Alternative Photocatalysts To TiO2 For The Photocatalytic Reduction of CO2 2016 Applied Surface Science

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APSUSC-33542; No. of Pages 26
Applied Surface Science xxx (2016) xxxxxx
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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc
Alternative photocatalysts to TiO2 for the photocatalytic reduction of

CO2
Aspasia Nikokavoura, Christos Trapalis
Institute of Nanoscience & Nanotechnology, NCSR Demokritos, Agia Paraskevi Attikis, 15343, Athens, Greece
a r t i c l e
i n f o
Article history:
Received 20 May 2016
Received in revised form 24 June 2016
Accepted 27 June 2016
Available online xxx
Keywords:
Photocatalytic reduction
CO2
Photocatalysts
Semiconductors
Solar fuels
Articial photosynthesis
a b s t r a c t
The increased concentration of CO2 in the atmosphere, originating from the burning of fossil fuels in stationary and mobile sources, is referred as the Anthropogenic Greenhouse Effect and constitutes a major
environmental concern. The scientic community is highly concerned about the resulting enhancement
of the mean atmospheric temperature, so a vast diversity of methods has been applied. Thermochemical,
electrochemical, photocatalytic, photoelectrochemical processes, as well as combination of solar electricity generation and water splitting processes have been performed in order to lower the CO2 atmospheric
levels. Photocatalytic methods are environmental friendly and succeed in reducing the atmospheric CO2
concentration and producing fuels or/and useful organic compounds at the same time. The most common photocatalysts for the CO2 reduction are the inorganic, the carbon based semiconductors and the
hybrids based on semiconductors, which combine stability, low cost and appropriate structure in order to
accomplish redox reactions. In this review, inorganic semiconductors such as single-metal oxide, mixedmetal oxides, metal oxide composites, layered double hydroxides (LDHs), salt composites, carbon based
semiconductors such as graphene based composites, CNT composites, g-C3 N4 composites and hybrid
organic-inorganic materials (ZIFs) were studied. TiO2 and Ti based photocatalysts are extensively studied
and therefore in this review they are not mentioned.
2016 Elsevier B.V. All rights reserved.
1. Introduction
1.1. Solar energy solar fuels
The sun constitutes the major energy source in Earth, by providing in one hour all the energy needed by humanity for one year. The
basic problem for the inhabitants of the Earth, is that they are not
able to exploit these huge amounts of energy [1]. The total emitted
solar radiation reaching the Earths surface is composed of infrared
radiation (52%, >700 nm), visible radiation (43%, 400700 nm) and
ultraviolet radiation (5%, <400 nm). There are several types of solar
energy collectors, some of them have at surface and collect the
Abbreviations: AC, activated carbon; ATP, adenosine-tri-phosphate; CB, conduction band; CCS, carbon capture and storage; CNTs, carbon nano-tubes; CTA,
cetyl-trimethyl-ammonium; DAC, direct air capture; DHF, di-hydro-furan; DMF,
di-methyl-formamide; LDHs, layered double hydroxides; NADPH, nicotinamide
adenine dinucleotide phosp-hate; OFMR, optical ber monolith reactors; PEC,
photo-electrochemical reduction; RGO, reduced graphene oxide; SSR, solid state
reaction; THF, tetra-hydro-furan; VB, valence band; ZIFs, zeolitic imidazolate frameworks.
Corresponding author.
E-mail address: c.trapalis@inn.demokritos.gr (C. Trapalis).
solar irradiation without concentrating it, so its intensity is rather

low. There are also solar energy collectors that concentrate the solar
irradiation (such as reectors and luminescent solar collectors) but
they are not commercially available because they are not stable and
they exhibit inadequate collection efciency [2]. For over 50 years,
serious attempts have also been performed in order to produce
useful compounds-fuels by utilizing solar energy.
The solar fuels are compounds produced via a biomimetic
approach that have captured and stored solar energy in their chemical bonds (chemical energy) [3]. The production of solar fuels is a
great challenge for the scientic community. Solar fuels constitute a
broad group of chemicals that can be used for electricity generation,
transport and industrial purposes. The two main categories of solar
fuels are (a) hydrogen and (b) carbon based fuels such as methanol
(CH3 OH), carbon monoxide (CO) and methane (CH4 ). Another signicant goal for the scientists is the large scale production of the
solar fuels, their transportation, their storage and the opportunity
to be commercially available [1].
http://dx.doi.org/10.1016/j.apsusc.2016.06.172
0169-4332/ 2016 Elsevier B.V. All rights reserved.
Please cite this article in press as: A. Nikokavoura, C. Trapalis, Alternative photocatalysts to TiO2 for the photocatalytic reduction of CO2 ,
Appl. Surf. Sci. (2016), http://dx.doi.org/10.1016/j.apsusc.2016.06.172
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1.2. Production of solar fuels

1.2.1. Hydrogen-water splitting
Hydrogen (H2 ) is a very useful solar fuel with serious advantages
and disadvantages. As major advantages are considered, its abundance in water and biomass, its convenient storage as hydride, the
absence of pollutants after its combustion and the high amount of
energy released when it is used as a fuel. On the other hand, hydrogen must be highly compressed during its transportation and this is
an expensive process or it must be stored as a metal hydride which
is an expensive and rather dangerous process too [4]. It is a transport fuel but it is also used in many industries. In nature, hydrogen
is produced from water splitting via various molecular reactions
involving PSII (photobiological water splitting). The water splitting
mechanism includes the formation of a large number of reaction
intermediates which nally produce dioxygen, electrons and protons. Advanced techniques have shown an interaction between the
metal center which acts as a catalyst and its protein environment
that induce the oxidation of the water molecules. The mechanism
of the biological formation of hydrogen by the reaction of electrons
and protons, formed from photosynthesis (PSI or PSII), is not fully
understood, but it is clear that enzymes such as hydrogenases and
nitrogenases play a crucial role, as they produce hydrogen from
protons and electrons formed via water splitting [5]. By mimicking
the nature, scientists tried to use to advantage the most abundant material in Earth, water, in order to produce hydrogen. Steam
reforming, constitutes a process which involves the generation of
hydrogen from CH4 and steam (H2 O) via the production of CO, is
mainly used for hydrogen production. Besides, hydrogen is generated by coal gasication, a process that involves the reaction of coal
with O2 and steam at high temperature and pressure and produces
mainly a mixture of hydrogen, methane, CO2 and CO. Biological,
pyrolysis and thermochemical processes that use the biomass are
also used for the production of H2 . All these conventional methods followed for the formation of H2 require enhanced amounts
of energy. Besides, the formation of pollutants such as CO2 , as
byproducts, is not avoided. It is also widely known that hydrogen
is produced via electrolytic or thermochemical or photobiological
or photocatalytic water splitting. The thermochemical water splitting uses the heat from the sun, whereas the photocatalytic water
splitting uses the sunlight irradiation and photocatalysts i.e. materials that accelerate the reaction, they are found in tiny amounts in
the reaction mixture and they are not consumed at the end of the
reaction. The general principle is that the energy of the absorbed
photons must be higher than the band-gap energy of the photocatalyst, in order to achieve the photogeneration of electrons and
holes participating in the redox reactions which produce hydrogen
and oxygen. Specically, photoinduced electrons, transported from
the valence band (VB) of the photocatalyst to the conduction band
(CB), reduce H+ to form H2 , on its surface. Photogenerated holes
oxidize H2 O to H+ and O2 in VB. Photocatalysts such as the TiO2
analogues and other metal oxides and salt composites have been
widely used [4,6].
1.2.2. Carbon based fuels natural/articial photosynthesis
The natural photosynthesis is the way of the biological world
to produce organic fuels, such as sugars, using mainly two abundant compounds, H2 O and CO2 , via the harvest and exploitation
of solar energy. The natural photosynthetic process exhibits low
overall efciency, still it constitutes an inspiration for scientists in
order to produce useful fuels from CO2 , H2 O and sunlight. The natural photosynthesis involves the utilization of compounds that can
be oxidized producing electrons, compounds that can be reduced
from these electrons producing fuels and of course solar irradiation. Green plants, algae and cyanobacteria absorb the solar energy
in order to oxidize water to O2 , protons and electrons. The pho-
togenerated electrons possess adequate negative redox potential,

thus they are able to reduce photogenerated protons and CO2 in
order to form hydrogen gas, carbohydrates and lipids. Plants consist
of a number of subsystems combined together, so that to perform
the photosynthetic process. Antenna systems are responsible for
targeting the appropriate wavelengths of light and transporting
that energy to the reaction centers, where the transfer of photoinduced electrons takes place and charge separated states are
formed. Water oxidation and O2 formation is accomplished at the
reaction center in PSII after the absorption of four photons whilst
H+ and CO2 reduction is carried out by the biological molecule
NADPH (nicotinamide adenine dinucleotide phosphate). The formation of ATP (adenosine triphosphate), which has a key role in the
transportation of energy by several enzymes and the generation
of transmembrane proton gradients is also realized by reduction
mechanisms. In conclusion natural photosynthesis is a very complicated exergonic process, consisting of a large number of redox
reactions which lead to the production of carbon based fuels [7,8].
On the other hand, by the term articial photosynthesis is meant
the utilization of CO2 , renewable (solar) energy, synthetic catalysts
and water in order to produce a large range of fuels/chemicals such
as hydrogen and carbon based compounds [9]. Water is used as
reductant that is the electron source. In articial photosynthesis
the rst step is the absorption of the ultraviolet or visible radiation. The second step is the charge generation and separation and
the last step is the catalytic reaction [10]. Inspired by the natural photosynthesis, where chlorophyll molecules diffuse sunlight,
articial photosynthetic reactions also need the presence of light
harvesting complexes, such as dye sensitizers. The photon capture
is followed by the electron-transfer reactions that lead to charge
separation. This means that electrons and positive holes move apart
in order to avoid charge recombination, leading to the formation
of potent oxidizing or reducing species. These species drive the
desirable redox reactions such as CO2 reduction. A major difference between natural and articial photosynthesis is the capability
of biological systems to induce self repair. Unfortunately, until now
there is no man-made photocatalyst with the ability to retrieve the
loss of reactivity during operation [11,12]. The articial photosynthesis products are used as synthetic fuels for transportation and
storage or as useful industrial materials (plastics, fertilizers, pharmaceuticals, chemicals etc.) [1]. The greatest benet is obtained in
case that a direct conversion of solar energy into fuels is achieved.
The use of water as a raw material is an important perspective too.
The catalysts for the articial photosynthesis may be either nanomaterials with nature guided design, or molecular compounds or
solid state components, or combinations of them. Their common
feature is the way that they participate in the multielectron redox
reactions during the articial photosynthesis process. Abundant
or less abundant materials can be used as homogeneous or heterogeneous catalysts. The most common molecular catalysts are
based on ruthenium and constitute model systems for the study
of articial photosynthesis [13,14]. In Fig. 1 a comparison of natural photosynthesis and articial photosynthesis is shown [14]. One
principal scientic goal currently is the enhancement of the photocatalytic efciency in the CO2 reduction by using technical means.
Methanol and methane are the most important solar fuels resulting from the photocatalytic CO2 xation as they can store a lot of
hydrogen. Other possible products are CO, HCOOH, HCHO and H2
[15].
1.3. Why the reduction of CO2 in the atmosphere is so important?
Greenhouse effect and mitigation of CO2
The burning of fossil fuels, apart from their depleting them, has
raised serious environmental issues, such as the anthropogenic
Greenhouse effect which is considered as one of the most seri-
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Fig. 1. Comparison of natural photosynthesis and articial photosynthesis [14].
Fig. 2. Carbon dioxide neutral cycle with renewable methanol and liquid fuel production [18].
ous environmental problems on Earth. CO2 is one of the main

greenhouse gases emitted by the combustion of coal, petroleum
and natural gas in stationary and mobile sources and therefore its
contribution to global warming is signicant. Other important longliving greenhouse gases are: CH4 , N2 O and CFCs. By that means,
these gases absorb infrared light irradiation and re-emmit it in the
atmosphere, where it is trapped, resulting in global warming [16].
It is estimated that the CO2 concentration in the atmosphere
rises every year at a rate higher than 2% and as a result, the average
temperature on the Earths surface has increased around 0.40.8 C
over the last century. It is predicted that the mean global temperature may rise by 1.9 C and that the level of CO2 might climb to
590 ppm. Global warming causes the melting of the ice at the poles,
the expansion of the oceans and the loss of large ice quantities
from Greenland and Antarctica which cause an increase of the sea
level. The extreme meteorological phenomena (abnormal winds,
aridity, oods) constitute some extra consequences of the Greenhouse effect. For example, a decrease in rainfall in certain areas
may diminish the required water supplies for people, ecosystems,
agriculture. The enhanced precipitation in other areas constitutes
an extra worrisome factor. Besides, the last 25 years the increase in
CO2 concentration is spectacular and may lead to a possible alteration of the radiative balance on the planet. On the other hand, CO2
certainly is an important gas in the atmosphere because it takes
part in the Carbon cycle as a carbon source [1720]. Generally, in
order to achieve the decrease in the CO2 concentration in the atmosphere, the carbon dioxide neutral cycle, otherwise known as the
net carbon neutral cycle, should be completed. Several steps are
important for the maintenance of this cycle, such as the recycling
of CO2 after the fuels combustion, the use of renewable energy
(wind energy, direct solar energy etc.) for the CO2 reduction, the
capturing and recycling of CO2 not only from the point source but
also from the atmosphere In Fig. 2 the carbon dioxide cycle with
renewable methanol and liquid fuel is presented [18].
Beyond the articial photosynthesis way to reduce the CO2 concentration in the atmosphere, there is also the Carbon Capture
and Storage (CCS) pathway. CCS comprises the collection of CO2
emissions mainly from the industry and the power stations, the
generation of almost pure CO2 using a wide range of techniques,
and its transportation after compression and liquication, to the
seabed or other geological deposits. CCS has important drawbacks,
as CO2 from the transportation, the residential and the commer-
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2. Photocatalytic approaches/mechanism for the reduction

of CO2 -main categories of photocatalysts
Fig. 3. CO2 emission from different sectors [21].
cial sectors cannot be exploited. Furthermore, the CO2 separation

from other gases needs large amounts of energy. Direct air capture
(DAC) involves an alternative process with lower energy requirements. DAC involves the reaction of the weakly acidic CO2 with an
alkali component in order to separate it, in the form of salt, from
other neutral gases such as nitrogen and oxygen. Following that,
a regeneration process of the CO2 from the salt and the recycling
of the alkali component take place. DAC may be performed anywhere, so the pressurization and transportation via pipelines of
CO2 is minimized [19,21]. In conclusion, pressurization, liquication and transportation of CO2 raise the cost of these processes.
Furthermore, the cost of the required energy to convert CO2 into
chemicals is rather high, there are no convenient commitments in
order to increase the CO2 originating chemicals and the governments do not support economically these actions [22,23]. In Fig. 3
the CO2 emission from various sectors is presented [21].
Furthermore, the reduction of the CO2 concentration in the
atmosphere can be accomplished via the thermochemical, electrochemical, photocatalytic, photoelectrochemical processes, as well
as the combination of solar electricity generation, water splitting
and CO2 reduction. Each of them has advantages and disadvantages. The main handicap of all the thermochemical approaches is
that they require high temperatures, which means that the cost
of heat supply is signicantly raised. In other words, by following
these thermochemical processes the energy costs are very high,
whereas, actual mitigation of the atmospheric CO2 does not take
place [2426].
The electrocatalysis involves the use of electrodes and an external circuit. Specically, at the anode, water is oxidized to give O2
and electrons. These electrons arrive at the cathode via an external circuit and reduce CO2 to several products such as CO, CH3 OH
etc. In the case that appropriate electrodes and catalysts are used,
high product yields are obtained. Besides, the reduction and oxidation reactions are performed in different spaces and thus the
interference between the two kinds of reactions and their products
is totally avoided. From the opposing point of view, the electrodes
may be easily deactivated, or they are not rather stable. Also, the
competitive reaction, the water splitting, affects the CO2 reduction efciency. Apparently, the combination of photovoltaics (PV)
and electrocatalysis is proved to be friendlier for the environment
[24,2729].
The photocatalytic approach (articial photosynthesis) constitutes a very convenient way to reduce the atmospheric CO2 , by
using solar energy, which is the most abundant kind of energy on
Earth. Photocatalytic reduction of CO2 or articial photosynthesis,
as it is called, succeeds in reducing CO2 concentration in the atmosphere and generating fuels or/and useful organics at the same
time [10,30]. Certainly, although the energy of the Sun is cheap
and abundant, it is impossible to be exploited in the nights or in
cloudy days, thus it is important to store it in a convenient way
which involves high energy densities. Besides, reduction of CO2
requires large amounts of solar energy due to CO2 thermodynamics.
Still, as far as the CO2 reduction is concerned, photocatalytic methods seem to be environmental friendly and they are preferred over
other methods such as thermochemical or electrochemical ones. By
the term of photocatalysis is meant the direct conversion of solar
energy into chemical energy. Photocatalytic conversion of CO2 into
a vast variety of useful compounds such as CO, CH4 , CH3 OH, HCHO,
HCOOH is conducted either in liquid or in gas phase. In case that
water molecules are present, two basic reactions take place, the
rst one is the photoinduced water splitting to oxygen and hydrogen (1), and the second one is the combination of the photoinduced
activation of CO2 and the oxidation of water (2):
h + 2H2 O 2H2 + O2
(1)
h + H2 O + CO2 Fuel + O2
(2)
Generally, a photocatalytic system for the CO2 reduction must

