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 2 ( 2 0 1 7 ) 9 4 6 7 e9 4 8 1

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Review Article

Quantum dots as enhancer in photocatalytic

hydrogen evolution: A review

Debasmita Kandi, Satyabadi Martha**, K.M. Parida*

Centre for Nano Science and Nano Technology, Institute of Technical Education and Research, Siksha ‘O’
Anusandhan University, Bhubaneswar, 751030, India

article info abstract

Article history: Advanced energy conversion processes like photochemical and photoelectrochemical
Received 11 November 2016 water splitting now a day plays a very important role in challenging the present energy
Received in revised form crisis of our world. The successful utilization of this process depends on development of
13 February 2017 highly efficient, more stable, low cost and outstanding environmental benign semi-
Accepted 23 February 2017 conductor materials. From recent advancements, it is revealed that quantum dots (QDs)
Available online 20 March 2017 are very outstanding and promising material for the mentioned processes due to their
favorable physical and chemical characteristics like high absorption co-efficient, quantum
Keywords: confinement effect, thermal, chemical, mechanical and optical stability, high conductivity
Quantum dots and recyclability. In this review article, we have clearly explained the importance of QDs in
Enhancer water splitting along with the general mechanism involved in the process. Following that
Hydrogen the enhancement of different materials like metal oxides, layered double hydroxides (LDH),
Visible light carbonaceous materials (g-C3N4, benzene and benzene like materials) by QDs have dis-
cussed in the field of water splitting.
© 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Contents

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9468
Importance of QDs for photocatalytic water splitting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9468
Enhancement of photocatalytic activity of different semiconductors by QDs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9469
Enhancement in hydrogen generation of metal oxides by QDs modification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9470
Enhancement in hydrogen generation of LDHs by QDs modification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9474
Enhancement in hydrogen generation of g- C3N4 by QDs modification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9474
Enhancement in catalytic activity of graphene and graphene like materials by QDs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9476
Summary and outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9476
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9477

* Corresponding author. Fax: þ91 674 2350642.

** Corresponding author. Fax: þ91 674 2350642.
E-mail addresses: martha.satyabadi@gmail.com (S. Martha), kulamaniparida@soauniversity.ac.in, paridakulamani@yahoo.com
(K.M. Parida).
http://dx.doi.org/10.1016/j.ijhydene.2017.02.166
0360-3199/© 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
9468 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 2 ( 2 0 1 7 ) 9 4 6 7 e9 4 8 1
Introduction
Nanoscience has become one of the most intensely studied
areas of research over the last few decades. In the last three
decades quantum dots as a very effective nanomaterial have
drawn much attention in the field of various research and
development like electrocatalysis, LEDs, solid state lighting,
displays, Infrared photodetectors, photovoltaics, transistors,
quantum computing, medical imaging, biosensors and many
others [1e6]. QDs have also been established as a very efficient
material (enhancer) in the field of photocatalytic water
splitting.
QDs are zero dimensional semiconductor nano crystals or
nano crystallites usually composed of group IIeVI, IIIeV or
IVeVI elements and are defined as particles with physical
dimension smaller than the exciton Bohr radius or de-Broglie's
wavelength. But now-a-days QDs of elements like carbon [7],
silicon [8], bismuth [9] and noble metal [10] are established.
Small QDs such as colloidal semiconductor nano crystals can
be as small as 1e10 nm which contains 10e50 atoms in
diameter and 100e100,000 atoms within the quantum dot
volume [11]. Quantum dot is considered to be zero dimen-
sional and named as dot because the motion of electrons,
holes and excitons is restricted in all 3 dimensions. As a result
of which a quasi-zero dimensional system is formed. The
word ‘quantum’ is included in its name because one property
of it is analogous to quantum mechanical particle in a box in
which the energy is inversely related to the size of the box. In
the same manner, the band gap energy of semiconductor
nanocrystal (QD) increases as the particle size decreases. In
other words the electron and hole energy states within the
nanocrystals are discrete and band gap is a function of QD
diameter. QDs are also known as “artificial atoms” because it
shows the real atom behavior i.e. the electrons are confined to
quantized states with discrete energies. Because of quanti-
zation there is enhancement of band gap as compared to bulk
semiconductors. The difference between atom and QD is that
QDs consists of hundreds or thousands of atoms having
different shape, size and energy.
Various reviews have been reported on synthesis methods,
characterization, surface chemistry, nature of capping agents
and optoelectronic properties of QDs [12e15]. Therefore; we
limit our domain to depth discussion on modification of
certain semiconductor materials by QDs and cover one very
crucial photocatalytic application i.e. water splitting. This re-
view has evidently clarified the importance of QDs in photo-
catalytic water splitting on the basis of Gerischer theory [16].
In the next section, the role of QDs for the improvement in
catalytic activity of different semiconductors and carbona-
ceous materials has been discussed. The semiconductor ma-
terials included here are metal oxides, layered double
hydroxides, and the carbonaceous materials are g-C3N4, ben-
zene and benzene like materials. We have focused on the
recent developments in the utilization of QDs as sensitizer
and the mechanism of water splitting associated with above
mentioned materials. For the first time, our review represents
a different angle of QDs which is brand spanking new and it is
expected that this review will try to make up the deficiency of
current energy status. Desirably, new perspectives towards
research and developments of QDs will be accessible in a
productive manner with the help of this review article.
Many semiconductor photocatalysts have been developed
for photocatalytic as well as photoelectrochemial water
splitting but among them the role of quantum dot is very
idiosyncratic. Hence the benevolent use and importance of
quantum dots in water splitting is described in the following
section of our review.
Importance of QDs for photocatalytic water
splitting
There are many efforts devoted in the last decades for utiliz-
ing quantum dots in photocatalysis. Ultra small sized quan-
tum dots are widely delved as sensitizer because of their high
extinction coefficients, quantum confinement effect and large
intrinsic dipole moments. The beneficial effects of QDs in
water splitting are shown pictorially in Fig. 1(a). In the field of
photocatalytic water splitting the former two properties plays
very vital role. In comparison to other semiconductors, QDs
have high value of extinction coefficients in visible region of
solar spectrum i.e. maximum probability of minimizing the
recombination of charge carriers and reinforcement of charge
injection processes. It can be explained as bulk semiconductor
materials show weak interaction with photons while very
small amount of QDs have more capacity to interact with
photons resulting maximum flux of photons. This is because
QDs can emit up to 3 electrons per photon of solar radiation
whereas it is only one electron in case of semiconductor bulk
materials. This multiple exciton generation property is only
possible due to quantum confinement effect of QDs and is
noticed only when the particle size is very small enough with
widening of band gap and the energy level spacing is more
than kT where the symbols carry their usual meaning, k is
Boltzmann's constant and T is temperature. According to
Gerischer theory [16], band gap of the QDs decreases with
increasing size which opens up the path to cover the entire
solar spectrum. Additionally, in case of large band semi-
conductor materials the transfer of electrons from CB of QDs
to that of semiconductor can be made thermodynamically
favorable and is shown in Fig. 1(b). This is because the CB edge
position can be moved towards more negative potential and
VB edge position towards more positive potential with
decreasing the particle size or increasing the band gap (Fig. 2).
As a consequence the free energy change required for
migration of electron from QD to semiconductor decreases
and the thermodynamic driving force increases which in-
creases the interfacial charge transfer. Homles et al. [17] has
proved this charge transfer with CdSe QDs by plotting a graph
between normalized photocatalytic proton reduction rates
with respect to band gap on logarithm scale results a loga-
rithm dependence relationship between these two parame-
ters. This relation is also supported by Gerischer theory but at
illuminated semiconductoreelectrolyte surface. As per this
theory
" #
ðDG  lÞ2
kRed a exp
4kTl
 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 2 ( 2 0 1 7 ) 9 4 6 7 e9 4 8 1 9469

