i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 3 ( 2 0 1 8 ) 1 3 1 4 5 e1 3 1 5 7

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Facile synthesis of noble-metal free polygonal

Zn2TiO4 nanostructures for highly efficient
photocatalytic hydrogen evolution under solar light
irradiation

Saikumar Manchala a, Lakshmana Reddy Nagappagari b,

Shankar Muthukonda Venkatakrishnan b, Vishnu Shanker a,*
a
Department of Chemistry, National Institute of Technology, Warangal 506004, Telangana, India
b
Nano Catalysis and Solar Fuels Research Laboratory, Department of Materials Science and Nanotechnology, Yogi
Vemana University, Vemanapuram, Kadapa 516005, Andhra Pradesh, India

article info abstract

Article history: Designing of noble-metal free and morphologically controlled advanced photocatalysts for
Received 28 February 2018 photocatalytic water splitting using solar light is of huge interest today. In the present
Received in revised form work, novel polygonal Zn2TiO4 (ZTO) nanostructures have been synthesized by citricacid
1 May 2018 assisted solid state method for the first time and synthesized nanostructures were char-
Accepted 7 May 2018 acterized by using various techniques like PXRD, UV-Vis-DRS, PL, FT-IR, BET, FE-SEM and
Available online 1 June 2018 TEM for their structural, optical, chemical, surface and morphological properties. The PXRD
and UV-Vis-DRS analysis show the existence of cubic and tetragonal phases. FE-SEM and
Keywords: TEM results confirm the formation of polygonal ZTO nanostructures. Synthesised ZTO
Polygonal Zn2TiO4 nanostructures have been potentially applied for solar light-driven photocatalytic
ZnO hydrogen evaluation from water splitting and compare the photocatalytic activity with
TiO2 synthesized conventional Zn2TiO4 and commercially available TiO2, ZnO photocatalysts. A
Hydrogen evolution high rate of 529 mmolh
1g
1 solar light-driven photocatalytic H2 evolution has been ach-
Noble-metal free ieved by using a small amount (5 mg) of polygonal Zn2TiO4 nanostructures from glycerol-
water solution. The enhanced photocatalytic performance of the polygonal Zn2TiO4
nanostructures compare to conventional Zn2TiO4 under solar light irradiation is due to the
large surface area and low recombination rate. However having the same bandgap, the
polygonal Zn2TiO4 nanostructures have shown enhanced photocatalytic performance than
that of commercially available TiO2, ZnO photocatalysts.
© 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

to prepare for the possible depletion of fossil fuel supplies in

Introduction the forthcoming years, an alternative green, carbon-free and
renewable energy sources must be developed. One of the most
In order to meet increasing global shortage of energy, reduce attractive possible technologies to address these problems in
environmental deterioration and help our environment, and the world is the conversion of solar energy into chemical

