Journal of Cleaner Production 345 (2022) 131139

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Journal of Cleaner Production

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

Recent advances on gadolinium-based nano-photocatalysts for

environmental remediation and clean energy production: Properties,
fabrication, defect engineering and toxicity
G. Harini, S. Balasurya, S. Sudheer Khan, PhD *
Nanobiotechnology Laboratory, Department of Biotechnology, Bannari Amman Institute of Technology, Sathyamangalam, Tamil Nadu, India

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

Handling Editor: Bin Chen In recent years, gadolinium (Gd)-based photocatalysts have been gaining attention for their exquisite properties
and have been exploited as potential photocatalyst for environmental remediation. This review provides a
Keywords: comprehensive review on the photocatalytic activity of Gd-based nano-materials and their extensive application
Gd-nanomaterials in environmental water treatment. Furthermore, this review describes the synthesis methods, optimization pa­
Modification techniques
rameters, modification techniques, multifarious utilization, and anti-stokes upconversion properties of Gd
Photocatalytic applications
nanomaterials. In addition, the drawbacks of Gd-based nanomaterials were discussed and have been addressed
Toxicity studies
with modification techniques. Photocatalytic application of Gd-based nanoparticles (NPs), nanocomposite (NCs)/
heterojunctions, dopants, and upconversion NPs has been discussed in detail. This review especially focuses on
the influence of trivalent Gd dopant on the physical, magnetic, and photocatalytic properties of the most
exploited host semiconductor photocatalysts. Furthermore, other photocatalytic applications of Gd NPs including
hydrogen evolution, CO2 reduction, and heavy metal removal have also been discussed. Toxicity studies on
various forms of Gd have been evaluated to extend its application to industrial scale. Overall, this review sheds
light on the recent developments in Gd-based nanomaterial in terms of its application in pollutant removal,
advantages, and toxicity aspects.

1. Introduction high efficiency, and reproducibility (Mishra et al., 2019). Photocatalysis

Availability of consumable water has become a rising concern due to
the contamination of the majority of water bodies. The majority of these
contaminants are organic pollutants such as organic dyes, antibiotics,
and pesticides, which are released from the paper, textile, and phar­
maceutical industries (Kumar et al., 2020a). According to previous lit­
eratures, almost 17–20% of industrial wastewater comprise of organic
dyes as a source from textile dyeing and treatment, which are environ­
mentally persistent to conventional remediation methods (Ge et al.,
2021). A broad spectrum of conventional treatment processes including
chemical coagulation activated sludge, carbon adsorption, filtration,
flocculation, and biodegradation has been widely employed over years.
However, these processes acquires certain disadvantages, which include
high chemical consumption, monitoring, high capital cost, and main­
tenance (Brijesh et al., 2009; Hussain et al., 2021). Advanced oxidation
process (AOP) has been considered as a highly efficient and promising
approach for the removal of organic pollutants owing to its simplicity,
is a versatile process that can be used for various applications including
pollutant degradation, antimicrobial applications, H2 production, CO2
reduction, and biomass conversion (Chen. et al., 2019; Sharma et al.,
2019; Kumar et al., 2021). The most widely exploited nanomaterials
including SnO2, WO3, ZnO, and TiO2 are considered to be promising
photocatalysts due to their extensive properties (Hasija et al., 2019;
Rono et al., 2020). Among them, TiO2 has been widely used for its low
toxicity, cost efficiency, high photosensitivity, water splitting capacity
and high oxidizing capacity (Raizada et al., 2017a; Tang et al., 2018).
However, these photocatalysts possess some drawbacks including low
quantum yield due to their fast electron-hole recombination rate, low
absorption in the visible region, and poor surface coverage (Yang and
Wang, 2018). Several modification techniques have been proposed to
overcome the aforementioned drawbacks including construction of
heterojunction/NCs, doping (metal/non-metal), and coupling the
intrinsic material with an upconversion phosphor (Yu et al., 2017; Lee
et al., 2020; Liu et al., 2009; Veiga et al., 2020; Singh et al., 2020;

* Corresponding author.
E-mail address: sudheerkhan@bitsathy.ac.in (S.S. Khan).

https://doi.org/10.1016/j.jclepro.2022.131139
Received 13 October 2021; Received in revised form 20 February 2022; Accepted 24 February 2022
Available online 26 February 2022
0959-6526/© 2022 Elsevier Ltd. All rights reserved.
G. Harini et al.
Raizada et al., 2017b).
The research progress on the rare earth metal-based photocatalysts
are far behind the sporadic and expensive late transition metals. Gd is a
rare earth metal with a variety of specialized widespread applications
such as contrast agents in MRI, phosphors in the television picture tubes,
neutron capture therapy for cancer, neutron absorber in nuclear re­
actors, and nowadays, as photocatalysts (Robertson and Rendina, 2021;
Janani et al., 2021). Gd-based nanomaterials have been reported to
serve as a potential and suitable catalyst for photocatalytic reactions
among the other rare earth elements owing to their empty 5d-orbital and
half-filled 4f-orbital (Hunagund et al., 2017). The half-filled f-orbitals of
Gd photocatalysts are believed to contribute to enhanced photocatalytic
performance by acquitting themselves as electron trap centers, which
eventually bring down charge carrier recombination. Moreover, as a
part of the lanthanide series, Gd can form complexes with numerous
Lewis bases, which helps to concentrate organic pollutants on the pho­
tocatalytic surface, thereby enhancing the photocatalytic performance
(Hunagund et al., 2017). Even though many of the Gd-based nano­
materials falls under the category of wide bandgap photocatalysts, its
versatile bandgap tunability and exquisite features including room
temperature superparamagnetic behavior, up-conversion ability makes
them overcome its limitations. Various synthesis methods, strategic
modification techniques were widely studied to enhance their photo­
catalytic performance. However, the vast majority of the currently
available literature on Gd nanomaterials was majorly focused on
biomedical applications and especially its exploitation as a contrast
agent in imaging techniques (Mcdonald and Mcdonald, 2020). It has
been observed that the available literatures either explicated the
exquisite properties and photocatalytic ability of all the lanthanide el­
ements or its influence on a particular intrinsic semiconductor nano­
material. This review attempts to provide a broad insight into the
photocatalytic ability of various forms of Gd-based nanomaterials and its
unique properties, which makes them a potential photocatalyst. The
predominant aim of the review is to provide an overview of the photo­
catalytic application of Gd-based nanomaterials, specifically, the role of
Gd on the enhancement of photocatalytic property of various intrinsic
host nanomaterials. In addition, the review also intends to provide a
better understanding of Gd photocatalysts on their redox abilities,
charge carrier dynamics, bandgap tunability, defect regulation,
anti-stokes up-conversion properties, and toxicity. Moreover, the
employment of Gd-based NPs and their application on various photo­
catalytic applications including pollutant removal, hydrogen evolution,
CO2 conversion, and heavy metal reduction has been briefly addressed.
Furthermore, perspective on its future development and challenges were
discussed in detail to extend its applicability as a potential
photocatalyst.
2. Properties of Gd
Gd is a malleable and ductile rare-earth element with solid silvery-
white colour. It crystallizes in hexagonal close-packed (alpha) form
and transforms to body-centered cubic (beta) form on heating at 1235 ◦ C
(Emsley, 1990). Gd (III) possesses the largest possible total spin (S =
7/2) and correspondingly very large spin magnetic moment owing to
their seven unpaired valence electrons (Pyykko, 2015). Subsequently,
these unpaired electrons bestow them with strong magnetic suscepti­
bility and the potential to absorb and emit light. Additionally, Gd is the
only lanthanide element to exhibit ferromagnetic behavior at room
temperature along with cobalt, iron, and nickel. The element becomes
strongly paramagnetic above 297K (Curie point-Tc), hence known as
Heisenberg ferromagnet. However, the aforementioned properties could
be manipulated by the purity scale of the obtained Gd, which could
broaden the paramagnetic-ferromagnetic transition temperature range
and significantly lower the Curie temperature (Tc) (Dan’kov et al.,
1998). Gadolinium (III) Oxide (Gd2O3), archaically known as gadolinia
is the most commonly available form of Gd. Under different production
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Journal of Cleaner Production 345 (2022) 131139
ambiances, Gd2O3 exhibits multifarious crystalline structures ranging
from cubic to monoclinic and hexagonal (Deng et al., 2018; Muneer
et al., 2015). These properties of Gd2O3 make it a potential applicant for
Imaging techniques, detectors, luminescent and biomedical devices
(Maalej et al., 2015; Zhydachevskyy et al., 2018). However, studies on
Gd2O3 as photocatalyst are scarcely available.
3. Synthesis, characteristics and photocatalytic application of
Gd-based nanomaterials
Gd NPs are widely studied for their extensive properties including
half-filled 4f orbital, paramagnetic behavior (room temperature), ther­
mal stability, and luminescent properties. The widely available Gd2O3
has often been exploited for a broad range of applications; however, its
wide bandgap (up to 5.2 eV) is still a concern for its employment as a
photocatalyst. Hence, Gd NPs have been synthesized in various forms as
titanate (GdTi2O7, GdTiO3), vanadate (GdVO4), tungstate (Gd2(WO4)3),
and as perovskites (GdXO3, Gd2XYO6) for its effective utilization in the
photocatalytic application, which is discussed in detail.
3.1. Gadolinium oxide (Gd2O3) NPs
Gd2O3 exhibits a wider bandgap which could respond only under UV
light. It was found to exhibit better photocatalytic activity than the
commercial TiO2 photocatalyst against chloramphenicol and here, •OH
(hydroxyl) radicals played as dominant reactive oxygen species (ROS)
(Dhanalakshmi et al., 2019). In a similar study, hydrothermally syn­
thesized Gd2O3 exhibited bandgap energy of 3.30 eV, where its photo­
catalytic activity was scrutinized under both visible and UV
illumination, as expected, it expressed no significant photocatalytic ac­
tivity under visible light owing to their wide bandgap but was found to
be active under UV light (Mkhalid, 2016). Several methods were
employed for the synthesizing of the Gd2O3 nanomaterial. Here, the
bandgap and the crystalline structure of the nanomaterial varies upon
environmental parameters employed during synthesis.
3.1.1. Concerns and challenges on the synthesis of Gd2O3
The crystalline phase of the Gd2O3 varies by different environmental
parameters such as temperature, time of interaction, volume of the re­
action mixture, density of the solution, and concentration of precursors.
This eventually contributes to the formation of various crystalline pha­
ses as tetragonal, monoclinic, trigonal, and their corresponding space
groups as P-4m2, C2/m, and P-3m1 respectively (Fig. 1a). Furthermore,
their corresponding bandgap energy was observed to be 1.32, 2.856, and
3.128 eV respectively (Fig. 1b).
3.2. Gadolinium tungstate (Gd2(WO4)3)NPs
Gd2(WO4)3 NPs has gained much attention owing to their exclusive
properties including ferroelectricity, low toxicity, excellent thermal and
chemical stability. Moreover, the photochemical properties of
Gd2(WO4)3 have been widely investigated for the tetrahedral geometry
of WO4, which exhibits excellent photochemical stability, high quantum
yield, and low phonon energy (Yadav et al., 2016; Huang and Hart,
2020). In comparison with Gd2O3, Gd2(WO4)3 has been found to have its
bandgap range from 2.74 to 4.2 eV, which exhibits photocatalytic ac­
tivity under both visible and UV regions in respective cases. Moreover,
the optimally produced Gd2(WO4)3 exhibited better photocatalytic
performance (99%) than the commercial TiO2 photocatalyst (44%)
under 60 min of UV irradiation (Nasrabadi et al., 2017; Liu and Zhou,
2019). Among various studies on the photocatalytic ability of
Gd2(WO4)3, only 2D nanoflake structured Gd2(WO4)3 was found to have
an optical absorption threshold at the visible region, owing to its narrow
bandgap (Periyasamy et al., 2019; Mosleh, 2017). Although, almost all
the reported cases of Gd2(WO4)3 photocatalyst were prepared via the
co-precipitation method, varied reaction conditions played a crucial role
G. Harini et al. Journal of Cleaner Production 345 (2022) 131139

Fig. 1. (a) Crystalline phases of different Gd based nanomaterials and (b) comparative analysis of bandgap of Gd based nanomaterials.

