pubs.acs.

org/JPCC Article

Controlled Loading of MoS2 on Hierarchical Porous TiO2 for

Enhanced Photocatalytic Hydrogen Evolution
Amritanjali Tiwari,* Amit Gautam, Saddam Sk, Deepak S. Gavali, Ranjit Thapa, and Ujjwal Pal*
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ABSTRACT: In this study, we garnered three important factors

simultaneously, namely, wormhole mesoporosity of TiO2 with well-
designed interfaces for effective charge transfers, precise loading of
MoS2 for plasmon induction, and increased surface area with
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exposed surface atoms and active sites. The controlled loading of

MoS2 on porous TiO2 (MPT) forms a heterojunction that
effectively modulates the interface engineering and thereby greatly
enhances hydrogen evolution. The synthesis of a photocatalyst is
based on a simple hydrothermal process that is well characterized.
The resulting composite materials were tested for hydrogen
evolution reactions. At optimum loading, MPT10 induced a
maximum hydrogen evolution rate of 1376 μmol h−1 g−1 with
2.28% apparent quantum yield (AQY), which was 10-fold higher
compared to the MCT10 (MoS2-commercial TiO2) H2 evolution rate of 138 μmol h−1 g−1 with 0.23% AQY under similar reaction
conditions. The shorter decay component, lower emission intensity, and higher estimated lifetime of MPT10 suggest its superiority
over other materials. Density functional theory (DFT) calculations have further revealed the active sites of MPT and hierarchical
porous TiO2 (HPT) to support the experimental hydrogen evolution reaction (HER). This study suggests an avenue to design an
efficient noble-metal-free photocatalyst for solar fuel productions.

■ INTRODUCTION
Due to the decline in nonrenewable resources and increasing
environmental pollution, significant attention has been given to
renewable and clean energy domains. Hydrogen (H2) is
considered as one of the most suitable energy carriers due to
its higher energy density per unit mass in comparison to the
other chemical fuels. In recent times, photocatalytic fission of
water has been considered an attractive solution for solar-to-
chemical H2 energy conversion.1−3 Therefore, the develop-
ment of an excellent, stable, efficient, and economical
photocatalyst for ultrahigh H2 production efficiency is
paramount to researchers.
Ever since the breakthrough research on H2 photogeneration
from water using TiO2 under UV-light irradiation,4 an
enormous amount of research has been conducted on
photochemical H2 evolution using different semiconductor-
based photocatalysts.5 However, the major drawbacks of TiO2
are its wide band gap (3.2 eV) and its fast charge annihilation
at photoinduced electron−hole pairs. Furthermore, Pt and
expensive noble metals are frequently used as cocatalysts for
water-splitting studies. A diverse range of supports and
techniques have been employed, such as doping, band-gap
engineering, and use of different cocatalysts (Pt, Au, Ag, etc.),
for a higher reduction of water.6−8 Therefore, the quest for
more effective hydrogen evolution reaction (HER) catalysts
with minimized use of precious metals has become an
increasingly important topic.
The design of a binary support through controlled synthesis
enabled a greater number of active sites in HER, such as two-
dimensional molybdenum sulfide (2D MoS2), which possesses
distinctive optoelectronic and catalytic properties and shows a
wide spectral response ranging from visible to near-IR light. It
improves the charge separation during photoirradiation of the
materials.9,10 The controlled synthesis of 2D metal chalcoge-
nides such as MoS2, upon band-gap engineering in the
resultant heterostructure composites, gives rise to active sites
that enhance the photocatalytic reactions.11,12 The hetero-
structured hybrid materials can be made by judicious tuning of
MoS2 and TiO2 morphology using specific synthesis processes.
Further, it is noted that MoS2 possesses a direct band gap (1.90
eV),13−15 high carrier mobility,16 etc., which lead to versatile
applications such as optoelectronic and nanoelectronic
devices.17−19 The nanosized MoS2 edge defects favored H2
Received: March 3, 2021
Revised: May 14, 2021
Published: May 27, 2021

© 2021 American Chemical Society https://doi.org/10.1021/acs.jpcc.1c01922

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adsorption.20−23 The sluggish electron-transfer process in TiO2
is usually addressed using a proper cocatalyst. In this context,
the main investigation here is the band-gap engineering of the
TiO2 particulate for more light harvesting in the HER process.
We then exploited the 2D structure of MoS2 nanoscale flakes
with a few layers that allowed unprecedented control over bulk
materials, resulting in improved active sites and H2 evolution
performance.24−32 The layered structure of MoS2 formation
occurs through the Mo atom where electrons are sandwiched
between the two s-orbitals of the molecule, and its dimension
reduced to the size of a monolayer on its transformation of the
band-gap pattern from indirect to direct energy gap. Therefore,
using MoS2 nanoscale flakes with a few layers is an important
strategy to enhance H2 production.24,25,33 In recent studies,
MoS2 was proved to have potential as a light-harvesting
semiconductor and exhibited some extent of plasmonic
properties, which could be one of the key factors working
synergistically at the interface of junction architectures.24,34−36
Accordingly, it is expected that MoS2-loaded semiconductors
would greatly enhance the photocatalytic activity and HER.
