Environmental Science and Pollution Research (2023) 30:98773–98786

https://doi.org/10.1007/s11356-023-25360-7

ADVANCED MATERIALS FOR ENERGY & APPLICATIONS

Architecting the Z‑scheme heterojunction of ­Gd2O3/g‑C3N4

nanocomposites for enhanced visible‑light‑induced photoactivity
towards organic pollutants degradation
Vikrant Singh Rao1 · Rishabh Sharma1,2 · Devina Rattan Paul1 · Miroslav Almáši3 · Anshu Sharma4 · Suresh Kumar5 ·
Satya Pal Nehra1

Received: 30 June 2022 / Accepted: 11 January 2023 / Published online: 27 January 2023
© The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature 2023

Abstract
A basic calcination process in one step was employed to create g-C3N4 photocatalytic composites modified by ­Gd2O3 nano-
particles. SEM (scanning electron microscopy), FTIR (Fourier-transform infrared spectroscopy), XRD (X-ray diffraction),
EIS (electrochemical impedance spectroscopy), PL (photoluminescence studies) as well as TEM (transmission electron
microscopy), XPS (X-ray photoelectron spectroscopy), and CV (cyclic voltammetry) were employed to explain the structural
traits, optical properties, and morphological features of the processed photocatalyst. The findings show that G ­ d2O3 (Gd) does
not affect the sample’s crystalline structure but rather increases g-C3N4 surface area by spreading it superficially. Furthermore,
Gd can redshift the light absorption peak, reduce the energy gap, and improve the efficiency with which photogenerated holes
and electrons are removed in g-C3N4. The surface morphology of g-C3N4, in particular, could be significantly enhanced. We
similarly employed three distinct photocatalytic complexes of ­Gd2O3 and g-C3N4 in 1:1, 2:1, and 3:1 proportions to degrade
methylene blue (MB). After 100 min in visible light (400–800 nm), the photodegradation rate of composites is 58.8% for 1:1
(GG1), 94.5% for 2:1 (GG2), and 92% for 3:1 (GG3). In addition to the MB dye, the photocatalytic activity of synthesized
materials was also studied for methyl orange. The result shows phenomenal degradation values, i.e.; for GG1 86%, GG2
96%, and for GG3 84.6%. The narrow band gap that separates the photogenerated electron and hole enhances g-C3N4 ability
to degrade photo-catalytically. From the result, we concluded that the photocurrent and cyclic photocatalytic degradation of
methylene blue shows that a composition of 2:1 ­Gd2O3/g-C3N4 has high photocatalytic stability.

Keywords Gd2O3 · g-C3N4 · Photocatalysts · Waste water treatment

Introduction

Because graphitic carbon nitride (g-C3N4) is made of carbon

Responsible Editor: Sami Rtimi and nitrogen, two of our planet’s most prevalent elements, it
is an organic semiconductor that is favorable to the environ-
Vikrant Singh Rao and Rishabh Sharma have contributed equally to ment (Paul et al. 2022). A metal-free semiconductor pho-
this work.
tocatalyst, graphitic carbon nitride (g-C3N4), has a lower
* Satya Pal Nehra band gap (2.7 eV, pH.7) (Sayed et al. 2021) than G ­ d 2O 3.
[email protected]; [email protected]
Rishabh Sharma 3
Department of Inorganic Chemistry, Faculty of Science,
[email protected]
P. J. Safarik University, Moyzesova 11, 041 54 Kosice,
1 Slovak Republic
Center of Excellence for Energy and Environmental
4
Studies, Deenbandhu Chhotu Ram University of Science Department of Physics, School of Engineering &
and Technology, Murthal 131039, Sonipat, India Technology (SoET), Central University of Haryana,
2 Mahendragarh 123031, India
Interdisciplinary Program in Climate Studies (IDPCS),
5
Indian Institute of Technology Bombay, Mumbai 400076, Department of Electronic Science, Kurukshetra University,
India Kurukshetra 1336119, India

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98774 Environmental Science and Pollution Research (2023) 30:98773–98786

