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 5 ( 2 0 2 0 ) 1 1 6 1 5 e1 1 6 2 4

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InP/TiO2 heterojunction for photoelectrochemical

water splitting under visible-light

Mang Niu a,*, Dapeng Cao b, Kunyan Sui a, Chunzhao Liu a,**
a
State Key Laboratory of Bio-fibers and Eco-textiles, Institute of Biochemical Engineering, College of Materials Science
and Engineering, Qingdao University, Qingdao 266071, PR China
b
State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029,
PR China

highlights graphical abstract

Thermal stable InP quantum dots

with ideal visible-light absorption
are designed.

The InP/TiO2 heterojunction has a
favorable type-II band aligment.

Energy barrier of hydrogen pro-
duction for InP/TiO2 hetero-
junction is 3.57 eV.

InP/TiO2 heterojunction is an
effective photocatalyst for water
splitting.

article info abstract

Article history: Hydrogen production through photoelectrochemical (PEC) water splitting on photocatalyst
Received 13 December 2019 is a green and clean method. In this study, we use density functional theory (DFT) calcu-
Received in revised form lations to find that the cage-like InP quantum dots (QDs) sensitized TiO2 is an effective
4 February 2020 photocatalyst for PEC water splitting under visible-light. A 16-ps first-principle molecular
Accepted 14 February 2020 dynamics (FPMD) simulation results indicate that the cage-like InP-12, InP-16, InP-20, InP-
Available online 11 March 2020 24, InP-28, and InP-36 QDs are stable at room temperature (300 K). Furthermore, the
calculated energy gaps of InP-16, InP-20, InP-24, InP-28, and InP-36 QDs are about 2.0 eV,
Keywords: which are suitable for visible-light absorption. Stable InP-20/TiO2 heterojunction structure
TiO2 was also obtained by FPMD simulation, and the electronic structure calculation result in-
Heterojunction dicates that the InP-20/TiO2 heterojunction has a favorable type-II band aligment, which
Hydrogen production could prevent the recombination of photoexcited carriers. Finally, the possible reaction
Density functional theory pathways of hydrogen production on InP-20/TiO2 heterojunction were investigated. It is
found that energy barrier of hydrogen production of the InP-20/TiO2 is 2.56 eV lower than