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G. Harini et al. Journal of Cleaner Production 345 (2022) 131139

in its optical, morphological, and photocatalytic properties leading to
the varied bandgap, crystalline phase, and surface area (Table 1).
3.2.1. Concerns and challenges on the synthesis of Gd2(WO4)3
Gd2(WO4)3 exhibits three predominant crystalline phases as two
monoclinic with C2/c and P21/c space group, and orthorhombic with
Pba2 space group. The bandgap energy of the Gd2(WO4)3 at monoclinic
and orthorhombic phases were found to be 3.7, 3.2, and 3.3 eV
respectively (Fig. 1b). Various reaction parameters during the synthesis
lead to change in their crystalline phase and thereby its bandgap energy.
3.2.1.1. Phases of Gd2(WO4)3. It has been found that the variation in
magnetic moment was observed upon change in the atomic arrangement
of the nanomaterial. The final magnetic moment of monoclinic
Gd2(WO4)3 with space group of C2/c and P21/c was observed to be
14.031 μB and 14 μB respectively. On the other hand, the magnetic
moment of orthorhombic Gd2(WO4)3 with space group of Pba2was
found to be 0.102 μB. Here, the orthorhombic phase shows a loss in
magnetic moment owing to its atomic arrangement.
3.3. Gadolinium vanadate (GdVO4) NPs
GdVO4 NPs have attracted intensive attention as a visible light active
photocatalytic material with a narrow bandgap, non-toxicity, and
luminescence properties, which has been widely applied in the field of
laser technology and optoelectronic devices (Nikolic et al., 2013). Being
a visible light photocatalyst, the bandgap of GdVO4 was observed to be
in the range of 2.2–2.95 eV, whose CB potential was found to be negative
enough to generate •O2− (superoxide) radicals. Accordingly, the studies
have reported the effective generation of •OH and O2. radicals, which
played a crucial role in the degradation of various target pollutants
under visible light (He et al., 2020; Shandilya et al., 2019; Vosoughifar,
2017). Furthermore, GdVO4 has been reported to be coupled with
various other semiconductor materials for better charge transfer and
efficiency. In comparison with oxide and tungstate form of Gd, vanadate
was observed to exhibit better photocatalytic performance in terms of its
bandgap tunability and redox potentials. Accordingly, studies have re­
ported wide usage of GdVO4 in the construction of heterojunctions for
tuning the bandgap and photocatalytic property of the host semi­
conductor photocatalysts.
3.3.1. Phase formation of GdVO4 NPs
GdVO4 NPs forms a crystalline tetragonal structure with space group
of I41/AMD with unit cell angular lattice of α (alpha) = β (beta) =
106.183◦ , γ (gamma) = 116.268◦ and the unit cell plane as a = b = c =
6.076 Å, 10.257 Å (Fig. 1a). The final magnetic moment of the GdVO4
NPs was 7 μB and the corresponding phase of bandgap energy was found
to be 2.975 eV, which is photocatalytically active under visible light.
3.4. Gadolinium titanate (Gd2Ti2O7) NPs
Gd2Ti2O7 NPs has been synthesized in various methods including sol-
gel, solid-state reaction, single crystal growth, molten salt route, pechini
process, calcination method, and chemical co-precipitation method
(Dharuman and Berchmans, 2013). However, Gd2Ti2O7 obtained from
many of these methods was reported to be suitable for luminescence and
magnetic studies. For photocatalytic application, literatures have re­
ported the utilization of the sol-gel method for the preparation of
Gd2Ti2O7 photocatalysts (Li et al., 2020, 2021). The bandgap of
Gd2Ti2O7 has been observed to be 3.3 eV, which has been reported to
generate •OH radicals as the predominant ROS. Moreover, the photo­
catalytic activity has been restricted to the UV region owing to its wide
bandgap. Perovskite type GdTiO3 has also been reported, however, their
photocatalytic activity is yet to be evaluated (Khalsa and Benedek,
2018).
3.4.1. Challenges and concerns on the synthesis of Gd2Ti2O7 NPs
Gd2Ti2O7 exhibits two predominant crystalline phases as cubic and
monoclinic with corresponding space groups as Fd-3m and C2/m
respectively. The bandgap energy of cubic and monoclinic phases of
Gd2Ti2O7 NPs were 0 eV and 2.423 eV (Fig. 1b). The change in the phase
of Gd2Ti2O7 NPs causes loss in the bandgap energy of the particle, where
the monoclinic phase was found to be photocatalytically active.
3.4.1.1. Phases of Gd2Ti2O7 NPs. The unit cell arrangement of cubic
Gd2Ti2O7 nanomaterial shows the angular lattice of α (alpha) = β (beta)
= γ (gamma) = 60◦ and the unit cell plane as a = b = c = 7.253 Å. In
addition, the unit cell arrangement of monoclinic Gd2Ti2O7 nano­
material shows the angular lattice of α (alpha) = β (beta) = 59.505◦ and
γ (gamma) = 59.635◦ and the unit cell plane as a = 7.442 Å, b = 7.442 Å
and c = 8.826 Å (Fig. 1a). The final magnetic moment of cubic and
monoclinic phases of Gd2Ti2O7 nanomaterial was 14.411 μB and 7 μB.
Here, the variation in the magnetic moment was attributed to the atomic
arrangement.
3.5. Gd perovskites and double perovskite NPs
Perovskite and double perovskite NPs have attracted significant
attention for their distinctive properties including tunable bandgap,
high charge carrier mobility, non-toxicity, large absorption coefficient,

Table 1
Synthesis method, characteristics and photocatalytic activity of GdNPs.
S. Nanoparticle Synthesis Methods Morphology Crystallite Band gap energy Pollutant Degradation Reference
No phase (eV) efficiency

1 Gd2O3 Hydrothermal method Nanorod Cubic 4.2 eV Chloramphenicol 100%/160 min Dhanalakshmi et al.
(2019)
2 Gd2Ti2O7(1.5) Sol-gel Pyrochlore Cubic between 3.48eV RBR-X-3B 100%/100 min Li et al. (2020)
(PEG1000) and 3.75eV
3 Gd2Ti2O7(1.2) Sol-gel Pyrochlore Cubic 3.36 eV RBR-X-3B 93.4%/150 min Li et al. (2021)
(TBOAH)
4 Gd2(WO4)3 Precipitation method Spherical Monoclinic 3.3 eV MO 74%/60 min Liu and Zhou (2019)
5 Gd2(WO4)3 Chemical Irregular Monoclinic 4.18 eV MB 99%/60 min Nasrabadi et al.
Precipitation method (2017)
6 GdVO4 Hydrothermal method Egg-shaped Monoclinic 2.2 eV MG, RhB, MB 96.2%/50min He et al. (2020)
89.2%/50 min
87.8%/50 min
7 GdVO4 Co-precipitation Spherical Tetragonal 2.95 eV MO 85%/70 min Vosoughifar (2017)
8 GdFeO3 Hydrothermal method Microsphere Orthorhombic 2.02 eV 4-Chlorophenol 85%/5h Li and Duan (2012)
9 Gd2CoMnO6 Pechini method Spherical, semi Orthorhombic 2.83 eV MV, ES, EBT 96%, 94%, 84%/ Mohassel et al.
spherical 90 min (2018a)
10 Gd2CoMnO6 Combustion method Orthorhombic 3.28 eV MV, ES, EBT 97%, 64%/90 min Mohassel et al.
(2018b)