Several reports of MoS2−TiO2 heterostructured nanocompo-
sites have been explored for improving the photocatalytic
hydrogen evolution by modulating the titanium dioxide
morphology and band gap through interband interac-
tion.35,37,38 For example, Xiang et al. reported that increasing
the specific surface area of MoS2 nanosheets on TiO2-graphene
hybrid structures increased the photocatalytic activity with a
H2 production rate of 165.3 μmol h−1 under ultraviolet light
illumination.38 Further, Liu et al. reported that MoS2 with a
growth-controlled process and loading of TiO2 had a
substantial impact on H2 generation. They explained that at
optimized conditions, the TiO2/MoS2(E) composite exhibited
impressive HER activity at a rate of 4300 μmol h−1 g−1, a much
higher activity (36 times) compared to pristine TiO2.34 On the
other hand, the reduced TiO2 with the MoS2 composite was
reported for the removal of methyl orange (MO) and H2
evolution.24 In particular, Yang et al. described plasmonic
properties in MoS2@TiO2 hybrid heterostructures, which
display impressive photocatalytic H2 generation.35 According
to Lin et al., MoS2/TiO2 at 10 wt % MoS2 and using methanol
as the sacrificial electron donor showed a H2 evolution of 1.93
mmol g−1 h−1.39 Yuan et al. reported that the 2D MoS2/g-
C3N4 materials exhibited a moderate activity of 1155 μmol h−1
g−1 with an apparent quantum yield of 6.8%.40 Visible-light-
induced H2 production systems over P-25 TiO2 loaded with
MoS2 heterostructured nanocomposites are well reported.
Thus, with reference to our earlier studies, we observed that
controlled morphology and tunable optoelectronic properties
of the photocatalyst play a vital role in electron−hole pair
generation and its further movement. As is known, the
application of hierarchical porous TiO2 with a layered MoS2
nanocomposite photocatalyst for solar-light-harvesting photo-
catalytic H2 production has not been reported yet.
Taking into account all of these critical parameters, we
focused on the synthesis of hierarchical porous TiO2 with
marigold-flower-like MoS2 nanocomposites via a simple and
well-characterized hydrothermal process. In previous reports,
the detailed synthesis and photophysical properties of
hierarchical porous TiO2 (HPT) and its HER capability have
been described.41,42 To achieve visible-light-harvesting H2
production activity, the prepared MoS2−HPT photocatalyst
is noble metal free and possesses unique photophysical
properties: visible-light response, controlled electron−hole
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recombination, and sustainable H2 production over prolonged
light irradiation due to the synergic effect of flowerlike MoS2
and the fibrous wormhole mesoporous channel of titanium
dioxide. The highest HER is obtained using MPT10 (MoS2 and
HPT with a 1:10 weight ratio) at a rate of 1376 μmol h−1 g−1
with 2.28% apparent quantum yield at 420 nm using the
sacrificial electron-donor (SED) mixture of Na2S and Na2SO3.
Moreover, the photocurrent density of the MPT10 photo-
catalyst is 0.55 μA cm−2, which is nearly 55 times higher than
HPT (0.01 μA cm−2), 7.0 times greater compared to MPT5
(0.08 μA cm−2), about 1.7 times greater compared to MPT15
(0.33 μA cm−2), and 2.2 times higher than MPT20 (0.25 μA
cm−2). Hence, the present study enabled a non-noble approach
to develop intimate and large contact interfaces for a robust
and efficient solar hydrogen generation system.
■
METHODS
Materials. Titanium(IV) isopropoxide (Ti{OCH(CH3)2}4,
99.99%), ammonium molybdate tetrahydrate
{(NH 4 ) 6 Mo 7 O 24 ·4H 2 O, 99.99%}, and thiourea (TU)
(NH2CSNH2, 99%) were procured from Sigma-Aldrich.
Absolute ethanol and deionized (DI) water were supplied by
Merck, Germany. All of the chemicals used in the present
study were used as received without further purification.
Syntheses of MoS2@HPT Nanostructured Hetero-
composites. The preparation process of hierarchical porous
TiO2 (HPT) has been adopted from previous reports (details
in the Supporting Information).41,43 Further, the marigold-
flower-like MoS2@HPT (MPT) nanostructured heterocompo-
sites were successfully prepared using a simple hydrothermal
process. First, 0.1 g of ammonium molybdate and 0.4 g of
thiourea (TU) were charged in 50 mL of deionized water. The
prepared solution was continuously stirred for 2 h. Then, 1.0 g
of the HPT catalyst was mixed into the reaction mixture and
stirred at room temperature (RT) for the next 30 min to
obtain a uniform reaction mixture. It was then shifted into a
hydrothermal system (Teflon-lined stainless steel autoclave)
and charged at 210 °C for 24 h. Subsequently, the system was
kept at RT for a natural cooling process. The black precipitates
of MPT composites were collected through filtration. The
products retrieved after filtration were washed and centrifuged
at 3500 rpm with distilled water and ethanol and then kept
under a vacuum for removal of the residual reactant at 60 °C
for 24 h. The obtained MoS2@HPT composite powder was
then dried at 80 °C for 12 h. Other controlled loading
catalysts, namely, MPT photocatalysts, were obtained over a
precise weight ratio variation of MoS2 and HPT using a similar
synthesis strategy of changing the mass ratios of the precursors.
