Applied Catalysis A: General 518 (2016) 48–59

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Applied Catalysis A: General

journal homepage: www.elsevier.com/locate/apcata

Towards the hydrogen production by photocatalysis

Gerardo Colón
Instituto de Ciencia de Materiales de Sevilla, Centro Mixto CSIC-Universidad de Sevilla, C/Américo Vespucio, 49 41092 Sevilla, Spain

a r t i c l e i n f o a b s t r a c t

Article history: Nowadays, problems derived from climate change urgently demand us to focus our attention on new
Received 23 July 2015 alternatives to fossil fuels. Within this framework, the photocatalytic production of hydrogen as a clean
Received in revised form fuel from oxygenates arises as a necessary option that must be considered. Thus, the development of
23 November 2015
highly efficient photocatalyst is crucial in order to achieve a viable technology under the industrial point
Accepted 24 November 2015
of view. For this sake, it is necessary to understand the principles of photoreforming reaction. In this brief
Available online 30 November 2015
review we will revisit the different photocatalytic materials proposed in the literature highlighting on
the role of different co-catalysts.
Keywords:
Photocatalysis © 2015 Elsevier B.V. All rights reserved.
Hydrogen production
Co-catalysts

1. Introduction ment, and offers unique opportunities, benefits and challenges. At

In the early 1874, the visionary writer Jules Verne predicted that
“water will be the coal of the future” in his science fiction tale “The
Mistery Island”. A century later, Fujishima and Honda could state in
the lab the prediction made by Verne [1]. In this widely referenced
experiment they showed that band gap excitation of anatase TiO2
in a photoelectrochemical cell with a Pt counter electrode and an
applied bias resulted in water splitting into hydrogen and oxygen.
This scientific result has becoming the inspiring step in the devel-
opment of a large studied field of the photocatalysis focusing on
the water splitting reaction. Although the extensive research over
the years in order to refine the process, nobody has come up with
a system that is both efficient and inexpensive enough to produce
sufficient hydrogen to be used as a clean-burning fuel on the roads,
in industry, and at home.
The relevancy of this discovery is getting more evident taking
into consideration the socioeconomical and environmental situa-
tion in the last decades. It is widely believed that hydrogen will
play an important role in this global system since it is considered
the ultimate clean energy carrier. Hydrogen can be produced from
a variety of feedstocks. These include fossil resources, such as nat-
ural gas and coal, as well as renewable resources, such as biomass
and water with input from renewable energy sources (e.g. sunlight,
wind, wave or hydro-power). A variety of process technologies can
be used, including chemical, biological, electrolytic, photolytic and
thermo-chemical [2]. Each one is in a different stage of develop-
E-mail address: gcolon@icmse.csic.es
present, H2 is mainly produced from CO and CH4 from fossil fuels by
a steam reforming reaction which is accomplished by coupling with
water gas shift and hydrogen purification reactions [3]. However,
the forthcoming effective reduction of fossil fuel reserves as well as
the serious environmental problems associated with CO2 produc-
tion has inspired the development of viable alternatives. Among
these, the solar photocatalytic application for hydrogen produc-
tion by photoreforming in which sunlight and water are used as
the hydrogen source is a highly appreciated alternative [4]. In spite
of these attractive particularities, the actual hydrogen production
rates are still far from a practical application status. Thus, several
reported works on high scale reactors indicated that the obtained
H2 productions are quite modest [5]. It is clear that the optimiza-
tion of the photocatalytic system is crucial in order to make this
attractive technology feasible under the industrial point of view.
In this sense, Rodríguez et al. recently showed that hydro-
gen generated from solar sources could be competitive with that
obtained from non-renewables, and point towards design strate-
gies that can significantly aid in the reduction of solar-fuels
production costs [6]. Similarly, Pinaud et al. clearly demonstrates
that if technical progress is made to meet material performance
targets and with appropriate plant-scale engineering, direct solar
hydrogen produced by water splitting reaction can be produced at
a cost which meets the US Department of Energy target thresh-
old of $2.00–$4.00 per kg H2 [7]. These authors performed an
exhaustive analysis which revealed that improvement in the
solar-to-hydrogen efficiency (STH, which correlates the hydrogen
production rate and energy of incidence solar light) of the panel-
based systems could substantially drive down their costs. For a

http://dx.doi.org/10.1016/j.apcata.2015.11.042
0926-860X/© 2015 Elsevier B.V. All rights reserved.
 G. Colón / Applied Catalysis A: General 518 (2016) 48–59
Fig. 1. Bandgaps and band edge positions of selected semiconductors in relation to the redox potentials for water splitting reaction.
given STH of 10% and a photocatalyst lifetime of ten years, the
price of hydrogen was estimated to be $1.6 per kg, which could
meet the mentioned target hydrogen price. In a recent perspective
analysis, Domen et al. argued that due to the limitation of UV-
active photocatalyst to increase the STH, it is necessary to develop
and activate narrow-band-gap semiconducting photocatalysts for
practical operation despite the present low activity of photocata-
lysts with absorption edge wavelengths longer than 600 nm for the
overall water-splitting reaction [8]. These authors finally conclude
that photocatalytic systems must be designed bearing scalability in
mind.
Over the last three decades the overall photocatalytic water
splitting process has been extensively studied pursuing to enhance
the photoefficiency of the process [9]. However, the earliest
research focused more on developing good photocatalysts than
Fig. 2. Morphology of anatase nanocrystals.
49
on actually understanding the process itself. Recent advances in
the tailoring of new photocatalysts for solar water splitting pass
through the comprehension of the band electronic structure which
subsequently would lead to improvements using band engineering.
2. General considerations on H2 production reaction
From a thermodynamic point of view the water splitting
reaction is energetically unfavoured process. Thus, water trans-
formation into H2 and O2 is an uphill reaction which needs the
standard Gibbs free energy change of 237 kJ/mol.
2 H+ + 2e− → H2 Hydrogenevolutionhalfreaction
2OH− + 2 h+ → ½O2 + H2 OOxygenevolutionhalfreaction
H2 O → H2 + ½O2 Overallwatersplitting
The redox potentials for both reduction and oxidation processes
determine the possible candidate photocatalyst by the positions
of the valence and conduction bands and therefore strongly limit
the range of possible photocatalysts. Both the reduction and oxi-
dation potentials of water should lie within the band gap of the
photocatalyst.
Regarding to the formal electronic structure of a potential pho-
tocatalyst for H2 production, there are two important requirements
to be accomplished: (i) The band gap should be 1.23 eV < Eg <
3.26 eV. (ii) The band positions should be located as follows: the
bottom of the conduction band should be more negative than the
redox potential of H+ /H2 (0 V vs NHE) meanwhile the top of the
valence band should be more positive than the redox potential of
O2 /H2 O (1.23 V).
Thus, from a thermodynamic point of view the water splitting
reaction should be easily achieved using a photoinduced catalytic
process involving any materials which satisfy the above conditions.
However, the overall photocatalytic water splitting reaction is an
endothermic reaction. This means that, in order to overcome such
an energy barrier, photons of higher energy are needed.
Within the great number of photoactive semiconductors pro-
posed for water splitting ans photoreforming reactions, till now
50 G. Colón / Applied Catalysis A: General 518 (2016) 48–59

