Inorganic Chemistry Communications 129 (2021) 108618

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Inorganic Chemistry Communications

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

Short communication

Green synthesis of spherical TiO2 nanoparticles using Citrus Limetta

extract: Excellent photocatalytic water decontamination agent for RhB dye
Ghulam Nabi a, b, *, Abdul Majid c, Asma Riaz a, Thamer Alharbi c, Muhammad Arshad Kamran d,
Mansour Al-Habardi c
a
Nanotechnology Lab, Department of Physics, University of Gujrat, Gujrat, Pakistan
b
Research Centre of Materials Science, Beijing Institute of Technology, Beijing 100081, People’s Republic of China
c
Department of Physics, Faculty of Science, Majmaah University, Majmaah 11952, Saudi Arabia
d
Department of Physics, University of Okara, Okara 56300, Pakistan

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

Keywords: In this research work, TiO2 nanoparticles has been prepared by eco-friendly green synthesis technique using
Green synthesis Citrus Limetta extract which is rarely used. The citric acid present within the extract acted as reducing and
TiO2 capping agent for nanoparticles resulting pure TiO2 nanoparticles. The synthesized nanoparticles are charac­
Optical properties
terized by using X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spec­
RhB dye
Photocatalytic properties
troscopy (EDS), transmission electron microscopy (TEM), UV–vis spectroscopy and photoluminescence (PL)
Decontaminations analysis. The synthesized nanoparticles are approximately 80–100 nm in size, spherical in shape and distribution
of the nanoparticles was almost uniform all over the sample. The calculated band gap of nanoparticles was 3.22
eV which confirmed the formation of anatase phase TiO2 nanoparticles. The enhanced photocatalytic activity
with respect to time and catalyst concentration was examined for RhB acting as a model dye which is better than
many reported results. Almost 90% dye was degraded within 80 min which shows its excellent photocatalytic
efficiency.

1. Introduction Titanium dioxide is well known synthesized nanomaterial due to its

Almost 50% of pollutant present in water are organic nature which
cannot be discarded by conventional methods [1]. The advanced
oxidation processes have gained popularity due to conversion of organic
pollutant into simpler products (CO2 and H2O) in presence of water. In
last few decades, several techniques have been reported for the treat­
ment of organic pollutants in waste water and air. Among them the
photo catalysis of metal nanoparticles has gained interest of many re­
searchers [2,3]. Nano catalysis has gained advantages due to large
surface area and easy removal of reaction mixture that make the catalyst
reusable. Nanomaterials have optical, chemical and physical properties
that mainly depend on their size and shape. Metal oxide nanoparticles
possess various magnetic, electronic, and optical properties. Various
metal oxide nanoparticles have been synthesized including ZnO, SnO2,
CoCr2O4, VO2, Fe3O4, MgFeCrO4, Mg0.5Zn0.5FeMnO4, CoMnCrO4 ,
ZnAl2O4@ZnO, TiO2 [4–13]. Among them, TiO2 has been used in
various areas including waste water remedies and medicinal purposes
due to its astonishing properties [14,15].
numerous properties i.e. high thermal and chemical stability, biocom­
patibility, low cost, high refractive index and oxygen vacancies in lattice
structure[16,17]. TiO2 is a metal oxide semiconductor which exist in
both amorphous and crystalline form. TiO2 mostly exist in three crys­
talline phases i.e. rutile, anatase and brookite [18]. Anatase and rutile
are tetragonal structures with di-pyramidal and prismatic habits
respectively. While brookite is in orthorhombic pattern. Anatase is the
most preferable form because of having high surface area, high potential
energy for photo generated charge carriers and better photocatalytic
activity [19]. TiO2 has various uses such as pigments, food additives,
toothpaste, plastics, cosmetics, solar cells, pharmaceutical, skin care
products and capacitors [16,20]. It also includes properties like large
band gap, hydrophobicity, non-wettability. On industrial scale TiO2
finds applications such as photocatalysis, chemical sensors, dye sensi­
tized solar cells, lithium ion batteries, anti-microbial products, textiles,
chemical sensors and electrochemistry [21].
Numerous methods have been developed to synthesize TiO2 nano­
particles such as sol–gel [22], hydrothermal [23], co-precipitation [24],

* Corresponding author at: Nanotechnology Lab, Department of Physics, University of Gujrat, Gujrat, Pakistan.
E-mail addresses: gnwattoo@yahoo.com (G. Nabi), a.abdulmajid@mu.edu.sa (A. Majid).