(a) capture photons of light irradiation effectively, (b) produce
efciently photoinduced electrons and holes that (c) they are
transferred quickly to the photocatalyst surface (d) to the appropriate catalytic sites where CO2 is reduced (e) without recombining
quickly.
The combination of photochemical and electrochemical processes in order to reduce CO2 into valuable fuels constitutes the
photoelectrochemical (PEC) reduction of CO2 . The disadvantage of
this process is that it is electricity-dependent but its advantage is
its higher efciency due to the lowering of the recombination rate
of photogenerated electrons and holes. The difference between the
electrochemical and the PEC reduction of CO2 , is that in the latter, the semiconductor electrode (photoelectrode) is irradiated by
UV or visible light with photon energy greater than the band-gap
energy of the semiconductor. External bias voltage is also necessary
for the PEC CO2 reduction. Then, photoexcited electrons are transported from the valence band to the conduction band and then they
travel via an external circuit to the cathode counter electrode where
they perform the reduction reactions, via the formation of CO2 *
radical anion. Still, recombination and corrosions of the photoinduced species are not avoided. Besides, electron-hole pairs travel
through the electrolyte and perform oxidation and reduction reactions on the surface of the appropriate electrodes. It is found that
photoelectrolysis of water and photoreduction of CO2 happen at
the same time during the PEC process. Generally, PEC is performed
in liquid phase solutions, either with homogeneous or with heterogeneous catalysts. Contrariwise, in electrochemical reduction
of CO2 over the cathode material, the electrons and protons originate from the anode material where water is oxidized via using
electric energy. A major disadvantage of the PEC process is the
inevitable degradation of the photoanode and the photocathode
due to their photoinstability. This disadvantage is usually cleared
by using non-corroding metallic layers on the surface of the semiconductor which prevent the contact of the electrolyte and the
semiconductor. Transition metal complexes of Ru, Re, bearing a
large variety of geometries, have been used as homogeneous cat-
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alysts for the CO2 reduction. Non-oxide semiconductors, such as

p-GaP, n- and p- GaAs, n-Si, p-InP, GaP, CdS, SiC [28], p-CuInS2 [31]
and oxide semiconductors such as WO3 , TiO2 , ZnO [28] are used as
cathode materials (heterogeneous photocatalysts) and reduce CO2
to CH4 , CH3 OH, HCHO and HCOOH after several hours of illumination. In other cases, a molecular catalyst may be attached onto the
surface of the photocathodic semiconductor [32].
In a PEC cell, CO2 has been reduced either by using p-InP semiconductor bearing a biological catalyst (enzyme) over its surface
or by using colloidal semiconductor suspensions [24,25,28]. Gas
phase PEC CO2 reduction has also been studied by using a TiO2
covered photoanode where gaseous H2 O, under light irradiation, is
converted into electrons and protons which reduce gaseous CO2 on
a metal loaded carbon based electrode, with high electron conversion efciency [33]. PEC reduction of CO2 in gas-phase has several
advantages such as the enhanced solubility of CO2 and the easier recovery of the products. The use of inexpensive and versatile
nanocarbon materials, contributed to the enhancement of the reactivity and selectivity of the CO2 reduction because they have not
only conductive properties but they also facilitate the electron
mobility, the mass transfer, the dispersion of metal nanoparticles (Pt, Fe) and the formation of active hydrogen species [34].
It has also been reported the study of a solar cell driven electrochemical process, where a two-electrode system, comprising of a
copper wire (cathode) and a platinum wire (anode) are involved.
The CO2 reduction takes place on the cathode and CO2 exists as
dilute aqueous KHCO3 solution. The production of a mixture of
organic compounds, such CH3 OH, HCHO, HCOOH, CH4 , is competitive to the H2 O splitting that produces H2 . The reaction mechanism
involves the excitation of the solar cell by sunlight irradiation, the
photogeneration of electrons and holes, the oxidation of H2 O to O2
and H+ on the anode and the passing of the H+ through a cation
exchange membrane to the cathode where H radicals are formed.
When two H radicals recombine, H2 is produced via a competitive
reaction to CO2 reduction [35].
Sometimes there are advantages in combining the solar water
splitting process with reactions of CO2 reduction. In that way,
hydrogen, produced by the water splitting, may reduce the CO2
to CH3 OH or other useful materials. For example, an electrolysis
cell, with a photoelectrode which absorbs UV/visible light irradiation (photons), generates electrons and holes which electrolyse
water to produce O2 and H2 . Certainly, there are several factors
that must be obeyed at the same time, the band-gap energy of the
photoelectrode must be low enough in order to absorb visible light
irradiation and high enough in order to generate electrons capable
of performing water splitting. Besides, the photoelectrode must be
stable, inexpensive and resistant to corrosion. Oxides (TiO2 , CaTiO3 ,
SrTiO3 ), composite oxides and double layered semiconductors have
been tested, but it is very challenging to satisfy all these demands
[24,29]. Alternatively, electricity can be generated via the usage of
solar energy, such as photovoltaics (PV) then by the usage of that
electricity, water splitting is performed via an electrolysis process
and the produced H2 may be used for the conversion of CO2 to
useful organic compounds. This idea is theoretically promising but
there are several difculties that must be overcome, such as the
high cost of the processes, the storage of H2 and the space needed
for the conversion of solar energy to electricity by the use of PV
[32].
Among all the above methods used for the reduction of
CO2 , the most promising one seems to be the photocatalytic
reduction because it is simple, friendly for the environment, nonelectricity/heat dependent and relatively costless.
The most widely used photocatalyst for the CO2 reduction is TiO2
semiconductor, then, titania based photocatalysts or titanates follow [36]. The properties of TiO2 , such as the band-gap energy, were
improved when it was loaded with metals or non-metals or when
it was modied to form for example nanotube arrays or dispersions

in zeolites [26]. Indeed, functionalized titanates have been recently
synthesized which exhibited rather high photocatalytic activities
under visible light irradiation [37]. As Ti based photocatalysts are
extensively studied, in this review, non-Ti based photocatalysts, are
studied as far as it concerns their structure, composition, physical
and chemical features, reactivity towards CO2 reduction and the
reaction mechanisms where they participate. During the last few
years, especially since 2012, a remarkable increase in the number of
the published papers in the research eld of the CO2 photocatalytic
reduction by non-TiO2 catalysts has been remarked, as shown in
Fig. 4. For that reason we believe that a wide scope review on this
subject would encourage researchers to continue their efforts in
this exciting and promising scientic eld.
The in depth study of the non-TiO2 photocalysts for the CO2
reduction is facilitated in case that they are categorized into several
groups depending on their structure/chemical nature. Inorganic
photocatalysts constitute the rst category which is consisted
of the following sub-categories of single-metal oxides, mixedmetal oxides, metal oxide composites, layered double hydroxides
(LDHs) and salt composites. Carbonaceous photocatalysts constitute the second, more recent, category, which is composed of the
sub-categories of graphene (GR), carbon nanotubes (CNTs) and
g-C3 N4 composites. Lately, a third category that of hybrid organicinorganic photocatalytic materials appeared. In Table 1, the main
groups of non-TiO2 photocatalysts for the reduction of CO2 , as
well as the type of the irradiation and the experimental conditions
required, are depicted.
The very low sensitivity to solar irradiation which is the
main disadvantage of TiO2 , was not bypassed for a large number of inorganic photocatalysts such as the single-metal oxides
and mixed-metal oxides. Contrariwise, metal oxide composites,
LDHs and salt composites absorb mainly in the visible part of
the spectrum exhibiting rather high photocatalytic efciencies. On
the other hand, almost all the carbonaceous and hybrid photocatalytic materials absorb visible light and this fact contributes to
their superiority. Additionally, they exhibit excellent electronic and
physicochemical properties which facilitate the mechanism of the
photocatalytic CO2 reduction, often resulting in amazing photocatalytic efciencies. Besides, the facile synthetic processes, the low
cost and the abundance of the raw materials make the preparation of carbonaceous photocatalysts more attractive and maybe
the most attractive candidates for the CO2 photocatalytic reduction
[38,39].
Generally, the most important factors that inuence the efciency of the photocatalytic reduction of CO2 are the degree of
visible light excitation, the charge excitation and transport, the
adsorption and activation of CO2 on the surface of the photocatalyst, the kinetics of the CO2 reduction and the possible undesirable
reactions tha may take place during the photocatalytic reduction
of CO2 , as shown in Fig. 5 [40].
3. Inorganic photocatalysts for CO2

reductionsemiconductors
Semiconductors are among the rst photocatalytic systems used
for the performance of solar driven reactions. They possess relatively high stability and they ensure mobility of charge carriers
enabling their transportation to the surface and letting the redox
reaction begin. They are also inexpensive materials [41]. When
semiconductors absorb light irradiation consisting of photons with
energy equal or greater than their band gap, photoexcitation takes
place. Electrons are excited from the valence band (VB) to the conduction band (CB) of the semiconductor leaving an unoccupied
state (electron hole) in the valence band. Most of the times, elec-
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Fig. 4. Number of published papers per year, in the eld of the photocatalytic CO2 reduction by alternative photocatalysts to TiO2 (Science Direct December 2015).
Table 1
Main categories of non-TiO2 photocatalysts for CO2 reduction.
Non-TiO2 photocatalyst description
Type of irradiation
Experimental conditions
Inorganic
Single-metal oxides
UV/VIS
Mixed-metal oxides
Metal oxide composites
Layered Double Hydroxides (LDHs)
UV/VIS
VIS (mainly)
UV/VIS
Salt composites
UV/VIS (mainly)
Solid-gas (catalyst-CO2 /H2 O, catalyst-CO2 /H2 ,

catalyst-CO2 /CH4 ) systems/Aqueous dispersions
Solid-gas (catalyst-CO2 /H2 O) systems/Aqueous dispersions
Solid-gas (catalyst-CO2 /H2 O) systems/Aqueous dispersions
Solid-gas (catalyst-CO2 /H2 O, catalyst-CO2 /H2 )
systems/Aqueous dispersions
Aqueous/organic solutions
Carbonaceous photocatalysts
Composite photocatalysts based on graphene (GR)
Composite photocatalysts based on carbon nanotubes (CNTs)
g-C3 N4 and composite photocatalysts based on g-C3 N4
VIS
VIS
VIS
Aqueous dispersions
Aqueous dispersions
Aqueous dispersions/Solid-gas (catalyst-CO2 /H2 O) systems
VIS
Aqueous/organic solutions
Hybrid organic-inorganic materials-Zeolitic imidazolate frameworks-ZIFs)
trons and holes recombine to release the absorbed energy as heat

or rarely as light and thats the reason behind the very low photocatalytic efciency. When they dont recombine, they migrate to
the surface of the semiconductor where they are trapped by the
adsorbed reactants and the photocatalytic redox reactions begin.
Conduction band electrons reduce adsorbed species on the surface
of the catalyst. On the other hand, valence band holes are oxidants,
evoking direct oxidation of the adsorbed species or indirect oxidation via surface-bound hydroxyl radicals formed by holes trapped
at the semiconductor surface [38,4245].
CO2 is a very stable molecule as it constitutes the combustion
nal product of all the carboneous fuels. The conversion process
to potential fuels is endothermic and therefore demands very high
sums of energy [46].
The photochemical reaction that takes place during the articial
photosynthesis is shown below:
CO2 + H2 O(orH2 ) + photocatalyst + h
Carbonaceous products + O2 [16]
Because of the thermodynamical inertness of the CO2 molecule,

the electrons reaching the semiconductor surface are not all capable of reducing CO2 . The reducing potential of a species is a measure
of its reducing power, and the higher (more negative) it is the
more reductive the species is. Therefore, photoexcited electrons
must have higher reduction potentials (more negative) than water
reduction producing H2 . Otherwise H2 will be produced from water
reduction which is a competitive reaction to the CO2 reduction.
Band levels of some simple and widely used semiconductors are
shown in Fig. 6 [46].
Furthermore, the reaction mechanism of CO2 reduction must
have multiple stages during which electrons and protons are transferred. In case of a single electron transfer to CO2 in order to produce
CO2 , the reduction potential is too high (E red = 1.9 V) making
the progress of the photocatalytic reaction very difcult. If a proton is simultaneously transferred to the CO2 , the radical anion
of CO2 * is produced, which is stabilized reducing the reduction
potential (E red = 1.23 V) and therefore making easier the progress
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Fig. 7. Diagram of photoexcitation and electron transfer process [47].
Fig. 5. Main factors inuencing the photocatalytic efciency of the reduction of CO2
and strategies for its enhancement [40].
Fig. 6. Band levels of simple semiconductors [46].
of the reaction. Generally, when protons and electrons are transferred simultaneously in many small, rapid successive steps the CO2
photoreduction is facilitated [47,48]. Depending on the number of
electrons used, the reaction product can be methane, methanol,
formaldehyde, carbon monoxide or formic acid. In Fig. 7 the photoexcitation and electron transfer process for the production of CO
is pictured [47]. The main reactions followed and values of reduction potentials at pH = 7 during the articial photosynthesis are
shown below:
CO2 + 2e CO2
E red = 1.90 V(VvsNHE)
CO2 + 2e + 2H+ HCOOH
CO2 + 2e + 2H+ CO + H2 O
CO2 + 4e + 4H+ HCHO + H2 O
CO2 + 6e + 6H+ CH3 OH + H2 O

CO2 + 8e + 8H+ CH4 + H2 O
2e + 2H+ H2
E red = 0.42 V(VvsNHE)[46, 47]
Although CO2 photoreduction is a very challenging process,

there are serious matters that hinder its worldwide use at this time.
The low efciency of the CO2 photocatalytic reduction is the major
problem, which is ascribed mainly to low visible light absorption of
the semiconductors. The band gap energy of a semiconductor determines which part of sunlight spectrum is absorbed. The wider the
band gap energy, the shorter the sunlight wavelengths absorbed.
When the band gap energy of a semiconductor is relatively high,
then only the ultraviolet part of the sunlight spectrum is absorbed,
meaning that only about 5% of the solar radiation reaching the
Earths surface can be utilized and the remaining 95% remains unexploited. As a result, low efciencies for the photocatalytic reactions
are observed.
Finding ways to reduce the band gap of a semiconductor is of
great importance because it would allow us to take advantage of
the visible part, which comprises almost half of the solar spectrum
[47,49]. Usually metal ions (ferric, tangstate, etc.), or non metal
ions (carbon, nitrogen etc.) doping of semiconductors has a positive
effect on the photoactivity in the visible part of the solar spectrum.
Besides, it is well accepted that noble metals (Au, Ag, Pd, Pt) doping contributes to the capture of CB electrons on the surface of
the photocatalysts and thus lowers the possibility of recombination of the photogenerated electrons/holes; additionally it reduces
the activation energy for the photocatalytic reduction of CO2 [50].
By the term doping is meant the assimilation of atoms or ions into
the bulk of a semiconductor crystallite without altering its surface
[38]. Doping must be performed at low concentrations in order to
avoid recombination of holes and electrons which is fostered by
the presence of metal ions. Furthermore, dopants must not distort
the semiconductor lattices, so it is very important for their concentrations not to exceed the allowed limits during semiconductor
synthesis. If dopants are found in the appropriate proportion into
the semiconductor, their photoactivity is signicantly improved.
Photosensitizers, such as organic dyes or quantum dots (QDs), combined with semiconductors, improve the photocatalytic efciency
because they increase the absorption at the visible part of the
spectrum. When a semiconductor absorbs visible radiation, photoexcited electrons transit from the dye to the conduction band
and therefore facilitate the progress of the photocatalytic reaction. Besides, the introduction of structural defects and the surface
plasmon resonance effect (SPR) increase the visible light excitation
[40,43,46,47].
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One other way to increase the photocatalytic efciency of the