Fig. 3. Possible homojunction formation by TiO2 polymorphs.

TiO2 is the most efficient one. However, the reported photonic
efficiencies from solar to hydrogen by TiO2 photocatalytic water-
splitting are still low. This is mainly due to the following reasons:
(1) Recombination of photo-generated electron/hole pairs: con-
duction band electrons can recombine with valence band holes
very quickly and release energy in the form of unproductive heat
or photons; (2) Competitive fast backward reaction: As mentioned
before the water cleavage into hydrogen and oxygen is an energy
unfavoured process, thus backward reaction could easily proceeds
and strongly competes with water splitting; (3) Failure to absorb
visible light photons: The band gap of TiO2 is about 3.2 eV and
only UV light can be utilized for hydrogen production. Since the
UV light only accounts for about 4% of the solar radiation energy,
the efficiency of process becomes drastically low.
In order to resolve the above mentioned handicaps different
approaches have been proposed in the literature.
Thus, the recombination of the photogenerated charge carriers
has been afforded since the starting research works are mainly
focused on TiO2 based catalysts [10]. Indeed, for pure TiO2 , non-
radiative recombination appears to be the main de-excitation
channel for anatase-based nanosystems. The study of structural
defects closely related to morphology variables such as size, shape,
secondary particle size and porosity play a key role in control-
ling light-matter interactions. Hence, numerous studies have been
devoted to overcome such problems, which include doping with
metal or non-metal elements [11–14], controlling the structure and
facets [15–17], and introducing defects into nanocrystals [18].
There are two main approaches for suppressing the reverse
reaction: either the use of sacrificial reagents or the creation of a
physical separation between the corresponding photoactive sites
on the surface of the photocatalyst. In this sense, the separation of
the photoactive sites would require surface separation of the photo-
generated electrons and holes which is commonly accomplished by
the use of specific co-catalyst. This point will be explicitly discussed
in Section 5.
As widely stated, water splitting reaction on TiO2 as model
semiconductor still shows a very low efficiency. Thermodynami-
cally, oxidation of water to produce O2 is more feasible than the
formation of peroxo and hydroxyl species. However, due to the
slow kinetics of the O2 evolution reaction, the formation of such
alternative species appears to become kinetically competitive with
O2 production. For this reason sacrificial agents such as methanol
or EDTA could be used to improve hydrogen productivity. Thus
the oxidation of sacrificial organic compounds by these highly
reactive species would enhance the performance of the reduction
half-reaction. If we consider renewable compounds as sacrificial
target molecules the environmental interest of the process would
be increased at the same time as efficiency. On this basis, pho-
toreforming can be considered a more feasible process than water
splitting under the thermodynamic point of view [19].
If we consider the H2 evolution half reaction by means of a pho-
toreforming process, a generally accepted mechanism involves the
oxidation of water molecules by photoinduced holes in the semi-
conductor. In this step, OH• radicals can be produced which can
attack the alcohol (acting as sacrificial agent in the oxidation half
reaction) and abstract an alpha hydrogen to form a • RCH2 -OH rad-
ical [20].
Photoreforming was initially studied by using methanol, the
simplest molecule, however in recent papers biomass derived
compounds were considered, providing this process an additional
interest. Thus, H2 were obtained from ethanol, [21,22]. glycerol
[23,24], glucose [25,26], sucrose [27], and other biomass derived
compounds [28].
In a recent paper Bahruji et al. studied in detail the H2 production
reaction by photoreforming of different alcohols and proposed a
chemical mechanism of H2 production reaction [29]. These authors
proposed interesting rules that could govern the alcohol photore-
forming reaction: (i) the alcohol must have a hydrogen in the
␣-position; (ii) primary alcohols undergo decarbonylation yield-
ing a single molecule of CO2 and hydrogen plus an alkane (the
exception being methanol which produces no alkane); (iii) methy-
lene groups produced in the reaction undergo complete oxidation
to yield carbon dioxide; (iv) the dominant pathway for methyl
Fig. 4. Schematic model of H2 evolution reaction on core/shell noble-metal/Cr2 O3
particulate system as a co-catalyst for photocatalytic overall water splitting
(Reprinted with permission from Ref. [94]. Copyright (2009) American Chemical
Society).
 G. Colón / Applied Catalysis A: General 518 (2016) 48–59 51

Fig. 5. (A) (a–f) SEM images of CdS-Te heterostructures prepared at reaction times of (a) 6 min, (b) 6.25 min, (c) 6.5 min, (d) 6.75 min, (e) 7.0 min, and (f) 10.0 min. (g) Growth
scheme for the shish-kebab-like CdS-Te heterostructures; (B) Comparison of the photocatalytic activities of (a) CdS, a CdS/Te mixture, and CdS-Te heterostructures and (b)
CdS-Te, NiS/CdS-Te, MoS2 /CdS-Te, and CdS-Te@Pt,Pd in a lactic acid aqueous solution under visible-light illumination (Reprinted with permission from Ref. [102]. Copyright
(2015) American Chemical Society).