* Corresponding author.
** Corresponding author.
E-mail addresses: mang.niu@qdu.edu.cn (M. Niu), czliu@qdu.edu.cn (C. Liu).
https://doi.org/10.1016/j.ijhydene.2020.02.094
0360-3199/© 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
11616 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 5 ( 2 0 2 0 ) 1 1 6 1 5 e1 1 6 2 4
pure TiO2. Our calculations imply that InP QDs sensitized anatase TiO2 is an effective
photocatalyst for visible-light PEC water splitting.
© 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Introduction
Hydrogen energy is regarded as the most promising clean
energy for human society. Photoelectrochemical (PEC) water
splitting on photocatalyst shows great potential to produce
hydrogen by harvesting solar energy. Since the first report is
presented by Fujishima in electrochemical photolysis of water
at TiO2[1], TiO2 has been widely used in PEC water splitting for
its strong redoxability, low cost and environmental harmless
[2e6]. However, due to its wide band gap, TiO2 absorbs only
ultraviolet part of the solar spectrum. The PEC water splitting
reaction can not take place under visible-light.
To improving the visible-light photocatalytic performance
of TiO2, there are several methods have been developed. One
of an effective approach is small-band-gap semiconductor
sensitization. The small-band-gap semiconductors have sig-
nificant visible-light absorption properties, which used as the
photosensitizers in TiO2-based photocatalysts. The semi-
conductor/TiO2 heterojunctions present higher photocatalytic
performance compared with bare TiO2 photocatalysts[7e9].
For example, it has been reported that the III-V semiconductor
InP was assembled on nano-TiO2 substrate using a hydro-
thermal method[10,11]. The band gap of bulk InP is about
1.35 eV, which is narrow enough for visible-light absorption,
and thus the electrocatalytic reduction of CO2 for InP/TiO2
heterojunction increased to 1.53 times by introducing visible-
light irradiation[11]. Unfortunately, the InP/TiO2 nanotubes
(NTs) had no photocatalytic reduction activity for water, as a
result of the band gap of bulk InP do not match the reduction
potential of H2O [11]. In fact, an effective method to modulate
the band gap of bulk InP is nano-crystallization[12e14]. As a
result of the quantum size effect, the band gap of low-
dimensional InP is larger than that of bulk InP[15,16]. It is
noticed that one-dimensional InP quantum rods (QRs) and
zero-dimensional InP quantum dots (QDs) were synthesized
via hydrothermal method and colloidal chemistry method,
respectively, the photoactive InP-QR/TiO2 and InP-QD/TiO2
composites were also prepared [17,18]. However, the photo-
catalytic performance of InP-QR/TiO2 and InP-QD/TiO2 com-
posites have not been reported. Since exploring the new
semiconductor photosensitizers with desired visible-light
absorption properties would greatly promote the wide appli-
cation of TiO2-based photocatalyst[19e21]. Here, we propose
using zero-dimensional InP QDs as the photosensitizers for
TiO2 photocatalysts. On one hand, the band gap of InP QD
could be enlarged to 2.0 eV through the quantum size effect
[18,22]. Therefore, InP QD has higher redox potential than the
bulk InP, which is beneficial to photocatalytic reaction[18,23].
On the other hand, photocatalytic reaction often occurs at the
interface of semiconductor/TiO2 heterojunction, so zero-
dimensional InP QDs could provide more active site of
photocatalytic reaction than the bulk InP, and thus enhancing
the visible-light PEC water splitting activity of InP/TiO2
heterojunction.
Here, we design cage-like InP QDs/TiO2 heterojunction
photocatalyst for visible-light PEC water splitting by using
density functional theory (DFT) calculations. It is well known
that the electronic structure and the optical absorption
property of QD were modulated by its cluster size, in order to
get the InP QDs with ideal visible-light absorption, firstly we
constructed cage-like InP QDs structures with different cluster
size. The thermal stability of these InP QDs and InP-20/
TiO2(101) heterojunction were studied by the first-principle
molecular dynamics (FPMD) calculations. Then the elec-
tronic properties of these InP QDs and InP-20/TiO2(101) het-
erojunction were investigated by hybrid DFT calculation.
Finally, the PEC water splitting reaction pathways of InP-20/
TiO2(101) heterojunction were discussed. Our calculation re-
sults suggested that the InP QDs sensitization could be an
effective method to enhance the PEC water splitting perfor-
mance of TiO2 photocatalyst under visible-light.
Computational details
Our DFT calculations were carried out by using the Vienna ab
initio simulation package (VASP)[24,25]. The interaction be-
tween the ionic cores and the valence electrons was described
by projector augmented wave (PAW) approach[26,27]. The
Perdew-Burke-Ernzerhof (PBE)[28] functional based on the
generalized gradient approximation (GGA) was used to treat
the nonlocal exchange and correlation energies. The cutoff
energy of wave function was set to 500 eV and gamma k-point
[29] sampling of the Brillouin zone was used for all
calculations.
The calculation models of cage-like InP QDs were con-
structed by referencing the most stable structures of B12N12,
B16N16, B20N20, B24N24, B28N28, and B36N36 cages. To ensure the
decoupling of the neighboring QDs, the In12P12, In16P16, In20P20
and In24P24 QDs were placed in the center of a 20  20  20
A3
cubic vacuum cage, the In28P28, and In36P36 QDs were placed in
the center of a 25  25  25

A3 cubic vacuum cage, respectively.
The In12P12, In16P16, In20P20, In24P24, In28P28, and In36P36 QDs
were labelled as InP-12, InP-16, InP-20, InP-24, InP-28, and InP-
36, respectively. The optimized structures were used for the
thermal stability, the electronic structure, and the optical
property calculations.
The FPMD simulation were performed to examine the
thermal stability of cage-like InP QDs by using VASP code. The
constant-temperature and constant-volume (NVT) ensemble
was used for FPMD simulation[30]. The temperature was
controlled at 300 K and the total simulation time was set to 16
ps with a time step of 2 fs.
 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 5 ( 2 0 2 0 ) 1 1 6 1 5 e1 1 6 2 4
Becasue the standard PBE functional often underestimate
the band gap of III-V group compounds[31,32]. To give more
accurate results, the electronic and the optical properties of
cage-like InP QDs were calculated by using the Heyd-Scuseria-
Ernzerhof (HSE06) [33,34] functional hybrid with 30% Hartree-
Fock (HF) exchange.
For the soft-landing of InP-20 QD on TiO2 surface, the
anatase TiO2(101) periodic slab was used to simulate the TiO2
surface, which has a 2  4 supercell with two-layer TiO2
atoms. A 25

A vacuum region was added above TiO2(101) slabs.
During the FPMD simulation, the InP-20 QD was initially
placed 3