Fig. 1 e Schematic presentation of (a) the beneficial effects of QDs sensitized photocatalysts for water splitting and (b) QD
sensitized photocatalysis.

Fig. 2 e Quantum size effect in nanocrystal [17].

Where, DG is the difference between the CB edge potential and
the proton reduction potential.
DG ¼  e (ECB E0 Red), E0 Red ¼ constant at a certain pH
In addition to this, EG a ECB
Thus kRed a exp (EG)
So it can be concluded that with the gradual increase of
band gap there is shifting of the conduction band edge posi-
tion more towards negative reduction potential and increase
of thermodynamic driving force which shows faster rate of
reduction reaction. That means small QDs can rapidly transfer
electrons in comparison to other semiconductors.
Summarily thanks to quantum confinement effect i.e. the
optical properties are size dependent provided the particle
size is smaller than exciton Bohr radius. These effects will
likely be used more often in advanced solar water splitting
devices. These advantages furnished due to high exciton co-
efficient and quantum confinement effect of QDs for har-
vesting visible light radiations and exploiting the charge
carriers makes them a most promising and eco-friendly
candidate for splitting of water in the visible region.
Utilizing these great advantages of QDs as sensitizer many
research groups have improved the catalytic activities of
semiconducting as well as conducting materials in the field of
photochemical and photo electrochemical water splitting
which is discussed in the following section.
Enhancement of photocatalytic activity of
different semiconductors by QDs
In the first step of photocatalysis, absorption of photon by the
catalysts excite electrons, hence it is necessary to improve
their solar photon absorption capacity. For this purpose, re-
searchers have reported various classes of semiconductor
materials, among them metal oxides, layered double hy-
droxides and g-C3N4 show better results for water splitting.
But their wider band gap, poor carrier mobility, poor light
absorption performance of the developed materials limits the
photocatalyic activity in the visible solar spectrum. Thus it is
very vital to develop narrow band gap catalysts that can cover
visible spectrum of sunlight. Various techniques like doping of
metal cation and anion, formation of solid solution, making
composite, developing mesoporous materials etc. have been
developed to enhance the catalytic activity of such photo-
catalytic materials. But in recent years QDs have drawn much
attention as an efficient sensitizer in the successful splitting of
9470 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 2 ( 2 0 1 7 ) 9 4 6 7 e9 4 8 1
water. In order to amplify the quantum efficiency of various
semiconductors, research community is now utilizing QDs
vigorously as enhancer. In our review we are trying to cover
the improvement of catalytic activity of some semiconductors
such as metal oxides, LDHs, g-C3N4 by compositing with QDs.
In addition to these semiconductors, we also include a good
conductor i.e. graphene. It is diagrammatically presented in
Fig. 3 and for convenience of readers, Table 1 contains list of
various QDs with their method of preparation, quantum yield
and application.
Enhancement in hydrogen generation of metal oxides by
QDs modification
Generally metal oxides (MO) nanomaterials are used in pho-
tocatalytic and PEC hydrogen generation which show splendid
mechanical flexibility, high specific area and chemical stabil-
ity. One of the major shortcomings of most MOs absorb in UV
region and very few in visible region. Hence in order to make
them as good photocatalysts for splitting of water under
visible radiation, band gap modulation is very necessary.
Generally the lowest unoccupied molecular orbital of metal
cations make the conduction bands of oxide semiconductors
and O 2p orbitals make the valence band. Thus in order to
make narrow band gap in metal oxide based system a new
valence band or an electron donor level (DL) of elements
excluding O 2p orbitals must be created as conduction band
level never be lowered [18]. To make it visible light active
several attempts have been taken; doping of metal [19e23],
doping of non-metal [24e39], co-doping of metal and
nonmetal [40e42], combining the large gap semiconductor
with low band gap material [43], single phase material [44,45],
and quantum dots sensitization [46,51e59].