4
G. Harini et al.
and multi-ferroic behavior (Mohapatra et al., 2015). Among the other
rare earth elements, perovskites of Gd are considered noteworthy, owing
to their magnetic moment and room temperature magnetocaloric effect
(Krishnamoorthy et al., 2015). Li and Duan (2012) reported the syn­
thesis of microsphere GdFeO3 via the hydrothermal method with
ethylene glycol (EG) and citrate acid for morphological modifications.
Moreover, it is observed that an increase in EG concentration resulted in
smaller nanoparticles with higher surface area. Photodegradation effi­
ciency of GdFeO3 with 4-Chlorophenol was found to be 85% with
excellent recoverability and reusability up to 5 cycles owing to its
paramagnetic behavior (Fig. 1d). Gd2CoMnO6 double perovskites were
synthesized via two different synthesis techniques: Stabilizing agents
assisted Pechini method and amino acid modified combustion method.
The nanostructure obtained from both of the synthesis methods
exhibited antiferromagnetic behavior owing to the strong exchange
interaction between (Co/Mn)-3d and Gd-4f sub-lattices. In both cases,
GCMO NSs exhibited better photocatalytic efficiency with MV. This
could be ascribed to the positive charge of MV (cationic contaminant),
which can be absorbed by GCMO NSs owing to the presence of oxygen
atoms with higher surface electron density on its surface (Mohassel
et al., 2018a, 2018b) (Table 1).
The aforementioned individual GdNPs exhibited various properties
and morphological characteristics owing to their synthesis methods and
reaction parameters. Therefore, it could be understood that the overall
performance of the photocatalyst relies on its physical properties such as
surface area, size, morphology, and pore structure. So, it is obvious that
the optimization of synthesis parameters such as precursors, reaction
conditions, stabilizing agents and surfactants are paramount for efficient
photocatalytic activity and has to be manipulated with care to accom­
plish the desired outcome.
4. Synthesis of Gd-based nanomaterials and their impact on
photocatalytic properties
The synthesis method plays a crucial role in various properties of Gd
nanomaterials, which includes crystallinity, size, morphology, surface
area, porosity, and thereby its photocatalytic activity. From the exper­
imental results, it could be observed that the synthesis time, tempera­
ture, solvent, and other external cues such as ultrasound, microwave
radiation pose a major impact on these aforesaid properties of the
product material. Studies have reported the synthesis of Gd-based
nanomaterials via co-precipitation, hydrothermal/solvothermal, sol-
gel, ball-milling and ultrasound-assisted methods (Supplementary Ma­
terial Fig. S3). The co-precipitation method is often featured for its
simplicity, rapid preparation, easy control over the size, and efficient
operation. It also serves as the widely exploited method for the prepa­
ration of GdNPs. Nasrabadi et al. (2017) reported co-precipitation syn­
thesis of Gd2(WO4)3, where the optimization of parameters including
precursor ratios and reactor temperature were found to positively
impact its size. Hydrothermal synthesis is typically carried out under
certain temperatures and pressure to obtain a morphology-specific
product. In a study by Dhanalakshmi et al. (2019) Gd2O3 was synthe­
sized hydrothermally to obtain nanorods, which exhibited excellent
photocatalytic activity owing to its large surface area. Sol-gel is a widely
applied method for NPs synthesis by condensation and hydrolysis of the
precursors, thereby ensuring high crystalline and pure product. Li et al.
(2020) reported the synthesis of Gd2Ti2O7 via sol-gel synthesis with
pore-forming agents including PEG1000 and TBAOH, which was found
to be in high crystallinity, reduced crystal aggregation, and rich in
inter-crystal holes. Ball milling is a shear-force dominant physical pro­
cess for the synthesis of NPs, which has been reported to induce abun­
dant defects, stains, and interfaces. Wu et al. (2019) reported the
synthesis of Gd2O3/TiO2 via ball milling method, which was found to
exhibit small crystallite size and subsequently large surface area,
resulting in enhanced photocatalytic performance.
Ultrasonication-assisted synthesis methods have recently been exploited
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Journal of Cleaner Production 345 (2022) 131139
for the fabrication of NCs (Shende et al., 2018; Jameel et al., 2020;
Kodarkar et al., 2021; Satdeve et al., 2019; Shirsath et al., 2017). He
et al. (2013) reported the synthesis of GdVO4/g-C3N4 NCs via ultra­
sonication assisted method, which resulted in a reduction in particle
size, enhanced surface area, and well deposition of GdVO4 over g-C3N4.
Many physical, chemical, and biological methods were applied for Gd
NPs synthesis, however, few of them were reported for photocatalytic
purposes, which suggests that those methods have to be explored to
further understand their photocatalytic properties.
5. Band alignments and redox potentials of Gd nanomaterials
The bandgap and redox potentials of semiconductor photocatalysts
have paramount importance for their application in photocatalysis. It is
well known that the highly reactive species including hydroxyl radicals
(•OH-), holes (h+), and superoxide radicals (•O2− ) break the pollutants
into end products. Here the •OH- radicals are generated by holes via
oxidizing water molecules and the •O2− radicals are produced by elec­
trons via reducing oxygen molecules. However, the redox potential for
generating •O2− and •OH- radicals were − 0.33 eV and +1.9 eV
respectively. For the generation of •OH- and •O2− radical, the VB and CB
potential of the semiconductor photocatalysts must be more positive
than 1.9 eV vs NHE and more negative than − 0.33 eV vs NHE respec­
tively (Wang and Wang, 2020). However, semiconductors with more
positive VB and more negative CB imply a wider bandgap. This wider
bandgap significantly affects the exploitation of solar light in the visible
region. The schematic representation of band positions and redox po­
tentials of half-reactions for some of the semiconductor photocatalysts is
addressed in Supplementary Material Fig. S1. Here, Gd2O3 with a wider
bandgap of 3.42 eV can utilize only the solar energy in the UV region,
but could generate a wide variety of radicals, has water splitting po­
tential and CO2 reducing capacity as the VB and CB potentials satisfies
the redox potentials of the aforesaid reactions. However, in the case of
Gd2CuO4, the bandgap energy is 1.4 eV which can utilize visible light,
but it could not meet all the aforesaid criteria owing to its low VB po­
tential. Hence, for a single component photocatalyst, the contradiction
among band gap, light absorption capacities, and redox abilities makes it
difficult to accomplish the higher photocatalytic activity. Besides, single
component photocatalysts also exhibit a higher charge recombination
rate and poor charge mobility, which could be overcome by coupling
with other semiconductors.
6. Strategies for design and fabrication of Gd based
nanomaterials for enhanced photocatalytic application
Design and fabrication of highly effective nanomaterials are essential
for enhanced photocatalytic application. To achieve highly efficient
photocatalytic performance, the photocatalyst should possess the
following characteristics: enhanced visible light excitation, improved
charge mobility, and separation (Orooji et al., 2020; He et al., 2022)
(Supplementary Material Fig. S2). However, many of the Gd-based
nanomaterials such as Gd2O3 possess a wide bandgap, which has its
optical absorption threshold only at the UV region. Moreover, many
ideal photocatalysts such as TiO2, ZnS, and ZnO are wide-bandgap
photocatalysts, which are photocatalytically active only under UV illu­
mination. To overcome the poor visible light excitation of NPs, impurity
doping and introducing structural defects has been considered to be
promising techniques (Mohassel et al., 2020; Zhou et al., 2018). In
accordance with this, Baeissa (2016) reported that Ag doping in GdFeO3
NPs significantly enhanced its photocatalytic activity by inhibiting
charge-carrier recombination and extending its absorption threshold to
the visible region. Additionally, Gd3+ serves as a potential dopant,
which was reported to enhance the visible light excitation and subse­
quently, the overall photocatalytic performance of many host materials
such as TiO2, ZnO, etc. Another issue is the fate of photo-induced elec­
tron-hole species: the excited species either travel to the photocatalytic
G. Harini et al.
surface or undergo recombination. For efficient photocatalytic perfor­
mance, the excitons should move to the photocatalytic surface and must
survive long enough to harness its redox abilities rather than undergoing
recombination. In short, it is essential to design photocatalytic materials
with increased charge mobility and enhanced charge separation. This
could be achieved by the construction of semiconductor hetero­
junctions, which are broadly discussed in the upcoming sessions.
7. Gd based NCs/heterojunctions
Multifunctional NCs/heterojunctions were always preferred over
pristine NPs owing to their integrated properties in a single system,
which is suitable for several futuristic applications (Chandel et al.,
2019). Rare earth-oxides are often explored for their beguiling physi­
cochemical properties including chemical durability, low phonon en­
ergy which makes them suitable for their utilization in
NCs/heterojunction (Salavati-Niasari et al., 2011). Among which Gd is
much suitable, owing to its half-filled 4f orbitals and empty 5d orbitals.
The empty 5d orbital avoids electron-hole recombination by acquitting
itself as e- trapping centers, whereas the inter 4f-5d and intra 5d-5d
interaction enhance the photocatalytic activity (Mohassel et al., 2019).
In addition to this, the superior magnetic property of Gd makes it a
potential candidate for NCs/heterojunction materials which makes
recoverability and reusability easier.
Single semiconductor photocatalysts face some drawbacks including
high recombination rate of photo-generated electron-hole pairs and low
reduction and oxidation abilities, which could be overcome by con­
structing heterojunctions. The heterojunction is generally defined as the
interface between different semiconductors with unequal band struc­
ture, which results in band alignment. Conventionally, there are three
types of photocatalysts: straddling-gap junctions (type I), staggered-gap
junctions (type II), and broken-gap junctions (type III). However, type II
Fig. 2. Represents (a) SEM micrograph of GdVO4-ZnO NPs, (b) RhB removal via photocatalytic degradation by GdVO4-ZnO NCs, (c) schematic illustration of
photocatalytic mechanism of GdVO4-ZnO nano-heterojunction. Reproduced with permission, Copyrights 2022 Elsevier (Thirumalai et al., 2017), (d) SEM micrograph
of Gd2O3–CdO NCs, (b) Recyclability of Gd2O3–CdO NCs and (e) schematic illustration of photocatalytic mechanism of Gd2O3–CdO heterojunction Reproduced with
permission. Copyrights 2022 Elsevier (Deif et al., 2021).
6
Journal of Cleaner Production 345 (2022) 131139
heterojunction, p-n heterojunctions, and direct Z–scheme hetero­
junctions are widely used (Low et al., 2017; Raizada et al., 2019a;
Raizada et al., 2019b; Sonu et al., 2019).
7.1. Type I heterojunction
Thirumalai et al. (2017) reported the synthesis of GdVO4-ZnO pho­
tocatalyst via hydrothermal method (Fig. 2a). ZnO showed a decrease in
bandgap energy from 3.26 to 2.85 eV on account of the addition of
GdVO4, which formed intermittent energy levels. Moreover, GdVO4 was
reported to suppress the radiative recombination rate of photogenerated
electrons and holes in ZnO, resulting in a higher photocatalytic activity
(Fig. 2c). Furthermore, the NCs exhibited excellent photodegradation of
RhB in sunlight than commercial TiO2 and its pristine NPs, owing to
vectorial electron transfer and electron capturing ability of GdVO4
(Table 2). Here, the oxygen molecule on the surface of GdVO4 captures
electrons from CB to form superoxide radicals, whereas holes in the VB
of ZnO react with water molecules to produce •OH radicals, which
thereby degrade the RhB dye. The photocatalytic efficiency was 98% for
degradation of RhB in 75 min under natural sunlight (Fig. 2b).
7.2. Type II heterojunction
Gd2O3 is a weak semiconductor with a wide bandgap up to 5.4 eV,
which gets activated only in the UV region. To overcome the drawbacks,
Gd2O3 is often combined with other semiconductor photocatalysts to
form heterojunctions (Deif et al., 2021; Murugalakshmi et al., 2020).
Deif et al. (2021) reported the synthesis of Gd2O3–CdO NCs via pre­
cipitation method. The n-type CdO with a bandgap around 3.41 eV was
found to decrease to 2.75 eV as an impact of Gd2O3. This red-shift in
bandgap energy was attributed to the quantum confinement effect of
Gd2O3–CdO mixed oxide NPs, which in turn modify their optical
G. Harini et al. Journal of Cleaner Production 345 (2022) 131139

Table 2
Synthesis methods, characteristics and photocatalytic activity of GdNCs/Heterojunctions.
S. NCs/Heterojunction Synthesis method Nanocomposite/Heterojunction Pollutant Degradation Reference
No photocatalyst type efficiency

1 GdVO4-ZnO Hydrothermal Type I heterojunction RhB 98%/75 min Thirumalai et al. (2017)
2 Gd2O3(15%)-CdO Precipitation Type II heterojunction MB 98.5%/120 min Deif et al. (2021)
3 GdVO4/g-C3N4 Milling and heating method Type II heterojunction RhB 96.7%/120 min He et al. (2013)
4 Ag/AgBr/GdVO4 Hydrothermal method Type II heterojunction RhB 80%/12 min Zhang et al. (2018)
5 Gd2O2CO3.ZnO.CuO Co-Precipitation p-n (CuO–ZnO) Phenanthrene 100%/120 min Mukwevho et al. (2019)
6 In2S3/Gd2O3 Ultrasound assisted p-n OTC, Cr(VI) 80%, 96% in 55 min Murugalakshmi et al.
hydrothermal (2020)
7 BiFeO3-GdFeO3 Sol-gel Z-Scheme MB 98%/9h Subramanian et al. (2019)
8 Gd2O3-Graphene Modified Hummers method Nanocomposite MB 50%/150 min Saravanan et al. (2018)
9 Gd2O3/Bi2O3@GO One pot hydrothermal Nanocomposite (Absorbant) MO 95%/45 min Das and Sharma (2020)
method
10 3MWCNT-Gd/TiO2 Sol-Gel Nanocomposite MB 98.7%/300 min Mamba et al. (2014)

absorption threshold to visible light. SEM images of Gd2O3–CdO NCs
illustrated the significant change in morphology, size, and distribution
of particles in comparison with pure CdO, thereby confirming chemical
interaction between Gd2O3 and CdO NPs (Fig. 2d). The photogenerated
CB electrons of CdO tend to diffuse to CB of Gd2O3, while the holes in VB
of Gd2O3 diffuse towards VB of CdO. This leads to efficient charge
separation and enhanced production of reactive oxygen species to
engage in photodegradation (Fig. 2f). The photodegradation efficiency
for MB was found to be 98.5% in 120 min under natural sunlight and it
also exhibited excellent stability (Fig. 2e). He (He et al., 2013) expli­
cated GdVO4/g-C3N4 heterojunction, which exhibited efficient charge
mobility and suppressed recombination rate in accordance with the
aforementioned work. The photocatalytic efficiency was reported to be
96.7% within 120 min under visible light irradiation. Zhang et al. (2018)
described the synthesis of Ag/AgBr/GdVO4 heterojunction via hydro­
thermal method. According to the literature, Ag NPs formed a schottkey
barrier with AgBr, and a type II heterojunction was observed among
AgBr and GdVO4. The heterojunction among AgBr and GdVO4 facilitates
efficient transfer of photo-induced electrons and holes. Moreover,
Ag/AgBr/GdVO4 NCs exhibited excellent photocatalytic efficiency of
80% for RhB under 12 min under visible light irradiation (Table 2).
7.3. p-n heterojunction
The p-n heterojunction accelerates electron-hole pair migration via
the synergy between band orientation of interface and internal electric