CO2 reduction is to couple two semiconductors together providing
that their reduction potentials are related and that the semiconductors interact adequately with each other. The result of this coupling
is the physical separation of charge carriers following their generation and the hampering of their recombination. Furthermore,
the semiconductor with the shorter band gap can act as a photosensitizer making the composite material absorbing visible light.
[43,51].
It is established that bulk semiconductor photocatalysts dont
exhibit the maximum of their reactivity in the CO2 reduction,
whereas, when they form nanoparticles, a signicant rise to their
reactivity is observed. Particle size of the photocatalyst has an
impact on the photocatalytic reactivity, but not so signicant. It
has been shown that the particle size of a semiconductor affects
the band gap energy. The smaller the particle is, the wider the
band gap becomes, altering the values of reduction potentials
and thus the reduction and oxidizing power. Besides, particle size
affects the tendency for recombination of separated species upon
their generation. The increase of the total surface area per volume
of a semiconductor also increases its photocatalytic reactivity by
increasing the number of reaction sites. Besides, the decrease of
the particle size leads to a considerable increase in the afnity of a
semiconductor to adsorb CO2 and thus enhances the photocatalytic
efciency [46,52].
Plenty of different morphologies of nanoparticles can be
achieved depending on reaction conditions during the semiconductor synthesis process. It has been shown that the morphological
and structural characteristics of a nanoparticle affect its photocatalytic reactivity. The separation of photoexcited electron-hole
pairs and their transfer to the surface of a semiconductor is
essentially assisted when hierarchical heterostructures are used.
Spherical nanoparticles (zero dimensional) have the advantage
of a high ratio surface/volume, so charge carriers have a short
distance to traverse before reaching the surface. When different
morphologies are combined, they may lead to the formation of a
hierarchical heterostructure with upgraded photocatalytic efciencies. For example when spherical nanoparticles (ZnO and Al2 O3 )
are combined with CdS nanowires, photocatalytic reactivity of the
hydrogen generation reaction is enhanced because of the resulting
high surface area and the efcient charge separation. Nanostructures can also assume the form of wires, tubes and belts (one
dimensional) differentiating themselves from the bulk semiconductors. It has been found that as the length of a nanoparticle
increases the same happens to its photocatalytic efciency. Besides,
hydrothermal and/or calcination processes usually improve the
photocatalytic reactivity of heterostructures owing to increased
porosity, chemical or thermal stability. Other morphologies include
the two dimensional structures with a platelet shape and the placing of chemical particles on them. In this way, high surface area
and remarkable electric properties are ensured for the semiconductor. Graphene or graphene-based composites are usually used as
platelet supports. Three dimensional mesoporous structures have
also been mentioned. For example, In(OH)3 with mesoporous structure exhibited almost 20 times higher photocatalytic efciency
towards the reduction of CO2 (0.8 mol CH4/ g* h) than that of nIn(OH)3 (0.04 mol CH4/ g* h) [53]. The 3D mesoporous structures
possess multidimensional domains at different levels and complex/fascinating pore structures. In this case, the large number of
multi-sized pores ensures the large specic area and the high rate
of transfer for the species. Besides, the CO2 molecules easily diffuse into the reaction sites and the products are easily removed
from them. As a consequence, the photocatalytic reactivity of the
semiconductor is highly enhanced. Some typical three dimensional structures (hierarchical nanostrucrures) are the urchin-like,
Fig. 8. Mechanism for the photoreduction of CO2 with H2 O over the ordered mesoporous Fe doped CeO2 [59].
brush-like, ower-like, tree-like, dendritic and branched structures

[38,51,54].
3.1. Single-metal oxides
The rst photocatalytic systems, studied for the CO2 reduction were the inorganic single-metal oxide semiconductors. The
photogenerated electrons are transferred from the VB to the CB,
forming electron/hole pairs (e /h+ ) which further reduce/oxidize
compounds adsorbed on the surface of the semiconductor [52]. The
most popular semiconductor is TiO2 , pure or modied, alone or in
composites. TiO2 semiconductors exhibit some great advantages
such as high stability, low cost and reduced toxicity [55]. Additionally, TiO2 exhibits enhanced photocatalytic efciencies during
photocatalytic reactions such as water splitting, detoxication etc.
Nevertheless, TiO2 exhibits a major disadvantage which is the limited sensitivity to sunlight. Absorbing only the ultraviolet part of
the electromagnetic solar radiation means that TiO2 absorbs only
5% of the solar energy reaching the Earths surface [38,43]. In order
to extend the absorbance to the visible part of the spectrum several modications of TiO2 photocatalysts have been realized as well
as a lot of other single-metal oxides, with lower values of bandgap energy, have been prepared. Certainly, common single-metal
oxides, such as WO3 , were found rather insufcient for the photocatalytic reduction of CO2 , due to their small value of band-gap
energy which favored the recombination of the photogenerated
species and their low CB edge potential [56].
3.1.1. Solid-gas systems
3.1.1.1. H2 O as the reducing agent. In many cases, the photocatalyst in the solid state reacted with a gas mixture of the reactants.
Pb3 O4 , BiOI, CeO2 reacted with a gas mixture of CO2 /H2 O, where
water was the reducing compound. In the case of hydrated Pb3 O4
(hematite), the enhanced number of water molecules on its surface was crucial. It was found that the increased transfer of oxygen
atoms from water molecules to the oxygen containing products, such as methanol, resulted in the increase in the amount
of products (2.6 mol CH3 OH/g* h/) [57]. Hierarchical structures
of BiOI produced CH4 (1.58 mol/g* 8 h) when they reacted with
H2 O, whereas the amount of the photocatalytic product was
almost the half (0.68 mol/g* 8 h) when BiOI was in the bulk form
[58]. Mesoporous Fe/CeO2 produced increased amounts of CO
(74.3 mol/g* h) and CH4 (17.3 mol/g* h) because of the Fe doping which formed an extra dopant energy band and the enhanced
number of chemisorbed oxygen species on its surface, as depicted
in Fig. 8. The reaction mechanism involves the CO2 adsorption on
the surface of the catalyst followed by the reaction of CO2 with pho-
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togenerated electrons via the formation of free radicals CO2 * [59].

ZnO is the most widely studied single-metal oxide photocatalyst
for the reduction of CO2 . It consists the TiO2 analogue, possesses
similar values of bang-gap energy with that, it is a low-cost product and it has not been regarded as a very environmentally harmful
compound [6062]. In the early 90s, ZnO in a clathrate hydrate
phase reacted with CO2 gas to nd that the presence of impurities
such as S, Si and P atoms, lowered the excitation energy of electrons and holes and therefore shifted the absorption of ZnO to the
visible part of the spectrum [63]. Studies upon Cu and N doped
mesoporous ZnO materials showed that the higher value of surface area of the samples prepared by the hydrothermal method
contributed to the increased photocatalytic activity compared to
those prepared by other methods (SC). The insertion of Cu into the
mesoporous ZnO also controlled the selectivity and increased the
photocatalytic activity since its dispersion and interaction with ZnO
was increased along with the absorption in the visible part of the
spectrum. Still, the optimum photocatalytic efciencies were not
rather impressive (1 mol CO/g* h) [60]. Sharifnia et al. synthesized
calcinated ZnO immobilized on stainless steel mesh. Calcination
led to the decrease of ZnO particles size, resulting in specic surface area increase and agglomeration decrease. Calcination also
improved the absorbance of photocatalysts in the UVvis region
of the spectrum and shifted the absorbance slightly towards the
visible area. Stainless steel mesh was selected as a support for ZnO,
owing to its large specic surface area, resistance to corrosions,
enhanced absorption of UV light irradiation and sufcient ventilation for gases transport [64]. Eventually, the conversion percentage
of CO2 to a group of oxygenated products, on the surface of the calcinated ZnO immobilized on stainless steel mesh was satisfactory
(9% after 5 h). Bartoszek et al. carried out experiments where moistened hematite photocatalysed the CO2 reduction when its surface
came in contact with a mixture of CO2 -H2 O in gas phase, giving an
explanation on the origin of methane in the atmosphere of Mars,
which had puzzled scientists. The role of water was found to be very
important; the higher the water on hematite surface, the higher
was the formation of oxygenates (methanol, acetone, formaldehyde, acetaldehyde). Generally, oxygenated molecules bearing two
or three carbon atoms, like acetone, might be produced via various
mechanisms which include photoinduced radical reactions (such
as the recombination of radicals from methanol and aldehydes)
[57,65]. Recently, a 5% CdS/WO3 photocatalyst was synthesized
and its photocatalytic activity for the CO2 reduction under visible light irradiation was found 1.02 mol CH4 /g* h, actually not
rather high. It was proved that CdS/WO3 heterostructure samples
form a hierarchical Z-Scheme which contributes to the enhancement of the photocatalytic activity, compared to that of the bare
samples, owing to the efcient spatial separation of the photogenerated electron/hole pairs. CdS nanoparticles were uniformly and
intimately dispersed on the surface of WO3 nanospheres and the
reduction reactions of CO2 took place on the CdS surface whereas
the oxidation reactions took place on the WO3 surface [66].
3.1.1.2. H2 as the reducing agent. When the photocatalyst in the

solid state reacted with a gas mixture of CO2 and H2 , the CO2
reduction proceeded via the dissociative adsorption of H2 on its surface. Ga2 O3 produced CO (3.6 mol/g* 5 h) upon reacting with CO2
molecules, whereas MgO and ZrO2 formed slightly higher amounts
of CO [67,68]. Calcinated ZnO immobilized on stainless steel mesh
reacted with a CO2 /H2 gas mixture but the conversion percentage
(3% after 5 h) was found to be lower compared to that obtained
when gas mixtures of CO2 /H2 O (9% after 5 h) or CO2 /CH4 (11% after
5 h) were used [64]. Hydrogenation of CO2 on the surface of NiO,
via a dissociative hydrogen adsorption on oxygen rich sites (surface
defects), resulted in a boost to the photocatalytic activity, which
was further enhanced when the calcination process took place at

temperatures below 400 C [69].
3.1.1.3. CH4 as the reducing agent. In the rare case that CH4 is the
reducing compound, the reaction mechanism involves the formation of free radicals CH3 * , H* , CO2* and the reaction among them
to produce mainly oxygenated compounds such as formates and
acetates. The solid photocatalyst (ZrO2 ) reacted with a gas mixture of CO2 and CH4 to form little amounts of CO (almost 1 mol
CO/g* 6 h) [68]. In addition, calcinated ZnO immobilized on stainless
steel mesh reacted with a CO2 /CH4 gas mixture displaying satisfactory conversion percentages of CO2 (11% after 5 h) [64,70]. Other
studies conrmed the effect of the amount of ZnO coated on mesh
on the photocatalytic activity, as it has impact on the active surface
of the catalyst [70]. In Fig. 9, SEM images of ZnO photocatalysts
coated on mesh are shown [70]. Moreover, efcient photosensitizers such as metallophthalocyanines (MPc), were added to ZnO
coated on stainless steel mesh in order to extend the absorbance of
ZnO into the visible part of the spectrum and thus enhance the photocatalytic activity (optimum conversion percentages of CO2 :23%
after 5 h) [71].
3.1.2. Aqueous dispersions
The photocatalysts were dispersed in water or aqueous
solutions and they reacted with CO2 in the gas phase. Interesting heterostructures, consisted of common cations, such as
ZnTe/ZnO, synthesized by hydrothermal methods, produced different amounts of CH4 , depending on the ZnO nanostructures
(optimum efciency: 100 mol CH4 /g* 5 h). The formation of heterojunctions via an intimate interfacing of ZnTe and ZnO, enhanced
the rate of the electron transfer between ZnTe and ZnO compared
to the recombination rate of the photogenerated species, and thus
increased the photocatalytic activity [72]. NiO dispersed in water
was found to be more efcient photocatalyst than other singlemetal oxides dispersed in aqueous solutions, such as ZnO, WO3 ,
Cu2 O, CuO. The enhanced photocatalytic activity of NiO (170 mol
CH3 OH/g* h), was attributed to the surface defects. Namely, vacant
oxygen spaces on the NiO surface strengthened the interactions
with CO2 molecules and facilitated the transportation of the photogenerated species [73,74]. Additionally, Yahaya et al. concluded
that the CO2 photoreduction to CH3 OH does not proceed via a single mechanism, as happens in the case of the reduction of free CO2 .
On the contrary, H2 CO3 formed by the CO2 dissolution in water
is responsible for the mechanisms such as the one in the H2 CO3
and carbonate ions reduction [57]. Peiqiang et al. demonstrated the
excellent photocatalytic property (1.8 mmol CH3 OH/L* m2* 6 h) of
one dimensional wedged N/CuO owing to the N doping which contributed to a red shift at the absorption of light as it introduced an
intermediate band between the VB and the CB of CuO and increased
the carrier mobility [75]. Aqueous suspensions of hydrous cuprous
oxide (Cu2 Ox H2 O) exhibited satisfying photocatalytic efciency
(24 mol CH3 OH/L* 20 mg). Tennakone et al. presumed that quick
removal of the holes in the Cu2 OxH2 O, due to their reaction with
OH ions found on the semiconductors surface, is responsible for
the high density of electrons and therefore the preference for multielectron processes [44].
3.2. Mixed-metal oxides
Mixed metal oxides, consisting of two or more kinds of metals and oxygen, have been widely used as photocatalysts for the
CO2 reduction. They possess semiconducting properties and their
aqueous suspensions, irradiated by visible light, have been mainly
studied. In most cases water plays the role of the reducing agent,
and it is oxidized to O2 and H+ ions. The latter, react directly with
CO2 molecules and photogenerated electrons or with CO2 * radi-
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Fig. 9. SEM images of photocatalysts coated on mesh: (a) uncoated mesh; (b) 5 g; (c) 6.5 g; (d) 8 g [70].
cals, in order to produce appropriate products, via many different

paths, depending on the values of the reduction potential of the
mixed-metal oxides.

3.2.1.1. H2 O as the reducing agent. Solid-gas systems where the
mixed-metal oxide photocatalyst is found in the solid state and
the reaction mixture of CO2 /H2 O is found in the gas phase have
been studied in a small extend. Concisely, solid Zn2 GeO4 , KNbO3 ,
HNbO3 and Bi2 WO6 reacted with CO2 and H2 O vapor via the
oxidation of water molecules to O2 and H+ ions and the reduction of CO2 by the H+ ions and the photogenerated electrons, as
it has already been referred when water plays the role of the
reducing compound. Bulk Zn2 GeO4 , exhibited very small photocatalytic activity (<1 mol CH4 /g* h) whereas nanoribbons of Zn2 GeO4
were found to be much more reactive photocatalysts (1.5 mol
CH4 /g* h, 6 mol CH4 /g* 14 h). The superiority of the latter could be
attributed to many factors, such as their enhanced specic surface
area (28.27 m2 /g vs 0.75 m2 /g), their extremely good crystal quality,
their increased lengths and ultrathin geometry which promote the
separation of photoinduced species, prevent the recombination of
them and promote the rapid transportation of the charge carriers.
It was also demonstrated that the loading of Pt (1% wt) or RuO2 (1%
wt) or even better the co-loading of Pt and RuO2 on the Zn2 GeO4
nanoribbon surface, further increased the rate of CH4 formation
(25 mol CH4 /g* h, 100 mol CH4 /g* 16 h) [76]. Signicantly lower
photocatalytic efciencies were observed for KNb3 O8 , HNb3 O8 and
Bi2 WO6 . Certainly in case that they did not have bulk structures
and they formed nanobelts and nanoplates, their activities were
importantly enhanced (3.58 mol CH4 /g* h, 1.71 mol CH4 /g* h and
1.1 mol CH4 /g* h, for HNbO3 , KNbO3 and Bi2 WO6 , respectively).
The formation of hydrogen bonds between water molecules and
the H on the HNb3 O8 surface deters the recombination of photoinduced electrons and holes because they are trapped on the
interlayer surface and therefore higher values of photocatalytic ef-
ciency are achieved [7779]. Sun et al. studied the photocatalytic

activity of ball-ower-like Bi2 WO6 , prepared by a hydrothermal
method without any organic precursor, under visible light. It was
found that the production of CO was hindered when the water
vapor was increased, due to the competitive absorption of CO2 and
H2 O on the basic sites of Bi2 WO6 . The highest photocatalytic activity (333 nmol CO/g* h) was observed in the condition with little H2 O
vapor, owing to the increased crystallinity, reduced recombination
rate of photogenerated species and increased stability of basic sites
on the surface of the photocatalyst, whereas the regeneration of the
catalyst by water washing, was found to be rather effective [80].
3.2.1.2. H2 as the reducing agent. Gas-solid systems, where the solid
photocatalyst react with a gas mixture of CO2 and H2 via chemisorption of CO2 molecules onto its surface, have been sparsely studied.
Generally, the decisive step of the reaction mechanism is the CO2
chemisorption, which is favored when the catalyst possesses basic
sites which facilitate the absorption of CO2 by altering its linear conformation and assisting the reduction by hydrogen. As the degree of
CO2 absorption enhances, the photocatalytic activity increases too.
LiTaO3 exhibited low photocatalytic activity (0.42 mol CO/g* 24 h),
signicantly lower than that of single-metal oxides such as Ga2 O3 ,
MgO and ZrO2 , which bear a larger number of basic sites on their
surface [81].
The following mixed-metal oxides: CaFe2 O4 , BiVO4 , LaCoO3 ,
NaBiO3 , NaNbO3 , KNbO3 , CuGaO2 , CuAlGaO4 , Bi2 WO6 and BaCeO3
were studied either in contact with small amounts of water,
or dispersed in aqueous solutions. Aqueous suspensions of ptype CaFe2 O4 , containing NaH2 PO2 and BaCO3 , saturated with
CO2 gas, produced mainly methanol and formaldehyde (2 mol
CH3 OH/g* 4 h and 3 mol HCHO/g* 4 h) via a direct mechanism
which did not involve the formation of CO2 * radicals. It was suggested that the photocatalytic reduction of CO2 took place at the
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interface constituted of solid CaFe2 O4 , solid BaCO3 and water where

