Accepted Article

Title: Enhanced solar hydrogen generation by a heterojunction of perovskite-type

La2Ti2O7 nanosheets doped with CdS quantum dots

Authors: Sujuan Hu; Mingshan Zhu

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Enhanced solar hydrogen generation by a heterojunction of
perovskite-type La2Ti2O7 nanosheets doped with CdS quantum
dots
Sujuan Hu[a] and Mingshan Zhu*[b]
Abstract: In this paper, a heterojunction of perovskite-type La2Ti2O7
(LTO)/CdS quantum dots (QDs) nanocomposite was prepared by
chemical bath deposition method. The solar light driven H2
generation results show that this CdS QDs/LTO heterojunction
exhibits great improvement on photocatalytic H2 production and
photoelectrochemical property in comparison with pure CdS QDs
and LTO nanosheets. A possible enhanced mechanism of
photoinduced interfacial charge transfer between CdS and LTO is
proposed for the heterojunction. The shift of CdS conduction band
(CB) edge can enlarge the CB potential difference between CdS
QDs and LTO, enhancing transferred driven force of interfacial
electrons and finally improving the two components separation
activity of photogenerated carriers. This study provides a promising
method for constructing an efficient photoinduced interfacial charge
transfer over LTO and CdS QDs heterojunction for photocatalytic
hydrogen production.
Introduction
Nowadays, the limited supply of fossil fuels (coal, oil, and
natural gas) and environmental pollution caused by consuming
fossil fuels are two serious international issues [1, 2]. Hydrogen,
which possesses high energy density (140 MJ Kg-1), abundant
and no carbon emission, has been forecasted to replace
traditional fossil fuels and become energy basis of the hydrogen
economy[3]. The challenge of hydrogen economy is to develop
sufficient quantities and low-cost hydrogen from non-fossil
nature resources. Utilizing abundant solar as energy carrier to
achieve conversion of solar to hydrogen is an attracting strategy
since Honda and Figishima first discovered the
photoelectrochemical (PEC) water splitting on a TiO 2 electrode
in 1972[4-6]. However, most of semiconductors have wide band
gap and high recombination rate of photogenerated electrons
and holes, which limit their solar-to-hydrogen (STH) efficiency.
Therefore, various studies have been focused on overcoming
these disadvantages and developing of visible-light driven, high
efficient, stable, and low-cost photocatalysts[7-11].
Perovskite oxides with (110) layered-structure have
received increasing attention because of their unique electronic
configuration, high chemical resistance, and interlayer spatial
structure[12, 13]. Among these perovskites, lanthanum titanate
(La2Ti2O7, LTO) has received major attention[14-18]. However, the
[a] Dr. S. Hu
Department of Chemistry
Kunming University, Kunming 650214, P.R. China
[b] Dr. M. Zhu
School of Materials Science and Chemical Engineering
Ningbo University, Ningbo 315211, P.R. China
E-mail: mingshanzhu@yahoo.com
10.1002/cplu.201600351
wide band gap and high recombination of carriers of LTO
prevent its applications in visible light and reduce the efficiency
of photocatalytic H2 production significantly.
Semiconductor quantum dots (QDs), as CdS, CdSe, CdTe,
and PbS, have been successfully applied in solar cells as
photosensitizer to replace traditional dye for improving the
incident photon-to-current efficiency (IPCE), for their narrow
band gaps, special photoelectric properties, and unique size-
tunable properties originating from the quantum confinement
effects[19-21]. Thus coupling CdS QDs with wide band gap
semiconductors can solve the low utilization of solar energy and
high recombination of carriers, achieving the band-structure
engineering of semiconductors and improving the conversion
efficiency of solar to hydrogen. Coupling wide band gap
semiconductor with narrow band gap semiconductor quantum
dots to form heterojunction structure with appropriate band
alignment can facilitate the transfer of interfacial charge and
increase the separation efficiency of photogenerated carriers.
Up to now, studies have been reported on semiconductor
quantum dots sensitized wide-band-gap semiconductor for
improving photocatalytic activity. Feng et al. adopted chemical
impregnation method to synthesize CdS QDs coupled g-C3N4
photocatalyst and applied it in photocatalytic hydrogen evolution.
By introduction of CdS QDs, the photocatalyst shows a red shift
and strong absorption in visible light region and efficient
separation of the photogenerated charge carriers [22]. However,
no detail studies have been investigated about the roles of
quantum dots in CdS QDs/LTO system on photocatalytic H2
evolution.
Herein, a heterojunction of perovskite-type LTO and CdS
QDs nanocomposite was prepared by chemical bath deposition
method. In this heterojunction, the conduction band (CB) and
valance band (VB) potential of LTO are both higher than those
of CdS QDs[23-25]. Thus a semiconductor II type of heterojunction
is easily formed when LTO is coupled with CdS QDs. A built-in
potential could be formed and photocarriers are distributing for
equilibrium in CdS QDs/LTO heterojunction. As considering the
advantages of large specific surface areas of LTO nanosheets,
the quantum confinement effect of CdS QDs, and the well-
matched band potential of LTO and CdS, the CdS QDs /LTO
heterojunction should result in the enhancing on the driven force
of the interfacial charge transfer and photocatalytic H 2 generation
ability. The solar light driven H2 generation results show that the
CdS QDs/LTO heterojunction exhibited great improvement on
photocatalytic H2 generation in comparison with pure CdS QDs
and LTO nanosheets. With an optimal CdS QDs decorated on
the surface of LTO nanosheets, the rate of hydrogen evolved
from CdS QDs/LTO heterojunction with Pt loaded reaches to
51.31 μmol h-1 g-1. This investigation shows a simple and
efficient method for constructing heterojunction system to
improve photocatalytic hydrogen evolution.
ChemPlusChem 10.1002/cplu.201600351