Fig. 3. (a) Represents SEM micrograph of In2S3/Gd2O3 NCs, Copyright 2022 Elsevier (Murugalakshmi et al., 2020) (b) FESEM image of Gd2O3/Bi2O3@GO NCs, (c)
TEM image of Gd2O3/Bi2O3@GO NCs, Copyright 2022 Elsevier (Das and Sharma, 2020) (d) photocatalytic degradation pathway of oxytetracycline mediated by
In2S3/Gd2O3 NCs, (e) schematic representation of photocatalytic mechanism of In2S3/Gd2O3 NCs Reproduced with permission. Copyright 2022 Elsevier (Mur­
ugalakshmi et al., 2020) (f) pictorial representation of the binding mechanism of Gd2O3/Bi2O3@GO NCs with MO dye. Copyrights 2022 Elsevier (Das and
Sharma, 2020).

7
G. Harini et al.
field (IEF). Multi-metal oxide heterocatalysts are widely used for their
excellent photocatalytic performance owing to their enhanced charge
carrier mobility and visible light absorption (Karthikeyan et al., 2020).
Herein, a report elucidated the synthesis of Gd2O2CO3.ZnO.CuONCs
with a p-n heterojunction between ZnO–CuO semiconductors. The NC
exhibited good photocatalytic efficiency against phenanthrene, ascribed
to low recombination rate, enhanced charge mobility, high surface area,
and visible light absorption (Mukwevho et al., 2019). Peculiarly, the
charge transfer efficiency is ascribed to the 4f orbital of Gd. Generally,
pristine n-type In2S3 semiconductor shows poor catalytic property
owing to its photocorrosion and high electron-hole recombination rate
(Yan et al., 2017; Gan et al., 2019). But when coupled with a p-type
semiconductor like Gd2O3, the resultant p-n heterojunction NCs
exhibited efficient charge separation and formation of strong interfacial
contact between the two materials which facilitates efficient charge
transfer (Fig. 3a and e). Notably, the band gap values slightly increased
with an increase in Gd2O3 concentration. This heterojunction NCs was
subjected to degradation studies with oxytetracycline (OTC) and Chro­
mium (Cr(VI)). Here, the electron transfer from CB of In2S3 to empty CB
of Gd2O3 was reported to be utilized for the reduction of Cr(VI) to Cr(III),
even though the VB holes of In2S3 (1.27 eV) had lower oxidizing po­
tential to produce•OH radicals, it directly oxidized OTC, thereby pro­
ducing completely mineralized end products (Fig. 3d) (Eq (3)).
Moreover, the NCs exhibited excellent stability. (Table 2) (Mur­
ugalakshmi et al., 2020).
In2S3/Gd2O3 + OTC →In2S3/Gd2O3—OTC (1)
+
In2S3/Gd2O3–OTC→In2S3(h –e− )Gd2O3—OTC (2)
+. − . −
OTC + h / O2 / OH →Intermediate products→CO2+H2O (3)
7.4. Z-scheme heterojunction
Z-scheme heterojunction has been widely studied for its high charge
separation efficiency, strong redox ability, and a wide light response
range (Sudhaik et al., 2020a, 2020b; Raizada et al., 2020a; Kumar et al.,
2020b). Study by Subramanian et al. (2019) reported heterogeneous
Z-scheme BiFeO3-GdFeO3 photocatalyst. According to the band edge
mechanism, the photogenerated electrons in the conduction band of
BiFeO3 move to GdFeO3, which traps the electron and produces suffi­
cient charge separation. It has been reported that the Gd3+ reduce to
Gd2+ with the help of excitons in the VB of GdFeO3. The reduced Gd2+
then re-oxidize into Gd3+ leading to the formation of •O2− radicals by
reacting with the surface oxygen, thereby enhancing the breakdown of
pollutants. Furthermore, the photocatalytic efficiency of the NCs was
found to be 98% for MB dye degradation under natural sunlight. How­
ever, research works on Gd-based Z-scheme heterojunctions were
scarcely available, which should be explored for better understanding
and further application (Table 2).
7.5. Gd-based carbon NCs
NCs of metal oxides with carbon-based materials like CNTs, gra­
phene poses paramount importance owing to their large surface area,
high stability, excellent electron mobility, and electrical conductivity
(Rao et al., 2021). Mamba et al. (2014) reported the synthesis of Gd2O3
decorated MWCNT/titania NCs (MWCNT-Gd/TiO2) via sol-gel method.
The NCs showed a significant red shift in the bandgap, owing to 4f
electron transitions in Gd. Moreover, the loading of Gd2O3 on the pho­
tocatalytic surface significantly minimized aggregation and served as an
efficient electron transfer channel. The photodegradation of MB was
observed to be 98.7% by 3MWCNT-Gd/TiO2NCs under visible irradia­
tion, which was significantly higher than that of MWCNT/TiO2 and
TiO2. Furthermore, MWCNT/TiO2 reported in various other studies
8
Journal of Cleaner Production 345 (2022) 131139
showed lower degradation capacity for MB, indicating the paramount
importance of Gd2O3 in MWCNT-Gd/TiO2 composite for better photo­
catalytic activity (Cong et al., 2011; Jiang et al., 2011). Another study
elucidated the utilization of Gd2O3-graphene NCs for the removal of MB
dye. The photocatalytic efficiency increased with an increase in gra­
phene concentration, owing to the higher oxygen reaction sites and
efficient charge separation (Saravanan et al., 2018). Nevertheless,
Gd2O3-graphene exhibited poor photocatalytic activity for MB than
3MWCNT-Gd/TiO2 (Table 2). It has also been observed that TiO2 and
Fe3O4 based graphene NCs have reported better photocatalytic perfor­
mance than Gd-based graphene NCs. This could be attributed to the
ability of Fe2O3-graphene system to participate in photo-Fenton re­
actions owing to the presence of Fe. In case of TiO2-graphene photo­
catalytic system, facet-oriented preparation of TiO2 enhances its
photocatalytic activity. However, the current literatures on
Gd-graphene NCs lack insights to explicate their inability to exert better
photocatalytic performance than Fe2O3 and TiO2 based graphene pho­
tocatalysts (Bhanvase et al., 2016, 2019; Barai et al., 2019, 2020; Kale
et al., 2020; Potle et al., 2020; Vardikar et al., 2018).
7.6. Adsorption ability of Gd photocatalysts
Adsorption is one of the prominent techniques for the removal of
hazardous compounds from water bodies. This method selectively
removes the pollutant from an aqueous state and transforms it into a
solid form. Being a lanthanide, Gd has the ability to form complex with
various organic compounds, which are usually Lewis bases such as al­
dehydes, alcohols, thiols, and amines. These functional groups of the
organic pollutant interact with the half-filled orbitals of Gd, thereby
resulting in the accumulation of organic pollutants on the photocatalytic
surface. Furthermore, literatures have reported increased active sites for
adsorption of pollutant molecules upon doping of Gd ions (Bashir et al.,
2022). Many literatures have reported the utilization of Gd2O3 as an
efficient adsorbent, owing to its high adsorbing capacity and magnetic
properties (Zhao et al., 2014). Furthermore, Gd2O3 has good chemical
durability and shares similar properties with Al(III) and Fe(III), which
could be exploited for heavy metal removal (Peng et al., 2017; Lin­
gamdinne et al., 2020). The decoration of Bi2O3, Gd2O3NPs on the
surface of Graphene Oxide (GO) is clearly depicted in Fig. 3b and c. The
presence of Gd2O3 and Bi2O3 strengthens the H-bonds and augment the
adsorption sites on GO surface (Fig. 3f). The adsorption capacity and
removal efficiency of Gd2O3/Bi2O3@GO for Methyl Orange (MO) was
observed to be 95%, which is greater than its single oxide composites
and many other adsorbents (Das and Sharma, 2020). In another study,
GO-Gd2O3 was exploited for the removal of As(V), in this regard, Gd2O3
has been used to assist GO for its selectivity towards phosphorous,
arsenic, and silicon at elevated temperatures (Lingamdinne et al., 2021;
Wiberg et al., 2001). Moreover, GO-Gd2O3NCs was also reported to be
efficient in the removal of Cr(III) and Pb(II) (Lee et al., 2016).
The aforementioned NCs/heterojunction exhibited excellent prop­
erties and photocatalytic activity than their respective pristine NPs in
terms of their reduced bandgap energy, suppressed electron-pair
recombination, enhanced interfacial electron transfer, high crystal­
linity, and stability.
8. Doping
Apart from the construction of heterojunctions, cationic doping is
regarded as one of the promising methods to overcome the concerns of
Gd NPs. Maity et al. (2021) reported Mn-doped GdFeO3, where Mn
substitution was observed at the octahedral Fe site. This resulted in a
reduction in bandgap energy and thereby enhanced visible-light pho­
tocatalysis. Moreover, the doping was observed to bring down the
recombination rate and enhance the photodegradation of RhB. In a
similar study, Ag was deposited over GdFeO3 rather than substituting in
the host lattice. Ag deposition has been observed to tune the bandgap of
G. Harini et al.
GdFeO3, which expressed gradual narrowing of bandgap upon Ag
deposition and enhanced photocatalytic activity (Baeissa, 2016). It
should be clarified that doping of cations can be exploited to improve
the photocatalytic performance of GdNPs and trivalent Gd3+ ions can
also be used as dopants to enhance the performance of other intrinsic
semiconductors. Furthermore, in both the cases, either surface deposi­
tion or lattice incorporation and sometimes both could occur, owing to
the atomic radius compatibility of dopant and that of the host. This may
result in defect or vacancy formation, which plays a major role in its
charge mobility and photocatalytic property.
9. Trivalent Gd ion as an efficient dopant
Doping of metal and non-metal ions into the semiconductor matrix
has been gaining attention for its ability to extent optical absorption
threshold, induce defect and thereby enhance the overall photocatalytic
efficiency (Soni et al., 2021). Gd ions are often investigated for their
ability to enhance photocatalytic activity by reducing the bandgap en­
ergy and generating impurity energy levels in the semiconductor. The 4f
orbital of trivalent Gd ions acts as sub-bandgap energy levels below the
conduction band of the semiconductor photocatalyst. Thereby, the
excited electrons eventually populate in the inserted 4f orbitals instead
of the intrinsic CB of the photocatalyst, which in turn narrows the
bandgap energy and extends the optical absorption threshold. Further­
more, it is well known that half-filled electronic configurations are more
stable. Gd3+ has a half-filled f-shell with seven electrons, which plays a
vital role in photocatalytic activity. This half-filled shell has the ability
to trap photo-excited electrons and could delay recombination, which
creates an imbalance in its configuration. But to return back to its stable
state, the excess electrons are released to reduce O2 on the photo­
catalytic surface to form •O2− which eventually participate in photo­
catalysis (Huang et al., 2013). Additionally, structural and
Fig. 4. a) SEM image and, (b) TEM image of Gd-TiO2,(c) schematic illustration of the photocatalytic mechanism of Gd-TiO2, Reproduced with permission, Copyrights
2022 Elsevier (Singh et al., 2019) (d) SEM micrograph and (e) TEM micrograph of Gd-ZnO, (f) Schematic illustration of the photocatalytic mechanism of Gd-ZnO.
Reproduced with permission, Copyrights 2022 Elsevier (Kumar and Sahare, 2014).
9
Journal of Cleaner Production 345 (2022) 131139
microstructural changes such as an increase in lattice parameters and
microstrain were also reported upon Gd doping (Zhang et al., 2017).
Moreover, it has been reported that doping of Gd ions raises VB
maximum with respect to the Fermi level, which in turn promotes the
intrinsic host material to a p-type semiconductor (Huang et al., 2016).
9.1. Influence of Gd doping on TiO2
TiO2 has been considered as a promising photocatalyst for its ver­
satile characteristics such as cost-effectiveness, chemical stability, high
oxidizing capacity, and non-toxicity (Ajmal et al., 2014). However, wide
bandgap and fast electron-hole recombination limit their application.
Compared to transition metals, rare earth metals with 4f, 5d, and 6s2
states are considered as ideal dopants for TiO2, which could modify their
crystal structure, optical and electronic properties (Prakash et al., 2021).
Many literatures have reported enhanced photocatalytic performance of
Gd-TiO2. The first-ever photocatalytic study of RE doped TiO2 (sol-gel)
was carried out by Xu et al. (2002) which demonstrated the nitrite
oxidation process of RE-TiO2 (RE = Er+3, Gd+3, Pr+3, Sm+3, Ce+3, La+3,
Nd+3) and pristine TiO2, among which Gd+3 doped TiO2 turned out to be
an excellent candidate among other lanthanide ions and its pristine NPs,
owing to high nitrite absorption, redshift in bandgap and suppression of
recombination. In a similar study reported by El-Bahy et al. (El-Bahy
et al., 2009), Gd doped TiO2 showed better photocatalytic performance
than other lanthanides, owing to high surface area, low bandgap energy,
and high pore volume. A study reported the synthesis of Gd-TiO2 via
Solvothermal method. The images of FESEM illustrated a mesospheric
structure of the sample (Fig. 4a), which shows that Gd only covers the
surface rather than making its way into the mesosphere (Fig. 4d) (Singh
et al., 2019). Generally, dopant either gets distributed on the surface or
enters the lattice as substitutional, interstitial, or both (Avram et al.,
2021). But due to the radius mismatch of Gd3+ (0.94 A) with Ti4+ (0.60
G. Harini et al. Journal of Cleaner Production 345 (2022) 131139