A above the TiO2(101) slab and only the top-layer TiO2
atoms were allowed to relax [30].
The possible reaction pathways of hydrogen generation on
InP-20/TiO2(101) heterojunction were calculated by the
climbing nudged elastic band (cNEB) method [35e37].
Results and discussion
Electronic structure of bulk InP
The optimized InP unit cell is shown in Fig. 1(a). As shown in
Fig. 1(a), the bulk InP has a zinc blende structure (space
group, F4  3m)[31]. A 2  2  2 InP supercell was used for
electronic structure calculation. The calculated band struc-
ture of bulk InP is displayed in Fig. 1(b). It is found that both
the conduction band minimum (CBM) and the valence band
maximum (VBM) of bulk InP are located at G point[32].
Therefore, the bulk InP is a direct band gap semiconductor.
The calculated band gap of bulk InP is 1.26 eV, which is
consistent with the experimental value (1.35 eV)[22].
Apparently, HSE06 functional hybrid with 30% HF exchange
reveals an accurate electronic structure of InP system.
Although the optical absorption of bulk InP reaches infrared
region due to its small band gap, the optical absorption of InP
QDs could be blue-shifted to visible-light region due to the
quantum size effect.
Fig. 1 e (a) The structure of bulk InP supercell. The dark and the light violet spheres represent In and P atoms, respectively;
(b) The energy band structure of bulk InP. The blue dashed line represents the Fermi leve. (For interpretation of the
references to color in this figure legend, the reader is referred to the Web version of this article.)
11617
Geometries of cage-like InP QDs
Both InP and BN are III-V group compounds, and thus their
QDs could have similar structures. The structures of cage-like
BN QDs (heterofullerenes) have been investigated systemati-
cally. Therefore, the cage-like InP-12, InP-16, InP-20, InP-24,
InP-28, and InP-36 QDs were constructed by referencing the
most stable structures of B12N12(Th) [38], B16N16(D2d) [39],
B20N20(C4h) [40], B24N24(S8) [41], B28N28(T) [42], and B36N36(Td)
[42] cages, respectively. The optimized structures of cage-like
InP-12, InP-16, InP-20, InP-24, InP-28, and InP-36 QDs are dis-
played in Fig. 2. It is shown that the InP-12 QD consists of four-
and six-membered rings and has Th symmetry. The InP-16 QD
has fully alternant structure with four-membered rings and
six-membered rings. It has D2d symmetry; InP-20 QD in C4h
symmetry has two eight-membered rings, eight four-
membered rings and twelve six-membered rings. The two-
isolated eight-membered rings are located at the ends of the
cage, and the eight four-membered rings alternatively around
the two eight-membered rings. The most stable InP-24 QD in
S8 symmetry has two eight-membered rings, eight four-
membered rings and sixteen six-membered rings. The most
favorable InP-28 and InP-36 QDs are composed of eight
equivalent triangular faces meeting at six four-membered
rings.
Although BN cages have identical geometries with corre-
sponding cage-like InP QDs, their electronic properties are
quite different. For example, the band gap of bulk h-BN is
4.7 eV [43]. As a result of quantum size effect, the energy gap of
BN cage is enlarged to 6.84 eV (B12N12)[44]. Therefore, BN cage
could not absorb visible-light.
Thermal stability of cage-like InP QDs
To examine the thermal stability of cage-like InP QDs, we
performed a 16-ps FPMD simulation with NVT ensemble for
these InP QDs. The temperatures and the free energies of
cage-like InP-12, InP-16, InP-20, InP-24, InP-28, and InP-36
11618 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 5 ( 2 0 2 0 ) 1 1 6 1 5 e1 1 6 2 4

Fig. 2 e The optimized structures of cage-like InP-12, InP-16, InP-20, InP-24, InP-28, and InP-36 QDs.

Fig. 3 e The structures of cage-like (a) InP-12, (b) InP-16, (c) InP-20, (d) InP-24, (e) InP-28, and (f)InP-36 QDs at different time
steps during FPMD simulation.