Moreover, high thermodynamic stability, safety for humans, that result in free radicals with a high oxidation potential
and ease of modification are all benefits of g-C3N4 (Alagh- (Li et al. 2021b). Compared to conventional approaches,
mandfard and Ghandi 2022). Although the visible light photocatalytic (Luo et al. 2022) oxidation technology pro-
response of g-C3N4 is limited (l < 450 nm) (Tian et al. 2021), vides significant benefits for the remediation of organic
its photocatalytic activity is inhibited by its rapid recombi- contaminants (Li et al. 2021c). As an illustration, consider
nation, small resistance, and specific surface area (Panchal the favorable reaction circumstances, the solar energy
et al. 2022). The photocatalytic activity of carbon nitride reaction capacity, the high degradation efficiency, and
and gadolinium oxide has not been extensively studied; only the low energy consumption (Zhou et al. 2021). Accord-
a few studies have been done (Zhou et al. 2021). Gadolin- ingly, it became more necessary to devise environmentally
ium oxide’s excellent physical and chemical characteristics safe photocatalysts (Rattan Paul and Nehra 2021). ­TiO2,
include a significant visible solar spectrum transmission a semiconductor photocatalyst (Luo et al. 2022) that has
coefficient, good insulation properties, excellent photochem- been used for decades has several benefits, including high
istry, photocatalysis consistency, and good crystal structure efficiency, cheap cost, and non-toxicity (Paul et al. 2020a).
stability (Chen et al. 2021)(Garg et al. 2022). Environment It can only absorb UV light, which makes up 4% of sun-
pollution, particularly organic dye effluent (Liu et al. 2021a), light, due to its large 3.2 eV band gap and poor quantum
which is being released at an increasing rate due to the rapid efficiency. As a result, there has been considerable interest
expansion of dyeing, coloring, and printing, has become in creating narrowband photocatalysts that react to visible
society’s central issue due to rapid industrialization and light (Zhou et al. 2021). A straightforward hydrothermal
population rise (Mariyappan et al. 2021). Among many, the process in one step was accustomed to making g-C 3N4/
one most worrisome is emerging pollutants such as water Gd2O3 photocatalytic material. We discovered through a
contamination, i.e., untreated organic contaminants from the range of property and photocatalytic performance investi-
textile industries (Chawda et al. 2019). As a result, it inspires gations that gadolinium is primarily dispersed in the form
researchers to create an environment-friendly system that of ­Gd2O3 on the surface of g-C3N4, which prevents it from
meets the environment’s needs (Ji et al. 2021). Because of altering the crystalline structure of g-C3N4 (Murugalak-
its eco-friendliness, using a photocatalyst to degrade organic shmi et al. 2020). The as-prepared composites’ improved
water contaminants is one of the most appealing approaches surface area and quantum efficiency contribute to their
(Huang et al. 2022). superior photocatalysis performance in the oxidation of
Advanced oxidation processes (AOPs) focus on generat- organic dyes (Zhou et al. 2021). From the preceding, it is
ing highly active free radicals on-site using solar energy or clear that it is worthwhile to investigate the impact of vari-
other energy sources (Paul et al. 2020a). One of the more ous metal dopants, and how a particular combination of
sophisticated oxidation techniques for reducing organic dopants might more effectively increase the photocatalytic
contaminants is photocatalytic oxidation (Rattan Paul activity of g-C3N4. In this article, a set of ­Gd2O3 co-doped
and Nehra 2021). The goal of photocatalysis is to con- g-C3N4 samples were synthesized by changing their pre-
vert electrons moving from the catalyst’s valence band to cursor’s weight ratios when added to urea. The activity of
its conduction band to break down organic contaminants photocatalytic degradation of MB dye was then assessed
utilizing clean energy from the sun (Li et al. 2021a). The in the composite samples, and the results are phenomenal
organic structure is then destroyed by a sequence of events (Table 1).