* Corresponding author.
E-mail address: vishnu@nitw.ac.in (V. Shanker).
https://doi.org/10.1016/j.ijhydene.2018.05.035
0360-3199/© 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
13146 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 3 ( 2 0 1 8 ) 1 3 1 4 5 e1 3 1 5 7
energy i.e; evolution of hydrogen molecules through water
splitting process, with the help of semiconductor-based pho-
tocatalysts, which is recognized as a clean and green pro-
duction [1e7]. Since the first report of hydrogen evolution
process by Fujishima and Honda through photo electro-
chemical water splitting on n-type TiO2 electrode using ul-
traviolet (UV) light [8], many active photocatalysts such as
various oxides [9], sulphides [10], and nitrides [11] have been
reported and extensively studied for heterogeneous photo-
catalytic water splitting for hydrogen evolution. Tailoring of
morphology, size-controlled and low cost noble-metal free
nanostructures have been a crucial issue in recent photo-
catalysis research, due to the fundamental shape and size
dependence of properties (physical & chemical) and applica-
tions [12e18]. But after four decades of global research the
modeling and development of morphology and size-
controlled advanced photocatalysts with the high surface
area, high efficiency, stability, low-cost, noble-metal free still
remains a great challenge.
Among the investigated semiconductors in the areas of
solar cells [19], gas sensors [20] and photocatalysis [9] titanium
dioxide (TiO2) and zinc oxide (ZnO) were recognised as a most
prominent materials, because of their excellent chemical sta-
bility, mechanical stability, inexpensive, availability, non-toxic
nature and wide band gap as well as their high photosensitivity
[21,22]. Synthesis of ZnO-TiO2 mixed binary oxide system has
been well established with following compounds namely zinc
ortho titanate (Zn2TiO4), zinc ortho di titanate (Zn3Ti2O7), zinc
meta titanate (ZnTiO3), zinc mesopenta titanate (Zn4Ti5Ol4),
and zinc para titanate (ZnTi3O7), Zn2Ti2O6, Zn2Ti3O8, and
Zn4Ti5O16 but only ZnTiO3, Zn2TiO4 and Zn2Ti3O8 are confirmed
to be stable. The precursors of the Zn/Ti ratio taken and prep-
aration method influence the phase formation of different
zinc titanates at different temperatures [23e26].
Actually, zinc ternary semiconductor oxides are a signifi-
cant class of materials with a molecular formula A2BO4
(A ¼ Zn, B¼ Si, Ti, Sn, Ge), widely used because of their elec-
tronic and optical properties as well as their applications in
photocatalysis, gas sensor, Li-ion battery, dye-sensitized solar
cells and hydrogen storage [27e30]. Among the reported zinc
ternary semiconductor oxides, zinc ortho titanate (Zn2TiO4)
attracted wide attention. Zn2TiO4 is an inverse spinel and the
stable phase of ZnO-TiO2 system [24]. It has been investigated
due to its wide range of applications in paint pigments, mi-
crowave dielectrics, catalysis as a leading regenerable catalyst
for removal of sulfur from coal gasification products, dye
sensitized solar cells, white light emitting diodes, gas sensors,
photocatalysis and extensively for low temperature co-fired
ceramics [26,31e33]. It is generally synthesized from TiO2
and ZnO by a conventional solid-state method at high tem-
peratures like 1350  C [34] and 1200  C [35] and typically when
a temperature below 1000  C is employed, prolonged heat
treatment time is required [32]. According to Yasumichi Mat-
sumoto theoretical prediction of band edge positions, Zn2TiO4
is a promising material for photo-reduction of water under UV
and near-visible light by having an ideal bandgap energy, as
well as the suitable band edge potentials [36]. Interestingly its
band gap is similar to that of precursors (commercially
available TiO2 and ZnO) used for the synthesis.
In the present work, an alternate facile synthesis method
has been employed such as the citric acid assisted solid state
reaction method for the synthesis of novel polygonal Zn2TiO4
nanoparticles at 1000  C for 2 h and we have carried out a
comparative study of photocatalytic properties of polygonal
Zn2TiO4 with conventional Zn2TiO4, and commercially avail-
able TiO2 and ZnO photocatalysts under solar light irradiation
for hydrogen evolution through water splitting. Recently,
Latesh Nikam et al. reported the synthesis of nanostructured
Zn2TiO4, Ag-doped Zn2TiO4 and Co-doped Zn2TiO4 by a com-
bustion method and applied for photocatalytic hydrogen
evolution from H2S splitting [24]. In the case of pure Zn2TiO4
and Ag-doped Zn2TiO4, the hydrogen evolution observed is
633 and 2784 mmolh
1g
1 respectively with 100 mg of catalyst
that is very high amount of catalyst used for the H2 evolution
compared to our present study i.e; 529 mmolh
1g
1 with 5 mg
of polygonal Zn2TiO4 photocatalyst. However, to the best of
our knowledge from the literature, there has been no report on
the synthesis of polygonal Zn2TiO4 nanostructures and its
photocatalytic application for H2 evolution from water split-
ting. Here we also presented the comparison study with con-
ventional Zn2TiO4, TiO2 and ZnO.
Experimental section
Materials
TiO2 (Sigma Aldrich, 99%), ZnO (Finar chemicals Ltd., 99%) and
Citric acid (Finar chemicals Ltd., 99.5%) have been used as
received. Double distilled (DD) water was used in all experi-
ments and all other reagents are at least of analytic reagent
grade and used without further purification.
Synthesis
In a typical procedure, polygonal Zn2TiO4 nanostructures have
been prepared by citric acid assisted solid-state method. ZnO
(0.732 g), TiO2 (1.278 g) powders were taken and mix with citric