Fig. 6. (A) Kubelka–Munk absorption spectra, photographs (the left inset) and Tauc plots (the right inset) of the as-synthesized samples D52, D55, D60 and D64.(b); (B) H2
evolution from samples (30 mg) in methanol (20 vol%) aqueous solution at pH 4.5 under visible light (>400 nm) irradiation. Samples were platinated with 1% mass Pt prior to
irradiation. Inset: relationship between the reaction rate and the calcination temperature (Reprinted from Ref. [115] with permission from the Royal Society of Chemistry.

groups produced at the surface from the photo-reforming process
is recombination with hydrogen and desorption. Other operational
parameters such as alcohol concentration and incident light inten-
sity have been reported to condition the progress of the reaction
[30,31].
In spite of the huge amount of results concerning to the hydro-
gen production by photoreforming, the productivity obtained in
each case is quite difficult to compare due to the high variety
of operational conditions (reactor type, flows, lamp types and
power,. . .). This fact would point out the strong necessity to stan-
dardize the results by providing the photonic efficiency.
3. Photoreforming from oxygenates
As above pointed out, the production of hydrogen by a photore-
forming process shows two clear advantages with respect to water
splitting reaction. Firstly the use of sacrificial agent which could
help in the reduction half-reaction and secondly the use of biomass
derived substrates would provide an added-value to the overall
process [32]. This coupled process represents an environmental
friendly and cost effective method for wastewater treatment, with
simultaneous production of energy.
52 G. Colón / Applied Catalysis A: General 518 (2016) 48–59
During photoreforming process, instead of water the organic
compounds can act as scavengers of photoinduced holes and photo-
generated oxygen, thereby retarding electron-hole recombination
as well as hydrogen–oxygen backward reaction. This way the
resulting hydrogen production rates become enhanced. As it can
be expected, in this case when complete oxidation of the sacrificial
agent is achieved, the rate of hydrogen production would drop to
values comparable to those obtained from pure water.
Within this framework, the use of biomass derived compounds
such as carbohydrates is gaining increasing interest as an abundant,
renewable and clean feedstock for hydrogen production [33,34].
Kawai et al. firstly demonstrated the possibility to convert carbo-
hydrates, not only sugar or starch but also cellulose, in the presence
of water and a RuO2 /TiO2 /Pt into hydrogen [35]. From this star-
ing result many attempts have been reported considering different
target molecules and catalysts. In this sense, as a general trend,
the complex molecular structure of carbohydrates with respect to
simple alcohols (methanol or ethanol) leads to a lower productiv-
ity. For this reason the mechanism of carbohydrate full degradation
still need of further studies in order to be improved.
Thus, Fu et al. investigated the photocatalytic reforming of glu-
cose over different noble metal supported TiO2 . They concluded
that glucose molecule would be bonded to the surface undercood-
inated Ti atoms through its hydroxyl groups. Once adsorbed, the
glucose molecule would trap a photogenerated hole, oxidizing and
forming a RCH2 O• radical. This radical would continue the reac-
tion through a further attack over another glucose molecule and
by a subsequent deprotonation and oxidation carboxylate species
could be formed. Finally, the [R COOH]− decarboxylates via a photo-
Kolbe reaction resulting in eventual CO2 . On the other hand, the H+
from glucose deprotonation will be transferred to the Pt particles
and then reduced to H2 by photogenerated electrons. They also
stated that the rate of hydrogen production is strongly dependent
on the initial pH of the solution, reaching the maximum produc-
tion at higher pH values (pH > 11). Glucose shows a pKa value of ca
12.3 so when the pH is far below this point, glucose is present in its
molecular form bonding to TiO2 surface by means of the hydroxyl
groups. At higher pH the molecule dissociates and the anionic form
of the molecule is able to capture more efficiently the photogener-
ated holes. At pH values higher than the pKa glucose molecule turns
negatively charged as TiO2 surface hampering the adsorption and
therefore the H2 evolution rate. Furthermore, the existence of ␣ and
␤ anomericity for saccharide molecule has also certain influence in
the reaction rate probably due to the way the molecule is adsorbed
at the surface [36]. Taking into account these mechanistic consid-
erations, as expected the hydrogen production by photoreforming
of mono-, di- and poly-saccharides decreased with increasing the
molecular complexity [37].
Another possibility arises from the use of different oxygenated
substrates non derived in this case from biomass such as waste
pollutants or even methane. In the first case, the possibility of the
assembly two interesting processes, hydrogen formation and pol-
lutant degradation, appears of great relevance [38]. Thus, a wide
variety of organic pollutants in water has been photoreformed
achieving in all cases to complete mineralization simultaneously
to the production of H2 . These examples include the degradation
of dyes [39], aldehydes [40], phenolic compounds [41] and even
olive mill wastewater [42]. As in the case of biomass derived sub-
strates, as the molecule is simpler the efficiency of the H2 evolution
is higher.
Finally the methane photoreforming has been also proved as
a feasible way to produce H2 [43,44]. When Pt/TiO2 was photoir-
radiated in the flow of water vapour and methane around room
temperature, hydrogen and carbon dioxide were the main prod-
ucts, and only trace amounts of ethane and carbon monoxide were
also observed.43 The hydrogen production rate over Pt/NaTaO3 :La
was two times higher than that over Pt/TiO2 and the reaction selec-
tively lasted for a long time without deactivation [45].
4. Different H2 producing photocatalysts
Since the first works describing the photocatalytic water
splitting reaction the number of systems proposed has been expo-