Table 1  Comparison of the present work with the recently reported works on MB dye degradation
Sr. no Precursor used Source of illumination Cphotocatlyst Cpollutant Photocatalytic degra- Refs
(mg ­mL−1) (mg ­L−1) dation efficiency (%)

1 Zinc carbonate basic dihydrate and urea Tungsten lamp 200 W 0.1 10 90 (Liu et al. 2015)
2 SSMP and urea UV lamp 365 nm 0.2 10 > 85 (Paul et al. 2020b)
3 Zinc nitrate and urea Tungsten lamp 500 W 0.33 3.2 86 (Liu et al. 2015)
4 Zinc nitrate and dicyandiamide Xenon lamp 300 W 1 10 78.6 (Yue et al. 2011)
5 Urea and Titanium oxide Xenon lamp 300 W 0.2 10 > 90 (Liu et al. 2019)
6 Melamine and Lanthanum nitrate Xenon lamp 300 W 0.6 20 > 91 (Zhang et al. 2021)
7 Urea, Zinc sulphate, and Silver nitrate Xenon lamp 300 W 0.3 10 80 (Panchal et al. 2019)
8 Urea and Gadolinium oxide Tungsten lamp 200 W 0.03 10 94 This work

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Environmental Science and Pollution Research (2023) 30:98773–98786 98775

Experiment details

Photocatalyst preparation

g‑C3N4 nanoparticle synthesis

A typical approach used 10 mL of distilled water to thor-

oughly dissolve 10 g of urea (­ CH4N2O) within a glass beaker
and dried using a hot air oven for 2 h at 60 °C (Murugalakshmi
et al. 2020). Further placed in a muffle furnace set at 2 °C/min
to achieve 550 °C and held at that temperature for 110 min
Fig. 1  One-step thermal polymerization technique used to create
in segment one, and then kept at that temperature for 3 h in g-C3N4/Gd2O3 photocatalytic composite material
segment two (Sharma et al. 2022). In the end, g-C3N4 was
created (Arora et al. 2022). Then 0.6 g mmol of G ­ d2O3 was
added and thoroughly stirred with a magnetic stirrer. After Morphological evaluation
that, ultrasonicate it for 1 h, or until the solution has been
homogenized. The produced solution was then dried for 1 h The appearance and nanostructure of ­G d 2 O 3 /g-C 3 N 4
at 100 °C (Jeon et al. 2021). After completely drying, a white were captured using SEM, as represented in Fig. 2a
solid residue was developed (Paul et al. 2020b). The entire and b g-C3N4 resembling sheet-like morphology. Fig-
white material was etched and transferred to a crucible kept ure 2c shows a magnified image of the best composite GG2
in a muffle furnace set at a heating rate of 2 °C/min to reach while confirming the produced G ­ d2O3 as a rod form. It
550 °C with the top securely wrapped to reduce gas loss and is imperative to emphasize that when g-C 3N4 nanoparti-
kept at room temperature for 3 h (Li et al. 2021c). The result- cles are bedaubed by G ­ d2O3 nanoparticles, the structure
ant substance was then allowed to cool naturally. The resulting of ­Gd2O3 is unchanged, but the surface becomes rougher.
material was extracted from the crucible, crushed to a fine ­Gd2O3 was found to be regular rods equally distributed
bright yellow powder, and labelled as GCN-Gd203 composite over of g-C3N4 surface. The components of the nanocom-
(Rattan Paul et al. 2019b). The immaculate graphitic carbon posite were verified (Fig. 2d) using the EDS graph (Li et al.
nitride was made by directly heating 10 g of urea using a 2021a). The peaks of Gd, N, C, and O are all visible. Fig-
furnace (Mariyappan et al. 2021). GCN-pure is a light pale ure 2e shows the elemental mapping for GG2, confirming
yellow powdered sample that was crushed to a fine powder. the presence of C, N, O, and Gd.

TEM analysis
Preparation of g‑C3N4/Gd2O3 composites
The transmission electron microscopy (TEM) image depic-
A simple one-step thermal polymerization technique utiliz- tion in Fig. 3 provides extensive insights into the produced
ing urea was used to create g-C3N4/Gd2O3 photocatalytic nano-composite shape and particle size. Individually, the
material (Fig. 1). Furthermore, other ratio combinations of rod-like ­Gd2O3 and the layered g-C3N4 were clearly discern-
g-C3N4/Gd2O3 (GG) were generated, with 0.6 g of GCN and ible in the reported TEM representations (Fig. 3a), and it
0.6 g ­Gd2O3 formed using the preceding procedure in a 1:1 was discovered that the ­Gd2O3 nanoparticles had an even
mass ratio (GG1), and 0.6 g GCN and 0.3 g ­Gd2O3 (GG2) surface and an estimated length of 64.3 nm. Figure 3b shows
together with 0.6 g GCN and 0.2 g G ­ d2O3 (GG3) formed in the TEM image of a single GG2 nanoparticle (Panchal et al.
2:1 and 3:1 mass ratio, respectively. 2022).