acid (0.576 g). The mixture was well ground by using mortar
and pestle and transfer to alumina crucible. The crucible was
placed in a programmable tubular furnace for 2 h and calcined
at 1000  C with slow heating rate (2  C/min), a white colour
powder was obtained. In this work, we believed that the
chelating agent, citric acid binds through its carboxylic end
and make a complex with the oxides of metals and while
raising the calcination temperature forms a carbonaceous
amorphous liquid. It served as a fuel for uniform distribution
of both the metal oxides. Substantial distribution of the
carbonaceous amorphous liquid helps in the formation of a
nanocrystalline product of polygonal Zn2TiO4 by avoids
agglomeration as well as furnishes a more number of
satisfactorily-separated nucleation sites. Conventional
Zn2TiO4 was synthesized without the addition of citric acid
under similar conditions. Furthermore, the synthesis pro-
cedure for the formation of conventional and polygonal
Zn2TiO4 nanostructures was shown in Scheme 1 and synthe-
sized nanostructures were named as conventional ZTO and
polygonal ZTO.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 3 ( 2 0 1 8 ) 1 3 1 4 5 e1 3 1 5 7
Scheme 1 e Schematic representation of the synthesis processes of conventional and polygonal Zn2TiO4 nanostructures.
Characterisation
Powder X-ray diffraction (PXRD) measurements have been
performed by using a PAN Analytical Advance X-ray diffrac-
tometer using Ni-filtered Cu Ka (l ¼ 1.5406 Å) radiation in a 2q
scan range between 10 and 90 . The surface morphology and
chemical composition of the photocatalysts have been recor-
ded by field emission scanning electron microscopy (FESEM,
JEM-2100F, JEOL, Japan) coupled with an energy dispersive X-
ray (EDX) spectrometry. Transmission electron microscopy
(TEM) and High resolution TEM (HRTEM) images have been
taken by using a JEOL JEM-2100 transmission electron micro-
scope at an acceleration voltage of 200 kV. Selected area EDS
elemental mapping images have been taken by using an Ox-
ford instruments, INCAx-act scanning electron microscope.
The real compositions of Zn and Ti in the samples have been
measured by Microwave plasma atomic emission spectrom-
etry (MP-AES) by using Agilent technologies-4210 microwave
plasma atomic emission spectrometer. Nitrogen adsorption-
desorption studies have been carried out by using a Quan-
tachrome NOVA 3000e. Brunauer-Emmett-Teller (BET) surface
areas have been determined over the relative pressure range
0.02e1.0. The optical properties of the photocatalysts have
been obtained by using Shimadzu UV-3600 visible diffuse
reflectance spectrophotometer (UVeVis DRS) with BaSO4 as
the reference material. Fourier transform infrared (FT-IR)
spectra have been recorded from 4000 to 400 cm
1 on a Per-
kinElmer Spectrum 100 FT-IR spectrophotometer in trans-
mission mode using the KBr pellet. Photo luminescence (PL)
spectra have been measured at room temperature on a Jasco
FP-8500 spectrofluorometer, using a xenon lamp as the exci-
tation source and 300 nm as the excitation wavelength.
Photocatalytic activity
The photocatalytic H2 evolution reactions have been carried
out in a 180 mL air tight rubber septum sealed quartz reactor
under solar light irradiation at ambient temperature and at-
mospheric pressure. The solar light intensity was observed
using digital lux meter (TES 1332A) for every hour between
13147
11:00 a.m. and 15:00 p.m. in the city of Kadapa, Andhra Pra-
desh State, INDIA. The average light intensity measured value
was approximately 8.5  104 lx during the course of light re-
actions. In a typical process, photocatalyst powders were
suspended into 5 vol % aqueous glycerol mixtures at a con-
centration of 50 mgL
1. Here glycerol was used as a hole
scavenger. Dark experiments have been carried out to ensure
uniform dispersion for at-least 30 min. The reaction suspen-
sion was evacuated and purged with high pure N2 gas for
atleast 30 min in order to remove dissolved gases present in
the homogeneous system. The evacuated reactor was irradi-
ated to natural solar light under magnetic stirring and the
gaseous sample was collected with an air tight syringe and
analyzed at regular time intervals. The volume of H2 gas
evolved via photocatalytic water splitting was quantified
using an offline gas chromatography (Shimadzu GC-2014 with
Molecular Sieve/5A) equipped with thermal conductivity de-
tector (TCD), at 70  C and N2 as a carrier gas.
Results and discussion
Characterisation of as-synthesised photocatalysts
First Powder X-Ray diffraction (PXRD) studies have been car-
ried out in order to investigate the crystallographic structure
and phase purity of as-synthesized conventional and polyg-
onal Zn2TiO4 nanostructures have been shown in Fig. 1. It
shows that the presence of spinel structure of Zn2TiO4. The
results indicate that the diffraction peaks due to conventional
and polygonal Zn2TiO4 were corresponds to both cubic phase
(JCPDS Card No. 86-0154), as well as tetragonal phase (JCPDS
card No. 86-0158). The XRD studies further supported by
HRTEM and SAED images.
FESEM and TEM have been carried out subsequently to
investigate the morphology of the resultant Zn2TiO4 nano-
structures. FE-SEM images (Fig. 2aed) revealed that the syn-
thesized conventional Zn2TiO4 were not shown any regular
morphology and the particles appeared to be agglomerated
without using any structure directing agent. Whereas, while
13148 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 3 ( 2 0 1 8 ) 1 3 1 4 5 e1 3 1 5 7