QDs during FPMD simulation were displayed in Fig. S1 and
Fig. S2, respectively (see in Supplementary material). The
temperature has been well controlled around 300 K, indi-
cating that the VASP is qualified for FPMD simulation.
Moreover, the convergent free energy of these cage-like InP
QDs indicate that these cage-like InP QDs are energetically
stable.
The structures of cage-like InP-12 QD at 8 ps, 12 ps and 16ps
during FPMD simulation were displayed in Fig. 3(a), and the
corresponding temperatures are 291 K, 302 K, and 271 K,
respectively. It is found that the cage-like InP-12 QD main-
tained the Th symmetry during FPMD simulation. Therefore,
the cage-like InP-12 QD is thermally stable at room tempera-
ture (300 K). The structure change of cage-like InP-16, InP-20,
 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 5 ( 2 0 2 0 ) 1 1 6 1 5 e1 1 6 2 4
InP-24, InP-28, and InP-36 QDs during FPMD simulation were
displayed in Fig. 3(b)e(f), respectively. It is found that the cage-
like InP-16, InP-20, and InP-24 QDs maintained their initial
symmetry during FPMD simulation. However, the structures
of cage-like InP-28 and InP-36 QDs have sunken In atoms, as
displayed in the blue ellipses in Fig. 3(e) and 3(f). The InP-36
cage has larger radius than InP-28 cage does, and InP-36
cage is close to sphere, thus the sunken In atoms has very
slight impact on the total energy U. On the contrary, the total
energy U of cage-like InP-28 QD is greatly affected by its
sunken In atoms. The calculation results show that these
cage-like InP QDs are thermally stable at room temperature
(300 K). The preparation of InP-12, InP-16, InP-20, InP-24, InP-
28, and InP-36 QDs have not been reported so far. Fortu-
nately, it is reported that the BN nanocage clusters (BnNn:
n ¼ 24e60) were synthesized by arc-melting method[43]. Both
BN and InP are III-V group semiconductor, we expected that
the cage-like InP-12, InP-16, InP-20, InP-24, InP-28, and InP-36
QDs could be experimentally synthesized through the same
method.
Electronic structures and optical properties of cage-like InP
QDs
The density of states (DOSs) of cage-like InP-16, InP-20, InP-24,
InP-28, and InP-36 QDs were calculated by HSE06 functionals
to investigate the electronic structures of these InP QDs, as
displayed in Fig. 4(a)-(f), respectively. For InP-12 QD, the en-
ergy gap between the highest occupied molecular orbital
(HOMO) and the lowest unoccupied molecular orbital (LUMO)
is about 1.0 eV. As a results, the optical absorption of InP-12
QD could cover the total infrared region. The calculated
HOMO-LUMO gap of InP-16, InP-20, InP-24, InP-28, and InP-36
Fig. 4 e The DOSs of cage-like (a) InP-12, (b) InP-16, (c) InP-20, (d) InP-24, (e) InP-28, and (f) InP-36 QDs. The black dashed lines
represent the Fermi level, and the HOMO and the LUMO of InP-12 QD are also illustrated.
11619
QDs is about 2.0 eV, which is ideal for visible-light absorption.
Furthermore, the redox potential of these InP QDs could be
higher than that of bulk InP as a result of the enlarged energy
gaps through the quantum size effect. The improved redox
potential is beneficial to photocatalytic reaction.
To investigate the optical absorption ability of InP QDs, we
calculated the imaginary part of the dielectric tensor ε2 ðuÞ.
Fig. 5(a)e(f) shows the HSE06 calculated ε2 ðuÞ curves of cage-
like InP-12, InP-16, InP-20, InP-24, InP-28, and InP-36 QDs,
respectively. For InP-12 QD, the optical absorption range is
200e1200 nm, this absorption range covers the visible and the
infrared region. It is found that the cage-like InP-16, InP-20,
InP-24, InP-28, and InP-36 QDs mainly absorb the visible
light (with a wavelength less than 600 nm) due to their proper
HOMO-LUMO gap of 2.0 eV. The calculated optical absorption
properties are in good agreement with the HOMO-LUMO gap
prediction.
Stable structure and electronic property of InP-20/TiO2(101)
heterojunction
Considering the computing power of FPMD simulation and the
optical absorption properties of InP QDs, we select InP-20 QD
as the photo-sensitizer for anatase TiO2. To get the stable
structure of InP-20/TiO2(101) heterojunction, we perform a 6.3
ps FPMD simulation with NVT ensemble. The temperatures
and the free energies of InP-20/TiO2(101) heterojunction dur-
ing FPMD simulation were displayed in Fig. S3(a) and Fig. S3(b),
respectively. The structures of InP-20/TiO2(101) hetero-
junction at 2 ps, 4 ps and 6.3 ps during FPMD simulation were
displayed in Fig. 6, and the corresponding temperatures are
280 K, 293 K, and 280 K, respectively. During FPMD simulation,
the overall cage structure of InP-20 QD exhibits little change,
11620 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 5 ( 2 0 2 0 ) 1 1 6 1 5 e1 1 6 2 4

Fig. 5 e The optical absorption properties of cage-like (a) InP-12, (b) InP-16, (c) InP-20, (d) InP-24, (e)InP-28, and (f) InP-36 QDs.