We further attempted to develop pure MoS2 through the same
process but without using the HPT (see details in Table S1).
The resulting MPT nanocomposites were labeled as MPT10,
M5PT, MPT1, MPT5, MPT15, MPT20, and MPT25 as per the wt
% ratio of MoS2 to HPT. The controlled porosity and
wormhole structural morphology, surface area, and hetero-
junction formation of MoS2/HPT were established using
analytical tools like scanning electron microscopy (SEM),
transmission electron microscopy (TEM), X-ray diffraction
(XRD), X-ray photoelectron spectroscopy (XPS), and
Brunauer−Emmett−Teller (BET).
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Figure 1. XRD of HPT, MoS2, and MoS2@HPT nanocomposites.
Figure 2. FESEM images of (a) HPT, (b) MoS2, (c) M5PT, (d) MPT1, (e) MPT5, (f) MPT10, (g) MPT15, (h) MPT20, and (i) MPT25.
■ RESULTS AND DISCUSSION
Phase Analysis. The structural phases of HPT, MoS2, and
MPTx heterocomposites were illustrated from powder XRD,
and the results are displayed in Figure 1. The diffraction peaks
of HPT were obtained at 2θ values of 25.3, 38.1, 48.1, 54.1,
55.3, and 62.9° ascribed to the (101), (103), (200), (105),
(211), and (204) planes of the anatase TiO2 (JCPDS 21-
1272), respectively.41,42 Further, the bare MoS2 sample reveals
three diffraction peaks at 14.1, 33.5, and 59.3° corresponding
to the (002), (100), and (110) planes of the few-layered
nanosheets of MoS2 (JCPDS card no. 65-1951).44,45 The
diffraction peaks of TiO2 and MoS2 were clearly observed in
MPT-hybrid composites, which suggests the successful
formation of MoS2@HPT heterocomposites. It was noted
that with an increase of HPT, the intensity of the diffraction
peak of TiO2 also increased proportionally, while the MoS2
(002) plane decreased (Figure 1), suggesting that the
introduction of HPT substantially inhibits the (002) plane
growth of the MoS2 crystal in the heterocomposite.44
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Morphology Analysis. The structural morphologies of
HPT, MoS2, and MPT nanocomposites were examined by field
emission scanning electron microscopy (FESEM), and the
images obtained are depicted in Figure 2. As shown in Figure
2a, the HPT sample contained the wormhole fibrous
morphology that led to multiple reflections and drove the
effective charge transfer toward the H2 production reaction. As
shown in Figure 2b, the as-synthesized MoS2 contained
marigold-flower-like structures assembled with several thin
nanopetals or nanosheets.46,47 The prepared M5PT, MPT1,
MPT5, and MPT10 heterocomposites show that some HPT
nanomaterials were decorated at MoS2 nanosheets (Figure 2c−
i) after the HPT was incorporated on MoS2. Further, when the
weight ratio of HPT on MoS2 was increased to 15, the surface
morphology of the as-synthesized MPT nanocomposite
interestingly changed to a wormhole fibrous shape similar to
HPT, which may be due to the higher volume ratio of the HPT
on the MoS2 surface. As an FESEM result, it was understood
that the volume ratio plays a vital role in modulating the
surface morphology.
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Figure 3. TEM images with low and high magnification of (a, b) HPT, (c, d) M5PT, (e, f) MPT1, (g, h) MPT5, (i, j) MPT10, and (k, l) MPT15
photocatalysts.