citric acid was used as a structure directing agent polygonal

Zn2TiO4 were obtained and shown different shapes of mor-
phologies, which further confirmed by TEM. TEM images
(Fig. 3aed) were shown triangular, cube, hexagonal and
spherical shape morphologies with smooth edges and a
smooth surface. Compare to conventional synthesis, new
methodology lead to the development of smooth surfaces of
individual polygonal Zn2TiO4 particles with dimensions
50 nme200 nm consistent with the FESEM and TEM images.
This indicates the citric acid plays a major role in order to
influence the formation of polygonal Zn2TiO4 nanostructures.
HRTEM and SAED images of the polygonal Zn2TiO4 nano-
structures were shown in Fig. 3eef. Lattice fringes are good
agreement with the (211) plane (dspacing ¼ 0.255 nm) and (400)
plane (dspacing ¼ 0.150 nm) of tetragonal phase of polygonal
Zn2TiO4 in the PXRD pattern.
Energy-dispersive X-ray spectroscopic (EDX) studies have
Fig. 1 e PXRD patterns of as-synthesized conventional and been carried out to determine the chemical composition of as-
polygonal Zn2TiO4. synthesized conventional and polygonal Zn2TiO4 nano-
structures and shown in Fig. 4aeb, which shows that Zn, Ti
and O elements can be observed in both the samples. Selected
area EDX elemental mapping has been carried out in order to
get further information on the distribution of elements in the

Fig. 2 e FESEM images of conventional (a, b) and polygonal (c, d) Zn2TiO4 nanostructures.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 3 ( 2 0 1 8 ) 1 3 1 4 5 e1 3 1 5 7 13149