https://doi.org/10.1016/j.inoche.2021.108618
Received 1 February 2021; Received in revised form 6 April 2021; Accepted 15 April 2021
Available online 19 April 2021
1387-7003/© 2021 Elsevier B.V. All rights reserved.
G. Nabi et al. Inorganic Chemistry Communications 129 (2021) 108618

Fig. 1. Flowchart of the synthesis of TiO2 nanoparticles.

salvo-thermal [25], direct oxidation method, electrodeposition [19],

chemical vapor deposition [26], and green synthesis. Chemical synthesis
of nanomaterials is toxic as well as have adverse effects on environment.
Green synthesis is proficient and eco-friendly method to synthesize
nanoparticles. The molecules present in plant extract act as both
reducing and capping agent and increase their stability [27]. They cease
the agglomeration of nanoparticles and require less energy for produc­
tion. The phytochemicals (which causes better yield by depositing the
reactants on the surface of catalyst) present in plant extract forms a layer
on the catalyst that prevents agglomeration and cause the time depen­
dent stability of synthesized nanoparticles [28]. The biosynthesis of
metal oxide nanoparticles utilizes the biomaterials such as plant ex­
tracts, fungi, enzymes, and microorganisms. The green synthesis has
advantages like biocompatibility for medical purposes, low cost, easy
handling and synthesis process. It is cost effective, non-toxic, environ­
mental friendly, and natural method to synthesize heterogeneous
nanocatalyst [29]. In the earlier research, TiO2 nanoparticles were
prepared by various capping agents like neem [30], orange [31], curry Fig. 2. XRD patterns of as synthesized TiO2 nanoparticles.
tree [32], papaya [33], pomegranate [34], cherry [35]. These nano­
particles were used in various applications. which was then calcinated at 550 ℃ for 2 h. The synthesis flow chart for
Here in this research, the use of Citrus limetta (commonly called as TiO2 nanoparticles is shown in Fig. 1.
sweet lime) in synthesis of TiO2 nanoparticles is reported first time to the
best of our knowledge. The extract of Citrus limetta acts as a capping
agent for the synthesis of TiO2 nanoparticles. The leaves of Citrus limetta 2.1. Characterization
are the rich source of rare chemicals such as poly methoxylated flavones
and flavones. Citrus fruit are efficient reducing gents that brings the The X-ray patterns were obtained by powder X-ray diffraction using
synthesis of nanoparticles [36]. The optical and photocatalytic proper­ the source of Cu – Kα radiations (λ = 0.15418 nm). The scanning elec­
ties were studied using UV–vis spectroscopy and PL analysis. The syn­ tron microscope images were taken by ZESIS – V80. The elemental
thesized nanoparticles exhibit enhanced photocatalytic efficiency analysis of synthesized material is done by using EDS – 8000. The UV–
(>90%) due to which they can be used as a photocatalyst for the vis absorption spectra were made by using Shimadzu, UV – 1800 spec­
degradation of organic dyes present within the water. trophotometer. The photoluminescence spectra were analyzed by FP –
8200, JASCO spectrometer with excitation wavelength of 375 nm.
2. Experimental section Photocatalytic Experiment
Rodhamine B (RhB) was used as a model dye to check the photo­
TiO2 nanoparticles were prepared by using extract of Citrus limetta. catalytic activity of synthesized nanoparticles. A cylindrical reaction cell
The extract was prepared by dissolving 6 g of leaves in 100 mL of having 100 mL volume along with circular water system was used in the
distilled water and boiled at 100 ℃ for 15 min. The extract was filtered experiment. Various dosage (0.1 g, 0.3 g, 0.5 g, 0.7 g) of synthesized
to be used further in the experiment. Then 2 g of titanium butoxide was nanoparticles were added to 50 mL distilled water containing 10 mg/L
added in 100 mL of distilled water and labeled this solution as A. 20 mL of dye under continuous magnetic stirring of 10 min in the dark. Then
of Citrus limetta extract was poured drop wise in solution A. The solu­ this mixture is illuminated with UV light using a homemade photo­
tion was stirred for 5 h and aged for 24 h at room temperature. The catalytic reactor. The degraded amount of RhB was checked after equal
solution was then dried at 150 ℃ for 2 h until the particles were formed intervals of time using UV–vis spectroscopy. Degrading of RhB was