It has been seen that there is significant enhancement of
photocatalyic activity of metal oxides after sensitized with
Fig. 3 e Schematic illustration of QDs and QDs modified
materials.
QD. Lian et al. [46] have developed a unique structure i.e.
plasmonic silver quantum dots with size of 1.3e21.0 nm
coupled with hierarchical TiO2 nanotube arrays (H-TiO2-
NTAs) photoelectrodes. The photo conversion efficiency has
been increased significantly and the H2 evolution rate is found
to be approximately 124.5 mmol cm2 h1 and shows photo-
current density of 0.104 mA/cm2 at a potential of 0.7 V versus
saturated calomel electrode (SCE). Under visible light irradia-
tion, the excited hot electrons from Ag QDs (sensitizer) are
transferred to the CB of H-TiO2-NTA surmounting the
Schottky barrier. In the meantime, it is expected that excited
electrons move along the wall of TiO2 nano tube arrays, which
furnish the fast transfer paths. In addition, the fast transfer of
electrons has been achieved by the ultra-small sized Ag QDs.
The external bias voltage motivates the electrons to go from
photoanode to cathode and produce H2 on the surface of
platinum foil (cathode) meanwhile the holes are utilized in
various oxidation reactions like the conversion of ethylene
glycol to glyoxal, oxalic acid or other additional products. With
some modifications Lee group [47] have designed and syn-
thesized a photocatalysts by coating a thin layer of amor-
phous TiO2 (a- TiO2) on CdSe NC QDs (2.5 nm) for hydrogen
evolution from water and 436 mmol/g$h amount of hydrogen
have been liberated. This coreeshell hetero structure facili-
tates the migration of electron from the conduction band of
CdSe core to the CB of a-TiO2 whereas the holes are localized
to the valence band of CdSe NCs. The migrated electrons are
utilized in the reduction of water to produce hydrogen. It is
examined that high potential level of CB of smaller QDs fa-
cilitates rate of electron transfer and consequently speed up
the photoreduction of water. Hensel et al. [48] have observed
that CdSe QD sensitized N-doped TiO2 nanostructures shows
greater photo response in comparision to N-doped TiO2 (TiO2:
N) or CdSe QD sensitized TiO2. QD sensitized TiO2 shows
photocurrent density of 2.75 mA/cm2 which is higher than
pristine TiO2 or TiO2: N. The reason behind the enhancement
is due to intense absorption of visible light by small sized CdSe
QDs (average diameter of 2.6 nm). The mechanism can be
understood by the following model shown in Fig. 4. It is pro-
posed on the basis of electronic states of various constituents
of the nanocomposite. Since the conduction band of bulk CdSe
is more negative i.e. 0.8 eV versus normal hydrogen elec-
trode NHE [49] than that of the TiO2 i.e. at 0.5 eV versus NHE
[50] so electrons are transferred efficiently from CB of CdSe QD
to that of TiO2. The CB of CdSe QD position can be made more
negative by decreasing the size of particle which is according
to quantum confinement effect [51,52]. As shown in Fig. 4
electrons are jumped from VB of CdSe QDs to some interme-
diate steps i.e. V0 of TiO2. As a result the charge separation and
photocurrent efficiency is increased tremendously due to
longer lifespan of electrons and holes [53,54].
Wang et al. [55] have fabricated CdS and CdSe QD co-
sensitized ZnO nanowire arrayed photoanode. This nano-
structure shows high IPCE of ~45% at 0 V vs. Ag/AgCl as it
exhibits strong absorption sensitized photoanodes (CdS-ZnO-
ZnO-CdS and CdSe-ZnO-ZnO-CdSe). This is due to the suitable
band alignment of the QDs and the ZnO NWs which facilitates
efficiently the migration of photoinduced electrons from the
QDs to the NWs. The Fermi levels of CdS, CdSe QDs and ZnO
NW are aligned and conduction band positions of the QDs are
Table 1 e List of various QDs with their method of preparation, quantum yield and application.
Sl.no QD Method Light source/reaction solution H2 evolution References
a
1 Ag QD/H- TiO2-NTAs composites electrochemical anodic oxidation 300 W Xe lamp, l > 420 nm/2 M 124.5 m mol cm2 h1 [46]
and electrodeposition method ethylene glycol and 0.5 M Na2SO4
solution
2 CdSe QD/a- TiO2 Ligand exchange and reflux 300 W Xe lamp, l > 420 nm/0.25 M 436 mmol/g$h [47]
method of Na2S and 0.35 M of Na2SO3
a
3 CdSe QD sensitized N-doped TiO2 CBD and hydrothermal method 1000 W Xe arc lamp/0.25 M Na2S photocurrent density: 2.75 mA/cm2 [48]

