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Applied Surface Science 391 (2017) 149174

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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 a b s t r a c t

Article history: The increased concentration of CO2 in the atmosphere, originating from the burning of fossil fuels in sta-
Received 20 May 2016 tionary and mobile sources, is referred as the Anthropogenic Greenhouse Effect and constitutes a major
Received in revised form 24 June 2016 environmental concern. The scientic community is highly concerned about the resulting enhancement
Accepted 27 June 2016
of the mean atmospheric temperature, so a vast diversity of methods has been applied. Thermochemical,
Available online 29 June 2016
electrochemical, photocatalytic, photoelectrochemical processes, as well as combination of solar electric-
ity generation and water splitting processes have been performed in order to lower the CO2 atmospheric
Keywords:
levels. Photocatalytic methods are environmental friendly and succeed in reducing the atmospheric CO2
Photocatalytic reduction
CO2
concentration and producing fuels or/and useful organic compounds at the same time. The most com-
Photocatalysts mon photocatalysts for the CO2 reduction are the inorganic, the carbon based semiconductors and the
Semiconductors hybrids based on semiconductors, which combine stability, low cost and appropriate structure in order to
Solar fuels accomplish redox reactions. In this review, inorganic semiconductors such as single-metal oxide, mixed-
Articial photosynthesis metal 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 solar irradiation without concentrating it, so its intensity is rather


low. There are also solar energy collectors that concentrate the solar
1.1. Solar energy solar fuels irradiation (such as reectors and luminescent solar collectors) but
they are not commercially available because they are not stable and
The sun constitutes the major energy source in Earth, by provid- they exhibit inadequate collection efciency [2]. For over 50 years,
ing in one hour all the energy needed by humanity for one year. The serious attempts have also been performed in order to produce
basic problem for the inhabitants of the Earth, is that they are not useful compounds-fuels by utilizing solar energy.
able to exploit these huge amounts of energy [1]. The total emitted The solar fuels are compounds produced via a biomimetic
solar radiation reaching the Earths surface is composed of infrared approach that have captured and stored solar energy in their chem-
radiation (52%, >700 nm), visible radiation (43%, 400700 nm) and ical bonds (chemical energy) [3]. The production of solar fuels is a
ultraviolet radiation (5%, <400 nm). There are several types of solar great challenge for the scientic community. Solar fuels constitute a
energy collectors, some of them have at surface and collect the 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 sig-
Abbreviations: AC, activated carbon; ATP, adenosine-tri-phosphate; CB, con-
nicant goal for the scientists is the large scale production of the
duction band; CCS, carbon capture and storage; CNTs, carbon nano-tubes; CTA,
cetyl-trimethyl-ammonium; DAC, direct air capture; DHF, di-hydro-furan; DMF,
solar fuels, their transportation, their storage and the opportunity
di-methyl-formamide; LDHs, layered double hydroxides; NADPH, nicotinamide to be commercially available [1].
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 frame-
works.
Corresponding author.
E-mail address: c.trapalis@inn.demokritos.gr (C. Trapalis).

http://dx.doi.org/10.1016/j.apsusc.2016.06.172
0169-4332/ 2016 Elsevier B.V. All rights reserved.
150 A. Nikokavoura, C. Trapalis / Applied Surface Science 391 (2017) 149174