2
G. Nabi et al.
Fig. 3. (a, b) Low and high magnification SEM images of TiO2 nanoparticles (c) Histogram size distribution of TiO2 nanoparticles (d) EDS spectra and elemental
composition of TiO2 (e) TEM analysis of TiO2 NPs- Inset is also TEM image of TiO2 nanoparticles (f) Contrast profile image across the individual NP showing its size.
checked with respect to time and amount of catalytic material.
3. Results and discussion
X-Ray pattern of synthesized TiO2 nanoparticles via green synthesis
is shown in Fig. 2. All the diffraction peaks are corresponding to the
JCPDS card #: 01–073-1764. The miller indices (hkl) of XRD peaks are
(1 0 1), (1 0 3), (0 0 4), (1 1 2), (2 0 0), (1 0 5), (2 1 1), (2 0 3), (2 2 0), (1 0 7),
(2 1 5). Debye-Scherrer formula is used to calculate the average grain
size of synthesized nanoparticles [11,12].
kλ
D=
βcosθ
Where k represents Scherrer constant (k = 0.89), λ wavelength of X-
ray, β full width half maximum (FWHM), D being the crystallite size and
2θ represents the angle of X-ray diffraction peak. The calculated grain
size of nanoparticles was about 45 nm. Further, the sharpness of peaks
clearly shows the crystalline nature of synthesized nanoparticles, which
is directly related to recombination of charge carriers and photo cata­
lytic efficiency.
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Inorganic Chemistry Communications 129 (2021) 108618
The anatase crystalline phase has been observed. No impurity peak
such as Ti is present in XRD pattern.
The shape, morphology and apparent grain size of synthesized
nanoparticles were examined by using scanning electron microscopy
(SEM). The low and high magnification SEM image of synthesized
nanoparticles is shown in Fig. 3 (a,b) respectively. Fig. 3 (b) shows that
the particles are uniformly distributed and spherical in shape with size
ranging from 80 to 100 nm. The Fig. 3 (c) shows the histogram size
distribution of TiO2 nanoparticles which shows that maximum number
of particles are lying in the range of 80–100 nm. The elemental
composition of nanoparticles is described by energy dispersive X-ray
spectroscopy (EDS). The EDS pattern of synthesized nanoparticles are
shown in Fig. 3 (d). Inset of Fig. 3 (d) is the weight and atomic per­
centages of TiO2 nano particles. The only presence of titanium and ox­
ygen peaks confirmed the formation of pure anatase TiO2. No other
impurity peaks have been observed. The shape and size of nanoparticles
were further analyzed by advance technique transmission electron mi­
croscopy (TEM). The TEM image of the nanoparticles have been
depicted in Fig. 3 (e) which also confirms that the nanoparticles are in
spherical shape and are in range of 80–100 nm which is in complete
G. Nabi et al.
Fig. 4. (a) Tauc plot and (inset) UV–vis pattern of TiO2 (b) PL spectra of TiO2 nanoparticles.
agreement with SEM results. More clear TEM image has also been added
in the inset of Fig. 3 (e). Contrast profile of TEM image of an individual
nanoparticles is shown in Fig. 3 (f) which confirmed the size of the
particle under observation is 100 nm.
Optical properties investigation is vital for photocatalytic study as it
describes the number of incident photon absorbed during the photo
catalytic process [37]. The optical properties of prepared samples were
analyzed by UV–vis spectroscopy. The absorption spectra and Tauc plot
of the prepared samples were shown in the Fig. 4(a). The UV–vis ab­
sorption spectra show that the higher absorption is in the range of
300–400 nm as shown inset of the Fig. 4 (a). The band gap of the pre­
pared samples was measured by the following Tauc Eq. (1) [13,38].
( )
(αhν)2/n = A hν − Eg (1)
Where α is the absorption coefficient, A is the proportionality con­
stant, hν is the incident photon energy and Eg is the band gap energy.
The value of n depends upon the type of optical transition of semi­
conductor (for direct transition n = 1 and for indirect n = 4) [39]. The
band gap energy is calculated by plotting the graph between (αhν)2 and
hν. The calculated direct bandgap of the TiO2 nanoparticles is 3.22 eV as
shown in Fig. 4 (a) which is also consistent with the literature [40].
Furthermore, the emission properties of synthesized TiO2 nano­
particles were examined by photoluminescence (PL) spectroscopy
technique at room temperature. Photoluminescence graph of green
synthesized TiO2 nanoparticles with excitation wavelength of 375 nm is
shown in Fig. 4 (b). The PL spectra of TiO2 nanoparticles shows a UV
emission peak at 385 nm and three visible emissions peaks at 406 nm,