Fig. 3 e TEM (aed) images of polygonal Zn2TiO4 nanostructures HRTEM (e,f) and SAED (g) images of polygonal Zn2TiO4
nanostructures.
13150 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 3 ( 2 0 1 8 ) 1 3 1 4 5 e1 3 1 5 7
Fig. 4 e EDX of as-synthesized conventional (a) and polygonal (b) Zn2TiO4 nanostructures.
sample and shown in Fig. 5, which shows the even distribu-
tion of Zn, Ti and O elements in the polygonal Zn2TiO4
nanostructures. MP-AES has been performed to know the
actual composition of as-synthesized conventional Zn2TiO4
and polygonal Zn2TiO4 nanostructures and the results shown
in Table 1. The results show that the real composition of
conventional Zn2TiO4 and polygonal Zn2TiO4 are Zn1.99Ti1.01O4
and Zn1.97Ti1.03O4, respectively.
N2 adsorptionedesorption measurements have been per-
formed to know the BET specific surface area of as-
synthesized polygonal Zn2TiO4 and conventional Zn2TiO4
nanostructures. According to classifications of IUPAC, the N2
adsorption-desorption isotherms of conventional and polyg-
onal Zn2TiO4 nanostructures exhibited the type-III isotherm
with H3-type hysteresis loop which is related to large meso-
pores or macro-pores surrounded via a matrix of smaller
pores. As can be seen from Fig. 6, the BET specific surface area
of polygonal Zn2TiO4 is 3.495 m2g
1 which is much higher than
that of conventional Zn2TiO4 (0.740 m2g
1). Comparatively, a
large specific surface area of polygonal Zn2TiO4 (five-fold to
the conventional Zn2TiO4) was utilized for the superior
adsorption as well as provides a number of surface reactive
sites for the photocatalytic process. Therefore, it leads to the
improvement of the photocatalytic efficiency/rate.
The UV-Vis DRS of as-synthesized conventional and
polygonal Zn2TiO4 nanostructures have been shown in Fig. 7a.
Conventional and polygonal Zn2TiO4 were shown two ab-
sorption edges in the optical spectrum which indicate the
existence of Zn2TiO4 in two phases i.e; cubic and tetragonal.
The associated optical band gaps were calculated using the
following Tauc equation (1) [37].


1=2
ðahwÞ ¼ B hw
Eg (1)
Here, a is the absorption coefficient, B is band tailing
parameter, Eg is band gap of the semiconductor, and hw is the
energy of the photons from Einstein's equation [38]. According
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 3 ( 2 0 1 8 ) 1 3 1 4 5 e1 3 1 5 7 13151

Table 1 e MP-AES analysis results of as-synthesized

conventional and polygonal Zn2TiO4.
S.No. Samples MP-AES (Wt %) Zn: Ti (mol %)
Zn Ti
1 Polygonal Zn2TiO4 53.2 19.96 2:1.02
Zn1.99Ti1.01O4
2 Conventional Zn2TiO4 52.36 20.7 2:1.08
Zn1.95Ti1.05O4

to Tauc plots have been shown in Fig. 7b the cut off observed
at 413 nm is attributed to tetragonal phase of conventional
and polygonal Zn2TiO4 with the corresponding band gap
found to be 3 eV.
The FT-IR spectra of as-synthesized conventional and
polygonal Zn2TiO4 nanostructures have been shown in Fig. 8.
It shows that the broad band has been observed at 3600-
3100 cm
1 was originated from stretching vibrations of hy-
droxyl groups of chemisorbed and/or physisorbed water
molecules. The 1650 cm
1 band arises from bending vibra-
tions of hydroxyl groups. The C]O stretching vibrations were
expressed at 1568 cm
1. In the spectra, the bands observed in
the region 1000-400 cm
1 due to metal-oxygen linkages. A
broad and weak band around 713 cm
1 corresponding to the
ZnOn polyhedron and the broad band around ~594 and one
more weak and small band at ~435 cm
1 corresponding to the
stretching vibrations in the octahedral TiO6 group which ap-
pears in all kinds of zinc titanates [39].
Photoluminescence (PL) spectroscopic measurements of
synthesized photocatalysts have been subsequently used to
examine the migration, transfer, and recombination pro-
cesses of the photoexcited charge carriers and shown in Fig. 9.
The emission spectra revealed a strong emission peak at
345 nm, following broad emission peak at 420 nm and a weak
emission peak at 468 nm for both conventional and polygonal
Zn2TiO4. The emission peaks at 345 and 420 nm corresponding
to the band to band transitions. These were mentioned as NBE
(near band edge) emissions which are closed to the absorption
noticed at 340 and 418 nm in absorption spectra [40]. The
emission peak at 468 nm may be due to the presence of defects
like Zn2þ and O2
vacancies [24]. However, the emission peak
intensities of the polygonal Zn2TiO4 is smaller, indicating the
slower recombination rate of photo excited charge carriers
compares to conventional Zn2TiO4. Due to the high surface
area: volume ratio of the polygonal Zn2TiO4, the lower
recombination rate was tentatively confirmed to surface
charge trapping of photoexcited charge carriers. Therefore, it
leads to the improvement of the photocatalytic efficiency.