To further understand the structural properties and confirm
the composite constituents, HPT and MPT nanocomposites
were analyzed by TEM and high-resolution transmission
electron microscopy (HRTEM) (Figure 3). Figure 3a,b
demonstrates that the HPT displays the anatase phase of the
TiO2 (101) plane. The TEM images of M5PT, MPT1, MPT5,
and MPT10 heterocomposites illustrated in Figure 3c−j reveal
that the MoS2 layers decreased with an increase in the amount
of HPT on the MoS2 surface. Further, the surface morphology
of MoS2 changed from layer to particle at a higher volume ratio
of porous TiO2 on the MoS2 surface, as shown in Figure 3k,l of
the MPT15 photocatalyst. Moreover, each composite consists
of two different lattice spacings, one with d = 0.354 nm, which
matches with the (101) plane of anatase TiO2, and the other
fringes with d = 0.65 nm, which matches with the (002) plane
of MoS2. Some cross-lattice fringes were observed in the
HRTEM images, which clearly indicate the successful
formation of the heterojunction between MoS2 and hier-
archical porous TiO2. The composite formation was also
confirmed by high-angle annular dark field (HAADF) and
energy dispersive X-ray (EDX) images (Figure S1). The
synergistic effects were beneficial for the fast photogenerated
electron transfer and further improvement in photocatalytic
performances.48
Surface Analysis. The Brunauer−Emmett−Teller (BET)
adsorption isotherms and Barrett−Joyner−Halenda (BJH)
pore-size distribution patterns of different MPT nano-
composites are shown in Figures 4 and S5. To achieve higher
photocatalytic H2 production efficiency, electron and hole
transporting materials should have a higher surface area. The
N2 adsorption−desorption isotherms of all nanocomposites
show type IV isotherm patterns with H3 hysteresis loops
attributed to the mesoporous nature. We also found that the
BET specific surface areas increased with increasing optimal
loading amount of HPT on the MoS2 surface and then
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decreased, as given in Table 1. Further, the estimated BET
surface areas of M5PT, MPT1, MPT5, MPT10, MPT15, MPT20,
and MPT25 were found to be 22.08, 24.23, 35.47, 49.29, 46.80,
37.84, and 33.65 m2 g−1, respectively. The BJH pore-size
distribution graphs of M5PT, MPT1, MPT5, MPT10, MPT15,
MPT20, and MPT25 nanocomposites are shown in Figures 4
and S5 (inset); the evaluated pore sizes were 2.86, 5.11, 16.35,
5.44, 12.81, 13.38, and 14.11 nm, respectively (Table 1). It is
interesting to mention that the surface area of the MoS2@HPT
nanocomposites enhanced with an increase in the amount of
both precursors. On the basis of the above results, it can be
envisioned that porous networks exposed the active sites,
which in turn play a significant role in improving the HER and
reducing the charge recombination. The obtained results were
consistent with the SEM and XRD analyses.
XPS Analysis. Further, we performed XPS analysis to
examine the elemental composition and elemental states of the
best-performing material (MPT10), as shown in Figure 5. The
full surface scan XPS spectrum also corroborated the fact that
the prepared photocatalyst was composed of Ti, O, Mo, and S
elements (Figure 5a). As illustrated in Figure 5b, the high-
resolution XPS spectra of Ti 2p at 458.3 and 465.3 eV could be
ascribed to Ti 2p3/2 and Ti 2p1/2, respectively. It was noted
that the O 1s peak appeared at a binding energy of 531.5 eV
(Figure 5c). The obtained results were compared with that of
the previous literature reports.38 Further, the high-resolution
XPS spectra in Figure 5d demonstrate two characteristics peaks
ascending at 228.9 and 232.3 eV, which can be attributed to
the energy values of Mo 3d5/2 and Mo 3d3/2, respectively,
suggesting the presence of Mo4+ in the MPT sample. The
binding energy values of S 2p1/2 and S 2p3/2 were observed at
163.5 and 162.3 eV, respectively (Figure 5e).35,37,38 Hence, the
results obtained from XPS data reinforce the fact that MoS2 is
successfully integrated onto the TiO2 surface and there is
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Figure 4. BET adsorption−desorption isotherm and Barrett−Joyner−Halenda (BJH) plots of MPTx nanocomposites.

Table 1. Photophysical Properties of MoS2-Hierarchical diffuse reflectance spectroscopy (DRS), as shown in Figure 6.
Porous TiO2 Nanocomposites The intrinsic absorption band located around 370 nm
specific surface area average pore size pore volume
corresponded to the porous TiO2 substrate, suggesting a
sample (m2 g−1)a (nm)b (cm3 g−1) band energy distance of ∼3.0 eV. Furthermore, a pronounced
M5PT 22.08 2.86 0.015 absorption edge ranging between 420 and 720 nm could be
MPT1 24.23 5.11 0.030 observed in the MoS2@HPT heterocomposites, which can be
MPT5 35.47 16.35 0.066 attributed to the plasmonic induction of MoS2 on the HPT
MPT10 49.29 5.44 0.150 surface. The band-gap energy of the prepared MoS2@HPT
MPT15 46.80 12.81 0.145
samples was determined by the Kubelka−Munk analysis and
MPT20 37.84 13.38 0.126
MPT25 33.65 14.11 0.118
extrapolations of the Tauc plot demonstrated in Figure
a S2.39,49,50 The estimated band-gap energy values of the
Specific surface area was calculated from the linear part of the BET
plot. bAverage pore diameter. prepared heterocomposite samples were found to be 1.95,
2.97, 2.95, 2.92, 3.0, and 3.01 eV corresponding to M5PT,
successful formation of MPT-hybrid composite elemental MPT1, MPT5, MPT10, MPT15, and MPT20 (Table 2 and Figure
characteristics. S2). The results suggest that the band-gap potential gradually
Optical Properties. The MoS2−HPT heterostructure’s narrows with an increase in the weight ratio of TiO2 to MoS2
solar-light-harvesting properties were examined by UV−vis in the composite. Moreover, the MPT10 photocatalyst has the
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Figure 5. XPS spectra of the MPT10 photocatalyst: (a) full scan, (b) Ti 2p, (c) O 1s, (d) Mo 3d, and (e) S 2p.