A), Gd ions are not expected to enter the lattice of TiO2. In certain cases,
a combination of substitutional doping and surface distribution occurs
(Zhao et al., 2008; Zalas, 2014). It has been noted that substitutional
doping results in a change of electronic structure and light absorption
efficiency of TiO2, whereas surface distribution results in repulsive
interaction among Gd3+ ions, which prevents coalescence of nano
crystallites and eventually inhibits the growth formation (Paul et al.,
2015; Chen et al., 2014a). In short, Gd doped TiO2 possesses high
anatase percentage, large surface area, smaller crystallite size, and
enhanced photocatalytic activity (Table 3).
TiO2 exhibits three predominant polymorphic states: metastable
anatase, metastable brookite and stable rutile, which in turn possess
distinct properties and subsequently, varied photocatalytic perfor­
mance. The phase transformation highly depends on the annealing
temperature and impurities (dopants and defects). Anatase exhibits
better photocatalytic performance than that of stable rutile phase owing
to its lighter effective mass, longer lifetime of photogenerated charge
carriers, and smaller particle size (Anitha and Khadar, 2020). In spite of
its versatile properties, there were few restraints to be considered. The
anatase phase has low thermal stability, which makes them vulnerable
to transform into rutile phase (<450-500 ◦ C) and a wide bandgap
(Hanaor and Sorrell, 2010). Literatures have reported that doping serves
as a prominent approach to suppress the phase transformation and to
tune the band gap. Studies have reported that the transformation of
anatase to rutile phase could be suppressed by Gd doping. Accordingly, a
study by Shi et al. reported the formation of the rutile phase of undoped
titania and anatase phase in Gd-TiO2 (Shi et al., 2014). Moreover, it was
found that hydrothermal treatment could facilitate the transformation to
the rutile phase even in the presence of Gd ions, which could be sup­
pressed by exploiting directing agents such as CTAB (Sudhaik et al.,
2020b; Bagwan et al., 2020; Zhu et al., 2005). In some cases, the
co-existence of multiple phases has also been reported, which could
have occurred as a result of substantial incorporation of Gd and oxygen
vacancy levels. Consequently, a study by Toloman et al. (2017) indi­
cated the presence of anatase Gd-TiO2 and the co-existence of the
brookite phase.
The pivotal point to be noted in these aforementioned studies is the
effect of doping of Gd3+ on anatase to rutile (A-R) transformation. In a
study by Graf et al. (2007), anatase phase was detected even after
annealing at 750 ◦ C in presence of Ce and Gd dopant. It was propounded
that the inhibition of phase transformation may occur as a result of
stabilization of the anatase phase by the formation of Ti–O-Gd bonds
with the surrounding Gd ions (Fig. 5a and b) (Perez et al., 2020).
However, another point to be considered is that the A-R transformation
kinetics is strongly affected by oxygen defect levels, which enhance the
transformation (Choudhury and Choudhury, 2013). Furthermore, oxy­
gen defect levels are directly influenced by the degree of dopant. In
short, dopants increase oxygen vacancies which could thereby enhance
the A-R transformation. Such a case was reported by Cheng et al. (2016),
where doping of Gd resulted in more oxygen vacancies, which thereby
facilitated the transformation to the rutile phase resulting in poor pho­
tocatalytic performance. It could be observed that Gd directly inhibits
the A-R transformation, but indirectly promotes the transformation.
Hence, it is necessary to optimize the dopant concentration to maintain
the oxygen defect levels and thereby control A-R transformation for
better photocatalytic performance.
9.2. Influence of Gd doping on ZnO NPs
ZnO semiconductor photocatalysts have been dealt with a pragmatic
approach, which is often exploited for its versatile photocatalytic
properties. However, ZnO possesses some drawbacks including fast

Table 3
Synthesis, Characteristic and photocatalytic degradation of pollutants by Gd doped/co-doped TiO2, ZnO and Ferrite photocatalysts.
S Photocatalyst Synthesis Method Localization of Crystalline phase Bandgap energy Pollutant Degradation Reference
NO Gd (eV) efficiency

1 S/Gd(0.6%)/TiO2 Sol-gel Doping Anatase 2.95–3.08eV Indigo 100%/50 min Agorku et al.
caramine (2014)
2 Gd/TiO2 (TG3.5) Hydrothermal Doping (Surface) anatase No data RhB 95.3%/10 min Zhao et al.
(2008)
3 Gd/TiO2(0.3%) Sol-gel Doping Anatase, 3.11–3.19eV RhB 93%/240 min Toloman et al.
(substitution) Brookite (2017)
4 Gd/TiO2 (0.5%) Hydrothermal Doping Rutile 3.54eV Acriflavine 92%/120 min Bagwan et al.
dye (2020)
5 Gd/TiO2 (2.5mol%) Ball milling Doping Anatase 3.07 eV RhB 97.9%/60 min Wu et al.
Gd2O3–TiO2 (0.5 mol%) method (Substitution) 3.12eV 84.6%/60 min (2019)
6 Gd, N, P/TiO2 TiCl4 hydrolysis Doping Anatase 3.0 eV 4-CP 93.6%/120 min Bashir et al.
(2022)
7 Gd(5 wt%)/ZnO Precipitation Doping Wurtzite No data MB 100%/45 min Jiang et al.
method (substitution) hexagonal (2016)
8 Gd(5%)/ZnO Sonochemical Doping Wurtzite 2.8eV AO7 100%/90 min Khataee et al.
method hexagonal (2019)
9 Gd(3%)/ZnO Precipitation Doping Wurtzite 3.07 eV MB 93%/90 min Selvaraj et al.
method hexagonal (2019)
10 Gd/ZnO (Zn0.999Gd.001O) Precipitation Doping Hexagonal 3.36eV MO 85.30%/90 min Dhir (2020)
method (substitution) Wurtzite
11 Gd/N/ZnO Precipitation Doping Wurtzite 3.09 eV MB 87%, 93%/60 min Alanazi et al.
method hexagonal (2021)
12 Gd/Nd/ZnO Hydrothermal Doping Wurtzite 3.03 eV MB 93%/120 min Akhtar et al.
method (substitution) hexagonal (2020)
13 Gd/Sn–BiFeO3-MXene Co-precipitation Doping Orthorhombic 1.4 eV CR 100%/120 min Tariq et al.
(BGFO-20Sn) (substitution) (2018)
14 Gd/BiFeO3 Sol-Gel Doping Rhombohedral No data RhB 94%/120 min Guo et al.
(substitution) (2010)
15 BGFO/N-rGO Hydrothermal Doping Orthorhombic 1.56 eV RhB 99%/2h Dixit et al.
method (substitution) (2021)
16 Gd/Sn–BiFeO3 (BGFO- Sol-Gel Doping Rhombohedral 2.03 eV CR, MB, MV 83%,64%,62% Irfan et al.
5Sn) (substitution) 95%,95%,62%/ (2017)
180 min
17 Fe3O4–TiO2:Gd Sol-gel Doping TiO2 Anatase No data RhB 100%/3h Popa et al.
(interstitial) (2018)