Photocatalytic hydrogen evolution

Furthermore, to confirm the H2 evolution from photocatalytic

water splitting, the H2-evolution potentials of all the synthe-
sized photocatalysts have been inspected under solar light
irradiation in an aqueous solution containing glycerol (5 vol %)
as the sacrificial hole scavenger. For comparison commer-
Fig. 5 e EDX elemental mapping images of polygonal cially available TiO2 and ZnO photocatalyst samples have
Zn2TiO4 nanostructures. been also tested for H2 evolution from photocatalytic water
13152 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 3 ( 2 0 1 8 ) 1 3 1 4 5 e1 3 1 5 7

Fig. 6 e Nitrogen adsorption-desorption studies of as-synthesized conventional (a) and polygonal (b) Zn2TiO4
nanostructures.

Fig. 7 e UV-Vis-DRS absorption plots (a) and Tauc plot (b) of as-synthesized conventional and polygonal Zn2TiO4
nanostructures.

Fig. 8 e FT-IR spectra of as-synthesized conventional and Fig. 9 e Room temperature PL Spectra of as-synthesised
polygonal Zn2TiO4 nanostructures. conventional and polygonal Zn2TiO4 nanostructures.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 3 ( 2 0 1 8 ) 1 3 1 4 5 e1 3 1 5 7 13153

splitting under similar conditions. No obvious H2 evolution

was noticed over all photocatalysts in the control experiments
(without photocatalyst), demonstrated that the H2 was truly
evaluated from the photocatalytic process. Table 2 shows the
results of the amount of H2 evolved under solar light irradia-
tion as well as catalyst amount of the synthesized conven-
tional, polygonal Zn2TiO4 and commercially available TiO2,
ZnO photocatalyst samples. Fig. 10a shows the analogical
studies of photocatalytic H2 evolution for synthesized con-
ventional, polygonal Zn2TiO4 and commercially available
TiO2, ZnO photocatalysts under solar light irradiation and
Fig. 10b shows the analogical studies of photocatalytic H2
evolution for synthesized conventional and polygonal Zn2TiO4
photocatalysts during 4 h solar light irradiation. Among all the
photocatalyst samples, polygonal Zn2TiO4 photocatalyst was
found to be excellent photocatalyst as compared to other
samples. The polygonal Zn2TiO4 showed H2 evaluation as high
as 529 mmolh
1g
1, which is higher than that of conventional
Zn2TiO4 (467 mmolh
1g
1) under solar light irradiation and
there is no H2 evolution for commercially available TiO2, ZnO.
This indicates that the Zn2TiO4 seems to be a polygonal
morphology which could lead to the proper bandgap and also
band edge potential for H2 evolution over other photocatalyst
samples. The high photocatalytic activity of polygonal
Zn2TiO4 compare to conventional Zn2TiO4 photocatalyst was
supported by BET and PL studies. Because of the introduction
of polygonal morphology, (1) the BET surface area increases,
which leads to high surface active sites for photocatalytic re-
action and (2) the PL intensity decreases, which leads to
slower recombination of charge carriers. Finally, higher sur-
face area: volume ratio and slower recombination rate of the
polygonal Zn2TiO4 was lead to high photocatalytic H2 evolu-
tion compared to conventional Zn2TiO4. Four typical time
courses of H2 evolution under solar light irradiation from two
different photocatalysts were shown in Fig. 10c. As noticed in
8c, the rates of hydrogen evolution by two different photo-
catalysts displayed a sharp linear increase during the entire
photocatalytic reactions, clearly gives the information about
stability and reproducibility of photocatalytic H2 evolved over
synthesized photocatalysts. Fig. 11 shows band gap and band
edge potentials of Zn2TiO4, TiO2 and ZnO photocatalysts re-
ported by Yasumichi Matsumoto [36]. Although the three
photocatalysts approximately have the same bandgap energy,
the conduction band potential of Zn2TiO4 is located at the
more negative position (ECB ¼
0.9 Vs NHE) than that of the
TiO2 (ECB ¼
0.1 Vs NHE) and ZnO (ECB ¼
0.1 Vs NHE). That is