Fig. 5. (a) BET nitrogen adsorption isotherm graph of the TiO2 nanoparticle (b) corresponding pore size distribution graph.
4
Inorganic Chemistry Communications 129 (2021) 108618
421 nm and 440 nm respectively. The UV emission peak at 385 nm is
ascribed by the band edge emission of the TiO2 nanoparticles that also
explain the band gap of the material. The calculated band gap corre­
sponding to the UV emission peak at 385 nm is 3.22 eV which is
consistent to Tauc plot band gap as shown in Fig. 4(a). In the PL of the
TiO2 nanoparticles three types of physical origins has been observed in
reported sample such as oxygen vacancies [41,42], self-trapped excitons
[41,43] and surface states defects [44]. The high surface to volume ratio
in TiO2 nanoparticles favor more oxygen vacancies due to large amount
of surface defects and most of the surface states of TiO2 are Ti4+ ions
adjacent to oxygen vacancies [45,46]. These defects are ascribed due to
the non-equilibrium growth condition of TiO2 nanoparticles which plays
a significant role in the photoluminescence of TiO2 which are consistent
with the literature [47]. Furthermore, two visible peaks at 406 nm and
440 nm are ascribed due to self-trapped excitons in TiO6 octahedral
[48]. The presence of oxygen vacancies in the TiO2 nanoparticles are
explained fairly by the blue emission peak at 440 nm and is consistent
with the literature [49].
The BET surface area for the prepared TiO2 nanoparticles was
analyzed by Brunauer–Emmett–Teller (BET) which is a sophisticated
analysis technique to measure the specific surface area of the materials.
The characteristic plot of N2 adsorption–desorption isotherm and pore
size distribution curves of the as-prepared TiO2 nanoparticles are shown
in Fig. 5 (a,b). The TiO2 nanoparticles displayed the isotherm of type-IV
(BDDT classification) with hysteresis loops at relative higher pressure
range of 0.55–1.0 which shows the absorption nature of the nano­
particles often found in agglomerated nanocrystals as shown in Fig. 5 (a)
G. Nabi et al.
Fig. 6. (a) UV–vis Absorption spectra with respect to time (b) with respect to catalyst variation (c, d) CC0 plot with respect to time and catalyst variation (e, f)ln CC0 plot
with respect to time and catalyst variation.
[5,6]. The corresponding pore-size distribution of the as-prepared TiO2
nanoparticles is shown in Fig. 5 (b). The pore size distributions graphs
specified that TiO2 has moderately narrow distribution. The BET surface
area of the as-prepared TiO2 nanoparticles was calculated about 120.22
m2/g. A high surface area can provide more surface active sites for the
adsorption of the reactive molecules, which leads the photocatalytic
process to be more efficient [4,7]. So, these nano-particles are effective
in photocatalytic activities.
Photocatalytic Properties
Rhodamine B (RhB) was used as model dye to check the photo­
catalytic properties of synthesized nanoparticles. The intensity versus
wavelength graphs were plotted after regular intervals of 20 min. The
intensity peaks decreased after every 20 min. The degradation of RhB
with respect to time and concentration has been depicted in the Fig. 6 (a
and b) respectively which shows gradual degradation of RhB with
respect to time. The CC0 versus irradiation time graphs were plotted as
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Inorganic Chemistry Communications 129 (2021) 108618
shown in the Fig. 5 (c) for the time whereas in Fig. 6 (d) the CC0 versus
irradiation time has been shown for different concentrations of catalyst.
More than 90% of dye degradation occurred within 80 min as shown in
Fig. 6 (c).
The color degradation of dye may result due to breakdown of chro­
mophores present within the dye which gives specific color to the dye
[50]. The ln CC0 versus irradiation time graphs were plotted as shown in
the Fig. 6 (e) and Fig. 6 (f). The increase in irradiation time increases the
photocatalytic activity as shown in the Fig. 6 (e) and increase in con­
centration also increases the photocatalytic activity. The UV irradiation
of light over the synthesized catalyst favor more injection of electrons in
conduction band of TiO2 by surface phonon resonance mechanism
which helps in generation of free radicals [51]. The generation of free
radicals have positive co-relation with degradation process, hence the
increase in catalyst concentration increases the photocatalytic activity.
The 0.7 g catalyst concentration have degraded the dye almost 100% as
G. Nabi et al. Inorganic Chemistry Communications 129 (2021) 108618