Fig. 6 e The structures of InP-20/TiO2(101) heterojunction at (a) 2 ps, (b) 4 ps, and (c) 6.3 ps during FPMD simulation.

indicating that the InP-20 QD is robust. Therefore, the cage-
like InP-20 QD is maintain its initial structure upon deposi-
tion to TiO2(101) surface. It is found that the InP-20/TiO2(101)
heterojunction is thermally stable at room temperature
(300 K).
The stable structure of InP-20/TiO2(101) heterojunction
was obtained by optimizing the FPMD simulation results via
DFT calculation. The optimized structure was then used for
electronic structure calculation. The HSE06 calculated DOSs
for InP-20/TiO2(101) heterojunction was displayed in Fig. 7(a).
It is indicated that the InP-20/TiO2(101) shows a favorable
type-II band alignment: since the HOMO-LUMO gap of InP-20
QD is about 2.0 eV, the electron can be excited from its
HOMO to its LUMO under visible-light. Meanwhile a hole is
yielded in HOMO. The energy states of LUMO in InP-20 QD is
higher than the energy states of conduction band (CB) in TiO2,
therefore, the photogenerated electron could be injected into
the CB of TiO2. Finally, photogenerated electron and hole stay
in the CB of TiO2 and in the HOMO of the InP-20 QD, respec-
tively. In fact, the hydrogen generation potential locates about
0.4 eV below the CBM and the water oxidation potential lo-
cates about 1.6 eV above the VBM of pure anatase TiO2.
Considering the broadening of HOMO in DOSs calculation, we
select the peak HOMO energy in Fig. 7(a) as the energy posi-
tion. It is found that the HOMO position of InP-20 QD is 1.37 eV
above the VBM of pure anatase TiO2, which matches the water
oxidation potential. As a result, the hydrogen generation and
water oxidation reactions can take place in TiO2 and InP-20
 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 5 ( 2 0 2 0 ) 1 1 6 1 5 e1 1 6 2 4 11621

Fig. 7 e (a) The HSE06 calculated DOSs of InP-20/TiO2(101) heterojunction. (b) The separation process of the photoexcited
carries in InP-20/TiO2(101) heterojunction.

QD, respectively [see in Fig. 7(b)]. Therefore, such type-II band
alignment in the InP-20/TiO2(101) is of great advantages for
the PEC water splitting reaction due to the effective separation
of photoexcited carries [7,45].
Reaction pathways of hydrogen generation on InP-20/
TiO2(101) heterojunction
In order to characterize the chemical reaction pathways of
water (H2O) splitting on InP-20/TiO2(101) heterojunction, we
have firstly calculated the possible adsorption structures of
H2O on InP-20/TiO2(101) heterojunction. The adsorption en-
ergy (Eads) is calculated by
Eads ¼ Eslab þ EH2O  EH2O=slab
where Eslab, EH2O, and EH2O/slab represent the total energy of the
InP-20/TiO2(101) heterojunction, the H2O molecule, and the
adsorbed H2OeInP-20/TiO2(101) system. The stable adsorption
has a positive Eads.
The optimized possible adsorption geometries of H2O
molecule on InP-20/TiO2(101) heterojunction were displayed
in Fig. 8. Generally, the H and O the atoms of H2O molecule
trend to combine with the In and P atoms of InP-20 QD,
respectively. As shown in Fig. 8(b), the O atom of H2O adsorbed
on five-coordinated Ti (Ti-5c) atom has a maximum adsorp-
tion energy of 0.78 eV. The adsorbed H2O is far away from InP-
20 QD, so the water splitting reaction in this geometry could be
similar with that in pure TiO2(101). As a result, we do not
discuss the chemical reaction pathways of water splitting in
Fig. 8(b). The global minimum structure of H2O adsorption on
InP-20/TiO2(101) heterojunction was displayed in Fig. 8(a),
with an adsorption energy of 0.59 eV. In this adsorption
configuration, the O atom in H2O bonds with P atom in InP-20
QD, and one of the H atom has an interaction with two-
coordinated (O-2c) atom of TiO2 slab. The H2O molecule was
(1)
adsorbed at the interface of InP-20/TiO2(101) heterojunction,
such adsorption structure could promote the H2O splitting.
The details for selecting the global minimum structures of the
first and the second H atom splitting of H2O are displayed in
Supplementary material (Figs. S4 and S5).
Based on the global minimum structures, we calculated the
chemical reaction pathways of hydrogen (H2) production on