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Results and Discussion

Crystal phase

The XRD patterns of CdS QDs/LTO are presented in Figure

1. For comparison, the XRD patterns of CdS QDs and 2D LTO
are also presented. Pure LTO shows a monoclinic phase with a
perovskite structure belonging to the P21 space group (JCPDS
81-1066). The peaks located at ca. 28.20o, 30.03o, 32.39o and
33.09o can be indexed to (040), (211), (002) and (012) crystal
planes of the monoclinic LTO phase and no other impurity phase
is detected. Pure CdS QDs show a cubic phase (JCPDS 42-
1411). The peaks located at ca. 26.58o, 43.95o, and 51.93o can
be indexed to (111), (220), and (311) crystal planes. After
compositing CdS QDs with LTO, the diffraction peaks of cubic
phase CdS appear. Besides, the intensities of CdS diffraction
peaks are strengthened with the increase of CdS QDs amount,
as shown in the ellipse frame in Figure 1.

Figure 2. Typical TEM images of LTO (A) and CdS QDs/LTO (2:1) (B~F).

UV-vis absorption

UV-Vis diffuse reflectance spectra (UV-DRS) spectra of

Figure 1. XRD patterns of CdS QDs, LTO and CdS QDs/LTO nanocomposites.
Morphology and microstructure
Usually, the quantum dimension effect is appeared when
particle sizes of group elements of II-IV or III-V semiconductor
range of 1~10 nm. It is clear to see that pure LTO shows
irregular thin two-dimensional (2D) nanosheets (Figure 2A).
After compositing CdS QDs with LTO, a homogeneous
dispersion of CdS QDs with a diameter of 5~10 nm upon the
surface of 2D LTO nanosheets and no obvious aggregation is
observed (Figure 2B~2F). By measuring the lattice parameters
and comparing with the standard data in JCPDS, the interplanar
distance of 0.275 nm is in good agreement with the d-spacing of
the (002) planes of monoclinic LTO and the interplanar
distances of 0.335 and 0.23 nm are in good agreement with the
d-spacing of the (111) and (220) planes of cubic CdS,
respectively.
pure CdS QDs, 2D LTO nanosheets, and CdS QDs/LTO
nanocomposites are shown in Figure 3. For CdS QDs and LTO
nanosheets, the DRS spectra present steep absorption edges at
approximately 340 and 560 nm, respectively, which can be
assigned to the intrinsic bandgap absorption of CdS QDs and
LTO. The band gap energies for CdS QDs and LTO estimated
from the intercept of the tangent to the plots are 2.28 and 3.94
eV by Kubelka-Munk method (Figure S1). The DRS spectra of
the CdS QDs/LTO nanocomposites are composed of the
absorption spectra of CdS QDs (340~560 nm) and LTO
nanosheets (250~340 nm), implying the respective crystal
structure of LTO and CdS QDs is reserved when the
heterojunction was formed. Besides, with the increase of CdS
QDs amount, the absorption edges present obvious red-shift
and absorption intensities in visible-light region are improved.
These results suggest that the introduction of CdS QDs in LTO
has successfully extended the absorption range to visible-light
region.
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Figure 3. DRS spectra of CdS QDs, LTO and CdS QDs/LTO nanocomposites.
XPS spectra
Figure 4. XPS spectra of CdS QDs/LTO (2:1) nanocomposite. (A) Full
spectra; (B) La 3d; (C) Ti 2p; (D) O 1s; (E) S 2p and (F) Cd 3d.
XPS was performed to further reveal the chemical
compositions of CdS QDs/LTO nanocomposite, as shown in
Figure 4. Figure 4A is the full spectra of CdS QDs/LTO
nanocomposite. Seven peaks (Figure 4B) originate from the
spin-orbital splitting of the La 3d3/2 and La 3d5/2[26, 27]. The
characteristic peaks located at 464.1 and 458.7 eV correspond
to Ti 2p1/2 and Ti 2p3/2, respectively (Figure 4C)[28]. Two oxygen
signals at 531.84 and 529.80 eV in Figure 4D are attributed to
the surface adsorption oxygen and lattice oxygen, respectively [29].
Two characteristic peaks at 163.12 and 161.98 eV (Figure 4E)
10.1002/cplu.201600351
are attributed to the doublet of S 2p1/2 and S 2p3/2, respectively[30].
The characteristic peaks attributed to the binding energy for Cd