1.2. Production of solar fuels togenerated electrons possess adequate negative redox potential,
thus they are able to reduce photogenerated protons and CO2 in
1.2.1. Hydrogen-water splitting order to form hydrogen gas, carbohydrates and lipids. Plants consist
Hydrogen (H2 ) is a very useful solar fuel with serious advantages of a number of subsystems combined together, so that to perform
and disadvantages. As major advantages are considered, its abun- the photosynthetic process. Antenna systems are responsible for
dance in water and biomass, its convenient storage as hydride, the targeting the appropriate wavelengths of light and transporting
absence of pollutants after its combustion and the high amount of that energy to the reaction centers, where the transfer of pho-
energy released when it is used as a fuel. On the other hand, hydro- toinduced electrons takes place and charge separated states are
gen must be highly compressed during its transportation and this is formed. Water oxidation and O2 formation is accomplished at the
an expensive process or it must be stored as a metal hydride which reaction center in PSII after the absorption of four photons whilst
is an expensive and rather dangerous process too [4]. It is a trans- H+ and CO2 reduction is carried out by the biological molecule
port fuel but it is also used in many industries. In nature, hydrogen NADPH (nicotinamide adenine dinucleotide phosphate). The for-
is produced from water splitting via various molecular reactions mation of ATP (adenosine triphosphate), which has a key role in the
involving PSII (photobiological water splitting). The water splitting transportation of energy by several enzymes and the generation
mechanism includes the formation of a large number of reaction of transmembrane proton gradients is also realized by reduction
intermediates which nally produce dioxygen, electrons and pro- mechanisms. In conclusion natural photosynthesis is a very com-
tons. Advanced techniques have shown an interaction between the plicated exergonic process, consisting of a large number of redox
metal center which acts as a catalyst and its protein environment reactions which lead to the production of carbon based fuels [7,8].
that induce the oxidation of the water molecules. The mechanism On the other hand, by the term articial photosynthesis is meant
of the biological formation of hydrogen by the reaction of electrons the utilization of CO2 , renewable (solar) energy, synthetic catalysts
and protons, formed from photosynthesis (PSI or PSII), is not fully and water in order to produce a large range of fuels/chemicals such
understood, but it is clear that enzymes such as hydrogenases and as hydrogen and carbon based compounds [9]. Water is used as
nitrogenases play a crucial role, as they produce hydrogen from reductant that is the electron source. In articial photosynthesis
protons and electrons formed via water splitting [5]. By mimicking the rst step is the absorption of the ultraviolet or visible radia-
the nature, scientists tried to use to advantage the most abun- tion. The second step is the charge generation and separation and
dant material in Earth, water, in order to produce hydrogen. Steam the last step is the catalytic reaction [10]. Inspired by the natu-
reforming, constitutes a process which involves the generation of ral photosynthesis, where chlorophyll molecules diffuse sunlight,
hydrogen from CH4 and steam (H2 O) via the production of CO, is articial photosynthetic reactions also need the presence of light
mainly used for hydrogen production. Besides, hydrogen is gener- harvesting complexes, such as dye sensitizers. The photon capture
ated by coal gasication, a process that involves the reaction of coal is followed by the electron-transfer reactions that lead to charge
with O2 and steam at high temperature and pressure and produces separation. This means that electrons and positive holes move apart
mainly a mixture of hydrogen, methane, CO2 and CO. Biological, in order to avoid charge recombination, leading to the formation
pyrolysis and thermochemical processes that use the biomass are of potent oxidizing or reducing species. These species drive the
also used for the production of H2 . All these conventional meth- desirable redox reactions such as CO2 reduction. A major differ-
ods followed for the formation of H2 require enhanced amounts ence between natural and articial photosynthesis is the capability
of energy. Besides, the formation of pollutants such as CO2 , as of biological systems to induce self repair. Unfortunately, until now
byproducts, is not avoided. It is also widely known that hydrogen there is no man-made photocatalyst with the ability to retrieve the
is produced via electrolytic or thermochemical or photobiological loss of reactivity during operation [11,12]. The articial photosyn-
or photocatalytic water splitting. The thermochemical water split- thesis products are used as synthetic fuels for transportation and
ting uses the heat from the sun, whereas the photocatalytic water storage or as useful industrial materials (plastics, fertilizers, phar-
splitting uses the sunlight irradiation and photocatalysts i.e. mate- maceuticals, chemicals etc.) [1]. The greatest benet is obtained in
rials that accelerate the reaction, they are found in tiny amounts in case that a direct conversion of solar energy into fuels is achieved.
the reaction mixture and they are not consumed at the end of the The use of water as a raw material is an important perspective too.
reaction. The general principle is that the energy of the absorbed The catalysts for the articial photosynthesis may be either nano-
photons must be higher than the band-gap energy of the photo- materials with nature guided design, or molecular compounds or
catalyst, in order to achieve the photogeneration of electrons and solid state components, or combinations of them. Their common
holes participating in the redox reactions which produce hydrogen feature is the way that they participate in the multielectron redox
and oxygen. Specically, photoinduced electrons, transported from reactions during the articial photosynthesis process. Abundant
the valence band (VB) of the photocatalyst to the conduction band or less abundant materials can be used as homogeneous or het-
(CB), reduce H+ to form H2 , on its surface. Photogenerated holes erogeneous catalysts. The most common molecular catalysts are
oxidize H2 O to H+ and O2 in VB. Photocatalysts such as the TiO2 based on ruthenium and constitute model systems for the study
analogues and other metal oxides and salt composites have been of articial photosynthesis [13,14]. In Fig. 1 a comparison of natu-
widely used [4,6]. ral photosynthesis and articial photosynthesis is shown [14]. One
principal scientic goal currently is the enhancement of the photo-
1.2.2. Carbon based fuels natural/articial photosynthesis catalytic efciency in the CO2 reduction by using technical means.
The natural photosynthesis is the way of the biological world Methanol and methane are the most important solar fuels result-
to produce organic fuels, such as sugars, using mainly two abun- ing from the photocatalytic CO2 xation as they can store a lot of
dant compounds, H2 O and CO2 , via the harvest and exploitation hydrogen. Other possible products are CO, HCOOH, HCHO and H2
of solar energy. The natural photosynthetic process exhibits low [15].
overall efciency, still it constitutes an inspiration for scientists in
order to produce useful fuels from CO2 , H2 O and sunlight. The nat- 1.3. Why the reduction of CO2 in the atmosphere is so important?
ural photosynthesis involves the utilization of compounds that can Greenhouse effect and mitigation of CO2
be oxidized producing electrons, compounds that can be reduced
from these electrons producing fuels and of course solar irradia- The burning of fossil fuels, apart from their depleting them, has
tion. Green plants, algae and cyanobacteria absorb the solar energy raised serious environmental issues, such as the anthropogenic
in order to oxidize water to O2 , protons and electrons. The pho- Greenhouse effect which is considered as one of the most seri-
A. Nikokavoura, C. Trapalis / Applied Surface Science 391 (2017) 149174 151