Figure 6. (a) UV−vis absorption spectra, (b) Mott−Schottky (MS) plot at 1000 Hz frequency of MPTx heterocomposites, and (c) Mott−Schottky
plot at 1000 Hz frequency of HPT.

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Table 2. Photocatalytic Hydrogen Production Activity of assessed and compared in Figures 7a and S3. The bare porous
the Prepared Heterocomposites TiO2 revealed negligible H2 production activity under visible
light. However, MPTx heterostructures showed obvious
band gap H2 yield H2 rate AQY
catalyst (eV) (μmol gcat−1) (μmol h−1 gcat−1) (%) photocatalytic activities toward H2 production because of
M5PT 1.95 387 78 0.13
their impressive visible-light response and the surface
MPT1 2.97 598 120 0.20 plasmonic resonance of MoS2 nanosheets. A series of loading
MPT5 2.95 654 130 0.22 amounts of MoS2 nanosheets on the porous TiO2 surface were
MPT10 2.92 6879 1376 2.28 examined to calibrate the photocatalytic HER activity. The
MPT15 3.00 4725 945 1.57 superior photocatalytic response of MPT heterostructures
MPT20 3.01 2272 454 0.75 obtained at a loading ratio of 1 wt % MoS2 to 10 wt % porous
MCT 690 138 0.23 TiO2 at the rate of H2 evolution is 1376 μmol h−1 gcat−1, which
is higher than the other ratios of MPTx heterostructures.
Furthermore, as tabulated in Table 2, the MPT10 photocatalyst
maximum photon-harvesting ability and better charge-trans- exhibited a higher H2 production rate and apparent quantum
port properties toward solar energy conversion.34,35 yield (2.28%) compared to M5PT (0.13%), MPT1 (0.20%),
Mott−Schottky (MS) measurements were employed to MPT5 (0.22%), MPT15 (1.57%), and MPT20 (0.75%). It could
confirm the nanostructures in p−n junctions and determine be because the higher loading of MoS2 on the porous TiO2
the flat-band positions of MPTx samples. The Mott−Schottky surface hinders the photoexcited charge-transfer process
slopes positively shifted in the composite (Figure 6b) between HPT, assuming the porous TiO2 as the core and
compared to HPT (Figure 6c); simultaneously, the n-type the MoS2 nanosheet as the shell; however, lower loading leads
and p-type characteristics of the semiconductor, which were to low efficiency of the surface plasmon resonance or deficient
observed in the Mott−Schottky image of MPTx, confirmed the visible-light absorption. Moreover, on optimal loading of MoS2
formation of the p−n junction.51,52 The obtained flat-band on the porous TiO2 surface, it acted as an efficient light-
position (Vfb) results of the Mott−Schottky measurement for
harvester photocatalyst, which provided efficient charge
MPT10 was −0.63 eV vs Ag/AgCl (i.e., −0.71 eV vs NHE),
separation to prevent electron−hole recombination, which in
which was more negative compared to the electrode potential
turn improved the HER activity. The H2 production activity is
of H+/H2 (−0.41 V vs NHE, pH = 7)53,54 and fulfilled the
thermodynamic requirement in the HER process. In the same also examined in the presence and absence of SED. Figure S6
manner, the CB could be calculated as −0.51 eV vs NHE for shows the magnitude to be about 17 orders lower in true
MPT5, −0.44 eV vs NHE for MPT15, and −0.48 eV vs NHE water-splitting reactions, as expected. This is because the
for MPT20 nanomaterial samples. Further, the valenceband consumption rate of the positive h+ hole is the limiting kinetic
(VB) positions were at 2.44, 2.29, 2.56, and 2.53 eV vs NHE step.56,57
for MPT5, MPT10, MPT15, and MPT20, respectively. The The surface plasmonic effect of the MPT10 composite was
estimated energy band structures favored the suitability of further affirmed by a wavelength-dependent photocatalytic
efficient charge injection, separation, and transfer of photo- process under various monochromatic light sources (λ = 500,
induced electrons and holes.55 550, 600, 650, and 700 nm) using corresponding narrow band-
Photocatalytic Hydrogen Production Activity. Encour- pass filters. As displayed in Figure 7b, the spectral-dependent
aged by the above characterization results, the photocatalytic H2 evolution rates are about 17, 29, and 5.75 μmol h−1 gcat−1 at
experiments for H2 production were performed under 500, 550, and 600 nm, respectively, while no H2 evolution was
simulated solar light irradiation of a 300 W Xe lamp using found at 650 and 700 nm. The relative photoabsorption and
20 mg of the prepared MoS2@HPT in 30 mL of an aqueous hydrogen evolution consistency over simulated sunlight
suspension containing 0.35 M Na2S and 0.25 M Na2SO3. The signifies that the enhanced photoactivity was mainly due to
photocatalytic H2 evolution activities of MPTx samples were induction of the plasmonic effect between blue and green

Figure 7. (a) Histogram of comparative photocatalytic H2 generation activities of the MPTx photocatalyst in 30 mL of the mixed aqueous solution
containing 0.35 M Na2S and 0.25 M Na2SO3 as sacrificial agents under visible-light illumination as the lighting source. (b) Controlled H2 evolution
rate as a function of the wavelength by monochromatic light irradiation after 4 h.