3d3/2 and Cd 3d5/2 are also observed at 412.11 and 405.31 eV,
respectively, as shown in Figure 4F[31].
Photocatalytic H2 production activity
Figure 5. Photocatalytic H2 evolution rates of CdS QDs, LTO, and CdS
QDs/LTO nanocomposites (without Pt loaded (A) and with 1 wt% Pt loaded
(B)).
Cubic phase CdS QDs and LTO nanosheets present
extremely low photocatalytic H2 production rates (Figure 5A),
which due to the fast recombination of photogenerated electrons
and holes and large band gap of the LTO, respectively. The H2
production rates are enhanced after compositing CdS QDs with
LTO. Besides, the H2 production rate increases with enhancing
the CdS QDs/LTO molar ratio from 1:1 to 2:1, and subsequently
decrease significantly upon further increasing the molar ratio to
3:1. A possible reason for the enhancement is the heterojunction
effect existing between CdS QDs and LTO. Increasing the
amounts of CdS QDs is actually providing more H2 production
heterojunctions. However, introducing excessive CdS QDs are
likely shielding LTO from exposure to incident light, resulting in
the decrease of H2 production rate.
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Due to the Fermi energy level of Pt is always lower than that
of semiconductors, Schottky junction would be formed when Pt
intimately contacts with CdS QDs/LTO[32, 33]. The electric field
formed in the Schottky junction helps photogenerated electrons
migrate to the surface of CdS QDs/LTO and are entrapped by
the Pt[34,35]. Accordingly, the Pt loading of the CdS QDs/LTO was
investigated. The interface of the deposition of Pt nanoparticles
on the surface of CdS QDs/LTO nanosheets was investigated,
as shown in Figure S2. The interplanar distances of 0.220, 0.278
and 0.285 nm are in good agreement with the d-spacing of the
(111), (002) and (200) planes of Pt, LTO and CdS, respectively.
This result confirms the formation of Pt nanoparticles on the
surface of CdS and LTO nanosheets surfaces.
The H2 production rates of different Pt loading amounts on
the surface of LTO nanosheets were studied in Figure S3. The
photocatalytic H2 production rate of pure LTO is extremely low,
however, the loading of Pt results in a substantial improvement
of the H2 evolution rate. With the increasing of Pt loading up to 1
wt%, the rate of H2 evolution increases to 10.26 μmol g-1 h-1.
Further increasing of Pt loading up to 2 wt% drastically
decreases the photocatalytic activity. High Pt loading amount
could result in covering the surface active sites of LTO and
hindering its contact with sacrificial reagent. Besides, excessive
loading of Pt on the surface of LTO that could shield the incident
light, and thus prevent the light absorption and generation of
photogenerated electrons and holes inside the semiconductor.
Furthermore, the H2 production rates of Pt loaded on different
samples were investigated, as summarized in Table 1 and
shown in Figure 5(B). The Pt (1 wt%)-CdS QDs/LTO (2:1)
nanocomposite exhibits the maximum photoactivity (51.31 μmol
h-1 g-1 with an apparent quantum efficiency (AQE) of 0.31%),
which is 6.43 times higher than that of pure LTO.
Table 1 Photocatalytic H2 evolution rates of CdS QDs, LTO and CdS
QDs/LTO nanocomposites with and without 1 wt% Pt.
CdS QDs LTO 1:1 2:1 3:1
Without Pt 0.12 0.31 0.99 3.30 0.20
With 1 wt% Pt 0.29 10.26 4.46 51.3 16.1
Mechanism of enhanced photoactivity
Based on the above experimental results and analyses, we
inferred that the formation of heterojunction between CdS QDs
and LTO led to the improvement of performance. Firstly, the
band structures of CdS QDs and LTO are studied for further
verifying the effect of CdS QDs/LTO heterojunction on
photocatalytic H2 production. The band positions of CdS QDs
and LTO can be predicted according to the empirical formulas
(1) and (2)[36]:
(1)
10.1002/cplu.201600351
(2)
Where χ is the absolute electronegativity of the
semiconductor, expressed as the eometric mean of the absolute