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 CO2 concentration is spectacular and may lead to a possible alter-
greenhouse gases emitted by the combustion of coal, petroleum ation of the radiative balance on the planet. On the other hand, CO2
and natural gas in stationary and mobile sources and therefore its certainly is an important gas in the atmosphere because it takes
contribution to global warming is signicant. Other important long- part in the Carbon cycle as a carbon source [1720]. Generally, in
living greenhouse gases are: CH4 , N2 O and CFCs. By that means, order to achieve the decrease in the CO2 concentration in the atmo-
these gases absorb infrared light irradiation and re-emmit it in the sphere, the carbon dioxide neutral cycle, otherwise known as the
atmosphere, where it is trapped, resulting in global warming [16]. net carbon neutral cycle, should be completed. Several steps are
It is estimated that the CO2 concentration in the atmosphere important for the maintenance of this cycle, such as the recycling
rises every year at a rate higher than 2% and as a result, the average of CO2 after the fuels combustion, the use of renewable energy
temperature on the Earths surface has increased around 0.40.8 C (wind energy, direct solar energy etc.) for the CO2 reduction, the
over the last century. It is predicted that the mean global temper- capturing and recycling of CO2 not only from the point source but
ature may rise by 1.9 C and that the level of CO2 might climb to also from the atmosphere In Fig. 2 the carbon dioxide cycle with
590 ppm. Global warming causes the melting of the ice at the poles, renewable methanol and liquid fuel is presented [18].
the expansion of the oceans and the loss of large ice quantities Beyond the articial photosynthesis way to reduce the CO2 con-
from Greenland and Antarctica which cause an increase of the sea centration in the atmosphere, there is also the Carbon Capture
level. The extreme meteorological phenomena (abnormal winds, and Storage (CCS) pathway. CCS comprises the collection of CO2
aridity, oods) constitute some extra consequences of the Green- emissions mainly from the industry and the power stations, the
house effect. For example, a decrease in rainfall in certain areas generation of almost pure CO2 using a wide range of techniques,
may diminish the required water supplies for people, ecosystems, and its transportation after compression and liquication, to the
agriculture. The enhanced precipitation in other areas constitutes seabed or other geological deposits. CCS has important drawbacks,
an extra worrisome factor. Besides, the last 25 years the increase in as CO2 from the transportation, the residential and the commer-
152 A. Nikokavoura, C. Trapalis / Applied Surface Science 391 (2017) 149174