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 2 ( 2 0 1 7 ) 9 4 6 7 e9 4 8 1
and 0.35 M Na2SO3 solution
a
4 CdS and CdSe QD co-sensitized ZnO nanowire Hydrothermal and CBD method 1000 W Xe arc lamp/0.25 M Na2S Photocurrent density of ~12 mA/cm2 at [55]
and 0.35 M Na2SO3 solution 0.4 V vs Ag/AgCl.
IPCE: 45%
a
5 CdSe QD-sensitized Au/TiO2 nanocomposite emulsion-based bottom-up self- 1000 W Xe arc lamp/0.2 mol/L Na2S 0.8 mA/cm2 [56]
assembly (EBS) method and CBD and 0.3 mol/L Na2SO3 IPCE: 50%
method
6 Pt-(CdS QD/TiO2) film Doctor blade and CBD method 150 W Xe lamp 5.407 mmol cm2 h1 [57]
a
7 CdSe/H- TiO2 e Sunlight illumination Photocurrent density: 16.2 mA/cm2 [59]
100 mW cm2/0.24 M Na2S and
0.35 M Na2SO3
8 CdS QD-g-C3N4 composite Chemical impregnation method 300 W Xe arc lamp (l >400 nm)/25% 17.27 mmol h1 [88]
methanol solution
9 CdS/g-C3N4 composites Solvothermal method 300-W xenon lamp (l > 420 nm)/ 4.494 mmol h1 g1 [89]
0.1 M L-ascorbic acid
a
10 Si quantum dots/TiO2 Nanotube Arrays Chemical etching 500 W Xenon lamp/0.5 M Na2SO4 Photoconversion efficiency 1.6 times than [114]
Composite Electrodes pristine TiO2
11 ZnS/CdSe/CdS QDs SILAR and CBD method Solar radiation of 75 mW cm2/ 3.2 mmol min1 [115]
0.25 mol L1 Na2S and 0.125 mol L1
Na2SO3
12 ZnO/CdS heterostructures magnetically cilia film Hydrothermal method 300 W xenon lamp/0.1 M Na2S and 2.7 times than individual components [116]
0.1 M Na2SO3
13 QDs-Cu2S/BiOBr Precipitation method 300 W Xe lamp (l <400 nm)/0.1 M 717 mmol/g [117]
Na2S and 0.5 M Na2SO3
14 InN/InGaN QDs Plasma-assisted molecular beam 1000 W Xenon arc lamp/3 M H2SO4 133 mmol h1 cm2 [118]
epitaxy at 460  C with 0.5 M Na2SO4 salt
15 CdS QD/Cd2SnO4 Solution combustion method 1 sun illumination/0.24 M Na2S and 20 mmol h1 cm2, [119]
0.35 M Na2SO3.
a
16 Graphene QD @ ZnO nanowires (GQDs@ZnO Chemical oxidation and 150 W Xe lamp (100 mW cm2)/ 0.34 mA/cm2 IPCE:0.42% [120]
NWs) hydrothermal method 0.5 M Na2SO4
17 (i) CuInS2 QD Solvothermal synthesis Visible light l > 400 nm/Na2S 3610 mmol h1, [121]
(ii) TiO2/CuInS2 QDs/CdS (0.35 M)/Na2SO3 (0.25 M) (i)Quantum efficiency (QE): 4.74%.
(ii)QE: 41%
18 g-C3N4 quantum dots Thermal-chemical etching process visible light irradiation 137.84 mmol h1 [122]
(l > 420 nm)/triethanolamine
a
19 CdS/Cu2S co-sensitized TiO2 branched nanorod SILAR method 300 W Xe lamp (100 mW cm2) 13.65 mA [123]
arrays 0.35 M Na2S and 0.25 M Na2SO3

9471
(continued on next page)
 9472
Table 1 e (continued )
Sl.no QD Method Light source/reaction solution H2 evolution References
20 ZnO QD Solegel method Xe lamp/0.35 M Na2S and 0.25 M 260 mmol h1 g1, [124]
Na2SO3
21 CdS QDs decorated screw-likeSnO2 SILAR method 500 W Xe lamp/0.25 M Na2S and 159.6 mmol (h cm2)1 [125]
nanostructures 0.35 M Na2SO3
22 Ultra-thin TiO2 nanosheets decorated Pd QD e formaldehyde solution 250 mL g1 min1 [126]
23 CdSe QDs/zirconium titanium phosphate (ZTP) Solvothermal method visible light irradiation 905.4 mmol in 3 h [127]
(l  420 nm), 20 mL of 0.02 M Na2S,
24 CdS QDs/ZnO nanorod SILAR method Xe lamp (100 mW cm2), 1 M Na2S 490 mmol h1, photocurrent density: [128]

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 2 ( 2 0 1 7 ) 9 4 6 7 e9 4 8 1
6.51 mA/cm2
25 CdS QDs/Au nanoparticles Self-assembly method 500 W Xe lamp (l  420 nm), Na2S 550 mmol in 10 h [129]
0.1 M,
Na2SO3 0.1 M
26 Graphene QDs/TiO2 nanotube array Impregnation method 300 W Xe lamp, 1 M Na2S and 0.1 M 18.5 mmol h1 [130]
Na2SO3
27 Au@CdS coreeshell nanostructure Self-assembly method 0.1 M Na2SO3 and 0.1 M Na2S, 201.9 mmol h1g1 [131]
visible light (l  420 nm)
a
28 CdSe QDs/a-Fe2O3 Spray pyrolysis. 150 W Xenon lamp, 1 M NaOH Photocurrent density of 550 mA cm2 [132]
29 CoSx QDs/TiO2 Precipitationedeposition method Ethanol, 300 W Xe lamp, 0.5 M 838.9 mmol h1 g1 [133]
Na2SO4
30 CdSeeZnS QDs/Au-Pt alloy Surface linkage method 300-W Xe lamp, Na2S (0.5 M) and 190 mmol in 2 h [134]
Na2SO3 (0.5 M)
a
31 ZnO QDs/a-Fe2O3 Electrodeposition method 150 W Xe arc lamp, 1 M NaOH 6 mL h1 cm2 at 0.75 V/SCE.2.84 mA/cm2 [135]
at 0.75 V/SCE
32 CdS/H-3D-TiO2/Pt-wire Hydrothermal and CBD method Visible light:100 mWcm2 0.5 M 18.42 mmol cm2 h1, 8.77 mA/cm2, [136]
Na2Se0.5 M Na2SO3
33 CdS and CdTeS QDs Hydrothermal technique Visible light, ascorbic acid and 9.3, 8 mmol g1 h1 [137]
CoCl2$6H2O
a
34 WO3/Ag/CdS NRs Hydrothermal method 1 M H2SO4 1.38 mA/cm2 at 0.6 V vs Ag/AgCl [138]