nentially grown [46,47]. As mentioned in the previous section,
suitable materials should fit the band energy conditions in order to
proceed the water oxidation and reduction reactions. Considering
these electronic pre-requirements many photoactive semiconduc-
tors have been studied (Fig. 1).
Among these TiO2 , SrTiO3 , and La:NaTaO3 were firstly studied
though their major disadvantage is that they only absorb light in
the ultraviolet region of the solar spectrum [48,49]. However, in
spite of the large number of the proposed systems, only a few actu-
ally show an appreciable activity for water photolysis. Recently,
other UV-active systems such as Nb- and Ta-based oxides have
been also considered for this reaction [50]. In this sense, in a recent
paper, Soldat et al. proposed new types of BaTaO3 system prepared
by a citrate route. The obtained photocatalysts showed interest-
ing hydrogen production rates associated to the improved charge
carrier separation [51].
In the last years most relevant results regarding such systems
are related to TiO2 based photocatalysts. In this case the research
has been focused in the structural and morphological modification
of TiO2 , the development of two or more components photocatalyst
that are more complicated than TiO2 or its the combination with a
wide range of possible co-catalysts.
Thus, it has been reported that the particular morphology of TiO2
could have a notable effect on the H2 production (Fig. 2) [52].
Teng et al. argued that owing to the higher surface energy of the
{0 0 1} TiO2 facets, nanosheet-based photocatalyst shows higher
hydrogen production activity and recyclability than the nanorod-
based one.
In the same direction, Wang et al. also pointed out that hierarchi-
cal anatase TiO2 nanoflowers consisting of {0 0 1} facet dominating
nanosheets shows improved photocatalytic H2 evolution [53]. The
coexistence of different exposed planes could promote electron
transfer from {0 0 1} to {0 1 0} when they are photoexcited enhanc-
ing the photoexcited carrier lifetimes which is closely linked to the
number of {0 0 1}–{0 1 0} quasi-heterojunctions. Similarly, Wang
et al. also showed that the preparation of TiO2 particles with a high
percentage of reactive facets (∼85%) leads to 1.4–5 times higher
performance than their counterparts in photocatalytic hydrogen
production [54]. On the contrary, Gordon et al. proposed exactly the
opposed trend [55]. These authors argued that the photocatalytic
activities of oxygen deficient anatase Pt-TiO2 showing preferen-
tially {1 0 1} facet exposed are more active for the production
of hydrogen from methanolic solutions under solar illumination.
Therefore the control of the reactive facet of TiO2 has clearly turned
as a promising strategy for increasing the hydrogen production that
needs further studies.
Besides these specific studies concerning to the exposed facets,
the origin of the intrinsic photoactivity for hydrogen production
related to the structural and/or morphological features of TiO2 is
still not clear enough. In a recent paper, Montes-Navajas et al. tried
propose a correlation between the structural and morphological
features of different bare commercial TiO2 (without any supported
co-catalyst) [56]. Unfortunately, from their results it was possible
to conclude that upon solar irradiation the photocatalytic activity
tendency appears difficult to rationalize. These authors found that
it was not possible to correlate well with crystallographic phases
present and it seems to derive from more complex interplay of
different factors such as the presence of impurities, surface area,
 G. Colón / Applied Catalysis A: General 518 (2016) 48–59
Fig. 7. Proposed electronic diagram for TiO2 /g-C3 N4 heterostructures for the pho-
tocatalytic hydrogen production (Reprinted with permission from Ref. [72]).
degree of crystallinity, particle size and morphology. Thus, from all
the TiO2 samples studied it results that Evonik P25 showed the best
H2 production. In this sense, Obregón et al. recently point out the
strong influence of structural and morphological features of TiO2
on the Cu active sites with the hydrogen evolution production [57].
In spite of the complexity in certain cases, heterostructured sys-
tems provide an attractive and flexible approach for enhancing the
reaction efficiency. Two or more semiconductors coupling with the
appropriate electronic band positions would lead to a more effi-
cient separation of the photoinduced charge carriers [58–60]. As
discussed in the previous section, for the particular case of H2 pro-
duction through proton reduction, the studied systems must have
conduction band levels sufficiently higher than the H+ /H2 redox
potential. Following this approach different heterojunctions based
on TiO2 coupled with other semiconductors such as CdS [61–63],
ZnO [64], SnO2 [65], WO3 [66], Bi2 O3 [67], Fe2 O3 [68], ZrO2 [69,70],
MoO3 [71], g-C3 N4 [72,73] or graphene [74,75] to form heterojunc-
tions. Among these proposed composite systems CdS decorated
TiO2 have received considerable attention due to the appropriate
band alignment which leads to a highly efficient electron trans-
fer. In this sense Fang et al. proposed a ternary design in which a
transfer path for the photoexcited electrons of CdS to the core Au
particles via the TiO2 nanocrystal bridge effectively suppresses the
electron-hole recombination on the CdS photocatalyst [62]. Sim-
ilarly, Zhou et al. proposed different CdS/M/TiO2 (M = Au, Ag, Pt,
Pd) ternary heterojunctions for efficient photocatalytic hydrogen
evolution [76]
Furthermore the different band structure of TiO2 polymorphs
has been also used, in this case for homojunction formations, show-
ing enhanced charge separation (Fig. 3). Thus, anatase-rutile and
anatase-brookite heterostructures has been reported to exhibit
better H2 production with respect to the single TiO2 catalysts
[77–82].
Indeed, by choosing the adequate anatase-rutile fraction and
modification of in the TiO2 it is possible not only to enhance the
reaction rate but also supress the CO production during photore-
forming reaction [83].
This selectivity improving could be caused by the modifica-