electronegativity of the constituent atoms (χCd=3.66, χS=6.39,
χLa=3.72, χTi=4.92, χO=7.67)[37]; EVB is VB potential; ECB is CB
potential; Eg is the band gap energy of the semiconductor; Ee is
the energy of free electrons on the hydrogen scale (~4.5 eV).
The predicted band edge positions of CdS QDs and LTO are
shown in Table 2.
Table 2 The values of the calculated χ, Eg, ECB, and EVB for CdS QDs and
LTO.
Semiconductor χ (eV) Eg (eV) ECB (eV) EVB (eV)
CdS QDs 4.84 2.28 -0.80 1.48
LTO 6.20 3.94 -0.27 3.67
Generally, CdS QDs and LTO have different Fermi level
positions. When CdS QDs contacts with LTO forming
heterojunctions in dark condition, electrons photogenerated from
CdS QDs will flow into LTO and form accumulation layers,
meanwhile, holes produced in LTO flow into CdS QDs and form
depletion layers. Therefore, the potential barrier and the built-in
potential are established. Under the influence of built-in potential,
charges are redistributing for equilibrium, which will make the
semiconductors, CH3OH and H2O have a same Fermi level. No
oxidation or reduction reaction is happened. However, the
thermodynamic equilibrium is broken and quasi-Fermi levels are
built for CdS QDs/LTO heterojunctions when they are
illuminated under solar illumination. Specifically, under solar
irradiation only the photogenerated electrons in CdS QDs which
have enough energy to stride over the potential barrier can
transport to LTO. The same principle can be applied to the
4:1 transfer of photogenerated holes from LTO to CdS QDs.
0.192
Whereas, a small of potential difference exists between CdS
QDs VB potential and LTO CB potential resulting in the
8.29
photogenerated electrons in the accumulation layers of the LTO
and the holes in the depletion layers of the CdS QDs are easily
recombined with each other. After that, the accumulated holes in
LTO and the accumulated electrons in CdS QDs can form a
photovoltage, opposite to the built-in potential, resulting in the
anodic and cathodic shifts of the quasi-Fermi level of the LTO
and CdS QDs (Figure 6)[38, 39]. For Pt loading system, the
accumulated electrons in CdS QDs and residual in LTO are
transferred to Pt cocatalyst to generate H2 owing to the Schottky
junction between semiconductors and Pt. Accordingly, both type
II heterojunction and Schottky junction are key junctions in the
photocatalytic enhancement. Type II heterojunction in CdS
QDs/LTO is favored to photoinduced interfacial charge transfer
upon excitation and promoting the separation efficiency of
photogenerated electrons and holes, while Schottky junction in
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Pt loading-semiconductor helps trap photogenerated electrons
for H2O reduction. On the other hand, the accumulated holes in
LTO are oxidized by sacrificial reagents.
Figure 6. Proposed mechanism of the separation of photoelectrons and holes
in Pt loading CdS QDs/LTO nanocomposite.
of photocurrent values indicating that CdS QDs, LTO, and CdS
QDs/LTO heterojunction are stable and photoresponses are
quite reversible (Figure 8A). EIS Nyquist analysis is used to
study the effect of photoinduced interfacial electrons transfer
(Figure 8B and Figure S4). The arc of CdS QDs/LTO is smaller
than those of CdS QDs and LTO in the high-frequency region,
implying that CdS QDs/LTO has faster interfacial electron
transfer and more effective separation of photogenerated
electron-hole pairs[40-43]. Photoluminescence (PL) spectra are
performed for further verifying the effect of separation of
photogenerated electron-hole pairs (Figure 9). It can be seen
that CdS QDs/LTO displays dramatically diminished of PL
intensity as compared with CdS QDs, suggesting that
recombination of photogenerated electron-hole pairs of
heterojunction is efficiently suppressed. These results are in well
accordance with photo-electrochemical performances and
photocatalytic H2 production activities.