CO2 and CO3 2 were more reactive [82]. Aqueous NaOH suspensions of BiVO4 produced methanol or ethanol, depending on the
available amount of CO2 . The determinant role of the crystal structure to the photocatalytic activity was studied, to nd that in
monoclinic BiVO4 (30 mol ethanol/g* 80 min) there is a higher tendency to form Bi O bonds with CO3 2 ions than in tetragonal
BiVO4 (2 mol ethanol/g* 80 min) and thus the transfer of photogenerated electrons from vanadium to CO3 2 is facilitated. The
important role of the NaOH solution was partly attributed to its
action as a hole scavenger which helps the separation of photoinduced species, and to its ability to dissolve more CO2 than water
[83]. Aqueous NaOH suspensions of lamellar BiVO4 exhibited satisfying photocatalytic activity in methanol (35 mol methanol/g* 6 h)
as in the current study, the available amount of CO2 was relatively
lower than in case of monoclinic/tetragonal BiVO4 and the formation of one carbon atom products was favored [83,84]. A reaction
mechanism, which involves the oxidation of water molecules to O2
by the photogenerated holes and the reduction of CO2 to methanol
by the photogenerated electrons on the surface of the lamellar
BiVO4 was proposed [84]. The effect of the preparation method
of NaBiO3 to the photocatalytic reduction of CO2 was found to
be crucial when NaBiO3 nanopowders were synthesized through
hydrothermal, sol-gel and dehydration methods. The diversication in the crystallinity, the specic surface area and the size
and shape of the particles produced via each method resulted
in different photocatalytic activities. Namely, the photocatalytic
efciency of NaBiO3 samples synthesized by the sol-gel method
was several times higher than those prepared by other methods,
owing to the smaller size of their crystallites, the higher value of
specic area and the lower band gap energy (sol-gel: 0.6 mol
CH3 OH/g* h, hydrothermal: 0.37 mol CH3 OH/g* h, dehydration:
0.037 mol CH3 OH/g * h) [85]. Not really hopeful photocatalytic
efciencies were observed for NaNbO3 and KNbO3 , by Shi et al.
(2.3 ppm CH4 /h and 7 ppm CH4 /h). However it was reported that
possibly the low photocatalytic activities are attributed to the small
values of specic surface area of the samples and therefore they
could be easily improved [86]. Besides, Shi et al. demonstrated that
NaNbO3 nanowires, prepared by a combination of hydrothermal
and heating processes, exhibited tenfold increase in the photocatalytic activity (1600 ppm CH4 /g* 150 min) compared to that of bulk
NaNbO3 , prepared by SSR (140 ppm CH4 /g* 150 min) [87]. In separate studies, the effect of the crystal structure and Pt doping on
the photocatalytic activity, were studied concurrently. The superiority of cubic Pt/NaNbO3 (1.3 mol CH4 /g* h and 4.2 mol CH4 /g* h)
over the orthogonal Pt/NaNbO3 (0.5 mol CH4 /g* h and 1.5 mol
CH4 /g* h) was obvious. Apparently, the transfer of the photogenerated electrons is facilitated in the cubic crystal lattice, owing to its
differentiated electronic structure [88]. Lekse et al. studied the photocatalytic activity of delafossites ABO2 (where A is a metal such as
Cu, Ag, Pt, Pd, B and B is a metal such as Al, Ga, Y, Fe) which have
hexagonal, rhombohedral or randomly substituted rhombohydral
structure and consist of alternating layers of octahedrally B metal
atoms spaced by two coordinated A metal atoms. Namely, CuGaO2 ,
even if it was doped with Fe, exhibited low photocatalytic activity
(9 ppm CO/g* h), as the only effect of Fe doping was the shifted the
absorption towards higher wavelengths (lower values of band-gap
energy) [89]. On the contrary, aqueous acidic solution with Fe+2
ions (pH = 2.6) of cube-like shaped Pt/CuAlGaO4 , synthesized via
the solid state fusion method, exhibited improved photocatalytic
efciency (8 mol CH3 OH/g* h), when they were put in a novel twin
reactor and reacted with a mixture of CO/CO2 . The singularity of the
twin reactor was the division of H2 and O2 producing photocatalysts into two compartments separated by a membrane. As a result,
in the one compartment H2 was generated and simultaneously
reacted with CO2 to produce mainly methanol, whereas in the other
11
compartment O2 was evolved [90]. LaCoO3 displayed notable photocatalytic efciency (40 mol HCOOH/g* h), which was found to be
tripled in case of the synergistic doping with C and Fe (130 mol
HCOOH/g* h) [91]. The modication of Bi2 WO6 microspheres with
conducting polymers (PPy, PANI, PTh) increased the absorption in
the visible area of the spectrum, decreased the recombination rate
of the photogenerated electron-hole pairs and facilitated the charge
transfer efciency, resulting in enhancement of the photocatalytic
activity by 2.8 times, compared to that of bare Bi2 WO6 . As the
CB of Bi2 WO6 is found too low for the CO2 photoreduction to gas
products such as CH4 and CO, the main products detected under
visible light irradiation, were methanol (56.5 mol CH3 OH/g* 4 h)
and ethanol (20.5 mol CH3 CH2 OH/g* 4 h) [92]. Various cocatalyst
nanoparticles (Ag, Au, Pt, CuO and RuO2 ) enhanced the photocatalytic activity of perovskite-type BaCeO3 for the CO2 reduction,
under UV light irradiation. Especially, 0.3%Ag/BaCeO3 was found to
be the more effective photocatalyst among the others, but generally
not rather effective (4 mol CH4 /g* 7 h). The cubic crystal structure
of Ag nanoparticles found on the surface of BaCeO3 promoted the
close contact between Ag and BaCeO3 leading to the formation of
an active center which lowered the activation energy of the reaction and facilitated the separation of the photogenerated species
[93].
3.3. Metal oxide composites
The combination of two metal oxides in order to prepare
photocatalysts with ameliorated photocatalytic efciency for the
reduction of CO2 has also been attempted. NiO consists one of
the most widely studied metal oxides cocatalysts. In the crushing
majority, the reaction mixture, either in the gas or liquid phase,
composed of CO2 and H2 O. The main products of the photocatalytic reduction of CO2 with H2 O, under visible light irradiation,
were CH3 OH CH4 .
3.3.1.1. H2 O as the reducing agent. Solid NiO/InTaO4 photocatalyst
has reacted with a gas mixture of gaseous CO2 and water vapors
in an optical ber photoreactor, composed of assembled optical
bers with pure silica core and a polymeric shield (optimal efciency: 21.0 mol CH3 OH/g* h at 75 C) [94] as well as in a monolith
photoreactor with internal channels covered with a layer of the
catalyst, over a lower SiO2 sublayer (0.16 mol CH3 OH/g* h) [95].
On the other hand, multifunctional Pt (0.5%wt)/ZnAl2 O4 /ZnGaNO
with mesoporous structure, small band-gap energy, enhanced gas
adsorption capacity and basicity, owing to the presence of ZnAl2 O4 ,
increased the light absorbance and assisted the fast migration of
the photogenerated species, resulting in satisfying photocatalytic
activity (38 mol CH4 /g* 8 h) [96].
The effect of the nature of the supporting materials (basic
or acidic) on the selectivity and the photocatalytic activity has
been analyzed for CuO/ZnO supported on MgO (8 mol CH4 /g* h
and 0.8 mol C2 H6 /g* h). It was deduced that basic supporting
materials interact more thoroughly with the reactive site of the
semiconductor and thus favor the formation of dimerized products [97]. Potassium bicarbonate (0.2 M) aqueous suspensions of
NiO(1%wt)/InTaO samples, where NiO particles were randomly
dispersed in InTaO4 agglomerates (12 m), exhibited mediocre
photocatalytic activity (1.394 mol CH3 OH/g* h). NiO acted as an
electron acceptor and so improved the photocatalytic activity compared to that of bare InTaO4 samples. Methanol was produced
via 6 electron reduction processes where CO2 or H2 CO3 or CO3 2
etc. were reduced by InTaO4 because of the more negative reduction potential of the conduction band of InTaO4 compared to
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ARTICLE IN PRESS
those of methanol yield [98]. Wu et al. demonstrated the decisive

role of the photoreactor in the photocatalytic activity. NiO/InTaO4
aqueous suspensions, exhibited almost ten times lower activity
(2.8 mol CH3 OH/g* h) when they were put in a quartz reactor
compared to that obtained when NiO/InTaO4 reacted in an optical
ber reactor (21 mol CH3 OH/g* h), even if in both cases the photocatalsyts were synthesized by the same method (sol-gel). The
photoreaction mechanism involves electron transportation from
the valence band of InTaO4 to the NiO cluster found on its surface. Adsorbed hydrogen atoms produced from H2 O dissociation
into H+ and OH and electrons on NiO, initially react with CO2
and then via the formation of HCOO, H2 COO, H2 CO and CH3 O,
methanol is nally formed. Holes found in the valence band of
InTaO4 react with OH ions and via the formation of OH* radicals, H2 O2 and O2 generate O2 [94]. In order to decrease the band
gap of InTaO4 , it was dopped with N, as it has been demonstrated
that when the valence band constitutes of both N 2p and O 2p
orbitals it is shifted upwards and therefore the band gap is shortened. Regarding the addition of NiO, it has been conrmed that
it is an efcient cocatalyst because it acts as an electron acceptor and thus prevents the electron-hole recombination. However,
the mismatching of the conduction bands of InTaO4 and NiO prevents the electron transfer from InTaO4 to NiO. Liu et al. used
a Ni@NiO core-shell structure where the metallic Ni layer facilitated the transportation of photoinduced electrons from InTaO4
valence band to the NiO surface and thus enhanced the photocatalytic efciency. The morphological analysis of Ni@NiO/N-InTaO4
showed that nanoparticles of the cocatalyst (Ni@NiO) were randomly deposited over the InTaO4 surface. It was found that InTaO4
was the least efcient photocatalyst with the lowest rate of CH3 OH
formation (50 mol CH3 OH/g* h), N-InTaO4 was more efcient
(130 mol CH3 OH/g* h) and Ni@NiO/N-InTaO4 was the most efcient photocatalyst (170 mol CH3 OH/g* h). That was expected
because N doping effectively decreased the band gap, enhanced
the absorbance of visible light irradiation. Besides, Ni@NiO coreshell structure, due its higher electronegativity compared to that
of Ta, assisted the migration of electrons from the InTaO4 surface to the NiO nanoparticles, where the reduction of the carbon
source (CO2 , H2 CO3 and CO3 2 ) began [99]. Aqueous potassium
bicarbonate suspensions of NiO/InNbO4 and Co3 O4 /InNbO4 exhibited similar but rather low photocatalytic activities (1.6 mol
CH3 OH/g* h and 1.5 mol CH3 OH/g* h, respectively). Still, they were
slightly higher than those of pure InNbO4 [100]. More recent studies on the photocatalytic activity of aqueous KHCO3 suspensions of
NiO/InVO4 demonstrated that the generation of little holes (surface defects) on the InVO4 surface after the deposition of NiO,
resulted in the formation of more active sites and thus higher
photocatalytic activity (1.102 mol/g* h for InVO4 vs 1.526 mol
CH3 OH/g* h for NiO/InVO4 ). Additionally, the photocatalytic efciency was enhanced because NiO/InVO4 absorbs more intensely
in the visible part of the spectrum, owing to the formation of a subband on the upper end of the VB [101]. Studies of the photocatalytic
activity of aqueous suspensions of Ni/Ni3 (BO3 )2 /NiO nanoparticles
(0.41 mol CH4 /g*h, 4 mol CH4 /g*10 h) demonstrated that it is
importantly enhanced compared to that of Ni3 (BO3 )2 (0.14 mol
CH4 /g*h, 1.5 mol CH4 /g*10 h) and Ni3 (BO3 )2 /NiO (0.16 mol
CH4 /g* h, 1.6 mol CH4 /g*10 h), owing to the presence of Ni which
facilitated the separation of the photogenerated species and delay
their recombination. Namely, the reaction mechanism of CO2
reduction on the surface of Ni/Ni3 (BO3 )2 /NiO heterostructures
(shown in Fig. 10), involved (a) the transfer of the photogenerated
electrons from the CB of NiO to the CB of Ni3 (BO3 )2 and then to
the Fermi level of Ni, (b) the transfer of the photogenerated holes
from the VB of Ni3 (BO3 )2 to the VB of NiO where they oxidize
water molecules to O2 and H+ ions and c) the reduction of CO2
molecules by H+ ions and photogenerated electrons found on the
Fig. 10. Proposed mechanism for the photocatalytic reduction of CO2 on the surface
of Ni/Ni3 (BO3 )2 /NiO, under visible light irradiation [102].
Fermi level of Ni, to produce CH4 . The formation of CH4 was favored
as the Fermi level of Ni constitutes an electron rich region where
the performance of reactions requiring a large number of electrons
is promoted [102].
3.4. Layered double hydroxides (LDHs)

Layered double hydroxides (LDHs) are thought to be compounds
with the layered structure of brucite (Mg(OH)2 ), with a hexagonal crystal structure. They are constituted of positively charged
sheets with the general type [MII 1-x MIII x (OH)2 ]x+ which indicates
that some trivalent cations have taken the place of the divalent
cations. Anions are placed between two cationic layers in order
to ensure the neutral charge of the LDH. Besides, water is present
between the cationic layers. It is conrmed that the mass of water
present in a LDH is almost 50% of the total mass of cations forming
the positively charged layers. MII can be one of the following metals: Mg, Mn, Fe, Co, Ni, Cu, Zn, MIII can be one of the followings Al,
Cr, Mn, Fe, Ga and the value of x usually varies between 0.170.33.
Intercalated anions can be the followings: CO3 2 , SO4 2 , NO3 ,
Cl , OH . LDHs are efcient photocatalysts for the CO2 reduction
because they exhibit a great sorption capacity for CO2 in the space
between the cationic sheets. On the other hand, Teramura et al.
and Tanaka et al. demonstrated that simple mixtures of the same
metal hydroxides exhibit signicantly lower photocatalytic activity. This fact indicates that the unique structure of LDHs facilitates
the CO2 dissolution in the LDH interlayers and therefore its reaction with surrounded water molecules to produce CO and O2 via the
formation of photogenerated pairs of electrons and holes. Besides,
the choice of the cations present in the LDH inuences its semiconductor properties, the kind of the products (usually CO and/or
CH3 OH) and therefore its photocatalytic activitiy. LDHs constitute
the only layered materials with photocatalytic properties which are
formed by positively charged sheets, in contrast to the montmorillonites, smectites and kaolinites which are formed by negatively
charged layers. In fact LDHs exhibit higher sorption capacity for CO2
than montmorillonites and similar to that of zeolites [103,104]. The
evaluation of the photocatalytic activity of LDHs was performed in
solid-gas systems, where the solid catalyst reacted with a gaseous
mixture of CO2 /H2 O or CO2 /H2 , as well as in aqueous suspensions,
under UV irradiation.
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ARTICLE IN PRESS