tion of the surface acidity/basicity features of the homojunction.
Therefore the control of this simple homojunction would provide
interesting additional benefits to hydrogen production reaction.
Besides traditional oxide photocatalysts mostly based on TiO2
systems different alternatives have been studied. Thus, for the sake
to propose alternative materials able to use the visible region of the
solar spectrum other systems like (Ga1−x Znx )(N1−x Ox ) [84], Fe2 O3
53
[85], WO3 [86,87], CdS and g-C3 N4 [88,89] have been explored
as potential photocatalysts. In this sense, (Ga1−x Znx )(N1−x Ox ) sys-
tem has been extensively studied by Domen’s group for the overall
water splitting reaction [90,91]. This solid solution alone shows a
scarce photoactivity, however when it is loaded with a specific co-
catalysts the reaction proceeds with a high hydrogen yield [92]. By
the moment, this system loaded with Rh2−y Cry O3 co-catalyst shows
the best visible light photocatalyst for water splitting, reaching a
quantum efficiency of 5.6% under visible light irradiation (Fig. 4)
[93,94].
Among the new photocatalysts for hydrogen production
recently proposed in the literature, perhaps the most interesting
ones are metal sulphides and graphitic carbon nitride. This par-
ticular interest is based in their notably photoactivity under visible
light irradiation. The origin of the visible photoactivity of metal sul-
phides can be attributed to the participation of S 3p orbitals (being
more negative than O 2p) on the construction of the valence band,
which increase the width of the band itself. Therefore, in contrast to
metal oxides many of them (CdS, MoS, AgS) exhibit a narrow band
gap. In spite of their remarkable visible photoactivity, there exists
an inherent drawback, i.e., photocorrosion in which chalcogenide
itself could be oxidized by the photogenerated holes [95]. Among
the available sulphides, CdS with band gap of 2.4 eV is probably the
best-studied metal sulphide photocatalyst for hydrogen produc-
tion reaction, although its high toxicity upon photocorrosion. Such
problem greatly obstructs its practical application due firstly to the
loss of activity and more importantly to the metal leakage pollution
(particularly serious in the case of cadmium) produced during the
reaction. It is believed that photocorrosion occurs in these chalco-
genide photocatalysts when their activity irreversibly decreases
even with the re-addition of sacrificial agent. Various efforts have
been made to improve the stability of sulphide-based photocata-
lysts and retain its high photoactivity. The use of specific sacrificial
reagent which would hinder the sulphide photocorrosion process
is widely reported as a first attempt to stabilize the sulphide struc-
ture against photocorrosion. Thus, S2− , SO4 2− or S2 O3 2− species
have been extensively used as sacrificial hole scavenger [46]. In
the presence of such species, chalcogenides show a remarkable
photoactivity for water reduction.
Regarding to the photocatalytic systems, the proposed
approaches passed through the coupling sulphides with wide-
bandgap semiconductor or oxidation co-catalyst [96], and
constructing a solid solution [97–99], complex core–shell [100] or
shelter [101] heterostructures which could protect the unstable
semiconductor inside the core. An exotic example of the prepara-
tion of complex heterostructures is reported by Hu et al. [102] These
authors described a series of multi-heterostructured metal chalco-
genides (CdS-Te, NiS/CdS-Te, and MoS2 /CdS-Te) with a surprising
shish-kebab-like morphology synthesized by a microwave-assisted
pyrolysis of dithiocarbamate precursors (Fig. 5). CdS-Te and CdS-
Te-based composites exhibited enhanced photocatalytic activity
and photostability for water splitting into H2 .
In recent years, a considerable attention has been paid to CuInS2
due to its environmentally benign metal components with respect
to CdS based photocatalysts and excellent solar-harvesting prop-
erties. CuInS2 is a direct bandgap (∼1.5 eV) semiconductor which
has a large optical absorption coefficient (>105 cm−1 ) and is con-
sidered a promising semiconductor for photovoltaic devices and
other optoelectronic applications [103]. As in the case of CdS dif-
ferent heterostructured systems complex have been reported in
the last years in order to enhance its photocatalytic performance
[104,105].
As an example, a complex ternary solid solution formed by
AgInS2 -CuInS2 -ZnS was proposed by Tsuji et al . some years ago
[106]. Then, other solid solutions based on CuInS2 have been
reported. Thus, Ren et al . described the preparation of a (CuIn)x
54 G. Colón / Applied Catalysis A: General 518 (2016) 48–59
Fig. 8. Schematic illustration of photocatalytic water splitting over a semiconductor photocatalyst loaded with H2 − and O2 − evolution co-catalysts. (Reprinted from Ref.
with permission from the Royal Society of Chemistry).
Cd2(1−x) S2 solid solution by a hydrothermal method [107]. Loading
of Pt as co-catalyst results in a substantial improvement in H2 evo-
lution (2456 ␮mol/h · g) with respect to Pt-loaded pure CdS (40.2
␮mol/h · g). Moreover, these authors reported that the activity of
this system shows a high stability in the photocatalytic process after
long use experiments.
Considering the high number of research works publish in the
last years, the second promising candidate for hydrogen production
reaction is g-C3 N4 [108]. Thus a high variety of complex sys-
tems have been proposed for the optimization of its photocatalytic
performance. These approaches passed through the formation of
surface coupling hybridization with other semiconductors (such as
TiO2 [109], SnO2 [110], CdS [111], or graphene [112]), construction
of mesoporous structures [113], doping with metal (Fe, Ag, Au, Pd)
or non-metal species (S, B and P) or sensitizing with organic dyes
[114]. Thus, although the intrinsic photocatalytic performance of
g-C3 N4 itself can be considered low, the control of the synthetic
parameters as well as the designing of complex heterostructures
leads in most of the cases to a notably photoactivity compared to
the former components.