Fig. 8 e The possible adsorption structures and the corresponding adsorption energies of H2O molecule on InP-20/TiO2(101)
heterojunction.
11622 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 5 ( 2 0 2 0 ) 1 1 6 1 5 e1 1 6 2 4
Fig. 9 e Chemical reaction pathways of hydrogen production on InP-20/TiO2 heterojunction. The energies barrier (eV),

and transition states (TSs) are also illustrated.
important bond length(A),
InP-20/TiO2 heterojunction, as shown in Fig. 9. The first, third,
and fifth structures represent the global minimum structures
of the adsorbed H2O molecule, the first splitted H atom and the
second splitted H atom on InP-20/TiO2 heterojunction,
respectively. The second and fourth structures represent the
transition states (TSs) between two global minimum struc-
tures. The relative energy of TSs is the energy barrier that need
to be surmounted from one global minimum structure to
another. Generally, the larger the energy barrier, the more
difficult the reaction. For the first H atom splitting of H2O, the
energy barrier 1.53 eV (TS-1) and the dissociated H atom
adsorbed on the O-2c atom of TiO2(101) surface. In the second
H atom splitting of H2O, the remaining H atom can approach
and bond with another nearest O-2c atom of TiO2(101) surface
(TS-2). The H2 generation need to surmount a energy barrier of
3.57 eV. Since the In atom of InP-20 QD could facilitate the
dissociation of the adsorbed H2O molecule, the first and the
second H atom splitting of H2O have relative low energy bar-
riers. The In atoms at the interface of InP-20/TiO2 hetero-
junction could be the active sites for water splitting reaction. It
is found that the splitted O atom and H2 molecule are adsor-
bed on InP-20 QD and TiO2(101) surface, respectively, which is
consistent with the electronic structure prediction. Further-
more, the distance between H2 and TiO2 slab was increased to
2.75
A, and thus H2 molecule can easily desorbs from the
TiO2(101) surface. As expected, the PEC water splitting reac-
tion occurs at the interface of InP-20/TiO2 heterojunction.
Therefore, zero-dimensional InP-20 QD could provide more
active sites than the bulk InP does. Globally, H2 generation on
InP-20/TiO2(101) heterojunction is endothermic by 1.77 eV,
and its H2 generation energy barrier is about 2.56 eV lower
than pure anatase TiO2 [3], indicating that InP-20 QD sensiti-
zation could significantly enhance the PEC water splitting
performance of TiO2 photocatalyst. Our calculation results
suggest that InP-20/TiO2(101) heterojunction is a promising
photocatalyst for hydrogen generation via visible-light PEC
water splitting reaction.
Conclusions
In this paper, we investigated the geometries, the thermal
stability, the electronic structures and the hydrogen generation
performance via PEC water splitting of cage-like InP QD sensi-
tized TiO2 photocatalyst by using first-principle calculations. It
is found that the structures of cage-like InP-12 (Th), InP-16 (D2d),
InP-20 (C4h), InP-24 (S8), InP-28 (T), and InP-36 (Td) QDs are
identical with the structures of corresponding BN cages. And
these cage-like InP QDs are stable at room temperature (300 K).
For InP-16, InP-20, InP-24, InP-28, and InP-36 QDs, the HOMO-
LUMO gap is enlarged to 2.0 eV through the quantum size ef-
fect, which could enhance the visible-light absorption and the
redox potential of these InP QDs. Then, we select InP-20 QD as
the photo-sensitizer for anatase TiO2. The cage-like InP-20 QD is
maintain its initial structure upon deposition to TiO2(101) sur-
face. Therefore, the InP-20/TiO2(101) heterojunction is ther-
mally stable at room temperature (300 K). The HSE06 calculated
DOSs for InP-20/TiO2(101) heterojunction shows a favorable
type-II band alignment, which is of great advantages for the
photocatalytic reaction due to the effective separation of
photoexcited carries. Finally, the calculated H2 generation en-
ergy barrier of InP-20/TiO2(101) heterojunction is about 2.56 eV
lower than that of pure TiO2, indicating InP-20 QD sensitization
could significantly enhance the H2 generation of TiO2 photo-
catalyst. Since the PEC water splitting reaction occurs at the
interface of InP-20/TiO2 heterojunction, zero-dimensional InP-
20 QD could provide more active sites than the bulk InP does.
Our first-principle calculations suggest that the InP QDs
 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 5 ( 2 0 2 0 ) 1 1 6 1 5 e1 1 6 2 4
sensitized TiO2 is a promising photocatalyst for hydrogen
generation through visible-light PEC water splitting reaction.
Acknowledgements
The authors acknowledge support from the National Natural
Science Fund of China (Grant No. 21603275) and the Key
Research and Development Project of Shandong Province
(2019GSF109079) for funding this research.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.ijhydene.2020.02.094.
references
[1] Fujishima A, Honda K. Electrochemical photolysis of water at
a semiconductor electrode. Nature 1972;238:37e8.
[2] Herna  ndez-Alonso MD, Fresno F, Sua  rez S, Coronado JM.
Development of alternative photocatalysts to TiO2:
challenges and opportunities. Energy Environ Sci
2009;2:1231e57.
[3] Niu M, Zhang J, Cao DI. N-codoping modification of TiO2 for
enhanced photoelectrochemical H2O splitting in visible-light