As compared to bulk semiconductors, the efficiency of QDs is much better in the field of photocatalytic water splitting. The reason of high efficiency of QDs as compared to bulk semiconductors have
already been explained briefly in Section Importance of QDs for photocatalytic water splitting with special emphasis on quantum confinement effect. For comparison the efficiency of bulk semi-
conductor and the respective QDs are given in Table 2.
a
Tested for photoelectrochemical hydrogen production.
 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 2 ( 2 0 1 7 ) 9 4 6 7 e9 4 8 1 9473

[140,141]
[142,143]

[144,145]

[146,147]
[148,149]

[151,152]
[153,135]
[139,89]
Ref.

[150]
312.75 mmol h1 g1

99,823 mmol h1 g1

4.494 mmol h1 g1

(b) 67.7 m mol

3.98 mA/cm2
7.06 mA/cm2

2.84 mA/cm2
(a) 691 m mol
QDs

18 mA/mm2

15 mA/cm2
Photocatalytic activity
Bulk semiconductor

49.80 mmol g1 h1

71.6 mmol h1 g1

4152 mmol h1 g1

1.462 mA/cm2

(b) 15.9 m mol

3.58 mA/cm2

(a) 149 m mol

0.6 mA/cm2

1.5 mA/cm2
5.6 mA/cm2

visible light irradiation, 0.02 M Na2S

Solar light, glycerol-water solution

AM 1.5 illumination, 0.5 M Na2S

Fig. 4 e Proposed models for electron transfer at CdSe/TiO2

70 mW, 520 nm light-emitting

interface in a CdSe-TiO2: N sample [Reproduced from Ref.

Table 2 e Comparison study of photocatalytic activity of bulk semiconductor and QDs towards water splitting.

150 W Xe lamp, 1 M NaOH

[48]].
QDs

and 0.025 M NaSO3

closely present, as a result the photoexcited electrons formed

Light source/reaction solution

500 W Hg lamp
300 W Xe lamp

300 W Xe lamp
300 W Xe lamp

in CdSe is transported to the ZnO NWs through the CdS in-

diode (10 h)

termediate layer. At ZnO NWs the electrons are passed to the

cathode where hydrogen is produced in PEC device and the
holes left behind are consumed at anode-electrolyte interface
for oxidation process. The IPCE value is greatly increased
400 W Hg lamp, 10 vol % methanol
Visible light (l > 400 nm), 0.1 M of
solar illumination (100 mW cm2)

simply due to the electron transfer from CdSe QDs to ZnO NW

(l  420 nm), 10 vol. % lactic acid
70 mW, 520 nm light-emitting

which is favored by the band alignment between CdS and

(100 mW cm2), 0.1 M Na2SO4
Bulk semiconductor

500 W Xe lamp, 0.5 M Na2S

CdSe. Liu and coworkers have reported an average enhance-

150 W Xe lamp, 1 M NaOH

ment of photo electrochemical performance of 50% by syn-

visible-light irradiation
AM 1.5 illumination

thesizing CdSe QD-sensitized Au/TiO2 nanocomposite for PEC

Na2S and Na2SO3.

applications. Due to light scattering by Au NPs (6 nm), the light

absorption of CdSe QDs is increased which contributes sub-
Visible light

diode (10 h)
l  420 nm

stantial improvement of PEC performance [56]. Similar type of

work has done by Hong et al. [57]. They have designed Pt-(CdS/
TiO2) film by doctor blade method followed by chemical bath
deposition (CBD) method. CdS contents and size of it (5e7 nm)
CdS and CdSe QDs/ZnO NRs

in the nanocomposite efficiently control the rate of evolution

MoS2 QDs/CdS Core/Shell

of hydrogen. Higher the content of CdS higher is the electron

loss and henceforth the reduction of hydrogen production. It
CdS QDs/TiO2 NTAs

PbS QDs/ZnO NW
CdS QDs-Au-TiO2

ZnO QDs/a-Fe2O3
(b)CdSe/CdS QDs

is because the electrons inside the photocatalyst may get

QDs
CdS QDs/g-C3N4

CuO QDs/TiO2

dissipated and the CdS QDs are coagulated with each other in
(a) CdSe QDs

spite of depositing on TiO2. The hydrogen evolution has found

to attain a maximum value of 5.407 mmol cm2 h1 in Pt-(CdS/
Catalyst

TiO2) film-typed photocatalysts having saturated value of Cd/

Ti ratio of 0.197. The IPCE value has been further increased by
Bulk semiconductor

Fan et al. [58] and chemical bath deposition technique was

MoS2/CdS Nanosheet

(b) CdSe/CdS DIRs

used to fabricate a highly efficient TiO2 photoelectrode by

CdS/TiO2 NTAs

growing seeds (4.2 nm CdSe QDs) on TiO2 thin film. After that
ZnO/CdS NWs
PbS/ZnO NW
TiO2-Au-CdS