In solid-gas systems, the reaction mechanism involves the diffusion of CO2 molecules in the internal and the interlayer space of
the LDH, resulting in the formation of hydrogen carbonate species,
which is a reaction intermediate.
3.4.1.1. H2 O as the reducing agent. Katsumata et al. studied the photocatalytic activity of Pd or Pt or Au dopped Zn-Cr LDHs which
was found satisfying (Pt (0.1%wt)/Zn-Cr LDH 7.8 mol CO/g* 3 h,
Pd (0.1%wt)/Zn-Cr LDH-4.3 mol CO/g* 3 h and Au (0.7%wt)/ZnCr LDH-3.8 mol CO/g* 3 h). It was also demonstrated that the
undopped Zn-Cr LDHs exhibited very low photocatalytic activity,
indicating the crucial role of Pt, Pd and Au which hinder the recombination of the photogenerated species and facilitate the progress
of the photocatalytic reactions which proceed via the involvement
of two electrons and produce CO [105].
3.4.1.2. H2 as the reducing agent. As mentioned above, the selectivity of the photocatalytic reduction of CO2 was strongly depended on
the LDH composition. Namely, Zn-GaIII , Zn-AlIII , Zn-Cu-GaIII and ZnCu-AlIII LDHs (shown in Fig. 11) produced CO and/or CH3 OH. It was
reported that the presence of Cu in the LDH structure enhanced the
production of CH3 OH, owing to the Cu-CO2 interactions. The latter
promote the reaction among CO2 molecules, H+ ions and photogenerated electrons, as CO2 molecules bind to Cu sites in the form of
hydrogen carbonate species. Besides, the insertion of Cu atoms in
the LDH structure lowers the band-gap energy and thus enhances
the photocatalytic activity. Characteristically, Zn-Cu-AlIII and ZnCu-GaIII LDHs produced 0.31 mol CH3 OH/g* h and 0.49 mol
CH3 OH/g* h, respectively. In the second case, Cu atoms were found
not only in the interlayer space but also inside the cationic layers, contributing to the faster diffusion of CO2 molecules which
form the hydrogen carbonate species. Still, the photocatalytic activities were very low [103,106,107]. Au/Zn-GaIII and Ag/Zn-GaIII LDHs
bearing Au or Ag nanoparticles on their surface, produced CH3 OH
and CO (0.201 mol CO/g* h and 0.03 mol CH3 OH/g* h, 0.102 mol
CO/g* h and 0.118 mol CH3 OH/g* h, respectively). Specically, in
Ag/Zn-GaIII LDH, Ag nanoparticles are electron donors owing to the
Surface Plasmonic Resonance (SPR) effect and the methanol yield
was higher, whereas, in Au/Zn-GaIII LDH, Au nanoparticles act as
electron traps and CO yield was extremely limited at the expense
of methanol [108].
The photocatalytic efciencies of the aqueous dispersions of
LDHs were found to be increased in comparison with those of
the solid-state systems. Cu-M-Al (M = Mg, Zn, Ni) LDHs exhibited
remarkable photocatalytic activity, especially Cu-Ni-Al LDH, owing
to its lowered band-gap energy and its increased specic surface
area (210 mol CH3 OH/g* h) [109]. In other study, Ni-Al LDH did
not produce CH3 OH, besides it exhibited lowered photocatalytic
activity (20 mol CO/g* 8 h), obviously due to the absence of Cu
[110].
3.5. Salts composites
Salts have been extensively used as photocatalysts for the CO2
reduction, in order to overcome several disadvantages of metaloxides, such as the high values of band-gap energy. In most cases,
their photocatalytic activity was studied in aqueous or organic suspensions, under visible light irradiation. The role of the solvent was
crucial and determined the selectivity of the reaction. The formation of CO2 * free radicals constituted the common intermediate
step of all the photocatalytic reactions, where often several reduc-
13
ing agents, such as 2-propanol, Na2 S etc., were added. ZnS and CdS
based photocatalysts were the most studied ones.
3.5.1. Aqueous/organic dispersions
It was reported that in non polar organic suspensions of CdS
and 2-propanol, CO was produced, whereas in polar ones HCOO
was also formed. Obviously, the reaction mechanisms depend on
the polarity of the solvent. In non polar solvents, CO2 * free radical is not solvated, so it is adsorbed on the surface of the catalyst,
where CO and H2 O are produced, via double protonation reactions.
In polar solvents CO2 * free radical is stabilized by solvation and
then HCOO is produced via protonation and reduction reactions.
Besides, the presence of thiols bound to Cd+2 ions, on the surface of CdS, led to the enhanced formation of HCOO , owing to
the decrease of the amount of adsorbed CO2 * free radical. Still,
thiol modied CdS, in DCM, exhibited low photocatalytic activity (0.5 mol HCOO /g* 7 h, 0.45 mol CO/g* 7 h, 0.5 mol H2 /g* 7 h
and 0.5 mol CH3 COCH3 /g* 7 h) [111,112]. Similar conclusions were
obtained by the study of Ru/ZnS suspensions in several solvents, as
shown in Fig. 12. During the use of non polar solvents, the photocatalytic activity was reduced, whereas the amount of CO was
increased, as mentioned above. Contrariwise, in polar solvents and
especially in water, the photocatalytic activity was enhanced, as
well as the production of HCOOH, resulting in remarkable photocatalytic efciencies ZnS (0.8 mmol HCOOH/dm3* h and 0.2 mmol
CO/dm3* h, 1.2 mmol HCOOH/dm3* 5 h and 0.4 mmol CO/dm3* 5 h).
The high polarity of the solvent, the great ability of Ru nanoparticles to absorb CO2 , to act as electron donors and to reduce the
activation energy surely contributed to these hopeful results [112].
Yanagida et al. demonstrated that the surface characteristics of ZnS
nanocrystallites (such as sulfur vacancies), which originate from
their preparation method, affected the selectivity and activity of
the photocatalytic CO2 reduction [113]. The addition of Cd2+ ions on
the surface of CdS, leads to the formation of surface defects and the
increase in the number of active sites on the surface of the catalyst.
For that reason, Cd2+ /CdS suspension in DMF (and triethanolamine
as electron donor) produced satisfying amounts of CO (30 mol
CO/g * 30 min), which nally formed condensed organic products
(benzophenone, acetophenone and benzyl halides) via the formation of a Cd2+ OCOCO2 intermediate complex [114].
The use of supporting materials for the enhancement of the
photocatalytic activity of ZnS and CdS salts gave remarkable
results. ZnS(13%)/SiO2 suspensions in 2,5-DHF (reducing agent),
produced seven times higher amounts of HCOO (7 mmol/g* 4 h),
than the unsupported ones (<1 mmol/g* 4 h). The surface dopping
of supported ZnS with excess of Zn+2 ions led to the optimum photocatalytic activity (10.3 mmol/g* 4 h). It is therefore
deducted that the use of porous supporting materials, the addition of excess of metal ions on the surface of the catalyst
and the presence of a reducing agent in the reaction mixture, combined together, result in the optimal photocatalytic
efciencies [115]. Several studies were performed in aqueous
suspensions of ZnS and CdS, supported on MMT, with CTA
stabilizer which prevents the agglomeration of salt nanoparticles. They exhibited noteworthy photocatalytic production of H2
(indeed by water splitting!)(CdS/MMT/CTA: 220 mol H2 /g* 25 h,
ZnS/MMT/CTA: 210 mol H2 /g* 25 h) and much lower production of
CH4 (CdS/MMT/CTA: 30 mol CH4 /g* 25 h, ZnS/MMT/CTA: 40 mol
CH4 /g* 25 h). The reaction mechanism for hydrogen production,
involves the oxidation of water molecules to O2 and H+ ions, the
formation of H* free radicals via the reaction of H+ with photogenerated electrons and nally the reaction between two radicals
H* to produce H2 . CH4 is formed either, via the reaction of CO2
with H2 , or via the reaction of CH3 * free radicals (originating
from CTA dissociation) with H* free radicals [116118]. The different amount of ZnS nanoparticles on the surface of MMT (4.2,
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Fig. 11. (A) Structure of Zn57-x-y Cux My III (OH)72 . 38H2O cluster models: (i) x = y = 0; (ii) x = 0, y = 12, M = Al; (iii) x = 0, y = 1, M = Ga; (iv) x = 1, y = 0; and (v) x = 1, y = 12, M = Al;
(B) Hydrogen carbonate species formed from the reaction of CO2 with the surface hydroxyl group of Zn57-x-y Cux My III (OH)72 . 38H2 O [103].
Fig. 12. Possible reaction mechanisms for the photocatalytic CO2 reduction on the surface of Ru/ZnS nanoparticles, in polar and nonpolar solvents [112].
3.1 2%wt ZnS) was also found to be important as it affects

the extent of the agglomeration and the uniform distribution and
therefore the photocatalytic activity (optimal efciency for the ZnS
(3.1%wt)/MMT: 300 mol H2 /g* 24 h, 28 mol CH4 /g* 24 h, 3 mol
CO/g* 24 h) [119]. The prominent role of the geometric features
of a photoreactor was also studied in aqueous ZnS/MMT suspensions. Between two stirred batch annular reactors the one whose
geometry secured the optimum mixing of the reactants, exhibited almost 23 times higher photocatalytic efciency (380 mol
H2 /g* h, 30 mol CH4 /g* h, 4 mol CO/g* h and 3.2 mol CH3 OH/g* h
versus 140 mol H2 /g* h, 8 mol CH4 /g, 0.5 mol CO/g* h and
1.6 mol CH3 OH/g* h) [120].
A lot of studies have been carried out in colloids of CdS and ZnS,
containing sacrice compounds-electron donors (Na2 S, NaH2 PO2
etc.) or other compounds that determine the selectivity of the
photocatalytic reaction. For example, the addition of TMACl in
the reaction mixture contributed to the production of dimerized products, such as ions of acetic acid or oxalic acid, owing
to the formation of an aprotic layer on the surface of the cata-
lyst. Colloids of ZnS exhibited impressive photocatalytic activity

(optimum: 2300 mol oxalic ions/dm3* 48 h in pH = 14), whereas
that of CdS was much lower (136 mol formic ions/dm3* 42 h in
pH = 6) [121127]. Ni dopping of ZnS aimed to leverage the ability of Ni+2 ions to trap the photogenerated electrons and thus
to reduce the probability of recombination of the photogenerated species. Besides, it was expected that the double use of
methanol, as solvent and as sacrice compound and the hydrothermal preparation method of Ni/ZnS would improve signicantly the
photocatalytic efciency. Indeed, methanolic suspensios of Ni/ZnS
were more efcient (121.4 mol methyl formate/g* 24 h) than bare
ZnS (87.6 mol methyl formate/g* 24 h), but the difference was not
so dramatic [128]. Contrariwise, the formation of heterojunction
structures between CdS and Bi2 S3 , promoted the separation of photogenerated species, enhanced their lifetime, increased the specic
surface area and the absorption in the visible part of the spectrum
and therefore signicantly enhanced the photocatalytic activity of
their aqueous suspensions (613 mol CH3 OH/g* 5 h for CdS/Bi2 S3
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vs 201 mol CH3 OH/g* 5 h for Bi2 S3 and 314 mol CH3 OH/g* 5 h for
CdS) [129].
Excluding ZnS and CdS salt composites, several photocatalysts
based on other salts, have been studied but their photocatalytic
activity was not found to be notably high. Among them, aqueous
solutions of FeCl3 or Fe(OH)3 exhibited some photocatalytic activity (2.5 mol HCHO/g* 30 min) owing to the action of Fe+2 ions as
electron donors that facilitate the CO2 reduction via the formation
of CO2 * free radicals [130,131]. Cu2 O/SiC in the form of spherical
Cu2 O nanoparticles present in SiC agglomerates, exhibited satisfying photocatalytic efciency (191 mol CH3 OH/g* 5 h), owing to
the addition of the reducing agent Na2 SO3 in the reaction mixture
and the enrichment with Cu2 O, which improved the separation of
the photogenerated species and thus their lifetime (bare Cu2 O:
104 mol CH3 OH/g* 5 h and bare SiC: 153 mol CH3 OH/g* 5 h)
[132]. Methanolic solutions of CdIn2 S4 exhibted extraordinary
efciencies in formic methylester (5258 mol/g* 10 h), which was
produced via the esterication of CH3 OH HCOOH formed at the
VB of CdIn2 S4 . Besides, a correlation was performed, between the
preparation process of the photocatalyst and its selectivity/activity,
to nd that when CdIn2 S4 was synthesized from thiouria, the photocatalytic activity was doubled compared to that exhibited in
case that l-cystein was the staring material [133]. Aqueous alkaline solutions of CuInS2 and Zn-doped CuInS2 with highly ordered
nanoarray structure, where the role of Zn was to reduce the recombination rate of photogenerated species and the contact resistance,
were also found to be conspicuous photocatalysts for the CO2
reduction (0.012 M CH3 OH/h and 0.032 M CH3 OH/3 h) [134].
In special occasions, H2 was added to the aqueous reaction mixtures in order to enhance the photocatalytic activity. For example,
aqueous suspensions of the salt based photocatalyst reacted with a
gas mixture of CO2 /H2 . Namely, AgBr photocatalysts supported on
paligorskite have been prepared, in order to enhance their photocatalytic activity, owing to the increased surface area and porosity
and the negatively charged paligorskite surface. Besides, paligorskite has an increased gas absorption capacity for CO and H2 and
it exhibits high stability towards the effect of visible light irradiation. Eventually, even if the photocatalytic efciency of the aqueous
suspensions of AgBr/paligorskite (8 mol CH4 /g* h and 48 mol
CH4 /g* 10 h) was doubled compared to that of bare AgBr (3 mol
CH4 /g* h and 12 mol CH4 /g* 10 h), it remained moderate [135].
Also, moderate photocatalytic activity was performed by aqueous suspensions of Cux Agy Inz Znk Sm with RuO2 or Rh1.32 Cr0.66 O3 as
cocatalysts (optimum activity: 21.1 mol CH3 OH/g* h) but after the
addition of H2 , the activity was found to be almost ve times higher
(118.5 mol CH3 OH/g* h for RuO2 /Cu0.30 Ag0.07 In0.34 Zn1.31 S2 ). It
was reported that H2 reacts with the photogenerated holes to form
H* free radicals that facilitate the production of CH3 OH and hinder
its oxidation [136]. Furthermore, anomalous spherical nanoparticles of Co/MoS2 , synthesized by hydrothermal method, were used
for the photoelectrocatalytic reduction of CO2 to CH3 OH under visible light (35 mmol/L). The Co-doped MoS2 exhibited enhanced
photocatalytic activity compared to MoS2 , owing to the upward
shift of the CB and VB redox potentials, as well as the enhanced
specic surface area and the increased number of active sites [137].
3.5.2. Solid-gas system

The only study that refers to the evaluation of the photocatalytic
activity of a salt in a solid-gas system, did not lead to encouraging
results. CoTe reacted with a gas mixture of CO2 and H2 O to produce very low amounts of CH4 (1.8 mol CH4 /g* h and 4.97 mol
CH4 /g* 8 h). In this case the reaction mechanism proceeded via the
formation of a variety of free radicals such as H* , CO2 * , CO* , C* ,
CH3 * , CH* and CH2 * [138].
15
Fig. 13. Redox potential values (eV vs NHE) of GR and several common semiconductors [140].
4. Carbonaceous photocatalysts for CO2 reduction