In this sense, Wu et al. reported that the photocatalytic activity
of g-C3 N4 is strongly related to the presence of structural defects
generated during the calcination process. These defects produce
additional optical absorption in the visible spectra of g-C3 N4 and
weakened photoluminescence [115]. These authors demonstrated
that the structural control could have a strong impact on the final
hydrogen production of g-C3 N4 (Fig. 6).
The photoactivity enhancement could also be achieved by the
formation of heterostructure systems. By coupling process, g-C3 N4
based heterostructures can be formed by combining with visible
light active semiconductor materials (such as CdS, Bi2 WO3 , and
BiOI), leading to a more efficient photogenerated charge separation
if the band diagram of both fit adequately.
In addition, it can combine with large band gap photocatalysts
(such as TiO2 , ZnO, and ZnWO4 ), which can largely broaden the
application of the g-C3 N4 based nanocomposites (Fig. 7).
5. The co-catalyst factor
As discussed in Section 2, in order to achieve a large-scale and
sustainable hydrogen production process from water, the photo-
catalytic system usually requires a high efficient photocatalyst.
Therefore, most of the proposed photocatalyst are oxide type
exhibiting an n-type character. That means that upon excitation,
they would readily accumulate excited holes on their surfaces
showing high oxygen evolution activity. In this case, the coun-
terpart excited electrons would prefer to stay in the bulk of the
semiconductor; as a result, metal nanoparticles can often effec-
tively transport such electrons to the surface by guiding them along
the metal–semiconductor interface [116]. Thus, the participation
of a co-catalyst has been extensively considered for the hydrogen
production reaction which could improve either reduction or oxi-
dation half-reactions (Fig. 8) [117,118]. Although along this section
we will focus our attention to reduction co-catalyst due the great
impact in the H2 production reaction, it can be highlighted that
for O2 evolution reaction several co-catalysts (such as MnOx, IrOx,
CoOx or CoPi) have been also proposed [72,117,119].
As mentioned, practically the whole studied photocatalytic sys-
tems need a high-active co-catalyst for reducing the overpotential
of proton reduction and enhancing hydrogen evolution efficiency.
For the wide number of metal co-catalysts discussed, different
roles have been proposed in the literature which tried to explain
the function of such co-catalysts in the reaction. The first role
invoked concerns to the improvement of the electron-hole life-
time by trapping of photogenerated travelling electrons. Another
possibility argued is related to its participation in the reaction
of the organic with the surface, usually through dehydrogena-
tion/decarbonylation reactions [120]. Even more, Joo et al. recently
proposed an alternative striking pathway that does not involve
electron transfer to the metal but requires the metal co-catalyst to
act as a catalyst for the recombination of the hydrogen atoms made
via the reduction of protons on the surface of the semiconductor
instead [121].
Till now this task assumed for reduction co-catalysts has been
reasonably accomplished by noble metals (Pt, Au, Ag or Pd). The
most accepted mechanism explaining the interaction between the
metal and the active semiconductor involves the creation of a
Schottky barrier that would inject electrons from the semiconduc-
tor conduction band toward the metal Fermi level [122]. By driving
the photogenerated electrons to the metal active sites they serve
as cathodic centers for H2 production. This leads to the increase
in the electron transfer rate to the adsorbed species, retarding the
possibility of their recombination with holes. Noble metals gen-
erally show a more stable metallic state which would prevent its
oxidation during water splitting reaction making them useful as
active co-catalysts. The main drawback for a widespread use is
 G. Colón / Applied Catalysis A: General 518 (2016) 48–59
their scarcity and the subsequent high price of them. For this rea-
son, alternative transition metal co-catalysts such as Cu, Ni or Fe
have been widely proposed [123]. However, metals in an oxidised
state are expected to follow a different electron transfer mechanism
due to the loss of metallic properties. Moreover, in recent papers
it has been proposed transition sulphides such as CuS [124], NiS
[125] or MoS [126] as effective hydrogen production co-catalysts.
However, as it was stated previously such candidates suffer dras-
tic anodic photocorrosion processes and trend to form S or sulfate
[127]. Finally, the last approach to novel co-catalyst systems con-
sist on bimetallic formulations by mixing different noble metals
or noble-transition metals. In the following sub-sections we will
describe in more details the results obtained by noble metal and
transition metal based co-catalysts.
5.1. Noble metal based co-catalysts
As it was mentioned before, the occurrence of dispersed metal
particles on the semiconductor catalyst would increase the elec-
tron transfer to the adsorbed species and therefore enhance the
efficiency of the process. This point is of great relevance for
the photocatalytic hydrogen production reaction. Historically, the
traditional metal co-catalysts used were based on noble metal par-
ticles [128]. On the basis of the large literature describing the
parameters that would govern the co-catalysts efficiency, a clear
view of their role is still limited.
As pointed out by Yoshida et al. the efficiency of different noble
metal co-catalysts can be related to the work function of each one
[32]. In principle, the work function of each metal should then play
a role in the formation of Schottky barrier. Taking into account
this consideration, Pt appears as the most active noble metal for
hydrogen generation. In spite of this general conclusion, the final
hydrogen production efficiency is strongly dependent not only on
the type of metal co-catalyst but also on its nature and concen-
tration [129]. In this sense, the preparation procedure used for the
metal decoration could have great influence on its final photocat-