(a) CdSe QRs

ZnO/a-Fe2O3
CdS/g-C3N4

the film was covered by ZnS layer followed by post sintering

Core shell

CuO/TiO2

process at 400  C. The power conversion efficiency is found to

be 3.21% and IPCE peak values is 73%. Photocurrent of
14.86 mA/cm2 has been reported which is surprisingly very
higher than photoelectrodes prepared by only seed growing
Sl no.

method, CBD method and non-post sintering methods. In

1

2
3

5
6

8
9

comparison to CdSe QD modified thin film TiO2, hybrid

9474 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 2 ( 2 0 1 7 ) 9 4 6 7 e9 4 8 1
mesoporous TiO2 shows better photocatalytic activity. This
work has been established by Kim et al. [59] and they have
synthesized a QD sensitized mesoporous which is a sandwich
like heterostructure. The top layer is made up of mesoporous
TiO2 and the bottom is a surface textured TiO2 inverse opal
layer. It is reported that maximum photocurrent density
(~1.6 mA/cm2) is exhibited by CdSe/H-TiO2 and which is 35%
more efficient than CdSe/P25. Under filtered exposure condi-
tions CdSe/H-TiO2 shows a greatest current density of
14.2 mA/cm2 in visible region and under UVevisible irradia-
tion the efficiency is nearly 88%. The mechanism involves the
transfer of electrons from quantum dots to the conduction
band of TiO2, from where the electrons are withdrawn to the
counter electrode and the hydrogen generation reaction oc-
curs. Meanwhile, the holes diffused to the surface of TiO2 or
CdSe oxidize S2.
From the above discussion, it can be concluded that CdSe
QDs sensitized hybrid TiO2 (H-TiO2) shows better activity than
that of CdSe QDs sensitized N-doped TiO2 which in turn shows
better result than CdSe QDs sensitized Au-doped TiO2. As Au
and CdSe QDs act as light trapping as well as scattering agent,
CdSe QDs/Au/TiO2 showed fewer enhancements in photo-
current but in case of N-doped TiO2 the enhanced photocur-
rent is due to strong visible light absorption of CdSe QDs and
the formation of oxygen vacancy in TiO2 lattice by the doped
N-atoms. It can be explained as the excited electrons migrated
from N0 levels to V0 level which is situated below than the H2
reduction potential; the electrons are efficiently utilized to
enhance the photocurrent instead of H2 generation. In com-
parison to chalcogenide QDs modified TiO2, noble metal QD
like Ag QDs modified TiO2 have showed nominal current. This
is because of larger size of Ag QDs (1.3e21.0 nm) compared to
chalcogenide QDs (2.5e7 nm) which could defense the multi-
reflection of absorbed light inside the TiO2 NTAs.
Enhancement in hydrogen generation of LDHs by QDs
modification
Layered double hydroxides (LDHs) are two dimensional
hydrotalcite like anionic clays containing positively charged
metals and replaceable interlayer anions and water mole-
cules with the formula [M 2þ1-x M 3þx (OH)2](A n) x/n$m H2O
where M 2þ and M 3þ are divalent and trivalent metals,
respectively; A n is the interlayer anion [60]. Most important
characteristics property of LDH is that it possesses high
surface area which is helpful in the adsorption and amiable
exchange of anions. Moreover, it has both hydrophobic and
hydrophilic nature. Their specific structure and flexibility in
chemical composition proves it as a very efficient semi-
conductor material in the field of photocatalytic water split-
ting and degradation of pollutants [61e64]. In addition to this,
highly active mixed metal oxides are formed when LDH de-
composes in the temperature range of 300e600  C which
have been used in various photocatalytic processes [65e67].
But on the other side poor charge carrier mobility and fast
electron hole recombination process suppresses their cata-
lytic efficiency. So to improve the activity several attempts
like incursion of carbon materials [68e72], conductive
organic polymers [73,74] and quantum dots [75,76] have been
executed.
Till today there are few works have been done on QDs
sensitized LDH materials and we hope this review article will
be the source for further wide research. Quantum dot shows
high photocatalytic activity for visible-light-induced H2 gen-
eration. QDs sensitized LDH have been investigated as an
efficient photocatalyst for the effective generation of
hydrogen under visible light irradiation. Tang et al. [75] have
designed CQD (carbon quantum dot)/NiFe- LDH complex
which show better photocatalytic activity (Fig. 5) than the pure
NiFe-LDH. Overpotential of ~235 mV in 1 M KOH has reported
by this group at a current density of 10 mA/cm2. The electro-
catalytic property of NiFe-LDH is further enhanced by CQDs
on account of fast electron transfer and electron storage
characteristic. Due to the presence of functional groups on
surface of CQDs, it shows some electrostatic interaction with
the LDH and significantly boosts the electrocatalytic activity
and durability of LDH. These special characteristics are due to
the small size of CQDs (5 nm) which provide specific surface
area for electro catalytic reactions which in turn increases the
electro catalytic activities and longevity of NiFe-LDH. In
addition to these, size dependent up-converted PL behavior,