region. J Phys Chem C 2017;121:26202e8.
[4] Hao R, Wang G, Tang H, Sun L, Xu C, Han D. Template-free
preparation of macro/mesoporous g-C3N4/TiO2
heterojunction photocatalysts with enhanced visible light
photocatalytic activity. Appl Catal B Environ 2016;187:47e58.
[5] Xu D, Li L, He R, Qi L, Zhang L, Cheng B. Noble metal-free
RGO/TiO2 composite nanofiber with enhanced photocatalytic
H2-production performance. Appl Surf Sci 2018;434:620e5.
[6] He H, Lin J, Fu W, Wang X, Wang H, Zeng Q, Gu Q, Li Y, Yan C,
Tay BK, Xue C, Hu X, Pantelides S, Zhou W, Liu Z. MoS2/TiO2
edge-on heterostructure for efficient photocatalytic
hydrogen evolution. Adv Energy Mater 2016;6.
[7] Hu M, Xing Z, Cao Y, Li Z, Yan X, Xiu Z, Zhao T, Yang S,
Zhou W. Ti3þ self-doped mesoporous black TiO2/SiO2/g-C3N4
sheets heterojunctions as remarkable visible-lightdriven
photocatalysts. Appl Catal B Environ 2018;226:499e508.
[8] Niu M, Cheng D, Cao D. Understanding the mechanism of
photocatalysis enhancements in the graphene-like
semiconductor sheet/TiO2 composites. J Phys Chem C
2014;118:5954e60.
[9] Li K, Chai B, Peng T, Mao J, Zan L. Preparation of AgIn5S8/TiO2
heterojunction nanocomposite and its enhanced
photocatalytic H2 production property under visible light.
ACS Catal 2013;3:170e7.
[10] Liu S, Xu Y, Han X, Chai L. The competing growth and optical
performances of indium phosphide/titanium dioxide (InP/
TiO2) composites. Mater Res Express 2019;6:086217.
[11] Li P, Sui X, Xu J, Jing H, Wu C, Peng H, Lu J, Yin H. Worm-like
InP/TiO2 NTs heterojunction with unmatched energy band
photo-enhanced electrocatalytic reduction of CO2 to
methanol. Chem Eng J 2014;247:25e32.
[12] Alivisatos AP. Semiconductor clusters, nanocrystals, and
quantum dots. Science 1996;271:933e7.
[13] Alexandre SS, Chacham H, Nunes R. Structure and energetics
of boron nitride fullerenes: the role of stoichiometry. Phys
Rev B 2001;63:045402.
11623
[14] Petta JR, Johnson AC, Taylor JM, Laird EA, Yacoby A,
Lukin MD, Marcus CM, Hanson MP, Gossard AC. Coherent
manipulation of coupled electron spins in semiconductor
quantum dots. Science 2005;309:2180e4.
[15] Kroutvar M, Ducommun Y, Heiss D, Bichler M, Schuh D,
Abstreiter G, Finley JJ. Optically programmable electron spin
memory using semiconductor quantum dots. Nature
2004;432:81.
[16] Dai X, Zhang Z, Jin Y, Niu Y, Cao H, Liang X, Chen L, Wang J,
Peng X. Solution-processed, high-performance light-emitting
diodes based on quantum dots. Nature 2014;515:96.
[17] Nedeljkovic  JM, Micic
 OI, Ahrenkiel SP, Miedaner A, Nozik AJ.
Growth of InP nanostructures via reaction of indium droplets
with phosphide Ions: synthesis of InP quantum rods and
InPTiO2 composites. J Am Chem Soc 2004;126:2632e9.
[18] Zaban A, Mic ic
 O, Gregg B, Nozik A. Photosensitization of
nanoporous TiO2 electrodes with InP quantum dots.
Langmuir 1998;14:3153e6.
[19] Baker DR, Kamat PV. Photosensitization of TiO2 nanostructures
with CdS quantum dots: particulate versus tubular support
architectures. Adv Funct Mater 2009;19:805e11.
[20] Qin N, Liu Y, Wu W, Shen L, Chen X, Li Z, Wu L. One-
dimensional CdS/TiO2 nanofiber composites as efficient
lisible-light-driven photocatalysts for selective organic
transformation: synthesis, characterization, and
performance. Langmuir 2015;31:1203e9.
[21] Zhao F, Rong Y, Wan J, Hu Z, Peng Z, Wang B. MoS2 quantum
dots@ TiO2 nanotube composites with enhanced
photoexcited charge separation and high-efficiency visible-
light driven photocatalysis. Nanotechnology 2018;29:105403.
[22] Pavesi L, Piazza F, Rudra A, Carlin J, Ilegems M. Temperature
dependence of the InP band gap from A photoluminescence
study. Phys Rev B 1991;44:9052.
[23] Mic ic
 OI, Sprague J, Lu Z, Nozik AJ. Highly efficient band-edge
emission from InP quantum dots. Appl Phys Lett
1996;68:3150e2.
[24] Kresse G, Hafner J. Ab-initio molecular-dynamics simulation
of the liquid-metaleamorphous-semiconductor transition in
germanium. Phys Rev B 1994;49:14251e69.
[25] Kresse G, Furthmüller J. Efficient iterative schemes for ab-
initio total-energy calculations using a plane-wave basis set.
Phys Rev B 1996;54:11169e86.
[26] Blo€ chl PE. Projector augmented-wave method. Phys Rev B
1994;50:17953e79.
[27] Kresse G, Joubert D. From ultrasoft pseudopotentials to the
projector augmented-wave method. Phys Rev B
1999;59:1758e75.
[28] Hammer B, Hansen LB, Nørskov JK. Improved adsorption
energetics within density-functional theory using revised
perdew-burke-ernzerhof functionals. Phys Rev B
1999;59:7413e21.
[29] Monkhorst HJ, Pack JD. Special points for brillouin-zone
integrations. Phys Rev B 1976;13:5188e92.
[30] Li L, Gao Y, Li H, Zhao Y, Pei Y, Chen Z, Zeng XC. CO oxidation
on TiO2 (110) supported subnanometer gold clusters: size and
shape effects. J Am Chem Soc 2013;135:19336e46.
[31] Jiao ZY, Ma SH, Guo YL. Simulation of optical function for
phosphide crystals following the DFT band structure
calculations. Comput Theor Chem 2011;970:79e84.
[32] Wang Y, Yin H, Cao R, Zahid F, Zhu Y, Liu L, Wang J, Guo H.
Electronic structure of III-V zinc-blende semiconductors
from first principles. Phys Rev B 2013;87:235203.
[33] Heyd J, Scuseria GE, Ernzerhof M. Hybrid functionals based
on a screened coulomb potential. J Chem Phys
2003;118:8207e15.
[34] Paier J, Marsman M, Hummer K, Kresse G, Gerber IC,