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Figure 8. (a) Nyquist curves, (b) photocurrent density plot, (c) PL spectra, and (d) singlet excited-state lifetimes of the prepared photocatalysts in
methanol.
wavelengths. The higher H2 evolution rate obtained at 500 and
550 nm suggests plasmon-induced enhancement in HER.
Photoelectrochemical Studies. To gain further insights
into the mechanism of photocatalytic H2 generation and the
separation of photogenerated electrons and holes in these
MPTx heterostructures, we also performed electrochemical
impedance spectroscopy (EIS), photoluminescence (PL)
emission spectroscopy, and transient photocurrent measure-
ments. In that, EIS analysis was employed to evaluate the
internal resistance of the charge-transfer process of the
samples.58 The semicircular radius of Nyquist curves of
MPT10 exhibited a smaller diameter compared to those of
MPT5, MPT15, and MPT20 (Figure 8a), resulting in a higher
photocurrent response. The charge carrier transport ability of
MPT10 is faster than those of MPT5, MPT15, and MPT20.50
Moreover, it was also confirmed by EIS that the MPT10 hybrid
showed the lowest charge-transfer resistance, which signifi-
cantly accelerated the electron mobility compared to those of
the other MPTx photocatalysts.36 The photocurrent density of
the MPT10 photocatalyst was 0.55 μA cm−2, which was nearly
55 times that of HPT (0.01 μA cm−2), 7.0 times that of MPT5
(0.08 μA cm−2), about 1.7 times that of MPT15 (0.33 μA
cm−2), and 2.2 times that of MPT20 (0.25 μA cm−2) (Figure
8b). This suggests that the nanomaterial catalyst leads to
separation of photogenerated charges. The continuous increase
of photocurrent to the initial time could be due to the
photostability of the catalyst. Further, photoluminescence (PL)
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emission analysis was employed to detect the charge carrier
trapping and electron−hole recombination of the prepared
heterostructured materials during photocatalytic reactions
(Figure 8c). The photoluminescence spectra of bare TiO2,
MoS2, and MoS2@TiO2 nanocomposites excited at 320 nm are
presented in Figure 8c. The results showed that the TiO2
emission peak intensities at around 575 and 590 nm were
remarkably quenched by varying the MoS2 content. The results
can be ascribed to the beneficial interfacial photoexcited charge
transfers between the hierarchical porous TiO2 and MoS2 and
the MoS2 that acted as an electron sink, which in turn inhibited
the photogenerated charge recombination. The result corre-
sponds to an efficient charge separation in MoS2−TiO2, which
enhanced the HER of the nanomaterial samples. To gain a
clear understanding, we studied the electron−hole charge
separation dynamics of bare MoS2, porous TiO2, and MPTx
nanomaterials; the time-resolved fluorescence (TRF) decay
data were taken from the photoluminescence lifetime study
using the time-correlated single photon counting (TCSPC)
analysis in methanol. The TRF decay curves were fitted to a
triexponential decay function, which shows that three different
emission paths impact the TRF decay in MPTx. The
spectroscopic details are shown in Figures 8d and S7, and
their fluorescence transient (τ) fittings are tabulated in Table
S2. The obtained spectroscopic value revealed that the optimal
MoS2 loading on TiO2 and the periodically patterned
morphology provided the MPT10 photocatalyst with less
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J. Phys. Chem. C 2021, 125, 11950−11962
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Figure 9. (a) Side view of the MPT heterostructure. (b) Top view of the MPT heterostructure along with active sites shown by black circles. (c)
Free energy profile of the one-layer MPT heterostructure.
Figure 10. Side views of the charge density difference of hydrogen adsorbed at MPT, (a) O1, (b) O2, (c) O3, and (d) Ti sites.
trapping centers and prolonged lifetime of electrons at the
activation level as well as a pronounced HER. Moreover, the
average weighted lifetime of MPT10 (τavg = 1.19 ns) was
estimated to be significantly longer than those of MoS2 (τavg =
0.07 ns), MPT5 (τavg = 0.15 ns), MPT15 (τavg = 0.20 ns),
MPT20 (τavg = 0.21 ns), and porous TiO2 (τavg = 0.20 ns),
which correlated with the higher photocatalytic performance
observed for MPT10. It is interesting to note that a shorter
decay component, a lower emission intensity, and a higher
estimated lifetime of MPT10 suggest that the separation of the
photogenerated charge carrier efficiency becomes markedly
better by creating the heterojunction and pronounced
nonradiative rates in the MPT10 relative to the radiative rates
than the other MPTx nanocomposites. These data are in
agreement with the trend of the series of materials tested for
the HER.