electron storage property and supernal conductivity of CQDs
play a key role in the photocatalytic activities. Hence it is
concluded that the CQD/NiFe-LDH composite is a better oxy-
gen evolution reaction (OER) catalyst than either the pristine
NiFe-LDH or the other NiFe composites.
Enhancement in hydrogen generation of g- C3N4 by QDs
modification
Graphitic carbon nitride, g-C3N4 is the most thermally and
chemically stable visible light active photocatalyst (band gap
2.7 eV) and metal free allotrope of carbon nitride. g-C3N4
possesses flake like structure analogous to graphite contain-
ing alternative double bonds and the interlayer distance is
0.326 nm. This p-conjugated system facilitates the easy
delocalization of electrons throughout the framework. The tri-
s-triazine units interconnected with planar amino groups
constitutes the graphitic planes of g- C3N4 [77]. g-C3N4 shows
better photocatalytic activity for splitting of water into
hydrogen and oxygen under visible light irradiation [78e80]
because of smaller electronegativity of N and
Fig. 5 e Schematic model for the roles of CQDs in the high
electrocatalytic activity of CQD/NiFe-LDH nanocomposites
[Reproduced from Ref. [75]].
 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 2 ( 2 0 1 7 ) 9 4 6 7 e9 4 8 1
Fig. 6 e Schematic of photogenerated charge transfer in the
CdS QDs/g-C3N4 system under visible light irradiation
[Reproduced from Ref. [88]].
correspondingly smaller band gaps of nitrides. The g-C3N4
photocatalyst is stable under light irradiation in water solu-
tion as well as in acid (HCl, pH ¼ 0) or base (NaOH, pH ¼ 14)
solutions. Moreover, the non-toxic nature of the precursors
and the simpler synthetic methods of g-C3N4 render it a
desirable photocatalyst for water splitting. It is capable of
producing both hydrogen and oxygen but on the contrary it
has many disadvantages. The main disadvantage is the high
recombination rate of its photogenerated electronehole pairs
[81]. To overcome this problem and to enhance its photo-
catalytic performance, a number of methods have been
exploited, such as porous structures [82], doping and coupling
of g-C3N4 with metals [83], graphene [84,85], activated by
protonation [86], and organic dyes [87]. But recent develop-
ment shows that when g-C3N4 is coupled with semiconductor
QDs, its photocatalytic activity increases tremendously.
It is believed that the enhanced photocatalytic activity is
due to the interfacial transfer of photogenerated electrons and
Fig. 7 e Schematic illustration of the PEC mechanism over the GNs-CdS QDs multilayered films [Reproduced from Ref. [107]].
9475
holes between g-C3N4 and QD which leads to charge separa-
tion on both parts. The mechanism of charge transfer in QDs/
g-C3N4 composite can be explained by taking the example of
CdS QDs/g-C3N4 composite which is shown in Fig. 6 [88]. Due
to difference in conduction band edge potentials the photo-
excited electrons in CB of g-C3N4 are migrated to the VB of CdS
QDs. And due to quantum size effect, VB of CdS QDs is lower
than that of g-C3N4; hence the photogenerated holes on the VB
of CdS QDs are transferred to the VB of g-C3N4. Hydrogen gas is
generated on the Pt nanoparticles by accumulating electrons
from VB of CdS QDs. Therefore, the photogenerated electrons
from CdS QDs and the efficient electronehole separation in
the CdS QDs/g-C3N4 heterostructure conduct a noticeable
increment of H2 production. Here, it is very important to
mention that after incorporation of CdS QD, the g-C3N4 has
shown efficient separation of the photogenerated charge
carriers and there is enhancement of the visible light photo-
catalytic H2 evolution activity.
Ge et al. [88] reported that 30 wt. % CdS QD-g-C3N4 com-
posite have showed the H2 evolution rate was
17.27 mmol h1under visible light irradiation which is ~9 times
that of pure g-C3N4. The presence of Pt co-catalyst plays major
role in enhanced H2 evolution. After this Cao et al. [89] pre-
pared in situ growth of CdS QDs on g-C3N4 nanosheets. The
12 wt % CdS QD and g-C3N4 composite have shown a signifi-
cant evolution rate of 4.494 mmol h1 g1 and this is surpris-
ingly 115 times greater than that of neat g-C3N4. From this
experiment it is clearly revealed that CdS content in the
composite plays a very crucial role in the charge separation
process. Optimum amount of CdS can uniformly disperse on
the surface of g-C3N4. As the CdS content increases, the
interface area of CdS- g-C3N4 also increases which facilitates
more transfer of electrons and holes between CdS QDs and g-
C3N4. But excess deposition of CdS QDs leads to aggregation
which leads to the reduction of interfacial surface area and
the also the charge separation efficiency. From this discus-
sion, it is concluded that TGA capped CdS QDs involving
chemical impregnation method is more efficient than CdS
QDs prepared by using DMSO by solvothermal method. The
loaded amount and the size of CdS QDs also determine the
rate of H2 evolution. It should be mentioned here that TGA
9476 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 2 ( 2 0 1 7 ) 9 4 6 7 e9 4 8 1