Functional group investigations using FT‑IR

Result and discussion The Fourier-transform infrared (FT-IR spectra) of g-C3N4,
­Gd2O3 nanoparticles, and GG nanocomposite were obtained in
In order to study the characteristics, structure, and appli- the 400–4000 ­cm−1 range and are displayed in Fig. 4. S-triazine
cations of the synthesized composites, various techniques was responsible for the most vital band in g-C3N4 at 801 ­cm−1,
have been utilized, such as FTIR, XRD, FESEM, EDS, and C–N bonds and C = N stretching bands were responsible
XPS, CV, and PL. Reusability testing and scavenger tests for other more crucial bands at about 880–1625 ­cm−1. For the
were then conducted to check the potential of composites. projected Gd-O stretching mode, a large vibration band with

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98776 Environmental Science and Pollution Research (2023) 30:98773–98786

Fig. 2  a SEM image of GCN. b, c Magnified image of GG2 composites. d EDS graph showing different components of nanocomposites present
in GG2 material. e Elemental mapping of GG2 sample

a range of 410 to 530 ­cm−1 has been seen in the FT-IR spec- stretching band of the C–O group), respectively, suggest that
tra of ­Gd2O3 and manufactured GG (Saravanan et al. 2018). soluble phytochemicals were involved in the formation of
Significant peaks in g-C3N4 and GG around 3050–3450 (N–H ­Gd2O3 photo-nanocomposite, which prevented nanoparticle
vibration) and 1065, 1129, 1215, and 1550 ­cm−1 (shifting of aggregation in solution (Chen et al. 2021).

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Environmental Science and Pollution Research (2023) 30:98773–98786 98777

Fig. 3  a TEM image of GCN at 100 nm. b TEM image of GG2 composite at 100 nm

Fig. 4  FT-IR spectra of pure g-C3N4 (black curve), GG1 (red curve), Fig. 5  XRD patterns of g-C3N4, Gd, GG1, GG2, and GG3 composites
GG2 (blue curve), and GG3 (pink curve) materials

XRD evaluation EIS studies

The X-ray diffraction (XRD) findings of pure ­Gd2O3, pristine The electrochemical impedance spectroscopy (EIS) or fre-
g-C3N4, and GG nanocomposite are given in Fig. 5. The two quency response analysis (FRA) was examined to deter-
reported values for the peaks of G ­ d2O3 nanoparticles are at mine the impedance of the composites in a 1 M H ­ 2SO4
26.31, 28.66, 29.52, 30.25, 31.12, 31.74, 32.61, 39.26, 41.23, solution. The applied frequency range for the measure-
42.46, 47.65, 51.22, 51.94, 53.92, 55.65, 56.52, 60.1, and 60.58° ment was 0.1 Hz to 100 kHz. Figure 6 displays the plot
(Fig. 5). PDF-2 card sequence, 00–012-0474, is associated with between actual impedance (Z′) and imaginary impedance
synthesized ­Gd2O3 nanoparticle XRD pattern. Similarly, the (Z″). Examining the effectiveness of charge separation at
g-C3N4 peaks have values of 13.25° and 27.66°, which corre- the interface is a vital function of the EIS Nyquist plot.
spond to all values of (100) and (002) crystallographic planes. The EIS Nyquist plot’s arc radius indicates that interface
The discovered C­ 3N4 diffraction peaks correspond to the JCPDS layer resistance occurs over the electrode’s surface. As
card number, 87–1526. The XRD results of GG nanocomposite seen in Fig. 6, synthetic GG2 samples had their Nyquist
perfectly match ­Gd2O3 and g-C3N4 altogether. properties drawn between the actual and fictitious imped-
ance portions (Yadav et al. 2022).