alytic performance. In fact, even when we use the same metal, the
deposition method clearly affects to the photoactivity [130,131].
As a general trend, the specific morphology (dispersion and metal
particle size) and oxidation state appears as the key parameters
which would condition the photocatalytic activity. Thus, Navarro
et al. stated that for particles in the metallic oxidation state the
morphology does not have a relevant influence indicating that the
active site would be located in the metal-semiconductor inter-
face [131]. On the contrary, for partial oxidised metal particles it
has been observed improved photoactivities probably due to bet-
ter e− conductivity of the partially charged Pt particles that may
enhance the trapping electrons and thereby extending the elec-
tron/hole carriers separation. In a recent paper Luo et al. stablished
an interesting correlation between electrocatalysis and photocatal-
ysis by noble metal based materials [132]. Thus, since in electrodes
for electrocatalytic applications the size and shape of noble metal
arise as a crucial parameter to be controlled, they proposed the
same condition for photocatalytic materials. These authors argued
that conventional deposition methods (photodeposition or impreg-
nation methods) do not allow controlling such morphological
parameters. Thus, they obtained nano-cubic and nano-spherical Pt
particles prepared via a shape-and-size-controlled synthesis and
loaded onto a CdS semiconductor. They finally stated that for both
morphologies cluster size is the determining parameter, being the
shape effect more significant for larger Pt particles than for smaller
particles. In the same line, Xing et al. have synthesized isolated
metal atoms (Pt, Pd, Rh, or Ru) stably by anchoring on TiO2 by a facile
one-step method [133]. Such isolated metal atom based photocat-
alysts show excellent stability for H2 evolution being 6–13-fold
more photoactive than the metal clusters loaded on TiO2 by the
55
traditional method. In this sense, Schweinberger et al. proposed
a successful method for preparing Pt clusters smaller than 2 nm
supported on CdS surface by means of laser ablation [134]. These
authors found that the maximum hydrogen production rate was
achieved by Pt46 cluster and described a clear size effect within
the studied sizes. Moreover, such size effect has been interpreted
by considering two electron transfer steps: first from the semicon-
ductor to the cluster and second from the cluster to the hydrogen
atom.
In a recent paper, Li et al. incorporated the metal particle local-
ization on the support as a crucial parameter to be considered [135].
Thus, when PtO clusters co-catalyst is located on the (0 0 1) face of
TiO2 the H2 production rate observed was higher. This fact has been
related to shorter migration path of the photogenerated electrons
compared with Pt at (0 0 1) face. This would result in a rapid capture
of photogenerated electrons by metallic clusters and their avoiding
electron/hole recombination.
In the case of gold, it is clear that deposition method affects in a
greater extent to the morphological features of the metal deposits
[136]. It is widely reported that gold deposition method difficulty
leads to small size and narrow distribution gold particles, espe-
cially when compared to platinum [137]. As mentioned before, the
greater ability of Pt with respect to Au to act as electron sink and
would be linked to the difference between their respective work
functions. This effect may be also associated to the smaller size of Pt
nanoparticles with respect to Au ones. Furtherly, in addition to the
particular metal morphological aspects the interface contact with
the support would be also of great importance. Thus, Jovic et al.
described that the creation of highly active three phase interfacial
sites “hot-spots” formed by the intimate contact of Au nanoparti-
cles with anatase and rutile would lead to enhanced photoactivity
[138].
A further aspect to be considered for gold and also silver
based co-catalysts concerns the possibility of visible photoactivity
through their plasmon excitation (Fig. 9) [139,140].
It has been reported that the localized surface plasmon (LSP) has
important applications in photocatalysis. This is mainly due to the
following aspects: (i) direct injection of energetic electrons to semi-
conductors, resembling dye sensitizations [141]; (ii) enhancement
of electron–hole pairs generation in the regions of semiconductor in
vicinity to the metal nanoparticles, due to amplified near-field elec-
tromagnetic field and resonant photon scattering, i.e. via resonant
energy transfer (RET) [142].
Within this excitation mode, the electronic mechanism and
reaction scheme drastically change (Fig. 9). Upon visible light irradi-
ation TiO2 is totally inactive and the Au NPs would act preferentially
as light harvesters injecting hot electrons into the conduction band
of TiO2 promoting water reduction to H2 . Considering this role
of light harvester, high visible light absorption by gold might be
the control parameter for the overall photocatalytic efficiency. In
this case, contrary to UV-irradiation conditions, the Au particle
size would not play a key role in the photocatalytic activity [143].
This reverse electronic mechanism would imply that the reduction
site would be placed at TiO2 and the oxidation site on the metal
nanoparticle.
Recently, Kowalska et al. reported the action spectra for different
Au-TiO2 systems with varying gold and TiO2 sizes for the iso-
propanol oxidation reaction [144]. They demonstrated that under
plasmonic excitation a direct relationship between the gold size
with the photocatalytic activity can be established. Thus, under
visible irradiation, the greater the gold particle size (e.g., broader
particle size distribution with larger mean and higher moments,
particularly the variance), the higher the efficiency exhibited due
to the larger number of photons absorbed. As above pointed out,
the higher performance observed in this case would be related
to the extended plasmonic effect observed on large particles. On
56 G. Colón / Applied Catalysis A: General 518 (2016) 48–59