Fig. 10 e a. Analogical studies of photocatalytic H2

Table 2 e Rate of H2 evolution for synthesized Polygonal evolution under solar light irradiation for TiO2 (A), ZnO (B),
Zn2TiO4, Conventional Zn2TiO4, TiO2 and ZnO under solar synthesized conventional (C) and Polygonal (D) Zn2TiO4
light irradiation.
photocatalysts. b. Analogical studies of photocatalytic H2
S.No. Photocatalyst Amount Rate of H2 evolution during 4 h under solar light irradiation for
(mg) Evolution mmolh
1g
1 synthesized conventional and polygonal Zn2TiO4
1 Polygonal Zn2TiO4 5 529 photocatalysts. c. H2 evolution rates of conventional and
2 Conventional Zn2TiO4 5 467 polygonal Zn2TiO4 photocatalysts under solar light
3 TiO2 5 No Activity
irradiation.
4 ZnO 5 No Activity
13154 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 3 ( 2 0 1 8 ) 1 3 1 4 5 e1 3 1 5 7

[17]. Therefore, polygonal Zn2TiO4 is a potential candidate for

photocatalytic water splitting process.
Amongst the zinc titanates reported, polygonal Zn2TiO4
has been established as an excellent photocatalyst. The
utmost H2 evolution (529 mmolh
1g
1 per 5 mg of photo-
catalyst) was obtained under solar light irradiation, which was
much higher than H2 produced using Zn2TiO4, Rh doped
Zn2TiO4 [24,41], ZnTiO3-TiO2 [42], TiO2-Zn2Ti3O8 [43], TiO2-ZnO
[44] shown in Table 3 and further these results are much better
than other photocatalysts i.e Hierarchical Cu2O nanocubes
[16], g-C3N4 sheets [45], MoS2 quantum dots [46], CdS nano-
particles [47], ZrO2 [48], In2S3 [49], Anatase and Rutile TiO2 [50],
CdS nanoparticles [51], TiO2 and Bi2O3 [52], g-C3N4 and WO3
[53], TiO2 [54], P25 (TiO2) [55], g-C3N4/Ag [56] shown in Table 4
so far reported.

Fig. 11 e The Bandgap and band edge positions of Zn2TiO4, Photocatalytic mechanism of H2 evolution from water
TiO2 and ZnO photocatalysts. splitting

The photocatalytic mechanism of H2 evolution by water split-

in the case of Zn2TiO4 an electron which is excited from
valence band edge to the conduction band edge has a higher
negative potential suited to reduce a hydrogen ion (Hþ), and a
hole also has a lower reduction potential which is present in
the valence band for decomposition of glycerol to Hþ and CO2.
The figure clearly consistent with this fact for polygonal
Zn2TiO4 and further compares it with the case of TiO2 and ZnO
ting under a solar light irradiation has been mentioned by many
researchers [16,45]. Fig. 12 is shown the proposed mechanism
for photocatalytic hydrogen evolution from a water-glycerol
solution of polygonal Zn2TiO4 under solar light irradiation.
When the reaction suspension is exposed to solar light, the
semiconductor photocatalyst produces electrons at conduction
þ
band edge (e
CB ) and holes at valence band edge (hVB ). The
comprehensive photocatalytic mechanism is specified below:

Table 3 e Reported rate of H2 evolution for zinc titanate families.

S.No. Photocatalyst Amount (mg) Rate of H2 Evolution (mmolh
1g
1) Reference
1 Polygonal Zn2TiO4 5 529 Present work
2 Conventional Zn2TiO4 5 467 Present work
3 Zn2TiO4 100 633 (From H2S splitting) [22]
4 Zn2TiO4 100 13.07 [36]
5 Rh doped Zn2TiO4 100 58.05 [36]
6 ZnTiO3-TiO2 50 6.8 [37]
7 TiO2-Zn2Ti3O8 0.1 10.16 [38]
8 TiO2-ZnO 500 203 [28]

Table 4 e Recent report of rate of H2 evolution using various photocatalysts.