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98778 Environmental Science and Pollution Research (2023) 30:98773–98786

Fig. 6  Nyquist plots of all the composites with fitted diagram of GG2 composite

Cyclic voltammetry Photoluminescence studies

Cyclic voltammetry (CV) tests were used to study electro- The photoluminescence (PL) emission spectra of the eco-
chemical properties. At different scanning rates, the GG2 friendly produced patches were studied for light-driven charge
composite’s CV curves were seen in the range of − 0.5 to movement. The PL emission peak in GG2 is between 420 and
0.5 V. Figure 7 displays the sample's CV curves. The area 450 nm (Fig. 8), demonstrating that the nanocomposites con-
of the plot is maximum for GG2, and also the anodic and tain various oxygen vacancies and defects. Spectra of various
cathodic peak for GG2 has a current density value. The quasi- PL emissions were contrasted.
rectangular CV curves represent the pseudocapacitive behav-
ior of composites with a high surface area, making it a good
candidate for rapid redox reactions (Danish et al. 2020).

Fig. 8  The photoluminescence emission spectra of GCN, GG1, GG3,

Fig. 7  Cyclic voltammetry (CV) of GG2, GG1, and GG3 composites and the best GG2 composite

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Environmental Science and Pollution Research (2023) 30:98773–98786 98779

Photocatalytic activity measurements The apparent rate constant for the degradation process
was found using the Langmuir-Hinshewood equation-based
One hundred millilitres of dye solution (10 ­mgL−.1) containing pseudo-first-order kinetic model (Paul et al. 2019).
0.01 g of sample were mixed together in a conical flask. Further,
it was stirred in the dark for 30 min to attain adsorption–desorp- XPS studies
tion equilibrium (Zhurenok et al. 2021). Two tungsten lights
were then used to irradiate the solution. At regular intervals The surface compositions and bonding states of the as-
throughout the experiment, 2 mL aliquots of the solution were prepared ­G d 2O 2 with GCN best composite, termed as
collected, centrifuged, and tested using a UV–Vis spectropho- GG2, were further investigated by XPS. It explained that
tometer (Sharma et al. 2022; Rattan Paul et al. 2019a). The the primary components of GG2 are C, N, O, and Gd. The
photocatalytic degradation efficiency was calculated as follows: binding energies of the C–C bond (Tayyab et al. 2022), ­sp2
where C is the concentration of solution at time t and C0 is the C (N = C–N), and -electron excitation in the tri-s-triazine
equilibrium adsorption/desorption concentration of solution at units, respectively, were ascribed to the XPS peak of C 1 s,
time t0 which can be divided into two peaks centring at 284.04
( ) and 287.47 eV, as shown in Fig. 9a. The N 1 s XPS peak
E = 1 − C∕C0 ∗ 100%
in Fig. 9c can be divided into three peaks at 397.8, 398.8,

Fig. 9  a XPS spectra of GG2

(black curve) composite; XPS
spectra of C 1 s (b), N 1 s (c), O
1 s (d), and Gd 4d (e)

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98780 Environmental Science and Pollution Research (2023) 30:98773–98786

and 400.1 eV. They could be attributed to the binding ener- Photocatalytic analysis
gies of the tri-s-triazine units’ ­sp2 N (C = N–C), N–H and
­e− excitation, respectively. In contrast, the O 1 s signal in As seen in Fig. 10, produced materials were used to analyze
Fig. 9d could be deconvoluted to 531.3 eV. Figure 9e indi- their photocatalytic degradation capability toward methyl-
cates the existence of Gd element in ­Gd2O3/g-C3N4 is in ene blue (MB) dye. As demonstrated in Fig. 10e, samples
­Gd3+ oxidation state at energies of 142.5 eV and 146.8 eV. of GG2 outperformed in terms of photocatalytic activity.
From the acquired XPS data, it is clear that the nanocom- The dye degradation potential of all different composites
posite contains all of the components (Gd, C, N, and O) was studied and compared with the GCN-pure and G ­ d 2O 3
and is in the GG2 oxidation state (­ O2− and G­ d3+). The high (Fig. 11a, b). In the case of GG2, the degrading efficiency
− +
separation efficiency of e­ -h pairs with remarkable redox was discovered to be 94.5% in 100 min. Three different pho-
ability was confirmed using XPS analysis. Therefore, the tocatalytic composites of ­Gd2O3 and g-C3N4 in the ratios of
above heterojunction is of Z-scheme. GG1, GG2, and GG3 were developed to destroy MB. After
100 min in visible light (400–800 nm), the photocatalytic