The interest about carbonaceous photocatalysts i.e. composite photocatalysts based on carbon (graphite, active carbon, black
carbon bers, carbon nanotubes, graphene and g-C3 N4 ), that usually contain compounds with semiconducting properties, has been
expressed recently. In the large majority of the studies, their photocatalytic activity for the CO2 reduction was evaluated during their
reaction with H2 O, via the oxidation of water molecules and the formation of free radicals CO2 * [139,140]. As far as the carbon-based
2D layered materials, such as graphene and g-C3 N4 , are concerned,
it is evidenced that their supporting properties, their adsorption
afnity for CO2 , the light utilization and the graphene/g-C3 N4 coupling determine their photocatalytic efciency [39].
4.1. Composite photocatalysts based on graphene (GR)
GR is already known as an electron transfer medium with large
specic surface area high chemical stability, excellent electronic
conductivity and good optical tranmittance, widely used in photocatalysis. Heteroatom (O, N, B, P and S) doped GR exhibits improved
conductive and optical properties and it favors the formation of heterojunctions which facilitate charge generation and transportation
and therefore enhance its photocatalytic activity [141,142]. Furthermore, graphene (GR) has been chemically modied in order to
obtain superior photocatalytic properties and it has been widely
used in composite photocatalysts of the type semiconductor/GR.
Owing to the existence of Fermi level and the even distribution of
semiconductor nanoparticles on their surface, they have exhibited
signicant photocatalytic activity. Fermi level is found lower than
the CB of most semiconductors (less negative value of reduction
potential), resulting in the transfer of photogenerated electrons
from the CB of the semiconductor to Fermi level of GR as shown
in Fig. 13. In that way, the mean free path traversed by the photogenerated electrons is elongated and the photocatalytic reactions
are facilitated. In case that Fermi level of GR is found higher than the
CB of the semiconductor (more negative value of reduction potential), the photogenerated electrons cant be transferred from the
semiconductor to GR, thus, the presence of a photosensetizer is
required (Fig. 13). Photosensitizers are sensitized by the absorption of photons and they produce electrons which follow the path
photosensitizer-GR-semiconductor-reactants quickly owing to
the high conductivity and the unique at structure of GR. Therefore the mean free path of electrons is elongated, resulting in
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ARTICLE IN PRESS
Fig. 14. Schematic diagram of the synthetic process of Cu2 O/RGO photocatalysts
[139].
Fig. 15. Schematic scheme of the proposed photocatalytic CO2 reduction on the
surface of ZnO/RGO photocatalyst [147].
reduction of the recombination rate between the photogenerated

species and enhancement of the photocatalytic activity. Besides,
owing to the formation of metal-carbon or metal-oxygen-carbon
bonds between GR and semiconductors, the band gap energy
diminishes and thus the photocatalyst absorbs in the visible part
of the spectrtum. Generally, Semiconductor/GR photocatalysts
exhibit higher photocatalytic activity compared to bare semiconductors as the synergistic effect plays an important role. For that
reason, the preparation of Semiconductor/GR composites constitutes an ambitious goal for the scientic community. The main
preparation processes followed for Semiconductor/GR photocatalysts are hydro/solvothermal, solution mixing and in situ growth
methods, which apparently affect their structure, morphology, size
and photocatalytic activity [39,140,143]. For example, the combination of a facile one-step green synthesis, the presence of
metal-oxygen-carbon bonds and the two dimensionality (2D) of
GR and GRO nanostructured composites, such as (BiO)2 CO3 /GR and
(BiO)2 CO3 /GRO, resulted in high photocatalytic activities owing to
their large surface areas and effective charge separation and transfer [144].
[147]. On the other hand, WO3 /RGO composite exhibited a very

low photocatalytic activity (0.1 mol CH4 /g* h) as a result of the
lowering of its oxidizing power (shift of the VB towards lower
values of oxidation potential) compared to that of WO3 , after the
addition of RGO [148]. The best photocatalytic activity among
the GR based photocatalysts was exhibited by hexamolybdate
clusters Cs2 Mo6 Bri 8 Bra 6 /GO and (TBA)2 Mo6 Bri 8 Bra 6 /GO diluted in
a mixture of H2 O/DMF (1644 mol CH3OH/g* 24 h and 1294 mol
CH3 OH/g* 24 h, respectively versus 439 mol CH3 OH/g* 24 h for
bare GO). In this case, the excitation of Mo6 units via the absorption
of visible light, facilitated the transfer of electrons to the CB of
GO where the reduction of CO2 to methanol takes place. Besides,
owing to the high mobility of charged species and its increased
specic surface area, GO enhances the photocatalytic activity
synergistically [149]. The photocatalytic efciency of aqueous
suspensions of carbon nanoparticles, bare or bearing metals (such
as Au) on their surface, which act as electron acceptors, was also
evaluated [150]. CdS nanorods/RGO composites photocatalytically
reduced CO2 to CH4 under visible light irradiation (2.51 mol CH4
g* h). The enhanced photocatalytic efciency, compared to that
of bare CdS nanorods, was attributed to the electron acceptor
properties of RGO and to the strong adsorption and activation of
CO2 molecules by RGO, through - conjugation interactions. The
content of RGO was 0.5% wt, thus its role was that of an efcient
and economic cocatalyst compared to noble metal Pt which did
not actually enhance the photocatalytic activity in a higher degree
[151,152].
4.1.1. Aqueous/organic suspensions

ZnO/RGO, Cu2 O/RGO, BiVO4 /RGO, WO3 /RGO, Cs2 Mo6
Bri 8 Bra 6 /GO and (TBA)2 Mo6 Bri 8 Bra 6 /GO consist characteristic
examples of composite photocatalysts based on GR. Aqueous
alkaline suspensions of Cu2 O/RGO and BiVO4 /RGO exhibited
similar photocatalytic activities in CH3 OH (41.5 mol/g* 10 h)
and CH3 CH2 OH (51.5 umol/g* 10 h) respectively [139,145]. The
presence of RGO sheets in the Cu2 O/RGO composite, prepared
by GO and Cu(AC)2 , as shown in Fig. 14, contributed to the
uniform distribution of Cu2 O nanoparticles on the RGO surface.
During the photocatalytic reduction of CO2 , the photogenerated
electrons were transferred from the CB of Cu2 O to the surface
of RGO which provided electrons to CO2 molecules [139]. It
was established that ZnO/GO nanocomposites, synthesized by
a solvothermal method, exhibit enhanced adsorption ability on
CO2 compared to that of bare ZnO and GO, therefore they could
form promising photocatalysts for the reduction of CO2 [146].
2D ZnO/RGO composites consisting of wrinkled GO sheets with
nicely distributed ZnO nanoparticles on their surface exhibited
remarkable photocatalytic activity (ZnO(10%wt)/RGO:263.1 mol
CH3 OH/g* 3 h), 5fold higher than that of bare ZnO (52.4 mol
CH3 OH/g* 3 h). The strong interaction between ZnO and RGO
resulted in inhibition of the fast recombination of the photogenerated holes and electrons and thus enhancement of the
photocatalytic activity. In Fig. 15 is clearly demonstrated that
GR acts in a similar way with RGO in the Cu2 O/RGO composite
4.2. Composite photocatalysts based on carbon nanotubes (CNTs)

aqueous suspensions
CNTs have been used for the amelioration of the photocatalytic
activity of carbonaceous composites, such as AgBr/CNT and plasmonic Ag/AgBr/CNT, because they constitute supporting materials
and they possess enhanced ability for storing electrons which are
used for the CO2 reduction. Aqueous suspensions of AgBr/CNT with
KHCO3 produced signicant amounts of CH4 , CH3 OH, CH3 CH2 OH
and CO (156, 94, 16 and 39 mol/g* 5 h, respectively). CNTs play the
role of an electron sink, which gathers the photogenerated electrons originating from the CB of AgBr and thus facilitates the CO2
reduction mechanism, as shown in Fig. 16. It was also reported that
as the length of CNTs was increased, the photocatalytic activity
was also increased, owing to the hindering of the recombination
of the photogenerated species and the binding of Ag+ ions on the
CNTs surface. Besides, the effect of several carbonaceous supporting materials, such as GP, EG, AC and GP, and the effect of pH of the
aqueous suspension on the photocatalytic activity, was studied. It
G Model
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17
Fig. 16. Schematic presentation of the photocatalytic CO2 reduction on the surface
of the Ag/AgBr/CNT photocatalyst, under visible light [153].
Fig. 18. Suggested schemes of photocatalytic reaction of WO3 /g-C3 N4 composites:

(a) charge separation and (b) Z-Scheme type [155].
Fig. 17. Overview of the photocatalytic reduction of CO2 with g-C3 N4 [157].
was demonstrated that the use of GP and CNTs led to the optimum photocatalytic efciencies because of their excellent electric
conductivity [153,154].
4.3. g-C3 N4 and composite photocatalysts based on g-C3 N4
g-C3 N4 constitutes the most studied carbonaceous photocatalyst for the CO2 reduction (Fig. 17), owing to its very negative value
of the CB reduction potential (1.42 V) and the small value of bandgap energy (2.67 eV), which contribute to its high reducing power
and the ability of absorbing in the visible part of the spectrum,
respectively. Besides, because of the formation of strong covalent
bonds between carbon and nitrogen atoms, g-C3 N4 is stable under
irradiation, in alkaline or acidic solutions, and it is synthesized via
simple and economic methods, such as the termal polycondensation of melamine at high temperatures (450 C) [155158]. During
the last years, improved synthetic processes leading to g-C3 N4
materials with high crystallinity and drastic modications of gC3 N4 surface (such as the introduction of heteromolecule dopants)
leading to the red shift of the optical absorption range and the
formation of heterostructures in g-C3 N4 , have been performed for
the enhancement of the overall photocatalytic activity towards the
CO2 reduction [159]. Its photocatalytic activity has been studied
in gas-solid systems, in which the solid catalyst reacted with a
gas mixture of CO2 /H2 O, as well as in aqueous suspensions. Still,
the basic disadvantage of g-C3 N4 is its moderately low oxidizing
power, for this reason, it is usually combined with an additional

material which possesses high oxidizing power and it is able to
oxidize water molecules. Thus, in case that the photocatalyst is
a g-C3 N4 composite, the reaction mechanism (heterojunction) is
either a charge separation mechanism or a Z-Scheme mechanism.
In the rst case (charge separation), the photogenerated electrons
are transferred from the CB of the constituent with the more negative value of reduction potential (usually this is g-C3 N4 ) to the CB
of the constituent with less negative value of reduction potential
(downwards), where the CO2 reduction is performed. To this effect,
the photogenerated holes are transported from the VB of the constituent with more positive value of oxidation potential to the VB
of the constituent with less positive value of oxidation potential
(upwards), where the oxidative reactions (such as water oxidation) take place. In this way, the separation of the photogenerated
species is promoted but the total redox ability of the photocatalyst
is lowered. In case of the Z-Scheme mechanism, the photogenerated
species are not transferred between the conduction bands and the
valence bands of the two constituents and thus the redox ability of
the composite photocatalyst is maintained [39,155,160,161]. The
suggested charge separation and Z-Scheme mechanisms, for the
photocatalytic reaction of WO3 /g-C3 N4 composites, are presented
in Fig. 18 [155].
4.3.1. Solid-gas systems-H2 O as the reducing agent

Outstanding photocatalytic activity (3.48 mmol CO/g* 7 h) was
exhibited by mesoporous cubic structured g-C3 N4 , owing to its 3D
structure and high specic surface area which enabled the activation of H2 O and CO2 molecules and the effective diffusion of CO2 in
the interior space of the catalyst [162]. In other study, 2D ordered
layers of g-C3 N4 with Pt nanoparticles distributed on their surface (Pt (1% wt)/g-C3 N4 ), synthesized from urea, exhibited higher
photocatalytic activity compared to that of bare g-C3 N4 because
Pt facilitated the transfer of the photogenerated species (0.06 umol
CH4 /g* h, 0.06 umol CH3 OH/g* h, 0.02 umol HCHO/g* h and 0.12 umol
CH4 /g* 7 h, 0.10 umol CH3 OH/g* 7 h, 0.022 umol HCHO/g* 7 h). Certainly, in case that the Pt percentage surpassed a certain value
(1%), the efciency was reduced, due to the re-formation of CO2
and H2 O, via the reaction of O2 with CH3 OH and HCHO [163]. Randomly ordered nanosheets of S/g-C3 N4 produced greater amounts
of methanol (1.12 umol CH3 OH/g* 3 h) than pure g-C3 N4 (0.81
umol CH3 OH/g* 3 h), because S/g-C3 N4 absorbs higher amounts of
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ARTICLE IN PRESS
Fig. 19. Proposed mechanism for the photocatalytic CO2 reduction on the surface of RGO/pCN [166].
visible irradiation (lower band-gap energy), as well as, S atoms

generate structural defects that enhance the photocatalytic efcieny [164]. Halogens of Ag were deposited on the surface of
protonated g-C3 N4 [AgX(X = Cl Br)/pCN], via a method which
involved deposition/precipitation processes with the aid of ultrasounds. During the reduction of AgX, Ag atoms displayed surface
plasma resonance effect. The enhanced photocatalytic activity of
Ag/AgBr(30%wt)/pCN (10.9 mol CH4 /g* 10 h) compared to that of
the pure constituents was attributed to the surface plasma resonance effect and to the formation of a heterojunction between
pCN and AgBr, into the hybrid photocatalyst. It was also reported
that the charge separation was more effective in Ag/AgBr/pCN
than in Ag/AgCl/pCN, and this was attributed to the right combination of the redox potentials of pCN and AgBr compared to
the combination of redox potentials of pCN and AgCl [165]. The
preparation of RGO/pCN photocatalysts via the combination of a
dispersion method with ultrasounds, accumulation by electrostatic
forces and - interactions and a reductive process with NaBH4 ,
led to the formation of 2D compounds with intimate contact in
width of the heterojunction connection. The latter contributed to
the rise of the photocatalytic activity of the hybrids (13.93 mol
CH4 /g* 10 h), compared to that of pure RGO and pCN. It was also
reported that RGO constituted an excellent accumulation center
for electrons that aided the reduction of CO2 to CH4 . Still, the high
excess of RGO (>15%) occupied the active catalytic centers at pCN
and thus the effective absorption of visible light and the number
of photogenerated electrons from pCN to RGO, were reduced. The
reaction mechanism involved the transportation of the photogenerated electrons from the VB of pCN to the CB and then to the
Fermi level of RGO for the reduction of CO2 to CO2 * as shown in
Fig. 19 [166]. For the rst time, it was demonstrated by Yu and Peng
et al. that g-C3 N4 /ZnO composites reduced CO2 to CH3 OH (0.6 mol
CH3 OH/g* h) via a direct Z-Scheme mechanism (and not the conventional charge separation mechanism) favored by the intimate
interfacial contact between the g-C3 N4 and ZnO phases [167].
4.3.2. Aqueous suspensions

Amine-functionalized g-C3 N4 , prepared via heating urea at
500 C and treatment by monoethanolamine solution, exhibited
higher CO2 adsorption capacity and thus enhanced photocatalytic activity for CO2 reduction under uv/visible light (0.34 mol
CH4 /g* h and 0.28 mol CH3 OH/g* h) compared to that of bare g-
C3 N4 (0.26 mol CH3 OH/g* h). It was inferred that HCO3 , formed
when CO2 was adsorbed on the g-C3 N4 surface, through acid-base
interactions with amino groups, in the presence of H2 O, was more
active than CO2 [168].
It was reported that in aqueous suspensions of WO3 (0.5%wt
Au)/g-C3 N4 , WO3 (0.5%wt Ag)/g-C3 N4 and SnO2-x (42.2%wt)/g-C3 N4
composite photocatalysts, which reacted with CO2 in the gas
phase, the Z-Scheme mechanism was followed. Layered structured Au or Ag/WO3 /g-C3 N4 composites, prepared via a planetary
mill process, mainly produced methanol (2500 nmol/g* 24 h and
1750 nmol/g* 24 h, respectively), whereas SnO2-x /g-C3 N4 composites, prepared by a simple calcination method, principally produced
CO (16 CO/g* h). Ag or Au nanoparticles in WO3 /g-C3 N4 composites participated in the reduction of CO2 , whereas the addition of
SnO2-x on the g-C3 N4 surface enhanced the specic surface area
and the absorption of visible light of the composite. In both cases,
it was demonstrated that in heterojunctions, where the Z-Scheme
mechanism is followed, an excellent mixing of the constituents is
required, otherwise, the photocatalytic activity appears very low,
because the mechanism cant be evolved. Therefore, it is proved that
the enhanced photocatalytic efciency is ascribed to the effective
separation of the photogenerated species, between WO3 and gC3 N4 and the retention of the high oxidizing and reducing power of
WO3 and g-C3 N4 , respectively [155,169]. Effective heterojunctions
between the constituents of g-C3 N4 /r-P (PCN-x), Pt (0.5%wt) In2 O3
(10%wt)/g-C3 N4 and ZnO/g-C3 N4 composites, led to high photocatalytic efciencies (295 mol CH4 /g* h, 159.2 ppm CH4 /g* 4 h and
30 mol CO/g* h, respectively). It was reported that in these three
cases, a charge separation mechanism was followed. The main
advantage of PCN-x composites, prepared by a solid state annealing method, is that they are composed of economic and non-toxic
materials which absorb visible light. g-C3 N4 nanosheets folded
on the edges of r-P surface formed effective heterojunctions that
facilitated the interfacing of g-C3 N4 and r-P and consequently
the transfer of charges between them [170]. In similar manner,
In2 O3 /g-C3 N4 composites, prepared by a solvothermal method, and
composed of In2 O3 nanoparticles on the g-C3 N4 surface, as well as
ZnO/g-C3 N4 composites, synthesized by an impregnation method,
with chemical bonds between ZnO and g-C3 N4 , exhibited enhanced
photocatalytic activity. In both cases, the photogenerated electrons
are transferred from the CB of g-C3 N4 to the CB of the second constituent and the reduction of CO2 molecules by the accumulated
electrons takes place [171,172].
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Even though, heterojunctions were formed between their