S.No. Photocatalyst Amount (mg) Rate of H2 Evolution (mmolh
1g
1) Reference
1 Polygonal Zn2TiO4 5 529 (Without co-catalyst) Present work
2 Conventional Zn2TiO4 5 467 (Without co-catalyst) Present work
3 Hierarchical Cu2O nanocubes 25 15 (0.6 wt% Pt) [16]
4 g-C3N4 sheets 50 108.5 (0.5 wt% Pt) [39]
5 MoS2 quantum dots 4 200 (Without co-catalyst) [40]
6 CdS nanoparticles 100 0.534 (Without co-catalyst) [41]
7 ZrO2 100 203 (Without co-catalyst) [42]
8 b-In2S3 50 91 (1 wt% Pt) [43]
9 Anatase and Rutile TiO2 50 37 and 5 (0.6 wt% Pt) [44]
10 CdS nanoparticles 50 172 (Without co-catalyst) [45]
11 TiO2 and Bi2O3 50 12.6 and 0 (Without co-catalyst) [46]
12 g-C3N4 and WO3 50 440 and traces (0.1 ml of H2PtCl6 (1 g/100 ml)) [47]
13 TiO2 100 10.3 (Without co-catalyst) [48]
14 P25 (TiO2) 50 172 (Without co-catalyst) [49]
15 g-C3N4/Ag 50 3.89 (Without co-catalyst) [50]
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 3 ( 2 0 1 8 ) 1 3 1 4 5 e1 3 1 5 7 13155

morphology has been confirmed by TEM studies. The syn-

thesized polygonal Zn2TiO4 nanostructures showed
outstanding photocatalytic properties for the H2 evolution
from the water splitting under irradiation of solar light
compare to conventional Zn2TiO4 and commercially available
TiO2, ZnO. The high photocatalytic activity for Zn2TiO4
nanostructures compare to commercially available TiO2, ZnO
has been explained by more negative conduction band po-
tential (ECB ¼
0.9 Vs NHE). For the H2 evolution from the
water splitting under irradiation of solar light, polygonal
Zn2TiO4 nanostructures showed 1.2 times higher photo-
catalytic activity than conventional Zn2TiO4 and exhibited
outstanding stability. The enhanced photocatalytic ability
originated from its polygonal morphology increase their sur-
face area and more attainable active sites on the surface and
decrease in the PL intensity compared to conventional
Zn2TiO4. The present work thus provides an insight into the
design and development of noble metal free and cost-effective
nanostructured semiconductor photocatalysts for diverse
photocatalytic applications like dye degradation, CO2 reduc-
tion, and sensing applications.

Fig. 12 e The proposed mechanism of H2 evolution from

water splitting under solar light irradiation over polygonal
Zn2TiO4 nanostructures. Acknowledgments

Author thankful to the MHRD, Govt. of India for providing

  fellowship and also thanks to SAIF, NEHU (North-Eastern Hill
ZTO þ hwðSun lightÞ/ZTO hþ
VB þ eCB /1½Excitation process University), Shillong for providing TEM facility.

   .

ZTO hþ þ
VB þ eCB /ZTO hVB ZTO eCB
references
/2½Charge transfer process


ZTO hþ
VB þ Glycerol þ H2 O/ZTO þ H
þ
þ Oxidized Intermediates/3½Holes trapping


ZTO hþ þ
VB þ Oxidized Intermediates/ZTO þ 14H þ 3CO2 /4


ZTO eCB þ 14Hþ /ZTO þ 7H2 /5½Hydrogen evolution process
The overall reaction is given below:
ZTO þ Glycerol þ 3H2 O þ hwðSun lightÞ/ZTO þ 7H2 þ 3CO2
In a nutshell, the Zn2TiO4 nanostructures were observed to
be excellent oxide photocatalysts for hydrogen production
from water splitting, which have high reduction potential and
lower oxidation potential. It is noteworthy that the polygonal
Zn2TiO4 nanostructures have been prepared for the first time.
Furthermore, the hydrogen evolution from water splitting
using polygonal Zn2TiO4 nanostructures under natural solar
light is hitherto unattempted.
Conclusions
In summary, phase pure and novel Zn2TiO4 nanostructures
with polygonal morphology have been successfully synthe-
sized by a facile solid state method employing citric acid as a
structure direct agent. This solid-state method avoids the
prolonged reaction times or several steps. The polygonal
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