Fig. 10  Photocatalytic degradation activity toward MB dye. a Pure GCN, b pure ­Gd2O3 (Gd), c GG1, d GG2, and e GG3

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Environmental Science and Pollution Research (2023) 30:98773–98786 98781

Fig. 11  a Comparison of photo-

catalytic activity. b ln(C0/C(t))
for MB degradation as a func-
tion of visible light irradiation
time for GG (1, 2, 3) samples,
GCN-pure, and ­Gd2O3

degradation rate of composites is 58.8% for GG1, 94.5% for photogenerated electrons and less photogenerated charge
GG2, and 92% for GG3. The reduced or small band gap sep- carrier recombination. Trapping studies were carried out to
arates the photoinduced electrons and holes, which boosts show the part dynamic species played in the degradation of
g-C3N4 photocatalytic degradation capacity. When exposed MB dye after 100 min of exposure to visible light, measured
to the light of the right intensity, a photocatalytic substance using a UV–vis spectrometer using 0.1 mM ascorbic acid
could produce electrons and holes (Chaudhary et al. 2021). (AA), 10 mM methanol (M), 10 mM potassium dichromate
­(K2Cr2O7), and 10 mM ammonium oxalate (AO) as ­O2•,
Scavenger test •OH radicals, e­ −, and ­h+ scavengers respectively. Figure 12
shows that AO significantly reduced photoactivity, indicat-
According to the discussion above, the GG2 composite ing that ­h+ played the primary role in the photodegradation
sample had increased adsorption and photoactivity com- process. The reduced degree to which AA and methanol
pared to pure GCN. Factors such as reduced band gap and inhibited photoactivity demonstrates that O ­ 2• and •OH reac-
enhanced surface area support the phenomena of synergism tive species are not the key players in process of photodeg-
among adsorption and photocatalysis may result from two radation. On the other hand, no obstruction to photoreduc-
vital evolutionary processes that occurred between the two tion was seen when ­K2Cr2O7 was present, indicating that
variants and may account for this reaction. The GG2 sam- ­e- played a minimal part in the photodegradation process.
ple showing a high surface area may offer more photo-cat-
alytically reactive sites, resulting in ­e- production of more Reusability experiment

Recyclability tests were performed for five-cyclic runs to

evaluate the reusability aspect of the manufactured GG2
sample (Fig. 13). After each photocatalytic experimental
run, the active photocatalyst was once again collected and
employed under the same conditions in the subsequent cycle.
The efficiency of photoactivity was observed to be nearly
constant for all test runs. A minor decrease in activity for
each cycle might be explained by the procedural loss of pho-
tocatalyst during test runs. TEM image of GG2 after 5 cycles
shows that there was no noticeable change in the morphol-
ogy of the composite, which is in very good agreement with
the stability of the synthesized composites.

Total organic carbon

In addition to the characteristics listed above, photocata-

lytic activity seen in the original test suggested that GG2
Fig. 12  Effect of electron, hole, ­O2•− and •OH, and scavengers on can mineralize MB. To assess the mineralization potential
MB dye degradation for 100 min of irradiation

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98782 Environmental Science and Pollution Research (2023) 30:98773–98786

Fig. 13  a The recyclability of GG2 after 5 cycles. b TEM image of GG2 after recyclability tests

of GG2, the total organic carbon (TOC) values were thus ­(Ee) as evaluated on the H scale (4.5 eV) (Sivasamy et al.
measured during MB degradation. Nearly 50% of full TOC 2020). The computed EVB and ECB were + 1.505 eV
was lost throughout the photodegradation, as shown in and − 1.165 eV for g-C 3N 4, and + 2.4 and − 0.6 eV for
Fig. 14, even though MB, a broad-spectrum cationic dye, ­Gd2O3, respectively (Meng et al. 2021). The CB and VB
was demonstrated to be stable in the environment. This positions mainly depend on the band gap of the nano-
declining trend of T ­ OCt/TOC0 acquired using GG2 is dis- material (Saravanan et al. 2021). The band gap of the
tinct over the timeline. Rapid mineralization is essential in nanomaterials varied based on the synthetic methodol-
the treatment of wastewater containing dyes to get rid of ogy. Related to the data obtained, a credible band dia-
intermediates that could provide dangers to the environment gram was concocted to elucidate the charge transfer and
and ecosystem. separation between g-C3N4 and G ­ d2O3. Thus, the excited
In addition to the MB dye, the photocatalytic activity of electrons and holes can be conclusively separated, rescind-
synthesized materials was also studied for methyl orange ing the achievability of charge carrier recombination (Liu
(MO, Fig. 15a–c). Samples were studied for their photocata- et al. 2021b). The calculated EVB and ECB for g-C3N4
lytic potential toward the photodegradation of MO dye solu- were + 1.505 eV and − 1.165 eV, whereas for ­Gd2O3, they
tion (Fig. 16a, b). The result shows phenomenal degradation were + 2.4 and − 0.6 eV, respectively. The band gap of the
values, i.e.; for GG1 86.0%, GG2 96.0%, and for GG3 84.6%
were observed during the analysis.