Figure 7. Schematic illustration of the potential and band positions in the CdS
QDs/LTO heterojunction.

In CdS QDs/LTO heterojunction structure, the narrower

band gap of CdS can make it as photosensitizer. Besides, the
smaller size of CdS (≤10 nm) also brings quantum effect and
can change the inner electronic configuration. To be specific, the
band gap of CdS becomes larger and the VB and CB edges shift
downward and upward, as shown in Figure 7. The shift of the
CB edges of CdS enlarges the CB potential difference between
CdS QDs and LTO, enhancing transferred driven force of
interfacial electrons and improving two components separation
activity of photogenerated carriers.

Photo−electrochemical activity
Figure 8. Transient photocurrent responses (A) and Nyquist plots of EIS (B)
Transient photocurrent responses (J−t) and electrochemical for CdS QDs, LTO and CdS QDs/LTO (2:1) under simulated solar irradiation.
impedance spectra (EIS) are performed to investigate the
separation of photogenerated carriers (Figure 8). Photocurrent is
formed mainly by transferring photogenerated electrons to the
photogenerated electrons on it. Besides, no obvious attenuation
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Figure 9. PL spectra of CdS QDs, LTO and CdS QDs/LTO (2:1).
Conclusions
To improve the STH efficiency of LTO, CdS quantum dots
were using as photosensitizer and modulator of photogenerated
electrons and holes to enhance the utilization efficiency of solar
and reduce the recombination rate of carriers. Firstly, chemical
bath deposition method was used to decorate CdS QDs on 2D
LTO nanosheets for investigating the synergistic effects of CdS
QDs and LTO on the photocatalytic H2 production activity. Due
to the appropriate band alignment between CdS and LTO that
allows photoinduced interfacial charge transfer upon excitation
and promotes the separation efficiency of photogenerated
electrons and holes, CdS QDs/LTO heterojunction exhibits
obvious improvement on photocatalytic H2 production and
photoelectrochemical property. Besides, the quantum effect of
CdS QDs in CdS QDs/LTO heterojunction enhances transferred
driven force of interfacial electrons and improves two
components separation activity of photogenerated. This current
investigation provides new opportunities for the development of
a facile synthesis yet efficient heterojuction on the photoinduced
hydrogen evolution system.
Scheme 1. Illustration for the preparation of the CdS QDs /LTO
nanocomposites.
10.1002/cplu.201600351
Experimental Section
Materials
All chemical reagents were purchased from Sinopharm Chemical
Reagent Co., Ltd. and used without further purification.
Preparation
LTO nanosheets were prepared by a hydrothermal method, as
reported in our previous works[18]. CdS QDs were deposited on freshly
prepared LTO nanosheets by CBD method[44]. 50 mL of 10 mmol/L
Cd(NO3)2 ethanol solution and 50 mL of 10 mmol/L Na2S aqueous
solutions containing 50 % ethanol (v/v) were first prepared, respectively.
Then, 0.5 g LTO nanosheets were immersed in Cd(NO3)2 aqueous
solution and stirred for 60 min for sufficient adsorbing Cd2+ on the surface
of LTO nanosheets. Then Na2S solution was dropwise added into the
above solution under vigorous stirring. This sequence corresponds to
one CBD cycle, as shown in Scheme 1. A series of CdS QDs/LTO
nanocomposites with different molar ratios (1:1, 2:1, 3:1, and 4:1) were
synthesized in a similar route by adjusting CBD cycles. A pure CdS QDs
were also synthesized following the same procedure in the absence of
LTO.
Characterization
X-ray diffraction (XRD) patterns were recorded using an X-ray