constituents, the following photocatalysts, CdMoO4 /g-C3 N4 and
g-C3 N4 -BAx didnt exhibit particularly high efciencies. Namely,
heterojunction between CdMoO4 and g-C3 N4 acted synergistically and increased the activity of the aqueous suspensions of
CdMoO4 /g-C3 N4 owing to the separation of the photogenerated
species, but generally, led to relative low amounts of products
(18 mol CO/g* h and 6 mol CH3 OH/g* h) [173]. Similar, moderate photocatalytic efciencies (56.3 mol CO/g* 4 h and 12.5 mol
H2 /g* 4 h) were exhibited by solutions of g-C3 N4 nanosheets modied with barbitouric acid (BA) (g-C3 N4 -BAx ) in a mixture of
H2 O/acetonitrile, containing Co(bpy)3 +2 and TEOA, as cocatalyst
and sacricing compoundelectron donor, respectively [157].
5. Hybrid organic-inorganic materials-zeolitic imidazolate

frameworks-(ZIFs)
The special structure of ZIFs, resembling to that of zeolites,
ensures their enhanced chemical and thermal stability, the high
values of specic surface area and the high absorption ability for
CO2 . Namely, ZIFs form tetrahedral networks by several transition
metals such as Cu, Zn and Co which are linked via imidazolate
connections. The interaction between the imidazolate connections plays a decisive role in the chemical modication and the
specication of their structure. Thus, owing to their special features, recently, ZIFs were studied as catalysts or as cocatalysts of a
molecular catalyst for the CO2 photocatalytic reduction. The photocatalytic activity of ZIFs was evaluated in aqueous, organic or
mixtures of aqueous and organic solutions. Emphasis was given
to the role of solvents-it was demonstrated that the optimum
efciencies of ZIFs were exhibited when aprotic solvents were
used, because they facilitated the more sufcient solvation of CO2
[174177].
Aqueous solutions of orthorhombic structured Cu(II)-ZIFs,
prepared by hydrothermal methods, exhibited extraordinary photocatalytic activity (1712 mol CH3 OH/g* 5 h), owing to synergistic
effect of the orthorhombic structure and the small band-gap
energy [174]. Wang et al. studied the use of a Co containing ZIF
(Co-ZIF-9) as cocatalyst for the photocatalytic reduction of CO2
together with a photosensitizer compound based on Ru. It was
reported that the presence of Ru increased the cost of the photocatalytic system furthermore, it wasnt stable enough [178]. Later
on, the same authors studied ZIFs (Co-ZIF-9) as cocatalysts in
combination with a semiconductor (CdS). Co-ZIF-9/CdS solutions
in a mixture of H2 O/acetonitrile, with bpy and TEOA, as electron mediating/donors systems, respectively, exhibited almost 45
times higher photocatalytic activity (50.4 mol CO/g* h and 11.1
H2 mol/g* h), compared to that of pure CdS. The accumulation
of the photogenerated electrons of CdS at the active centers of
Co-ZIF-9 and their reaction with the adsorbed CO2 molecules,
led to a signicant enhancement of the photocatalytic efciency.
Namely, it was deduced that the adsorption and diffusion of
the reactants was performed on the catalytic centers of Co-ZIF9 and that the electron transfer from the CB of CdS, after the
photoexcitation, was the rate determining step of the photocatalytic reaction. Besides, it was found that the role of imidazolate
based ligand in the Co-ZIF-9 structure was crucial by affecting positively the adsorption and activation of CO2 and thus its
conversion to CO. The effect of temperature and solvent in the
photocatalytic production of CO was also studied. It was demonstrated that the temperature enhancement resulted in desorption
of CO2 from the reaction system at temperatures higher than
40 C, whereas a certain amount of H2 O present in the reaction
mixture is essential in order to achieve CO selectivity. A possible reaction mechanism is depicted in Fig. 20 [179]. Except of
Fig. 20. Possible reaction mechanism for the Co-ZIF-9 cocatalysed photoreduction
of CO2 employing CdS as the light harvester [179].
Co-ZIF-9/CdS, the photocatalytic activity of hybrids consisting of

ZIF nanoparticles distributed on the surface of a material with
semiconducting properties was studied for Co-ZIF-9/g-C3 N4 and
ZIF-8/ZnGeO4 composites too. The highest photocatalytic efciencies were achieved in aprotic solvents such as MeCN, DMF, THF
and DMSO, owing to the Lewis acid-base interactions that facilitated the solvation of CO2 . It was reported that the activities
of Co-ZIF-9/g-C3 N4 and ZIF-8/ZnGeO4 (20.8 mol CO/g* 2 h and
2.44 mol CH3 OH/g* 10 h, respectively) were increased compared
to those of bare g-C3 N4 and ZnGeO4 . Thus, the synergistic effect
of the enhanced capability of ZIFs for CO2 adsorption, the crystallinity and the even distribution of the semiconducting material
on the surface of ZIF, resulted in efcient photocatalytic hybrids
[177,180,181].
6. Comparison and assessment of the activities of the main
photocatalytic systems/categories of catalysts
It was made comprehensible that an ideal photosynthetic system for the CO2 reduction must absorb effectively the solar
irradiation and produce large amounts of photogenerated species
which do not recombine rapidly, but they are transferred to the
active centers of the catalyst, where they react with CO2 molecules.
The most preferred photocatalysts possess low band-gap energy
and thus they absorb in the visible part of the spectrum in order
to achieve their excitation. As it was previously reported, in the
large majority of the studies, water was the reducing agent and
the reaction mechanism involved its oxidation by the photogenerated holes to produce oxygen and H+ ions and the formation of
free radicals CO2 * intermediates [7679]. Alternatively, but more
rarely, H2 was used as reducing agent and the photocatalytic reaction proceeded via the dissociative adsorption of H2 molecules on
the surface of the catalyst followed by the reaction with adsorbed
CO2 molecules or free radicals CO2 * [64,6769]. CH4 was the least
used reducing compound and in this case, the reaction mechanism involved the formation of free radicals such as CH2 * , CH3 *
etc. [64,68,70].
Attempts have been performed in order to compare the photocatalytic activities for the CO2 reduction of the main categories
of photocatalysts. Concisely, metal or non-metal dopped semiconductors with rather low band-gap energy, materials with special
morphology and/or heterojunctions formed between their components, were found to be more efcient photocatalysts. The
comparison between photocatalysts that belong to the same or different group is realized provided that it is understood that some
factors such as the reaction medium, the kind of reducing compound, the physical state of the photocatalytic system, the kind and
the special features of the photoreactor are different, and thus they
affect the activity and the selectivity of the photocatalytic reaction.
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Table 2
Selected metal oxides reported for CO2 reduction.
Photocatalyst description
Single-metal oxides
hydrated Pb3 O4 (hematite)
Hierarchical structures of
BiOI
Mesoporous Fe/CeO2
Cu/ZnO
ZnO immobilized on
stainless steel mesh
CdS(5%)/WO3
Ga2 O3
ZnO immobilized on
ZrO2
ZnO immobilized on
MPc/ZnO immobilized on
ZnTe/ZnO
NiO
1D wedged N/CuO
Cu2 Ox H2 O
Mixed-metal oxides
Zn2 GeO4 nanoribbons
Pt and RuO2 /Zn2 GeO4
nanoribbon
KNbO3 nanobelts
HNbO3 nanobelts
Bi2 WO6 nanoplates
ball-ower-like Bi2 WO6
LiTaO3
CaFe2 O4
monoclinic BiVO4
tetragonal BiVO4
lamellar BiVO4
NaBiO3
NaNbO3
NaNbO3 nanowires
KNbO3
Cubic Pt/NaNbO3
Orthogonal Pt/NaNbO3
Fe/CuGaO2 ,
cube-like shaped
Pt/CuAlGaO4
C/Fe/LaCoO3
Bi2 WO6 microspheres with
conducting polymers (PPy,
PANI, PTh)
0.3%Ag/BaCeO3
Metal oxide composites
NiO/InTaO4
NiO/InTaO4
Mesoporous Pt
(0.5%wt)/ZnAl2 O4 /ZnGaNO
CuO/ZnO (10%) supported on
MgO
NiO(1%wt)/InTaO
NiO/InTaO4
Ni@NiO/N-InTaO4
NiO/InNbO4
Co3 O4 /InNbO4
NiO/InVO4
Ni/Ni3 (BO3 )2 /NiO
Efciency
Type of irradiation
Ref. (year)
2.6 mol CH3 OH/g* h

1.58 CH4 mol/g* 8 h)
UV
Simulated sunlight
Solid-gas (catalyst-CO2 /H2 O) system

[57] (2011)
[58] (2014)
74.3 mol CO/g* h, 17.3

CH4 mol/g* h
1 mol CO/g* h
9% after 5 h
Simulated sunlight
[59] (2014)
VIS
UV

[60] (2013)
[64] (2013)
1.02 mol CH4 /g* h

3.6 CO mol/g* 5 h
3% after 5 h
VIS
UVVIS
UV

Solid-gas (catalyst-CO2 /H2 ) system
[66] (2015)
[67] (2010)
[64] (2013)
1 mol CO/g* 6 h
Solid-gas (catalyst-CO2 /CH4 ) system
[68] (1980)
11% after 5 h
high-pressure Hg-lamps or
sunlight
UV
[64] (2013)
23% after 5 h
VIS
[71] (2014)
100 mol CH4 /g* 5 h

170 mol CH3 OH/g* h
1.8 mmol CH3 OH/L* m2* 6 h
24 mol CH3 OH/L* 20 mg
VIS
UV
VIS
UVVIS
(200 W medium pressure
mercury lamp)
Aqueous dispersions
Aqueous dispersions
Aqueous dispersions
Aqueous dispersions
[72] (2015)
[73] (2004)
[75] (2014)
[44] (1989)
1.5 mol CH4 /g* h

25 mol CH4 /g* h
Solar irradiation
Solar irradiation

[76] (2010)
[76] (2010)
1.71 mol CH4 /g* h

3.58 mol CH4 /g* h
1.1 mol CH4 /g* h
333 nmol CO/g* h
0.42 mol CO/g* 24 h
2 mol CH3 OH/g* 4 h, 3 mol
HCHO/g* 4 h
30 mol ethanol/g* 80 min
2 mol ethanol/g* 80 min
35 mol CH3 OH/g* 6 h
0.6 mol CH3 OH/g* h (sol-gel)
0.37 mol CH3 OH/g* h
(hydrothermal)
2.3 ppm CH4 /h
1600 ppm CH4 /g* 150 min
7 ppm CH4 /h
1.3 mol CH4 /g* h
0.5 mol CH4 /g* h
9 ppm CO/g* h
8 mol CH3 OH/g* h
UV
UV
VIS
VIS
UV
UV

Aqueous dispersions containing NaH2 PO2 and BaCO3
[77] (2012)
[77] (2012)
[79] (2011)
[80] (2014)
[81] (2010)
[82] (1994)
VIS
VIS
VIS
VIS
Aqueous NaOH dispersions

Aqueous dispersions
[83] (2009)
[83] (2009)
[84] (2012)
[85] (2014)
UV
UV
UV
UV
UV
UV
VIS
Aqueous dispersions
Aqueous dispersions
Aqueous dispersions
Aqueous dispersions
Aqueous dispersions
Aqueous dispersions
Aqueous acidic dispersions with Fe+2 ions
[86] (2012)
[87] (2011)
[86] (2012)
[88] (2012)
[88] (2012)
[89] (2012)
[90] (2013)
130 mol HCOOH/g* h

56.5 mol CH3 OH/g* 4 h,
20.5 mol ethanol/g* 4 h
VIS
VIS
Aqueous dispersions
Aqueous dispersions
[91] (2009)
[92] (2015)
4 mol CH4 /g* 7 h
UV
Aqueous dispersions
[93] (2015)
21.0 mol CH3 OH/g* h (optical

ber reactor)
38 mol CH4 /g* 8 h
Simulated solar irradiation
[94] (2010)
VIS
VIS

[95] (2011)
[96] (2012)
UVVIS (mercury arc

lamp source (250 mW))
VIS
Simulated solar irradiation
Aqueous KHCO3 dispersions
[97] (1999)

Aqueous dispersions
[98] (2007)
[94] (2010)
VIS
VIS
VIS
VIS
UV
Aqueous dispersions
Aqueous dispersions
[99] (2011)
[100] (2012)
[100] (2012)
[101] (2015)
[102] (2015)
8 mol CH4 /g* h,

0.8 mol C2 H6 /g* h
2.8 mol CH3 OH/g* h
(quartz reactor)
170 mol CH3 OH/g* h
1.6 mol CH3 OH/g* h
1.5 mol CH3 OH/g* h
0.41 mol CH4 /g*h
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Table 3
Selected LDHs reported for CO2 reduction.
Efciency
Layered Double Hydroxides (LDHs)

7.8 mol CO/g* 3 h
Pt (0.1%wt)/Zn-Cr LDH
Pd (0.1%wt)/Zn-Cr LDH
4.3 mol CO/g* 3 h
Au (0.7%wt)/Zn-Cr LDH
3.8 mol CO/g* 3 h
0.201 mol CO/g* h,0.03 mol CH3 OH/g* h
Au/Zn-GaIII LDH
0.102 mol CO/g* h, 0.118 mol CH3 OH/g* h
Ag/Zn-GaIII LDH
Zn-Cu-AlIII LDH
Zn-Cu-GaIII LDH
Cu-Ni-Al LDH
210 mol CH3 OH/g* h
Ni-Al LDH
20 mol CO/g* 8 h
Type of irradiation
Ref. (year)
UV
UV
UV
VIS
VIS
UV
UV
VIS
UV

Aqueous dispersions
Aqueous dispersions
[105] (2013)
[105] (2013)
[105] (2013)
[108] (2014)
[108] (2014)
[107] (2014)
[107] (2014)
[109] (2015)
[110] (2015)
Table 4
Selected LDHs photocatalysts reported for CO2 reduction.
Salt composites
thiol modied CdS
Efciency
Type of irradiation
Ref. (year)
0.5 mol HCOO /g* 7 h, 0.45 mol

CO/g* 7 h, 0.5 mol H2 /g* 7 h, 0.5 mol
CH3 COCH3 /g* 7 h
UV-VIS
(500 W high
pressure mercury
arc lamp)
VIS
DCM and propanol (hole

scavenger)
[111] (1998)
[114] (1998)
UV
DMF and triethanolamine (as

electron donor)
Aqueous NaOH solutions
UVVIS
Aqueous colloids
[121] (1998)
VIS
UV
Basic aqueous dispersions

Aqueous solutions
[129] (2011)
[112] (2015)
UV
UV
2,5-DHF
[115] (1997)
[119] (2014)
UV
[118] (2013)
UV
Aqueous solutions
[120] (2011)
Cd2+ /CdS
30 mol CO/g * 30 min
CdS/MMT/CTA
220 mol H2 /g* 25 h, 30 mol

CH4 /g* 25 h
136 mol formic ions/dm3* 42 h
(pH = 6)
0.8 mmol HCOOH/dm3* h, 0.2 mmol
CO/dm3* h, 1.2 mmol HCOOH/dm3* 5 h,
0.4 mmol CO/dm3* 5 h
10.3 mmol HCOO /g* 4 h
300 mol H2 /g* 24 h, 28 mol
CH4 /g* 24 h, 3 mol CO/g* 24 h
210 mol H2 /g* 25 h, 40 mol
CH4 /g* 25 h
380 mol H2 /g* h, 30 mol CH4 /g* h,
4 mol CO/g* h, 3.2 mol CH3 OH/g* h
2300 mol oxalic ions/dm3* 48 h
(pH = 14)
121.4 mol methyl formate/g* 24 h
2.5 mol HCHO/g* 30 min
UVVIS
Aqueous colloids
[121] (1998)
UV
UV
VIS
[128] (2013)
[131] (1994)
[132] (2011)
5258 mol formic methylester/g* 10 h

0.012 M CH3 OH/h
VIS
VIS
Methanolic dispersions
Aqueous solutions
Anoxic aqueous solutions with
NaOH and Na2 SO3
Methanolic solutions
Aqueous alkaline solutions
8 mol CH4 /g* h
VIS
[135] (2012)
RuO2 /Cu0.30 Ag0.07 In0.34 Zn1.31 S2
VIS
CoTe
1.8 mol CH4 /g* h
VIS
Aqueous dispersions (H2

added)
Aqueous dispersions (H2
added)
Solid-gas (catalyst-CO2 /H2 O)
system
CdS
CdS/Bi2 S3
Ru/ZnS
Zn+2 /ZnS(13%)/SiO2
ZnS (3.1%wt)/MMT
ZnS/MMT/CTA
ZnS/MMT
ZnS
Ni (0.3%wt)/ZnS
Fe+2 ions (103 M)
Cu2 O/SiC
Cubic CdIn2 S4
Highly ordered nanoarray
structured Zn/CuInS2
AgBr/paligorskite
The photocatalytic efciencies of the most important metal oxides