capped CdS QDs are in the range of 2e5 nm whereas CdS QDs
Table 3 e List of abbreviations and their full forms used in
prepared by DMSO are of 5 nm. Hence, it can be concluded that
the review.
smaller the size of QDs more is the rate of H2 evolution.
Abbreviations Full form
BET BrunauereEmmetteTeller
Enhancement in catalytic activity of graphene BG Bilayer Graphene
CB Conduction Band
and graphene like materials by QDs
CBD Chemical Bath Deposition
CQD Carbon Quantum Dot
Graphene is a flat monomer of carbon atoms firmly held DIRs Dot in Rods
together to form a 2 dimensional honey comb lattice like DL Donor level
structure, and is an elementary building block for other DMSO Dimethyl sulfoxide
dimensional graphitic materials. It can be enfolded into 0 D EBS Emulsion Based bottom up Self-
assembly
fullerenes, rolled into 1D nanotube or stacked into 3D graphite
EPR Electron Paramagnetic resonance
[90]. Andre Geim and Konstantin Novoselov collected Nobel
FG Few layer Graphene
Prize in 2010 in physics for revolutionary experiments about FTO Fluorine-doped Tin Oxide
graphene. Till today three types of graphene have been found GNS Graphene Nanosheet
these are single layer graphene (SG), bilayer graphene (BG) and GO Graphene Oxide
few layer graphene (FG, number of layer 10). GQD Graphene Quantum Dot
Under ambient conditions the charge carrier mobility m can IPCE Incident Photon to Charge carrier
Efficiency
overstep 15,000 cm2 V1 S1 [91e94]. This can be significantly
LDH Layered Double Hydroxide
improved up to 100,000 cm2 V1 S1 [90]. Electron donor and
LED Light Emitting Diode
acceptor molecules alter the electrical conductivity. Conduc- NGO Nitrogen doped Graphene Oxide
tivity increases and decreases when graphene is associated NHE Normal Hydrogen Electrode
with electron acceptor and electron donor molecules respec- NP Nano Particles
tively. Due to its high surface area it is accepted as an efficient NS Nano Sheet
photocatalyst. Among the three types of graphenes, single NTA Nano Tube Array
NW Nano Wires
layer graphene is estimated to possess huge surface area of
PEC Photo Electro Chemical
about 2600 m2 g1 [95]. Also few layer graphene show large PL Photo Luminescence
surface area i.e. 270e1550 m2 g1 [96]. This value have been QD Quantum Dot
measured by the BrunauereEmmetteTeller (BET) method. QRs Quantum Rods
Hence it is concluded that the surface area of some of few SG Single layer Graphene
layer graphene approaches the value of single layer graphe- SILAR Successive Ionic Layer Absorption
and Reaction
nes. Instead of having these benefits graphene has some
TEM Transmission Electron Microscopy
bottlenecks. Single layer graphene are not stable in solution.
VB Valence Band
They get aggregated back to form graphite. Moreover the
production of single layer graphene is quite low by various
mass production methods [97e107] as the main product is result the electronehole charge separation efficiency and the
usually multiple layer graphene. These serious problems can photocurrent density are increased.
be overcome effectively by making composite with quantum Cao et al. [113] synthesized Graphene eCdS (G-CdS) directly
dots. Some few works in the field of photocatalysis have been from graphene oxide (GO) in dimethyl sulfoxide (DMSO). The
done till today and are explained below. decoration of CdS QDs reduces the aggregation of itself and
Xiao et al. [108] suggested that under visible light irradia- also the single layer graphene. The above mentioned two
tion, promising photo catalytic and photo electrochemical problems can be surpassed by the direct one pot synthesis of
performances are exhibited by graphene nano sheets (GNS)- G-CdS from GO. The one pot reaction is composed of the
CdS QDs multilayered films because of intimate interfacial simultaneous reduction of GO and loading of CdS on graphene
contact between GNs and CdS QDs. This intimate interfacial sheet. Most interestingly no molecular linkage is needed to
contact leads to a stacked structure in which CdS QDs and GNs bind CdS QDs and graphene sheets. They have shown the
are present alternately. This stacking structure is beneficial ultrafast transfer of electrons in the range of picoseconds
for shuttling of photo generated electrons from CdS QDs to from CdS QDs to the graphene sheets. This can be utilized in
GNs. In Fig. 7 it is shown that the work function of GNs is various photochemical applications by further
ca.4.42 eV [109,110] and work function of fluorine doped tin experimentations.
oxide (FTO) substrate is about 4.4 eV [111,95]. In the meantime The list of the abbreviations used in the review with their
CdS QDs with diameter of nearly 5.6 nm have band gap of full form is provided in Table 3.
about 2.25 eV. The position of conduction band of the CdS QDs
is at ca.3.98 eV and that of valence band is 6.23 eV [112,96].
From Fig. 7 it is clear that the location of CB of CdS above the Summary and outlook
work function of GNs facilitates the transfer of electron from
the CB of CdS QDs to GNs upon visible light irradiation. The In summary, the area of quantum dot research has drawn much
transferred electron is captured by GNs which is further attention by the scientific community. It has gained extensive
transferred to fluorine-doped tin oxide (FTO) substrate. As a applicability, recognition and much interest in recent years for
 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 2 ( 2 0 1 7 ) 9 4 6 7 e9 4 8 1
the development of solar energy conversion process. This re-
view gives a comprehensive description of basics of quantum
dot, type, uniqueness, modifications and applications towards
photocatalytic and photoelectrochemical water splitting for
hydrogen energy production. Quantum dots are well known for
its efficient visible light absorption in whole over the solar
spectrum. So the metal oxides are widely modified by the
quantum dots for the increment of the photocatalytic activity.
Very recently carbonaceous materials like g-C3N4, graphene
and benzene like materials are modified with quantum dots
which showed very good photocatalytic activity. Researchers
have developed quantum dot modified materials with aimed at
reproducibility and enhanced productivity which is the prime
reason for industrialization of hydrogen production technol-
ogy. The practical fabrication of quantum dot materials in
terms of size, shape, morphology, crystallinity and chemical
composition remains an active area of study in photocatalytic
research. The synthetic procedure to obtain highly visible light
active quantum dot materials is still a challenging task in terms
of long term stability under prolonged solar irradiation. Till to
date, InN/InGaN quantum showed highest PEC activity with
IPCE 56% but still stability is a question mark in terms of prac-
tical applications. It is expected that the inexpensive, environ-
mentally friendly quantum dot based materials will play an
important role in the hydrogen production under solar irradi-
ation and contribute much to the coming hydrogen based
economy. Due to the special nanostructure, size and shape
selectivity of the quantum dot based materials, it is not only
helpful for hydrogen economy but also extends its application
towards fuel cell application, lithium ion batteries, sensors and
solar cell. This review gives a pathway to develop new kind of
quantum dot based materials with special optical and elec-
tronic properties. As the review covers from basic to applica-
tions of quantum dot materials, it is more helpful for the
researcher those who are preliminary working on quantum dot
based materials.
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