time in min) as displays in Fig. 8d. The linear MG.
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.

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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 displays the mode of electron transfer and the alignment of
degradation band positions of SK-3. Eqs. (4) and (5) was used to calculate
We have performed radical (active species) trapping experi- the value of the conduction band (CB) and valence band (VB)
ments with SK-3 photocatalyst to understand the chief reac- edges, respectively [44e46].
tive species formed during the photocatalytic removal of MG.
ECB ¼ c  Ee  0:5Eg (4)
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. EVB ¼ c  Ee þ 0:5Eg (5)
The results of the radical trapping experiments displayed in In the above equations, c (Chi) denotes the electronega-
Fig. 10 reveals that the photocatalytic removal of MG in the tivity; the energy of free electron on hydrogen scale repre-
presence of PBQ was greatly inhibited in comparison to other sented by Ee and Eg shows the optical bandgap of
scavengers. It confirms that superoxide radicals (O-2 ) are the heterostructure material. The Ee value is Constant i.e.
main active species produced in the photocatalysis. KI (hþ (Ee ¼ 4.5 eV). Valance band (VB ¼ 1.55 eV) and conduction
scavenger) also affects MG degradation, but the effect is less band (CB ¼ 1.09 eV) of g-C3N4 is lying above than those of
than PBQ and higher to IPA. So O- þ 
2 ˃ h ˃ OH is the priority NiO (VB ¼ 2.9 eV, CB ¼ 0.4 eV), which facilitate the transfer
order of the active species generated during the photocatalytic of charge carrier (e and hþ). As shown from the band po-
reaction. sition of the SK-3 heterojunction nanocomposite behaves
like a typical type-II heterojunction photocatalyst. However,
4.6.3. Mechanism of photocatalytic degradation of MG if charge transfer takes place according to type-II, then the
The reason for the higher photocatalytic activity of SK-3 can transfer of electrons will take from CB of g-C3N4 to the CB of
be elucidated by a mechanism shown in Fig. 11, which 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 1 979

which may not have high reduction potential (only 0.40 eV  Higher rate of adsorption of dye on the surface of nano-
for CB of NiO) and oxidation potential (only 1.55 eV for VB of composite SK-3, because of larger surface area (22 m2/g)
g-C3N4) for generating O- 2 radicals (0.33 eV) and OH and pore diameter (40-50 nm).
(2.40 eV). From the staggered band structure of the nano-  g-C3N4 plays a vital role in the separation of the photo-
composite SK-3 and other experimental results, the most generated excitons (e/hþ).
appropriate photocatalytic mechanism of charge transfer in  A novel pen junction formed between g-C3N4 and NiO,
SK-3 photocatalyst follows the step scheme (S-scheme) responsible for the higher photocatalytic activity of the SK-
mechanism [50,51]. In this work, a novel heterojunction 3 nanocomposite.
nanocomposite following S-scheme was formed due to the  The primary reactive species formed in the photocatalytic
interaction of chemical bonds between the interfaces of the experiment is O-2 radical.
nanocomposite. The electrons from the CB of NiO and holes  For the mineralization of MG (2.76  105 moL/L), the
from the VB of g-C3N4, which are relatively useless, are now optimized amount of the catalyst (0.1 mg/mL) degrades
recombined with each other due to the effect of the internal 96% of the dye with good recyclability.
electric field and band bending interaction, while the useful  The synthesized SK-3 nanocomposite has much higher
electrons and holes in the CB of g-C3N4 and VB of NiO TOF (7.30  103 mol g1min1) than other reported pho-
having higher redox potential are retained. The electrons on tocatalysts for MG degradation.
the CB of g-C3N4 could reduce O2 to O-2 and holes on the VB  Photocatalyst SK-3 is an efficient candidate for the miner-
of NiO could oxidize OH to OH, which are the major active alization of the pollutant without photocorrosion.
species generated during the photocatalytic degradation
experiment.

4.6.4. Turn over frequency (TOF) and recyclability Declaration of Competing Interest
TOF of the SK-3 catalyst is calculated by using [52,53].
The authors declare that they have no known competing
Number of moles of reactant
Number of gram of catalyst
 Yield financial interests or personal relationships that could have
Turn Over Frequency ðTOFÞ ¼
time ðminÞ appeared to influence the work reported in this paper.
(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 Acknowledgements
in Table 2. From the table, we can see that SK-3 has a much
higher TOF than previously reported literature. To check the Suresh Kumar Pandey, Manish Kumar Tripathi acknowledge
reusability and stability of the SK-3 photocatalyst, we per- financial support (SRF) received from IIT (BHU). Authors also
formed the recyclability experiment and characterized the thanks central instrumental facility IIT (BHU) for availing
SK-3 photocatalyst through, HR-XRD, HR-TEM, and XPS after instrumental facilities.
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 Appendix A. Supplementary data
almost the same amount of MG up to the 3rd cycle, and
only a 5% decrement was observed in the 4th cycle. It shows Supplementary data to this article can be found online at
that the SK-3 photocatalyst is stable with good photo- https://doi.org/10.1016/j.jmrt.2021.01.059.
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 references
oxidation states of SK-3, which confirms the stability of the
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