(Table 2), LDHs (Table 3), salt composites (Table 4), carbonaceous
materials and ZIFs (Table 5), the kind of irradiation and the specic
experimental conditions are depicted.
As far as it concerns the single-metal oxides, the most widely
used photocatalytic systems were the solid-gas phase systems, in
which water vapor played the role of the reducing compound and
the catalyst was found in the solid state. The optimal photocatalytic
activity was exhibited by Fe/CeO2 (74.3 mol CO/g* h) [5765]. During the study of the aqueous suspensions of the single-metal oxide
catalyst, the highest photocatalytic activity was expressed by NiO
(170 mol CH3 OH/g* h), and it was increased in comparison with
that of Fe/CeO2 in the solid-gas phase system [44,7275]. UV irradiation was frequently used, apparently owing to the increased
band gap energy values of the semiconducting materials. On the
other hand, in case of doped single-metal oxides, the photocatalytic
[116] (2011)
[133] (2014)
[134] (2014)
[136] (2011)
[138] (2014)
reduction often took place under visible irradiation, apparently

owing to the decreased band gap energy values.
Studies on the photocatalytic efciency of the mixed-metal
oxides have shown that in most cases, their aqueous suspensions
were used and that the most remarkable results were displayed
by the ordered monoclinic BiVO4 (35 mol CH3 OH/g* 6 h) and Fe/C
doped LaCoO3 (130 mol HCOOH/g* h), where the synergistic effect
between Fe and C contributed signicantly to the enhancement of
the activity [44,75,8289,91]. Solid gas systems, where the reaction
mixture consisted of H2 O and CO2 , exhibited satisfactory photocatalytic efciencies, such that of RuO2 (1%wt)/Pt(1%wt)/ZnGeO4
(25 mol CH4 /g* h, 100 mol/CH4 /g* 16 h) [7679], whereas solidgas systems where H2 was the reducing agent, didnt produce
satisfying amounts of products [81]. Almost half of the mixed-metal
oxides were irradiated with UV light whereas the other halves were
irradiated with visible light.
G Model
ARTICLE IN PRESS
22
Table 5
Selected carbonaceous materials and ZIFs reported for CO2 reduction.
Efciency
Carbonaceous photocatalysts
Composite photocatalysts based on graphene (GR)
Cu2 O/RGO
41.5 mol/g* 10 h
BiVO4 /RGO
51.5 umol ethanol/g* 10 h
263.1 mol CH3 OH/g* 3 h
ZnO(10%wt)/RGO
WO3 /RGO
0.1 mol CH4 /g* h
1644 mol CH3 OH/g* 24 h
Cs2 Mo6 Bri 8 Bra 6 /GO
2.51 mol CH4 /g* h
CdS nanorods/RGO
Composite photocatalysts based on carbon nanotubes (CNTs)
Ag/AgBr/CNT
30 mol CH4 /g* 5 h, 16 mol
CH3 OH/g* 5 h, 3 mol ethanol/g* 5 h,
8 mol CO/g* 5 h (pH = 8)
156 mol CH4 /g* 5 h, 94 mol
AgBr/CNT
CH3 OH/g* 5 h, 16 mol ethanol/g* 5 h,
39 mol CO/g* 5 h (pH = 8)
g-C3 N4 and composite photocatalysts based on g-C3 N4
mesoporous g-C3 N4 (cubic)
3.48 mmol CO/g* 7 h
Pt (1% wt)/g-C3 N4
0.06 umol CH4 /g* h, 0.06 umol
CH3 OH/g* h, 0.02 umol HCHO/g* h
1.12 umol CH3 OH/g* 3 h
S/g-C3 N4
Ag/AgBr(30%wt)/pCN
10.9 mol CH4 /g* 10 h
RGO/pCN
13.93 mol CH4 /g* 10 h
Amine-functionalized g-C3 N4
0.34 mol CH4 /g* h, 0.28 mol
CH3 OH/g* h
Au/WO3 /g-C3 N4
2500 nmol CH3 OH/g* 24 h
Ag/WO3 /g-C3 N4
1750 nmol CH3 OH/g* 24 h
SnO2-x (42.2%wt)/g-C3 N4
16 mol CH3 OH/g* h
g-C3 N4 /r-P (PCN-x)
295 mol CH4 /g* h
159.2 ppm CH4 /g* 4 h
Pt (0.5%wt) In2 O3 (10%wt)/g-C3 N4
30 mol CO/g* h
ZnO/g-C3 N4
CdMoO4 /g-C3 N4
18 mol CO/g* h, 6 mol CH3 OH/g* h
56.3 mol CO/g* 4 h, 12.5 mol H2 /g* 4 h
g-C3 N4 -BAx
Hybrid organic-inorganic materials-Zeolitic imidazolate frameworks-ZIFs)
Orthorhombic Cu(II)-ZIFs
50.4 mol CO/g* h, 11.1 H2 mol/g* h
Co-ZIF-9/CdS
Co-ZIF-9/g-C3 N4
20.8 mol CO/g* 2 h
ZIF-8/ZnGeO4
2.44 mol CH3 OH/g* 10 h
The mixing of metal oxides in metal-oxide composites resulted

in the amelioration of their optical properties and thus the effective
photoexcitation of their VB electrons under visible irradiation. Also,
metal oxide composites were studied in depth as far as it concerns
their photocatalytic activity towards CO2 reduction with H2 O in
solid-gas systems as well as in aqueous suspensions. N/InTaO4 was
found to be the more efcient photocatalyst in a solid-gas reaction system (125 mol CH3 OH/g* h and 250 mol CH3 OH/g* 2 h)
whereas Ni@NiO/N-InTaO4 dispersed in aqueous solution exhibited
particularly high photocatalytic efciency (170 mol CH3 OH/g* h
and 310 mol CH3 OH/g* 2 h) owing to the presence of Ni, NiO which
acted as electron donors [94102].
The high absorption capacity for CO2 of LDHs constitutes the
basic factor that contributes to the very high photocatalytic activities. It is reported that the main products are CH3 OH and CO,
and the presence of Cu determines the selectivity of the reaction for methanol [103,104]. Aqueous suspensions of Cu-Ni-Al
LDH exhibited the highest photocatalytic efciencies in CH3 OH
(210 mol/g* h and 620 mol/g* 3 h) [102], whereas solid-gas systems where the reaction mixture was H2 O/CO2 or H2 /CO2 , didnt
exhibit signicant photocatalytic activities (from 0.2 mol to
20 mol product/g* h) [103,106108]. The percentage of UV light
absorbing LDHs is higher than that of visible light absorbing ones,
owing to their high values of band-gap energy.
The photocatalytic activity of salt composites was studied
mainly in their aqueous or organic solutions, where usually common reducing agents were added. Besides, the effect of the solvents
Type of irradiation
Ref. (year)
Simulated sunlight
Simulated sunlight
UVVIS
VIS
VIS
VIS

Anoxic aqueous alkaline solutions
Aqueous dispersions
H2 O/DMF
Aqueous acidic dispersions
[139] (2014)
[145] (2015)
[147] (2015)
[148] (2013)
[149] (2015)
[152] (2014)
VIS
Aqueous suspensions with KHCO3
[153] (2013)
VIS
Aqueous suspensions with KHCO3
[154] (2014)
VIS
VIS

[162] (2014)
[163] (2014)
VIS
VIS
VIS
VIS

Aqueous acidic dispersions
[164] (2015)
[165] (2015)
[166] (2015)
[168] (2015)
VIS
VIS
Simulated sunlight
VIS
VIS
Simulated sunlight
VIS
VIS
Aqueous dispersions
Aqueous dispersions
Aqueous dispersions
Aqueous dispersions
Aqueous dispersions
Aqueous dispersions
Aqueous dispersions
H2 O/acetonitrile, containing
Co(bpy)3 +2 and TEOA
[155] (2014)
[155] (2014)
[169] (2015)
[170] (2013)
[171] (2014)
[172] (2015)
[173] (2015)
[157] (2015)
VIS
VIS
VIS
Aqueous solutions
H2 O/acetonitrile, with bpy and TEOA
Aprotic solvents (MeCN, DMF, THF,
DMSO)
Aqueous dispersions
[174] (2013)
[179] (2015)
[180] (2014)
VIS
[181] (2013)
nature on the selectivity was conrmed, whereas extremely high

photocatalytic activities were mentioned, higher than those of
metal oxides and LDHs. Among the higher photocatalytic efciencies are those of Zn+2 /ZnS(13%wt)/SiO2 in 2,5-DHF (10.3 mmol
formats/4 h), aqueous suspensions of ZnS (3.1%wt)/MMT/CTA
(300 mol H2 /g* h), colloids of ZnS (2300 mol oxalates/dm3 ) and
methanolic solutions of CdIn2 S4 (5258 mol methyl formate/10 h)
[111138]. Except of the ZnS based salt composites which mainly
absorb UV irradiation, the majority of salt composites absorb visible
light and this fact makes them appealing photocatalysts for the CO2
reduction when they are dissolved in aqueous or organic mediums.
The most recently studied group of photocatalysts for the
CO2 reduction is that of carbonaceous catalysts which exhibited
very encouraging results. Except of their stability, carbonaceous
materials, based on GR, CNTs or g-C3 N4 , usually combined with
inorganic semiconductors, have exhibited outstanding photocatalytic activities [139,140]. In case of the composite carbonaceous
photocatalysts, the enhanced photocatalytic activities were
attributed to the generation of effective heterojunctions between
their components (charge separation mechanism or Z-Scheme).
The photocatalytic activity of carbonaceous photocatalysts has
been studied either in aqueous/organic suspensions or in gassolid systems where the gaseous reaction mixture consisted of
H2 O and CO2 . Aqueous suspensions of BiVO4 /RGO (51.5 mol
ethanol/g* 10 h), ZnO(10%wt)/RGO (263.1 mol CH3 OH/g* 3 h) and
solutions of Cs2 Mo6 Bri 8 Bra 6 /GO (1644 mol CH3 OH/g* 24 h) in
H2 O/DMF exhibited the most enhanced activities among the GR
G Model
ARTICLE IN PRESS
based carbonaceous photocatalysts [139,145,147150]. Among

the g-C3 N4 photocatalysts, the optimal photocatalytic activities
were exhibited by aqueous suspensions of g-C3 N4 /r-P (295 mol
CH4 /g* h) and S/g-C3 N4 (1.12 umol CH3 OH/g* 3 h) owing to its surface defects [155,157,170173]. ZIFs have also displayed satisfying
photocatalytic activities, the highest was that of the aqueous
suspensions of orthorhombic structured Cu(II) ZIFs (1712 mol
CH3 OH/g* 5 h) [174,179181]. Furthermore, all of them are visible
light active, i.e. they satisfy one of the basic requirements of an ideal
photocatalyst.
In conclusion, a rough comparison of the photocatalytic activity
among the main groups of photocatalysts, indicates that singlemetal oxides, mixed-metal oxides and metal oxide composites,
have exhibited similar photocatalytic efciencies (up to 170 mol
CH3 OH/g* h). LDHs have displayed slightly higher photocatalytic
activities (up to 210 mol CH3 OH/g* h), whereas salt composites, carbonaceous materials and ZIFs have exhibited even higher
photocatalytic efciencies, that reach the amount of 5258 mol
methyl formate/g* 10 h, 1644 mol CH3 OH/g* 24 h and 1712 mol
CH3 OH/g* 5 h. Generally, it can be deduced that the aqueous
suspensions or aqueous/organic solutions of the photocatalysts,
exhibited higher photocatalytic activities than their gas-solid systems.
7. Conclusions
The photocatalytic reduction of CO2 combines two great profits that take place concurrently: rstly, the lowering of the CO2
concentration in the atmosphere and thus the control of the amplication of the Greenhouse effect and secondly, the production
of useful chemicals and environmentally friendly fuels. Therefore it consists one of the greatest challenges for the scientic
community, even if there are many obstacles in the actualization
and the extended application of this concept in the real life. The
enhanced thermodynamic stability of CO2 , the incapacity of sufcient exploitation of the solar energy, transportation and storage
of the produced chemicals/fuels, the economic cost of manufacturing effective photoreactors, the loss of reactivity of photocatalysts
during operation, have been the major hindrances. On the other
hand, some groups of photocatalysts, such as the salt composites, ZIFs and carbonaceous hybrids have exhibited outstanding
photocatalytic efciencies, whereas at the same time, they are economic materials and they have been evaluated in rather efcacious
photoreactors (such as OFMRs). Therefore, as the latest studies in
this eld were very hopeful, scientists work intensely and promise
optimal and applicable results, translated into the preparation of
reactive photocatalysts for the conversion of the atmospheric CO2
wastes to environmental friendly and useful materials. Therefore,
we hope that this review will motivate the scientic community
to synthesize/modify alternative photocatalysts to TiO2 in order to
accomplish even higher photocatalytic activities for the CO2 reduction.
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Alternative Photocatalysts To TiO2 For The Photocatalytic Reduction of CO2 2016 Applied Surface Science

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G Model

APSUSC-33542; No. of Pages 26

Applied Surface Science xxx (2016) xxxxxx

Contents lists available at ScienceDirect

Applied Surface Science

Alternative photocatalysts to TiO2 for the photocatalytic reduction of

solar irradiation without concentrating it, so its intensity is rather

1.2. Production of solar fuels

togenerated electrons possess adequate negative redox potential,

Fig. 1. Comparison of natural photosynthesis and articial photosynthesis [14].

ous environmental problems on Earth. CO2 is one of the main

2. Photocatalytic approaches/mechanism for the reduction

Fig. 3. CO2 emission from different sectors [21].

cial sectors cannot be exploited. Furthermore, the CO2 separation

Generally, a photocatalytic system for the CO2 reduction must

alysts for the CO2 reduction. Non-oxide semiconductors, such as

it was modied to form for example nanotube arrays or dispersions

3. Inorganic photocatalysts for CO2

APSUSC-33542; No. of Pages 26

A. Nikokavoura, C. Trapalis / Applied Surface Science xxx (2016) xxxxxx

Solid-gas (catalyst-CO2 /H2 O, catalyst-CO2 /H2 ,

Hybrid organic-inorganic materials-Zeolitic imidazolate frameworks-ZIFs)

trons and holes recombine to release the absorbed energy as heat

Because of the thermodynamical inertness of the CO2 molecule,

APSUSC-33542; No. of Pages 26

A. Nikokavoura, C. Trapalis / Applied Surface Science xxx (2016) xxxxxx

Fig. 7. Diagram of photoexcitation and electron transfer process [47].

Fig. 6. Band levels of simple semiconductors [46].

E red = 1.90 V(VvsNHE)

CO2 + 2e + 2H+ HCOOH

E red = 0.61 V(VvsNHE)

E red = 0.53 V(VvsNHE)

CO2 + 4e + 4H+ HCHO + H2 O

E red = 0.48 V(VvsNHE)

CO2 + 6e + 6H+ CH3 OH + H2 O

E red = 0.38 V(VvsNHE)

E red = 0.24 V(VvsNHE)

E red = 0.42 V(VvsNHE)[46, 47]

Although CO2 photoreduction is a very challenging process,

One other way to increase the photocatalytic efciency of the

brush-like, ower-like, tree-like, dendritic and branched structures

togenerated electrons via the formation of free radicals CO2 * [59].

3.1.1.2. H2 as the reducing agent. When the photocatalyst in the

was further enhanced when the calcination process took place at

cals, in order to produce appropriate products, via many different

3.2.1. Solid-gas systems

ciency are achieved [7779]. Sun et al. studied the photocatalytic

interface constituted of solid CaFe2 O4 , solid BaCO3 and water where

those of methanol yield [98]. Wu et al. demonstrated the decisive

3.4. Layered double hydroxides (LDHs)

3.4.1. Solid-gas systems

3.1 2%wt ZnS) was also found to be important as it affects

lyst. Colloids of ZnS exhibited impressive photocatalytic activity

3.5.2. Solid-gas system

4. Carbonaceous photocatalysts for CO2 reduction

reduction of the recombination rate between the photogenerated

[147]. On the other hand, WO3 /RGO composite exhibited a very

4.1.1. Aqueous/organic suspensions

4.2. Composite photocatalysts based on carbon nanotubes (CNTs)

Fig. 18. Suggested schemes of photocatalytic reaction of WO3 /g-C3 N4 composites:

power, for this reason, it is usually combined with an additional

4.3.1. Solid-gas systems-H2 O as the reducing agent

visible irradiation (lower band-gap energy), as well as, S atoms