Computational Study. The free energy of H2 adsorption
(GH*) is a good indicator of the activity of H2 evolution in an
acidic medium. The HER activity can be estimated using the
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free energy profile. There are total three steps, which are
involved in the estimation of the free energy profile. The first
(GH+) and final (G1/2H2) steps are expected to be in equilibrium
at acidic conditions (pH = 0). The second step, hydrogen
adsorption (H*), is a key step to define the free energy profile.
The Gibbs free energy is calculated by the equation ΔGH = ΔE
− TΔS + ZPE, where ΔE denotes the change in the overall
energy (calculated from DFT) and ΔS and ZPE represent
changes in entropy and zero-point energy difference between
the adsorbed and the gas phase of hydrogen, respectively.
However, the ΔS and ZPE of the adsorbed hydrogen are
negligible compared to those of the gaseous phase at RT and
ambient pressure.
Using the first principles approach, the Gibbs free energy
(ΔGH) has been calculated to describe the HER activity. As
per the experimental result, HPT matches with the anatase
phase of the TiO2 (1 0 1) plane. To mimic the TiO2/MoS2
heterostructure, we used the (3 × 4 × 1) anatase phase of the
TiO2 structure and (5 × 5 × 1) MoS2 with the lattice
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J. Phys. Chem. C 2021, 125, 11950−11962
The Journal of Physical Chemistry C
mismatch of 4.66%, called MPT, as shown in Figure 9a. To
understand the HER activity, we studied two different
structures, namely, pristine MoS2 and MPT. For pristine
MoS2, the S site is considered as an active site, while in the case
of the MPT heterostructure, O1, O2, O3, and Ti sites were
considered as active sites, as shown in Figure 9b. O1, O2, O3,
and Ti sites can be defined as follows. O1 is the layer-one O
atom, which is attached to two Ti atoms. The bond lengths of
O with these Ti atoms are 1.79 and 1.91 Å. O2 is the layer-two
atom, which is attached to three Ti atoms having bond lengths
of 1.97, 2.02, and 1.97 Å. O3 is the layer-three atom, which is
also attached to three Ti atoms having the same bond length as
the O2 atom. The Ti site atom is attached to five O atoms and
one Ti atom having bond lengths of 1.976, 2.025, 1.979, 1.91,
1.79, and 2.73 Å. The free energy of hydrogen adsorption,
ΔGH, for pristine MoS2 is 1.93 eV, while in the case of the
MPT heterostructure, O1, O2, and O3 sites are more favorable
for the HER activity with ΔGH values of 0.42, 0.52, and 0.88
eV, as shown in Figure 9c. The ΔGH value of MoS2 agrees well
with reported works.59−61 For comparison, we calculated the
free energy of H adsorption on O1, O2, and O3 sites of the
HPT structure (anatase TiO2 surface of the 101 plane), and it
is estimated as 0.57, 0.65, and 1.01 eV, respectively (Figure
S4). The free energy of hydrogen adsorption, ΔGH, for the
pristine TiO2 layer and the three-layer MPT was further
examined to consider the modeling of the TiO2/MoS2
heterostructure with similar parameters and induced strain as
taken for the one-layer MPT (Figure S8). The obtained free
energy change (ΔGH) values of the three-layer MPT for O1,
O2, and O3 sites are 0.49, 0.61, and 0.98 eV, respectively,
which is higher than the free energy change (ΔGH) value of the
one-layer MPT and lower than the pristine TiO2 values for O1,
O2, and O3 sites of 0.57, 0.65, and 1.01 eV, respectively, as
tabulated in Table S3. Overall, we observed that the MoS2
layer helps in adsorption of the H atom by optimizing the free
energy.
To understand the electron-transfer pathway, we calculated
the charge density difference of the MPT heterostructure.
From the charge density difference of O1, O2, O3, and Ti sites
of the MPT heterostructure, it is clear that there is a small
charge transfer from hydrogen to oxygen sites (Figure 10),
whereas for Ti atoms, there is a negligible charge transfer
because Ti shares charge with five O and one Ti atom (Figure
10d), which is the main reason for not being able to adsorb the
hydrogen atom. To better understand the charge transfer and
adsorption of the hydrogen atom on the MPT surface, we
studied the occupancy of electrons on each oxygen atom. The
electron occupancies of O1, O2, and O3 sites of the MPT are
6.84e, 7.05e, and 7.06e, respectively. It confirms why O1 is
more active toward HER compared to the other sites. Less
occupancy on the O1 atom increases the affinity toward the H
atom, and it is found that it gains more charge during
adsorption of the H atom. Overall, from the DFT study, it is
clear that MPT heterostructure O sites are more favorable for
HER reactivity, while pristine MoS2 is not feasible for HER
activity.