Photocatalytic mechanism

The valence band and conduction band potentials for both

g-C3N4 and ­Gd2O3 were calculated in order to get insight
­ d2O3/g-C3N4 heterojunction
into the band structure of the G
explaining Eqs. (1) and (2):
EVB = χ − Ee + 0.5Eg (1)

ECB = EVB + Eg (2)

Therefore, the band gap energy ­(E g ) is calculated
using Tauc’s plot (2.67 eV for g-C 3N 4 and 3.34 eV for
­Gd2O3), the conduction band potential (ECB) of ­Gd2O3
and g-C3N4, the valence band potential (EVB), the elec-
tron negativity (EN), and the energy of free electrons Fig. 14  TOC removal rate of 10 mg/L MB using GG2 composite

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Environmental Science and Pollution Research (2023) 30:98773–98786 98783

Fig. 15  Photocatalytic degradation activity toward MO dye for a GG1, b GG2, and c GG3 composites

nanomaterial strongly influences the CB and VB loca- dissolution of ­O2. The hole in VB of g-C3N4 that thrives as
tions. Based on the synthesis approach, the band gap of the an auxiliary in the dilapidation operation can retaliate with
nanomaterials varies. According to the data, an accurate MB and MO molecules on the surface of the composite,
band diagram was created to explain how charges trans- engendering a degraded product (Zhurenok et al. 2021).
ferred between g-C 3N 4 and G ­ d 2O 3 and how they sepa- The interface between G ­ d2O3 and g-C3N4 is an efficacious
rated. By effectively separating the excited electrons and modus operand to discrete the photo-induced charges and
holes, charge carrier recombination is no longer possible lessen the recombination rate, ensuing in higher photocat-
(Mariyappan et al. 2021). In effect of the negativity of the alytic rendition. The translocation of photogenerated elec-
CB energy potential of g-C3N4, the relocation of photo- trons from CB of g-C3N4 to CB of G ­ d2O3 via heterojunc-
generated electrons from CB of g-C3N4 to CB of G ­ d 2O 3, tion becomes simple as a result of the negative of the CB
through heterojunction, becomes facile. Consequently, in energy potential of g-C3N4 (Fig. 17). Eventually, organic
order to prompt •O2−, which can squarely degrade MB and pollutants are broken down by ­h+ and ­O2 into the water
MO dye, the electron in CB of G ­ d2O3 will accelerate the and ­CO2, according to the proposed response mechanism.

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98784 Environmental Science and Pollution Research (2023) 30:98773–98786

Fig. 16  a Comparison of photo-

catalytic activity for MO dye of
GG1, GG2, and GG3 materials.
b ln(C0/C(t)) for MO degrada-
tion as a function of visible
light irradiation time for GG
(1, 2, 3) composites