10
G. Harini et al.
Fig. 5. a) Schematic illustration of interstitial and substitutional doping of Gd on TiO2, (b) pictorial representation of Gd induced suppression of phase trans­
formation in TiO2.
electron-hole recombination rate and photo corrosion (Lee et al., 2016).
Doping of Gd ions on ZnO has been reported to significantly overcome
the aforesaid drawbacks. ZnO serves as a compatible host for doping
Gd3+ ions, owing to less mismatch of ionic radius of Zn ion with Gd ion.
This suggests that Gd3+ can be incorporated in the ZnO lattice (Mithal
and Kundu, 2013). In the case of Gd-ZnO, Gd was observed to replace Zn
either substitutionally or interstitially, whereas it gets decorated on the
surface or undergoes partial substitution in TiO2 due to radius mismatch.
Moreover, the substitution of Zn by Gd was observed to augment Zn
vacancies and interstitial defects, which thereby alter the photocatalytic
properties. Marinho et al. (2019) elucidated the photocatalytic property
of Gd doped ZnO. Subsequently, the incorporation of Gd3+ ions into ZnO
lattice results in a bandgap shift towards the visible region. Such redshift
may attribute to the following reasons:
i) Coupling of donors induced impurity level with CB of ZnO
ii) Exchange interactions among sp-f and sp-d arising between band
electrons and localized d and f electrons of Gd3+ ions
iii) Spin-orbit coupling between O2− and Gd3+ sites.
In contrast, a blue shift in the bandgap is also observed, owing to size
quantized effects upon doping of Gd3+ ions. This blue shift is observed in
certain cases where doping of Gd3+ increases beyond its threshold
(Marinho et al., 2019; Kumar and Kavitha, 2021; Selvaraj et al., 2019).
Generally, Gd-ZnO based materials are obtained via facile
co-precipitation, sonochemical and hydrothermal methods, among
which a simple chemical precipitation method was employed often
(Table 3).
Several studies have reported that incorporation of Gd on ZnO
resulted in suppression of agglomeration, reduction in crystalline size,
enlargement of ZnO lattice, and increase in size uniformity (Selvaraj
11
Journal of Cleaner Production 345 (2022) 131139
et al., 2019; Dhir, 2020; Kumar and Sahare, 2014). In a study by Selvaraj
et al. (2019), Gd-ZnO was synthesized via co-precipitation method,
where the system was developed in an optimized growth mechanism
involving nucleation, fusion and aggregation via oriented Ostwald
ripening growth. The FESEM image shows the spherical-like
morphology of 3% Gd-ZnO with less agglomeration, owing to the
repulsive interaction of Gd3+ ions (Fig. 4e&f). The photocatalytic effi­
ciency of 3% Gd-ZnO was 93% over 90 min under visible light illumi­
nation. Furthermore, doped Gd3+ reduce to Gd2+ ion by reacting with
CB electrons of ZnO, which helps in the generation of superoxide radi­
cals and electron trapping (Fig. 4b).
Yakout et al. (Kumar and Sahare, 2014) synthesized Gd-based Li, Na,
Mn, or Fe co-doped ZnO to study their magnetic and photocatalytic
properties. This dual doping resulted in a red shift in the bandgap of ZnO
owing to the exchange interactions of sp-f or sp-d orbitals as mentioned
earlier. The result suggested the utilization of Gd/Mn dopants for effi­
cient magnetic properties due to their long-range ferromagnetic order.
Several studies were reported on co-doping of cationic dopants along
with Gd, which showed better photocatalytic performance and enriched
defects than pristine Gd doping. Akhtar et al. (2020) explicated the
photocatalytic ability of Gd–Nd co-doped ZnO, which resulted in a red
shift in wavelength, reduced recombination rate and enhanced internal
defect. In another study, co-doping of Gd–N in ZnO was found to in­
fluence the chemical environment between Zn and O in the lattice and
had a huge impact on the ratio of chemisorbed oxygen (Alanazi et al.,
2021).
9.3. Impact of Gd doping on ferrite nanomaterials
Ferrite NPs are a class of magnetic NPs possessing unique properties
such as high surface to volume ratio, superparamagnetism, dielectric
G. Harini et al. Journal of Cleaner Production 345 (2022) 131139

property, and high adsorption capacities (Liu et al., 2020). Gd doped
ferrites are usually prepared with micro-emulsion, hydrothermal
method, co-precipitation and sol-gel method (Irfan et al., 2017; Tariq
et al., 2018; Shahid et al., 2017). Doping of Gd to ferrite NPs could
impact their magnetic, dielectric and photocatalytic properties (Liaquat
et al., 2020). Shahid et al. (2017) reported increase in magnetic prop­
erties of MnFe2O4 as an impact of Gd3+ and Co2+ doping. This may be
attributed to the replacement of Gd3+ in the octahedral site of MnFe2O4,
whose magnetic moment is significantly higher than that of Fe3+.
Enhancement in saturated magnetism (Ms) and haracteri (Hc) along with
decreased dielectric loss was also observed, owing to the ferromagnetic
property of both Gd and Co. Furthermore, dielectric loss peculiarly owes
to the presence of Gd, as rare earth elements are generally known to
bring down dielectric loss (Guo et al., 2010). Literatures shows extensive
use of A-site doping in BiFeO3 (BFO) with Gd3+ owing to the lone pair of
Bi 6s2, which results in enhanced electrical and photocatalytic property
(Dixit et al., 2021). Irfan et al. (2017) elucidated the preparation and
properties of Gd+3 and Sn4+ co-doped BiFeO3, which exhibited restric­
tion of recombination and bandgap shift from 2.10eV to 2.03eV. Besides,
•O2− radicals were found to be the major contributor for photocatalytic
degradation, as a result of electron transfer from Gd–Sn co-dopants to
the photocatalytic surface. Moreover, the photocatalytic performance
was investigated with Congo red, methylene blue, and methyl violet,
which indicated the enhanced performance of BGFO-5Sn (Table 4). In a
similar study, Dixit et al. (2021) reported the synthesis of N-rGO sup­
ported A-site doped BiFeO3 via hydrothermal method (Supplementary
Material Fig. S3 a (i) and (ii)). The substitution of Gd in place of Bi lattice
resulted in restricted grain growth leading to enhanced photo-induced
electron hole separation and thereby better photocatalytic efficiency
(Supplementary Material Fig. S3 a(iii)). In accordance with the previous
study, •O2− radicals were found to be predominant ROS as a result of Gd
doping. Popa et al. (2018) demonstrated the effect of Gd doping on
magnetic and photocatalytic properties of Fe3O4–TiO2. The samples
exhibited superparamagnetism with saturation magnetizations influ­
enced by degree of doping. Apropos to undoped sample, 0.5% Gd doped
sample evinced smaller magnetization and 0.7%, 1% Gd doped samples
showed higher magnetization. It was also reported that the order of
magnetic moment of 4f7-Gd in the semiconductor could be either anti­
ferromagnetic (low doping) or ferromagnetic (high doping), owing to
carrier mediated magnetism brought by spin-down tunnelled electronic
states from Fermi level of Fe3O4. Additionally, the induced
anti-ferromagnetic order was reported to be favorable for photo­
catalysis, whereas the ferromagnetism of f-states diminishes the photo­
catalytic activity. Fe2O3–TiO2 with 0.5% Gd exhibited excellent
photodegradation with 80% efficiency for RhB (Table 3).
10. Gd induced lattice defects and their effect on photocatalytic
nanomaterial
One of the paramount factors determining the photocatalytic appli­
cability and efficiency of semiconductors is their ability to generate
photo-induced electron-hole pairs and prevention of recombination of
these charge carriers (Chade et al., 2018; Kumar et al., 2021; Raizada
et al., 2020b; Sharma et al., 2020). Many studies have reported that
defects could enhance charge separation efficiency, where the defect
serves as adsorption sites, thereby preventing recombination. However,
contradictory consequences were also observed, where defects would
serve as a recombination center which subsequently affects the photo­
catalytic process (Chen et al., 2014b). Doping of Gd ions causes
defects/distortions in the semiconductor lattice owing to the mismatch
of its larger ionic radius with the host ion. On the other hand, insufficient
energy supply may curb the substitution of Gd3+ to the lattice, in such
cases, these ions reside on the surface of the semiconductor, which
creates an imbalance of surface charge. This in turn produces surface
defects and oxygen vacancies (Liu et al., 2013). Sudhagar et al. (2014)
investigated the optical properties of Gd-TiO2, which reported an
extended light absorbance edge from UV to visible region upon Gd3+
doping. It has been reported that this phenomenon could have resulted
either via coupling of 4f orbitals of Gd3+ ion with crystal lattice of TiO2
or through the introduction of defect centers below the conduction band
of TiO2. Another study investigated the impact of Gd, N doping on TiO2,
where Gd3+ was reported to be incorporated in TiO2 lattice by substi­
tution of Ti4+ ions. The charge imbalance created by this substitution
resulted in the reduction of Ti4+ to Ti3+, where the produced Ti3+ served
as defect sites. It was observed that Gd, N–TiO2 exhibited much lower PL
intensities than N–TiO2 owing to the presence of Gd, which promotes
enhanced charge separation by introducing surface defects. The result
interpreted that the Gd doping-induced defects indeed play a vital role in

Table 4
Synthesis, Characteristics and various photocatalytic application of Gd based NPs.
Photocatalytic Gd nanomaterial Synthesis Method Role of GdNPs in enhanced Photocatalytic efficiency Reference
application photocatalytic efficiency

H2 evolution Rh and Gd co-doped Ca3Ti2O7 Solid State reaction Contribution of 4f orbital 5 times maximum activity Nishmoto et al.
than undoped samples (2009)
Gd/TiO2–CdS Mechanical mixed more negative potential of CB of 550 μmol/3h Peng et al.
method Gd doped sample interrupts (2013)
electron transferability
1
3D- GdVO4 One pot Appropriate band positions and 42 μmol h− Mazierski et al.
hydrothermal nanowire morphology (2019)
process
Gd2Ti2O7/GdCrO3 Solid state Formation of p-n heterojunction 246.3 μmol h− 1 Yakout (2018)
combustion and supressed recombination Quantum efficiency = 4.1%
method
CO2 Reduction Pd/Gd(OH)3 Hydrothermal Suppressed e− /h+ recombination CH3OH yield = 0.410 μmol Parida et al.
method and appropriate band positions g− 1 h− 1 (2011)
Cu2In2ZnS5/Gd2O2S:Tb Solvothermal Light down-converting effect, CH4 yield = 57.73 μmol g− 1 Liu et al. (2019)
method increased active sites, enhanced h− 1
charge separation
Heavy metal removal Gd0.2La0.2Ce0.2Hf0.2Zr0.2O2 and Co-precipitation Generation of oxygen vacancies as Cr(VI) Converted to less toxic Anandkumar
(Cr(VI), Pb(II), As Gd0.2La0.2Y0.2Hf0.2Zr0.2O2 a result of Gd3+ Cr(III) = 90 and 100 min et al. (2020)
(V)) Gd(OH)3/RGO Hydrothermal Morphological effect of Gd(OH)3 Cr(VI) to Cr(III) = 82%/120 Padhi et al.
method nanorod in efficient charge transfer min (2014)
Gd2O3-GO Hummer method Magnetic property of Gd Adsorption capacities of Pb Zhang et al.
(II) and Cr(III) = 83.04 and (2017)
17.97 mg/g
GO-Gd2O3 Hydrothermal Magnetic property and selectivity Adsorption capacity for As(V) Lingamdinne
method of Gd3+ towards As = 216.7 mg/g et al. (2021)