Fig. 7. Schematic diagram of photocatalytic mechanism of TiO2 catalyst.

shown in the Fig. 6 (f).

Table 1
The degradation rate constant of RhB was determined by using the
Degradation comparison of RhB with metal oxide nanoparticles.
Langmuir Hinshelwood (LH) model.
S Photocatalyst Synthesis Morphology Degradation Ref
C0 # Technique efficiency (%)
ln = kt
C 01 CoFe2O4- Hydrothermal Nanoparticles 94% [52]
Where C0 is the initial concentration of RhB dye, and C is the con­ graphene
02 ZnGa2O4 Hydrothermal Nanoparticles 99.8% [53]
centration after regular intervals of time. Where k represents the rate
03 Ag-ZnO Polymer Nanoparticles 77% [54]
constant which can be calculated from the slope of ln CC0 versus irradia­ network gel
tion time graph. All the curves are linear that shows the pseudo first 04 ZnO Extract Nanoparticles 84% [55]
order kinetics. The obtained values of rate constants are 0.017, 0.026, 05 CuO Green Nanoparticles 84% [55]
Synthesis
0.0814, 0.1742 for catalyst concentration 0.1 g, 0.3 g, 0.5 g, and 0.7 g 06 Fe2O3 Hydrothermal Nanoparticles 75% [56]
respectively. Higher rate constant shows the higher efficiency of cata­ 07 Prussian blue Green Nanoparticles 83% [57]
lytic activity. The excellent photocatalytic activity of anatase phased Synthesis
TiO2 nanoparticles is mostly attributed to their nano size, large specific 08 CuO -ZrO2 Impregnation Nanoparticles 80% [58]
09 CuS/BaTiO3 Anchoring Nanoparticles 81% [59]
surface area, phase purity and clean surfaces of the prepared nano­
10 RGO/WO3 Hydrothermal Nanoparticles 84% [60]
particles. The anatase TiO2 is generally considered to be more active 11 CuCr2O4/ Sol-gel Nanoparticles 83% [61]
than rutile phase for TiO2 photocatalyst. The clean surface and larger BiOBr
surface area of TiO2 nanoparticles is considered helpful for the RhB 12 TiO2 Green Nanoparticles >90% This
adsorption which further leads to higher photoexcited electrons transfer Synthesis Work

rate from RhB to TiO2 and accompanied with higher dye degradation
efficiency. tabulated in the Table 1
The free radicals have high oxidizing power which can destroy the As clear from the Table 1, it can be seen that synthesized TiO2
harmful organic pollutants like carboxylic acids. The schematic mech­ nanoparticles are also one of the most efficient nanoparticles for the
anism of photocatalytic reaction is shown in the degradation of the RhB which can be used effectively.
Fig. 7 and corresponding equations are also shown here [4]:
When sunlight falls on the photocatalyst, the following reactions take
4. Conclusion
place

Energy + Photocatalyst e− + h+ (1) Pure anatase phase titanium dioxide nanoparticles were synthesized
by cost effective and environmental friendly green synthesis method.
h+ H2O2 HO + h+ (2) The structural, compositional and optical characterization were studied
O − +
+ H HOO (3) by XRD, SEM, EDS and UV–Vis spectroscopy which proved the suc­
2
cessful synthesis of TiO2 nanoparticles. The size of the synthesized
HOO + HOO H 2O2 + O2 (4) nanoparticles was lying in the range of 80–100 nm. The calculated band
gap of the nanoparticles was 3.22 eV which was confirmed by UV–vis
e− H2O2 HO– + OH– (5)
absorption and PL spectroscopy. More than 90% RhB was degraded
O− 2 + H2 O2 HO– + OH– O2 (6) within 80 min which is competitive to other materials. The improve­
ment in visible light absorption and increase in photo assisted degra­
+
h + OH HO –
(7) dation of dyes due to smaller size, high light absorption and clean
surface of the nanoparticles. The high surface to volume ratio of nano­
HO + pollutants H2O + CO2 (8)
particles could have more active-adsorption sites and thus enhance
HOO + pollutants H2O + CO2 (9) photocatalytic performance. The excellent photocatalytic activity of
synthesized TiO2 nanoparticles proves that the prepared photo catalyst
When TiO2 is illuminated with light, the electrons from valance band is not only environment friendly but also have potential applications in
excites to conduction band thereby creating a hole in the valance band. purification of water.
These photogenerated charge carriers perform redox reactions, and
oxidize the oxygen molecule to superoxide ion while at the same time
CRediT authorship contribution statement
the water molecules are reduced to hydroxyl radicals. These radicals are
highly reactive and when they react with organic pollutant, they
Ghulam Nabi: Conceptualization, Supervision, Resources, Writing -
decompose them into simpler products [4,10,11,13].
review & editing. Abdul Majid: Conceptualization, Supervision. Asma
With the purpose to compare the efficiency of the different metal
Riaz: Methodology, Investigation, Data curation. Thamer Alharbi:
oxide materials for degradation of the RhB comprehensive data has been
Resources, Supervision. Muhammad Arshad Kamran: Resources,

6
G. Nabi et al. Inorganic Chemistry Communications 129 (2021) 108618

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