diffractometer (XRD, X’Pert pro. PANalytical B.V) with Cu Ka irradiation.
Transmission electron microscopy (TEM) observations were collected on
a JEOL JEM-2100 TEM. UV-Vis diffuse reflectance spectra (DRS) were
obtained on a Perkin-Elmer Lambda 35 UV-Vis spectrophotometer. X-ray
photoelectron spectroscopy (XPS) was performed on a KRATOS
AXIS165 X-ray photoelectron spectrometer. The binding energies were
referenced to the C1s line at 285.0 from adventitious carbon.
Photoluminescence (PL) spectra were measured on the Jobin–Yvon
LabRAM HR800-Horiba spectrometer with an excitation wavelength of
325 nm.
Photocatalytic activity
The photocatalytic reaction was carried out in a quartz flask under a
500 W Xe lamp (100 mW cm-2, CHF-XM 500, Beijing Trusttech Co., Ltd.)
irradiation at room temperature. 150 mL aqueous solution containing
25 %(v/v) methanol and 0.1 g photocatalyst powders were added in a
quartz flask. 1.0 wt % Pt cocatalyst was deposition on a LTO surface by
in-situ photoreduction of H2PtCl6, as reported in our previous works[21].
Before the photocatalytic experiments, the reaction vessel was deaerated
by bubbling nitrogen into the solution for 15 min and ensure anaerobic
conditions. Throughout the experiment, 1 mL gas was sampled
intermittently and hydrogen content was analyzed using a gas
chromatography (DongXi GC-A5000, with high purity Ar carrier gas)
equipped with a thermal conductivity detector. The H2 production rates
are calculated by the mole of H2 gas per amount of photocatalyst and
time. The AQE is calculated according to the following equation:
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number of reacted electrons
AQE [%]   100
number of incident photons
number of evolved 　H 2 molecules 2
  100
number of incident photons
Photo-electrochemical measurement
The photo-electrochemical experiment of the samples
conducted using an electrochemical analyzer (Zennium, Zahner) with a
three-electrode system consisting of a working electrode, a platinum
plate as a counter electrode, an Ag/AgCl (saturated KCl) as the reference
electrode, and in 1 M Na2SO4 solution as electrolyte. The working
electrode was prepared by the drop-coating method. FTO conducting
glass (approximately 1.5 cm × 2 cm) was firstly ultrasonically cleaned for
30 min in a mixed solution of deionized water, acetone, and ethanol with
volume ratios of 1:1:1. 0.2 g sample was ground with 0.06 g polyethylene
glycol (PEG, molecular weight: 20000 Da) and 0.5 mL water to make a
slurry. The slurry was then subsequently coated onto FTO glass
o [23] C. Y. Zhai, M. S. Zhu, F. Z. Pang, D. Bin, C. Lu, M. Cynthia Goh, P. Yang,
electrode. The resulting electrodes were dried and calcined at 450 C for
30 min. The working electrode was irradiated with a 500 W Xe lamp (100
mW cm-2, CHF-XM 500, Beijing Trusttech Co., Ltd.) during the
measurement[45-47].
Acknowledgements
This work is supported by Applied Basic Research
Programs of Yunnan Science and Technology Department (NO.
201601YB00002) and the Program of Introducing Talents of
Kunming University (YJL16003).
Keywords: CdS QDs • 2D-La2Ti2O7 • quantum effect •
heterojunction• photocatalytic H2 production
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Entry for the Table of Contents

FULL PAPER
A heterojunction of perovskite-type
LTO and CdS QDs was designed
to enhance solar light driven H2
generation owing to the efficient
interfacial charge transfer.
Sujuan Hu, Mingshan Zhu*
Page No. – Page No.
Enhanced solar hydrogen
generation by a heterojunction of
perovskite-type La2Ti2O7 nanosheets
doped with CdS quantum dots