12
G. Harini et al.
enhanced charge mobility and separation in TiO2 and as well as their
photocatalytic activity (Mandari et al., 2019). Lattice deformation of
ZnO was observed upon doping Gd3+, whereas the oxygen vacancies and
oxygen interstitials became stronger with increasing dopant concen­
tration. Subsequently, the enhanced photoconversion of RhB was
attributed to higher oxygen vacancies created by Gd doping on ZnO.
Furthermore, these oxygen vacancies have been reported to play a vital
role in the magnetic behavior of nanoparticles (Xiong et al., 2009; Rani
et al., 2020). According to the bound magnetic polarons (BMP) model,
bound electrons in defects like oxygen vacancies can couple Gd3+ ions
and cause overlapping of ferromagnetic regions, which results in
long-range ferromagnetic order (Coey et al., 2005). The aforementioned
cases involve distortion/expansion of host lattice owing to the larger
ionic radius of Gd ion. However, lattice contractions are also reported in
certain cases where the ionic radius of the host ion is larger than that of
Gd. For example, in the case of Gd3+/BiFeO3, the smaller ionic radius of
Gd3+ (0.938 A◦ ) with respect to Bi3+ (1.170 A◦ ), resulted in contraction
of lattice followed by a reduction in particle size. In a study by Zhang
et al. (2019), doping of Gd in BiFeO3 resulted in formation of more
surface defects, which captured the photo-induced electrons before
recombination. It could be understood from the aforementioned studies
that Gd induced defects and oxygen vacancies have a significant effect
on photocatalytic activity by constraining electron-hole recombination
and shifting absorption threshold. Additionally, the location of defects
and the relative ratio of bulk defects to surface defects in the photo­
catalyst have intense effects on their electronic and photocatalytic
properties (Zhuang et al., 2010; Devi and Anitha, 2020). Therefore, the
location and density of defects should be considered for photocatalytic
application.
11. Doping of Gd3þ ions on semiconductor photocatalysts
It is widely well known that doping of Gd3+ improves photocatalytic
efficiency of the host semiconductor photocatalyst by altering the
bandgap energy and promoting the separation of photogenerated charge
carriers. However, the contradictory impact of Gd doping on photo­
catalytic efficiency has to be addressed to improve its performance. The
dosage of dopant is a key factor in determining photocatalytic efficiency.
In many research works, the photocatalytic activity was found to in­
crease up-to a certain dopant concentration, followed by a poor photo­
catalytic activity with higher concentrations. The decrease in activity
can be correlated to the thickness of the space charge layer/depletion
region. The thickness of the space charge layer is inversely proportional
to the dopant concentration, which can be understood from the equation
(Eq. (4)) (Kumar et al., 2020c),
W = (2εε0 V/eNd )1/2 (4)
where W is the thickness of the space charge layer, ε and ε0 are the
dielectric constants of the semiconductor and the vacuum, V is the
surface potential and Nd is the number of dopant donor atoms. It can be
well understood from the equation that the increase in dopant content
(Nd) decreases the thickness of the space charge layer, which subse­
quently increases the electron-hole recombination. Additionally, at high
dopant concentration, the charge carriers undergo multiple trapping,
which eventually decreases the charge mobility rate (Shajahan et al.,
2020). Accordingly, experimental results have also supported the fact
that dopant concentration impacts the thickness of the space charge
layer indeed. Paul et al. (2015) reported that 0.03 mol Gd dopant on
TiO2 exhibited highest photocatalytic activity, whereas 0.07 mol
showed the lowest photocatalytic activity. In addition to this, due to the
large ionic radius of Gd3+ ions (0.938 A◦ ), it tends to form isolated
clusters and covers the photocatalytic surface at high doping concen­
trations as they cannot enter the semiconductor matrix. These clusters
act as charge carrier capture centers which eventually decrease their
photocatalytic performance (Tian et al., 2019). Hence, it is important to
13
Journal of Cleaner Production 345 (2022) 131139
optimize the dopant concentration to achieve a better photocatalytic
performance.
12. Properties of Gd nanomaterials for the enhanced
photocatalytic activity
As mentioned earlier, many efficient photocatalysts including TiO2,
ZnO and SnO2 has limitations in practical applications of being photo-
reactive only in UV range. Coupling of these photocatalysts with
upconversion phosphors is one of the assuring methods to solve this
issue. During the upconversion process, multiple low-energy photons
are absorbed sequentially to reach the excited state and one higher en­
ergy photon is released. These multiple NIR light photons are converted
into UV or visible light photons via fluorescent resonance energy
transfer (FRET) (Tian et al., 2019). Consequently, the upconverted
photon released in the UV–vis spectrum can be reabsorbed by the
semiconductor photocatalyst for its activation. This direct energy
migration between the UC materials and semiconductors under NIR
irradiation could promote the utilization of solar spectrum and enhance
photocatalytic efficiency (Shang et al., 2015). Upconversion nano­
particles (UCNPs) are generally comprised of a host matrix, activator
and sensitizer. Upon irradiation, the sensitizer gets excited and transfers
the energy to the activators through resonant interactions. Thereupon,
the activator gets relaxed non-radiatively and passes the energy to the
photocatalyst (Supplementary Material Fig. S3 b). NaYF4 is considered
an efficient host material for upconversion owing to its low phonon
energy and high absorption properties (Shi and Zhao, 2014). Currently,
literatures on NaYF4/Gd phosphors are scarcely available due to the
broad bandgap of Gd, whose first excited stack occurs above 30,000
cm− 1. Anyhow, Gd3+ as an ideal UV-sensitizer is commonly co-added
with other rare earth elements (Yb3+-Ho3+, Yb3+-Tm3+, Er3+), which
optimize the upconversion process by acting as an intermediate
sub-lattice [172].
Duo et al. (2016) reported the preparation of NaYF4/Gd3+, Yb3+,
Tm @TiO2 and NaYF4:/Gd3+, Yb3+, Tm3+@TiO2@Au. It was reported
3+
that Gd3+ ions in the host matrix had no significant effect in the
upconversion peaks and their positions; however, their influence in
photon process which populate the 1I6, 1D2, 1G4 and 3F3 emitting levels
has been observed. Klier and Kumke (2015) observed a strong influence
of Gd3+ concentration on the intensities of upconversion emission. With
increase in Gd3+ content, decrease in particle size from 274 nm to 46 nm
and lattice phase transition from α to β was observed. Both, crystal phase
change and decrease in particle size were reflected in the upconversion
luminescence properties. In a study by Mavengere and Kim (2018),
decrease in crystal size of NaYF4 was observed as a result of addition of
Si4+ and Gd+3 ions, thereby implying a significant decrease in bond
length of Gd3+. Consequently, as a promising sensitizer, Gd3+ ions
senstizes at 980 nm light and transferred the energy to Si4+ activator to
emit high energy photons, which could be utilized to perform upcon­
version driven photocatalysis. Furthermore, the photodegradation effi­
ciency of NaYF4 (Si and Gd): TiO2 was 95% for RhB under visible light.
Upconversion driven photocatalysis works with less energy consump­
tion and low catalyst dosage with an optimum quantum yield (Anwer
and Park, 2019). Anwer and Park (2019) elucidated the synthesis of
NaYF4: Yb3+, Gd3+, Tm3+@Bi2WO6 (UCNP@Bi2WO6) composite via
combustion and sol-gel method for photodegradation of Bisphenol A.
Photocatalytic activity for both UCNPs and Bi2WO6 was observed to be
negligible under NIR irradiation. However, as UCNPs@Bi2WO6NCs, the
system degraded BPA with an efficiency of 94% in low energy NIR
radiation.
13. Photocatalytic application
13.1. Pollutant removal
The photocatalytic removal of organic pollutants is one of the
G. Harini et al.
common applications of GdNPs besides biomedical applications. These
environmentally persistent pollutants were degraded by production of
ROS by GdNPs in the photocatalytic process. Gd photocatalysts have
been modified and Gd ions have been used for modifications of
numerous semiconductor photocatalyst for enhanced pollutant removal.
These pollutants include dyes, pharmaceutical products, pesticides and
heavy metals. Various industrial dyes including rhodamine B (RhB),
methyl orange (MO), methylene blue (MB), methyl violet, eriochrome
black T (EBT), erythrosine (ES), malachite green (MG), reactive brilliant
red X–3B (RBR-X-3B), crimson red (CR), acid orange 7 (AO7), indigo
caramine and acriflavine dye has been successfully degraded by Gd
based photocatalysts. From Tables 1-3, it could be observed that MB and
RhB are the most commonly used model contaminant for the evaluation
of photocatalytic activity of Gd NPs (Tables 1–3). Among different
modified forms of Gd NPs and Gd doped ZnO photocatalysts was found
to have enhanced degradation efficiency towards MB than other forms,
which either consumed much time or exhibited partial degradation at
short span (Table 3). Here, Gd-ZnO exhibited complete mineralization of
MB within 45 min under visible light. For the degradation of RhB, Gd
heterojunction photocatalysts and Gd doped photocatalyst exhibited
better photocatalytic performance (Tables 2 and 3). Peculiarly, GdVO4-
ZnO exhibited enhanced photodegradation efficiency with excellent
stability and Gd doped TiO2 achieved maximum degradation in short
duration of 10 min (Zhao et al., 2008).
13.2. Photocatalytic degradation of environmental pollutant
13.2.1. Reactive sites of antibiotics for differentROS
The reactive species such as •O2− and •OH plays the major role in
photodegradation of these antibiotics. It is obvious that the photo­
degradation pathway of each reactive species is different from each
other. The effect of ROS on degradation pathway is shown in Supple­
mentary material Supplementary Material Fig. S3. This in turn affects
the final toxicity of the water. Thus, more attention is required on the
ROSs effect on water toxicity. FEDS method was used for computational
prediction of attack sites of radicals on antibiotics. According to the
computational results, hþ, •O2− and •OH effectively took part in
degradation.
13.2.2. Degradation pathway of PhACs
It has been observed that ciprofloxacin and 4-chlorophenol is the
widely exploited model contaminant for the evaluation of photocatalytic
ability of Gd based nanomaterials. This section hereby provides an
elaborative insight on the photodegradation pathway of these contam­
inants upon the influence of Gd based nanomaterials. According to the
available literature, ROS plays a major role in the effective degradation
of PhACs by various modification technologies which depends upon the
nucleophilic and electrophilic attack of ROS. The theoretical calculation
of the degradation pathway of PhACs was used to predict the attack of
ROS using Fukui function rather than the photocatalytic degradation
pathway. For instance, the Fukui function on ciprofloxacin was calcu­
lated and the results conclude that the h+ ions attack the N1 and N4
sites; •OH− attacks the C15 and •O2− attacks at C14. Further, the
nucleophilic and electrophilic attack on 4-chlorophenol by FED was
calculated and the results finds that the site of action was observed,
where attack on the benzene ring causes the removal of chlorine and
addition of OH. Jiang et al. (2016) studied the photocatalytic degrada­
tion of 4-chlorophenol where •OH radicals serve as the predominant
ROS. Here, the experimental data concludes the formation of interme­
diate of ciprofloxacin by LC-MS analysis where •OH attacked at C3 and
the formation of other intermediates are attributed to the oxidation
which cause the complete mineralization of the PhACs. In addition, He
et al. (2020) studied the photocatalytic degradation of RhB and the
formation of intermediate was determined by the HPLC-MS, which
explicated the predominant role of •OH- and •O2− radicals. The radicals
attack at reaction site of N1 which results in the formation of P1, P2, P3,
14
Journal of Cleaner Production 345 (2022) 131139
P4, P5, P6, P7, P8, P9, P10, P11 and P12. Further, the formation of in­
termediate at P1 and P2 was mainly due to the attack of •O2− radical,
which cleaves the benzene ring. Here, we conclude that the degradation
pathway mainly depends up on the interaction of •OH− and •O2− .
13.3. Photocatalytic hydrogen production
Photocatalytic hydrogen production (H2 production)via water
splitting is one of the promising solutions for sustainable energy (Xia
et al., 2021). The Gd based nanomaterials were rarely applied in the
H2production than photocatalytic pollutant removal. Additionally,
among the available literatures, the research works were mainly con­