Angy  n JG. Screened hybrid density functionals applied to
a
solids. J Chem Phys 2006;124:154709.
11624 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 5 ( 2 0 2 0 ) 1 1 6 1 5 e1 1 6 2 4
[35] Henkelman G, Uberuaga BP, Jo  nsson H. A climbing image
nudged elastic band method for finding saddle points and
minimum energy paths. J Chem Phys 2000;113:9901e4.
[36] Henkelman G, Jo  nsson H. Improved tangent estimate in the
nudged elastic band method for finding minimum energy
paths and saddle points. J Chem Phys 2000;113:9978e85.
[37] Sheppard D, Terrell R, Henkelman G. Optimization methods
for finding minimum energy paths. J Chem Phys
2008;128:134106.
[38] Matxain JM, Eriksson LA, Mercero JM, Lopez X, Piris M,
Ugalde JM, Poater J, Matito E, Sola M. New solids based on
B12N12 fullerenes. J Phys Chem C 2007;111:13354e60.
[39] Strout DL. Fullerene-like cages versus alternant cages:
isomer stability of B13N13, B14N14, and B16N16. Chem Phys Lett
2004;383:95e8.
[40] Cui XY, Wu HS. Structure and stability of B20N20 cluster. Chin
J Chem 2005;23:117e20.
[41] Oku T, Nishiwaki A, Narita I, Gonda M. Formation and
structure of B24N24 clusters. Chem Phys Lett 2003;380:620e3.
[42] Oku T, Nishiwaki A, Narita I. Formation and atomic
structures of BnNn (n¼ 24e60) clusters studied by mass
spectrometry, high-resolution electron microscopy and
molecular orbital calculations. Phys B Condens Matter
2004;351:184e90.
[43] Giovannetti G, Khomyakov PA, Brocks G, Kelly PJ, Van Den
Brink J. Substrate-induced band gap in graphene on
hexagonal boron nitride: ab initio density functional
calculations. Phys Rev B 2007;76:073103.
[44] Soltani A, Baei MT, Mirarab M, Sheikhi M, Lemeski ET. The
electronic and structural properties of BN and BP nano-cages
interacting with OCN: a DFT study. J Phys Chem Solid
2014;75:1099e105.
[45] Rawool SA, Pai MR, Banerjee AM, Arya A, Ningthoujam R,
Tewari R, Rao R, Chalke B, Ayyub P, Tripathi A. Pn
heterojunctions in NiO: TiO2 composites with type-II band
Alignment assisting sunlight driven photocatalytic H2
generation. Appl Catal B Environ 2018;221:443e58.