Fig. 9. Different excitation scheme for Au-TiO2 systems.

the contrary, under UV conditions, smaller gold particles clearly the photocatalytic hydrogen production and the textural character-
produce higher photoactivities. Very recently, suggested that the istics of a Cu-doped TiO2 system [157]. In this case the photoactivity
co-existence of large (>10 nm) and small (<5 nm) Au nanoparti- was correlated to the Cu nanostructure obtained and especially
cles in Au-TiO2 catalysis prepared by multistep photodeposition with deterioration of the electronic interactions between the com-
method contributed to stronger SPR photoabsorption, enhanced H2 ponents of metal − semiconductor composites with growth of the
evolution rate from 2-propanol in aqueous suspensions under vis- metal nanoparticles size. On this basis, the interaction with TiO2
ible light irradiation. In these cases, smaller Au nanoparticles acted is expected to stabilize the copper oxides against photocorrosion
as a reduction site for H2 evolution. and could enhance the activity by a most efficient process. Thus,
Similarly, silver showing a slightly lower work function than well dispersed CuOx nanoparticles would be easily reduced during
Pt or Au has been used as a suitable co-catalyst for H2 produc- the reaction forming well dispersed copper metal particles which
tion reaction.32 However, probably due to the lower photoactivities would favour electron trapping. Recently, Valero et al. prepared
obtained the number of published papers is scarce. two set of Cu-TiO2 systems by means of different deposition meth-
ods [158]. They proposed that easily reduced Cu2+ species obtained
preferentially by chemical reduction method could be the respon-
5.2. Non-noble metal co-catalysts sible of the higher photoactivity of Cu-TiO2 (Fig. 10).
Moreover, the final metal cluster size, dispersion and oxidation
As it has been discussed in the previous section, platinum has state could be strongly influenced by the structural and surface sup-
been frequently used onto semiconductor surfaces as a co-catalyst. port features [57]. Although Ni-TiO2 system has been also proven
However, if we pursue a scaling up production for water splitting- to be an alternative candidate to noble metal co-catalyst systems
hydrogen generation, the use of any platinum-based (or in general
noble metal based) material is quite questionable due to the scarcity
of this noble metal on the Earth’s crust which lead to an important
economic problem. In this sense recent important advances have
been achieved in the direction of mimicking the catalytic active
sites of natural hydrogenases which are based on earth-abundant
elements such as Cu, Fe, Co, Ni [145–150]. Among these transition
metal co-catalysts and although the reported rates till now are still
far from those obtained for noble metals, copper based catalysts
appear as a promising candidate [151]. In spite of the great num-
ber of papers dedicated to the study of Cu-based photocatalysts for
hydrogen generation, the nature of the active copper species (Cu2 O
or CuO) and other external factors governing its photoactivity is less
understood [152]. As already mentioned, the oxidised state of tran-
sition metal co-catalysts makes a difference with respect to noble
metal ones and includes an additional parameter to be considered.
Thus, within the discussion about the copper active species, some
authors claimed that Cu2 O species are responsible for the photoac-
tivity for H2 generation from water reduction [153]. Thus, Xi et al.
correlated the presence of easily reducible Cu2 O species toward
metallic Cu during the H2 production reaction with the improved
photocatalytic activity. Similarly, Jung et al. associated the higher
photoactivity of Cu-TiO2 systems to the dispersion and reducibility
of CuOx (Cu+ /Cu0 ) species [154]. On the other hand, other authors
argued that the presence of CuO would be responsible for the
enhanced separation of photoinduced electrons and holes [155].
In the same direction, Ampelli et al. reported the improving effect
of Cu2+ incorporation into the TiO2 structure and the simultaneous
creation of oxygen vacancies [147]. Thus, embedded CuOx@TiO2
Fig. 10. (A) H2 production for (a) CuSTi and (b) CuSTr series. (c) Calculated photonic
systems showed higher photocatalytic performances with respect
efficiencies for Cu-doped TiO2 ; (B) Schematic insight of copper situation on different
to impregnated samples [156]. Within this context, Korzhak et al. samples. (Reprinted with permission from Ref. [158]. Copyright (2014) American
investigated the relationships between the quantum efficiencies of Chemical Society).
 G. Colón / Applied Catalysis A: General 518 (2016) 48–59
Fig. 11. (a) Photocatalytic H2 evolution using the as-prepared metal NPs supported on TiO2 catalyst materials. (b) The derived H2 production rates and apparent quantum
efficiencies (AQE) of the metal NPs supported on TiO2 catalyst materials (Reprinted from Ref. [164] with permission from the Royal Society of Chemistry).
little investigation in relation to photocatalytic H2 production can
be found in the literature. As in the case of copper based systems,
confusion exists as to whether NiO or Ni is the active co-catalyst
species [159,160] In a recent paper, Chen et al. presented interesting
experimental evidences suggesting that highly dispersed metallic
Ni (∼1 nm sized clusters) would be the active co-catalyst species
[161]. Moreover, the 0.5 wt.% Ni/TiO2 photocatalyst showed supe-
rior activity to a 2 wt.% Au/TiO2 reference photocatalyst.
5.3. Bimetallic co-catalysts
As afore mentioned, in a metal-semiconductor configuration
the excited electrons need overcome the Schottky in order to be
transferred from the semiconductor to the deposited metal. Thus
the height of the Schottky barrier would determine the efficiency
of electron transfer. The extent of the Schottky barrier is directly
related to the work function of metal as well as the conduction
band electron affinity of the semiconductor. Taking into consid-
eration this premise the work function of the metal could be
tuned by the introduction of another metal with different work
function [162]. The formation of a bimetallic co-catalyst has been
proposed to promote the photocatalytic activity of the TiO2 -based
photocatalytic system instead of their monometallic counterparts.
Several examples of this approach have recently appeared in the
literature considering noble metal and transition metal homo-
and heterojunction. As monometallic co-catalyst platinum has
been extensively used since it shows the higher photocatalytic
performance for hydrogen production. However different bimetal-
lic formulations have been proposed denoting the wide field to
be explored. Thus, bimetallic Pt-Au [163,164] or Pt-Ag [165,166]
have been recently proposed for the hydrogen production reaction
showing improved photoactivities with respect to the monometal-
lic co-catalyst (Fig. 11).
It is clear that noble metals are expensive and rare candidates
to be used even in low loading percentage, making their practi-
cal use certainly doubtful. The development of alternative noble
metals-free substitutes have been discussed in the previous section
pointing out copper and nickel as promising alternative to Pt.
Upon this consideration, it can be deduced that the Cu–Ni
bimetallic co-catalyst might have an expected better performance
due to the synergy between both metals [167]. The study of these
heterostructured co-catalysts in different configurations (core-
shell, alloys) is opening new possibilities in the development of
highly efficient photocatalysts for hydrogen generation.
On the basis of all the above discussion reported in the litera-
ture it is clear that different parameters could strongly determine
the role of co-catalyst in the photocatalytic hydrogen evolution
reaction. Thus, factors such as the loading amount, the dispersion
57
and size of co-catalyst metal particles have considerable influence
on the photocatalytic activity. These points would suggest that in
addition to the electrocatalytic activity of surface redox reactions,
electronic interaction at the co-catalyst-semiconductor interface is
crucial.
6. Conclusion
From the huge number of contributions published in the last
years it is clear that the photocatalytic hydrogen production reac-
tion from water is an attractive reaction. The potential conversion
of solar energy and renewable resources (such as alcohols or
biomass derivatives) into valuable fuels by photoreforming pro-
cess is undoubtedly not only attractive but also very necessary
under the point of view of the global sustainability. However,
much heavier efforts are needed to understand the behaviour of
complex molecules such as carbohydrates. As it can be envisaged
along this short overview the development of highly efficient pho-
tocatalytic material is by the moment a crucial task that might
be strongly reinforced. On one hand the investigation of highly
active semiconductors or heterostructured systems that could (i)
use as much as possible the solar radiation and (ii) optimize the
electronic mechanism of photogenerated pairs separation. Sec-
ondly the incorporation of efficient reduction (and even oxidation
co-catalysts, only slightly mentioned in this review) co-catalysts
economically suitable for this application that could enhance the
photocatalytic efficiency by improving the charge transfer to adsor-
bates. By now, the low quantum efficiencies reported and the
absence of adequate scaling-up studies, lead to practical lack of
industrial application. Unfortunately, we have to admit that Verne’s
prediction of a “solar fuels” industry from water is still no more
than a futuristic concept. For this reason the development of a suit-
able photocatalyst is extremely decisive and might encourage us to
emphasize our efforts for this scope.
Acknowledgments
The financial support by CTQ2014-60524-R project is fully
acknowledged.
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