cerned with Gd-Titania or other Gd based mixed semiconductor systems.
Nishmoto et al. (2009) studied the photocatalytic hydrogen generation
of Ca3Ti2O7 co-doped Rh and Ln (Ln = La, Pr, Nd, Eu, Gd, Yb, Y) pho­
tocatalyst. The result showed that Gd doped sample showed highest
activity and exhibited a 5-fold increase as compared with the undoped
sample. Contrarily, in another study, among the RE doped Pt/TiO2–CdS
samples, Gd doped samples exhibited lowest activity than the other
dopants owing to more negative potential of CB which affected the
efficient electron transfer (Peng et al., 2013). Mazierski et al. (2019)
reported that 3D GdVO4 NPs have appropriate CB and VB positions to
split water molecules with a narrow band gap, which utilize visible light
for H2 generation. A study by Parida et al. (2011) elucidated the
exploitation of Gd2Ti2O7/GdCrO3 composite for visible light driven
hydrogen production. It was observed that the visible light active
GdCrO3 act as sensitizer for the visible light inactive Gd2Ti2O7, which
eventually bring down recombination. The resultant showed excellent
H2 evolution (753.3 μmol/3 h) with quantum efficiency of 4.1%
(Table 4).
13.4. Photocatalytic CO2 reduction
Photocatalytic reduction of CO2 poses a major importance as the
world face a major threat by global warming. Accordingly, many
research works are carried out to design photocatalysts with high
selectivity, conversion efficiency and visible light harvesting ability
(Kawaguchi et al., 2018). A study reported the utilization of Pd doped
Gd(OH)3 NPs for photocatalytic conversion of CO2 to methanol. It has
been reported that Pd forms schottkey barrier on Gd(OH)3 and acquit
itself as electron traps, thereby facilitate charge mobility and hinders
recombination. Moreover, the NP was reported to exhibit excellent
conversion efficiency, visible light harvesting ability and reusability
up-to 5 cycles (Al-Mhyawi and Salam, 2018). Liu et al. (2019) coupled a
down converting phosphor (Gd2O2S: Tb) with Cu2In2ZnS5 (CIZS) to form
CG composite for the reduction of CO2 under full solar spectrum illu­
mination. Not just as a sensitizer, Gd2O2S: Tb was observed to affect the
reduction of CO2 at varying concentration. The CO2 reduction rate of CG
composite was significantly higher than CIZS, owing to synergetic effect,
suppression of charge carrier and enhanced charge mobility (Table 4).
13.5. Photocatalytic removal of heavy metals
Heavy metal pollutants are notorious water pollutants which pose
intimidating threat to biological entities. Removal or reduction of these
heavy metals has become a major challenge, which is often investigated
with photocatalytic method. Anandkumar et al. (2020) reported the
utilization of Gd0.2La0.2Ce0.2Hf0.2Zr0.2O2 (GLCHZ) and
Gd0.2La0.2Y0.2Hf0.2Zr0.2O2 (GLYHZ) for reduction of Cr(VI) under sun­
light. Both multi-component oxide photocatalyst exhibited narrow band
gap, optimum oxygen vacancies, and suppressed recombination, which
eventually lead to excellent photo reduction of Cr(VI) within 100 min.
Another study elucidated the synthesis of Gd(OH)3/RGO composite for
Cr(VI) reduction. This report stated the morphological impact of Gd
(OH)3 on photo reduction of Cr(VI), where the nanorod shaped Gd(OH)3
was found to exhibit better photoreduction than the spherical. This
G. Harini et al.
could be attributed to the fact that electron mobility is better along the
longitudinal shape, which eventually haracte recombination (Padhi
et al., 2014). Moreover, Cr(VI) reduction by other GdNPs including
Cu2In2ZnS5/Gd2O2S:Tb, In2S3/Gd2O3 and GO-Gd2O3 have been re­
ported (Padhi et al., 2014; Li and Duan, 2012; Raizada et al., 2019b). As
mentioned earlier, other heavy metals such as Pb(II) and As(V) have
been removed by GO-Gd2O3 photocatalyst (Table 4) (Low et al., 2017;
Raizada et al., 2019b).
14. Toxicity of Gd-based nanomaterials
The gaining popularity of NPs is followed by a raising concern on its
toxicity, which corresponds to their composition and size. The contin­
uous utilization of NPs for water treatment may raise concerns when it
comes to their compatibility with the environment. As discussed earlier,
Gd has been widely used in bio sensing, imaging, neutron capture
therapy and photocatalysis, which are most likely to interact with
humans, posing potential health hazards. The occurrence of Gd has been
estimated to be 1100 ng/L in surface water and up-to 90.5 μg/g in
sediments (Rogowska et al., 2018). Despite the fact that Gd is
non-essential to biota, they were unintentionally absorbed by organisms
and eventually pose an unavoidable impact on the environment.
Elemental Gd has been reported to enter the circulation and deposit in
various tissues including neural, lung, breast, kidney and liver tissues
(Balaram, 2019). Moreover, examination of post-mortem brain has
confirmed the deposition of Gd under the endothelial wall and neuronal
interstitium (McDonald et al., 2017). Free Gd+3 ions are reported to be
highly toxic as they could inhibit Ca2+-regulated cell signalling owing to
their similar ionic radius, which blocks several voltage-gated ion chan­
nels thereby disturbing physiological processes like neuronal trans­
mission, blood coagulation, contraction of skeletal, smooth, and cardiac
muscle (Unruh et al., 2020). Water-soluble Gd salts like chloride and
nitrate are mildly toxic via the oral route and insoluble Gd salts are
regarded as non-toxic (Yu et al., 2017). Some of the adverse effects of Gd
in various parts of the body are illustrated in Fig. 6a. A study by Liu (Liu
et al., 2021) investigated the impact of Gd stress on physiological and
molecular levels of Arabidopsis thaliana. It was found that the plant
growth, chlorophyll content and soluble protein have significantly
declined with high doses of Gd (200 μmol.L− 1). At the genetic level, high
doses induced DNA damage and low concentration of Gd induced DNA
methylation change (Fig. 6b). As we have discussed earlier, Gd-based
photocatalysts have distinct magnetic properties which could be tuned
by coupling with ferrite nanomaterials, which could be effectively
recovered from the reaction medium. However, furthermore in­
vestigations are needed to peculiarly elucidate and assess the toxic risk
factors of Gd photocatalysts for the welfare of the environment and to
extend its application to industrial scale.
15. Challenges
In the past few decades, Gd-based photocatalysts have been gaining
attention for their unique capacities and physicochemical properties. As
it is a booming field of research, the data provided in existing research
works are insufficient to arrive at any exact conclusions about its po­
tentials and ineptitude. To begin with, the separation and purification of
Gd from other lanthanides remain the first and foremost concerns. The
lanthanoid contraction and similar chemical properties make them
similar in size and observably indistinguishable. Inappropriate separa­
tion of the elements leads to the impurity of Gd which directly affects its
properties. Gd has been primarily reported for its unique magnetic,
crystalline, and luminescent properties. However, the purity of Gd has
been reported to widely affect their properties, thereby reducing its ef­
ficiency. Another major concern on its photocatalytic application is the
wide bandgap of certain Gd NPs, which makes them sensitizible only in
the UV region. However, selection of synthesis methods, optimization of
reaction parameters, modification techniques, and crystalline structures
15
Journal of Cleaner Production 345 (2022) 131139
of the Gd has been reported to play a vital role in its bandgap alignments
and thereby its photocatalytic efficiency. The available literatures
address the use of Gd as a dopant impurity on various host semi­
conductors, which reported enhanced photocatalytic performance and
adsorption threshold shift to visible region. However, modification
techniques for Gd-based photocatalysts were less. Besides the compel­
ling properties, the toxicity of Gd raises a major concern on its large-
scale application. Hence, more research works should be focused on
its toxicological studies to assess its risk on environment and human
heath.
16. Knowledge gap and perspective
Gd-based nanomaterials have been found to exhibit considerable
photocatalytic performance in UV and Vis region. Even though many of
them have a wide band gap, modification strategies have been found to
improve their performance in the visible region. However, there remains
some drawbacks, debatable concerns, and uncertainties about the Gd
based nanomaterials, which is elaboratively enlisted below: (i) Synthesis
methods – Eventhough, there are many reports about the exploitation of
numerous synthesis methods for the production of GdNPs, only few of
them were explored for photocatalytic application. It is necessary to
investigate the influence of synthesis methods over the property of
nanomaterials, which helps to design the experiment to get the desired
outcome. (ii) Heterogeneous photocatalysis – Reports on Gd-based
heterogeneous catalysts were observed to be insufficient to make any
concluding remark about its significance. Specifically, Z-Scheme-based
heterojunctions have to be explored further as it is considered as the
better way for charge transfer and photocatalytic performance. (iii)
Doping and defects – Eventhough, Gd3+ is validated to be a potential
dopant for defect formation and to shift light absorption threshold, there
were no sufficient research works on doping studies in Gd-based nano­
materials. (iv) Facet and surface engineering – Facet-oriented prepara­
tion of nanomaterials has been widely exploited to obtain nanomaterials
with desired crystal shape and exposed facets, which exhibits great in­
fluence on their optical, magnetic, physicochemical and photocatalytic
property. However, the currently available literatures on Gd NPs lacks
insights on facet-based synthesis and its consequential studies.
It is highly recommended to focus on these areas to explore all the
possibilities and capabilities of Gd-based nanomaterials. Moreover, up-
conversion-based photocatalytic studies on Gd-based host matrices
have to be accelerated. To overcome the wide band gap issue of Gd
materials, construction of well-aligned Z-scheme heterojunctions and
introduction of dopants are recommended.
17. Conclusion
Gd based nanomaterials has been observed to be a potential photo­
catalyst for photodegradation of pollutants under UV/Visible irradia­
tion. It can be noted that the synthesis methods indeed play a significant
role in particle size, morphology and other physical properties. From
this review, Gd NCs/heterojunctions were noted to exhibit excellent
photocatalytic activity with enhanced properties such as reduced band
gap energy, improved charge separation and stability than its individual
counterparts. Gd3+ dopants were found to exhibit significant impact on
phase transformation, magnetic and physical properties of the host
nano-material. Magnetic properties of Gd have been investigated and
found to have significant impact on photocatalytic performance and its
recoverability. Gd induced defects were found to have a positive impact
on the host material at optimum concentration. Upconversion studies on
Gd based UCNPs and host matrices were very few, but existing litera­
tures reported significant effect of upconversion driven photocatalysis.
Hence it is recommended that more works to be done to get a better
understanding on the impact of Gd. Not just for pollutant removal, Gd
based materials have served as a potential photocatalyst for other pho­
tocatalytic applications including hydrogen evolution, CO2 reduction
G. Harini et al. Journal of Cleaner Production 345 (2022) 131139

Fig. 6. Schematic representation of adverse effects of Gd (a) toxic effects in various organs and molecular mechanism in humans and (b) Physiological and Genotoxic
effect of high dose Gd in Arabidopsis thaliana.

16
G. Harini et al.
and heavy metal removal. Most of the reported literatures for the
aforesaid applications reported heterostructure NCs of Gd with other
semiconductor materials. Even though the role of Gd is validated,
further studies should focus on pristine GdNPs to provide a clear insight
on its individual potential. Regardless of the attractive application of Gd
NPs in water treatment, its environmental toxicity is still a concern. Even
though they have impressive magnetic properties for recovery, further
studies should peculiarly address the possibility of Gd toxicity from the
photocatalytic system to assess the risk and to extend its applicability to
industrial scale.
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.
Acknowledgement
Authors sincerely thank the management of Bannari Amman Insti­
tute of Technology, Tamil Nadu for providing the necessary facilities for
carrying out this work.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.jclepro.2022.131139.
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