Conclusion the composites photocatalytic degradation rate of MB were

58.8% for GG1, 94.5% for GG2, and 92% for GG3. The pho-
This experiment created GG composites with a straightfor- tocatalytic activity of synthesized materials was also studied
ward one-step thermal polymerization process. The struc- for methyl orange. The result shows phenomenal degrada-
tural morphology and elemental compositions of pristine tion values, i.e.; for GG1 86.0%, GG2 96.0 %, and for GG3
g-C3N4 and GG composites were studied using FT-IR, XRD, 84.6% were observed during the analysis. The reduced band
XPS, TEM and SEM. G ­ d2O3 was created during the thermal gap separates the photogenerated charge carriers, which
polymerization method, which spread homogeneously over increases g-C3N4 photocatalytic degradation capacity. We
the surface of GCN. The results show that adding ­Gd2O3 deduced from the photocurrent and cyclic photocatalytic
enhances the specific surface area and offers more active degradation of methylene blue that is GG2, GG composi-
sites. Three different photocatalytic composites of G ­ d 2O 3 tion has photocatalytic solid stability.
and g-C3N4 in the mass ratios 1:1, 2:1, 3:1 denoted GG1,
Acknowledgements Vikrant Singh Rao is highly thankful to Deen-
GG2, and GG3, respectively, were developed for photo- bandhu Chhotu Ram University of Science and Technology, Murthal,
catalytic degradation of methylene blue (MB) and methyl for providing University Research Scholarship (No. DCRUST/
orange (MO). After 100 min in visible light (400–800 nm), Sch./2022/242-247). Rishabh Sharma is highly thankful to Ministry of

Fig. 17  Proposed photocatalytic

mechanism for GCN-Gd2O3
photocatalyst

13

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Environmental Science and Pollution Research (2023) 30:98773–98786 98785

Education, Govt. of India for Prime Minister Research Fellowship sup- Nano-Metal Chem 0:1–7. https://d​ oi.o​ rg/1​ 0.1​ 080/2​ 47015​ 56.2​ 020.​
port reference no. PMRF-192002-1599. Anshu Sharma acknowledges 17900​00
the University Grants Commission, Ministry of Education, Govt. of Garg A, Almasi M, Bednarik J, Sharma R, Rao VS, Panchal P, Jain A,
India for providing Start-Up-Grant reference no. 30-545/2021 (BSR). Sharma A (2022) Gd(III) metal-organic framework as an effective
humidity sensor and its hydrogen adsorption properties. Chem-
Author contribution Vikrant Singh Rao and Rishabh Sharma: concep- osphere 305(1):135467. https://​doi.​org/​10.​1016/j.​chemo​sphere.​
tualization, methodology, investigation, roles/writing—original draft, 2022.​135467
and writing—review and editing. Devina Rattan Paul: methodology, Huang Y, Chen F, Guan Z et al (2022) S-Scheme BiOCl/MoSe2 hetero-
and roles/writing—original draft. Miroslav Almáši, Anshu Sharma, structure with enhanced photocatalytic activity for dyes and anti-
Suresh Kumar, and Satya Pal Nehra: supervision, project administra- biotics degradation under sunlight irradiation. Sensors 22:1–14.
tion, conceptualization, methodology, roles/writing—original draft, https://​doi.​org/​10.​3390/​s2209​3344
and writing—review and editing. Jeon S, Ko J-W, Ko W-B (2021) Synthesis of G ­ d2O3 nanoparticles and
their photocatalytic activity for degradation of azo dyes. Catalysts
Data availability The data are available on request. 11(6):742. https://​doi.​org/​10.​3390/​catal​11060​742
Ji J, Bao Y, Liu X et al (2021) Molybdenum-based heterogeneous cata-
Declarations lysts for the control of environmental pollutants. EcoMat 3:1–34.
https://​doi.​org/​10.​1002/​eom2.​12155
Consent to participate For this type of study, formal consent is not Li L, Wang F, Feng J, Guo S, Xu M Wang L, Quan J (2021a) Direct
required. Z-scheme ­GdFeO3 / g-C3N4 heterostructures with outstanding pho-
tocatalytic activity. Res Sq. https://​doi.​org/​10.​21203/​rs.3.​rs-​255210/​v1
Consent for publication Not applicable. Li R, Ma H, Shu J, Lian Z, Chen N, Ou S, Jin R, Li S, Yang H (2021b)
Surface engineering of copper sulfide-titania-graphitic carbon nitride
Competing interests The authors declare no competing interests. ternary nanohybrid as an efficient visible-light photocatalyst for pol-
lutant photodegradation. J Colloid Interface Sci 604:198–207. https://​
doi.​org/​10.​1016/j.​jcis.​2021.​07.​030
Li X, Yang J, Zhang W (2021c) Influence of tetrabutylammonium
hydroxide on the microstructural, optical and photocatalytic prop-
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