Mechanistic Pathway. Based on the results and
discussion, a plausible mechanism for H2 production over
the MPT photocatalyst is illustrated in Figure 11. It was
observed that the photoexcited electron was initiated upon
light illumination and the excited electrons from the VB of
TiO2 were injected into the CB of TiO2 for the creation of
charge pairs (electron−hole). The photogenerated electrons
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Figure 11. Schematic illustration of photocatalytic processes for
efficient solar-to-H2 conversion.
transformed from the CB of hierarchical porous TiO2 to
flowerlike MoS2 without any cocatalyst. This was due to the
comparative energy difference between TiO2CB (ECBTiO2 =
−0.51 V vs NHE, pH 7)62 and MoS2 (ECBMoS2 = −0.16 V vs
NHE, pH 7).63 It is interesting to note that the interfacial
contact area of MoS2@HPT nanocomposites plays a key role
in determining the superior H2 production performances of the
prepared materials, which is favorable for charge transfer from
TiO2 to MoS2 for H2 generation, resulting in improvement of
photocatalytic H2 production activities (Figure 11). Eventually,
the electron on the surface of MoS2 can react with the
absorbed protons for efficient H2 evolution, while the holes in
the VBs were regenerated to consume electrons from SED
(Na2S + Na2SO3) and drove the photocatalytic process in a
repeated manner.
■ CONCLUSIONS
In this work, it was shown that hierarchical porous TiO2 can be
interfaced successfully with marigold-flower-like MoS2 flakes
with intriguing photophysical properties, viz., visible-light
response, controlled electron−hole recombination, and
sustainable H2 production over prolonged light irradiation
due to the synergic effect of flowerlike MoS2 and the fibrous
wormhole mesoporous channel of TiO2. This investigation
provides useful information on the precisely controllable
synthesis of MoS2 and HPT-based hybrid heterojunction
materials for extensive photocatalytic and other energy-
harvesting applications. TEM results showed that MoS2
nanoflower layers decreased on decreasing the weight ratio
of MoS2 on the porous TiO2 surface and EDS mapping
confirmed the elemental composition as Mo, S, Ti, and O and
spatial distribution in the heterostructured sample. The
superior photocatalyst MPT10 at the optimal weight ratio
enhanced the hydrogen production results at a rate of 1376
μmol g−1 h−1 and a photocurrent density of 0.55 μA cm−2. The
results show the pronounced plasmonic effects on the
photoactivities and highlight the role of the heterojunction
structure in photocatalytic H2 production. We believe that the
present work would prove useful to extend the light-harvesting
capability, suppress the recombination process, and enhance
the photocatalytic performance.
https://doi.org/10.1021/acs.jpcc.1c01922
J. Phys. Chem. C 2021, 125, 11950−11962
The Journal of Physical Chemistry C
■
ASSOCIATED CONTENT
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.jpcc.1c01922.
Structural characterization, apparent quantum yield, and
turnover number calculation; HAADF and EDX images
of MPT10; Kubelka−Munk plots of MPTx; time-course
photocatalytic H2 production curves; true water-splitting
graph; free energy profile of anatase TiO2; and lifetime
graphs of the photocatalysts (PDF)
■
AUTHOR INFORMATION
Corresponding Authors
Amritanjali Tiwari − Department of Energy and
Environmental Engineering, CSIR-Indian Institute of
Chemical Technology, Hyderabad 500007, India;
orcid.org/0000-0001-5547-3903; Email: amritanjali4@
gmail.com
Ujjwal Pal − Department of Energy and Environmental
Engineering, CSIR-Indian Institute of Chemical Technology,
Hyderabad 500007, India; Academy of Scientific and
Innovative Research (AcSIR), CSIR-Human Resource
Development Centre (CSIR-HRDC) Campus, Ghaziabad
201002, Uttar Pradesh, India; orcid.org/0000-0002-
2110-4242; Email: upal03@gmail.com
Authors
Amit Gautam − Department of Energy and Environmental
Engineering, CSIR-Indian Institute of Chemical Technology,
Hyderabad 500007, India; Academy of Scientific and
Innovative Research (AcSIR), CSIR-Human Resource
Development Centre (CSIR-HRDC) Campus, Ghaziabad
201002, Uttar Pradesh, India
Saddam Sk − Department of Energy and Environmental
Engineering, CSIR-Indian Institute of Chemical Technology,
Hyderabad 500007, India
Deepak S. Gavali − Department of Physics, SRM University
AP, Amaravati 522240, Andhra Pradesh, India
Ranjit Thapa − Department of Physics, SRM UniversityAP,
Amaravati 522240, Andhra Pradesh, India; orcid.org/
0000-0002-9285-0525
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.jpcc.1c01922
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
The authors acknowledge the institutional in-house project P-
07 and the externally funded DAE/BRNS Nos. 34/14/03/
2018-BRNS/340 and DST/TMD/HFC/2k18/60. The au-
thors also acknowledge the High Performance Computing
Center, SRM IST, for providing the computational facility.
CSIR-IICT Communication No: IICT/Pubs./2020/273.
■
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