2. Photocatalytic approaches/mechanism for the reduction


of CO2 -main categories of photocatalysts

The photocatalytic approach (articial photosynthesis) consti-


tutes 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 atmo-
sphere 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 meth-
ods 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
Fig. 3. CO2 emission from different sectors [21].
rst one is the photoinduced water splitting to oxygen and hydro-
gen (1), and the second one is the combination of the photoinduced
activation of CO2 and the oxidation of water (2):
cial sectors cannot be exploited. Furthermore, the CO2 separation
from other gases needs large amounts of energy. Direct air capture h + 2H2 O 2H2 + O2 (1)
(DAC) involves an alternative process with lower energy require-
h + H2 O + CO2 Fuel + O2 (2)
ments. DAC involves the reaction of the weakly acidic CO2 with an
alkali component in order to separate it, in the form of salt, from Generally, a photocatalytic system for the CO2 reduction must
other neutral gases such as nitrogen and oxygen. Following that, (a) capture photons of light irradiation effectively, (b) produce
a regeneration process of the CO2 from the salt and the recycling efciently photoinduced electrons and holes that (c) they are
of the alkali component take place. DAC may be performed any- transferred quickly to the photocatalyst surface (d) to the appro-
where, so the pressurization and transportation via pipelines of priate catalytic sites where CO2 is reduced (e) without recombining
CO2 is minimized [19,21]. In conclusion, pressurization, liquica- quickly.
tion and transportation of CO2 raise the cost of these processes. The combination of photochemical and electrochemical pro-
Furthermore, the cost of the required energy to convert CO2 into cesses in order to reduce CO2 into valuable fuels constitutes the
chemicals is rather high, there are no convenient commitments in photoelectrochemical (PEC) reduction of CO2 . The disadvantage of
order to increase the CO2 originating chemicals and the govern- this process is that it is electricity-dependent but its advantage is
ments do not support economically these actions [22,23]. In Fig. 3 its higher efciency due to the lowering of the recombination rate
the CO2 emission from various sectors is presented [21]. of photogenerated electrons and holes. The difference between the
Furthermore, the reduction of the CO2 concentration in the electrochemical and the PEC reduction of CO2 , is that in the lat-
atmosphere can be accomplished via the thermochemical, electro- ter, the semiconductor electrode (photoelectrode) is irradiated by
chemical, photocatalytic, photoelectrochemical processes, as well UV or visible light with photon energy greater than the band-gap
as the combination of solar electricity generation, water splitting energy of the semiconductor. External bias voltage is also necessary
and CO2 reduction. Each of them has advantages and disadvan- for the PEC CO2 reduction. Then, photoexcited electrons are trans-
tages. The main handicap of all the thermochemical approaches is ported from the valence band to the conduction band and then they
that they require high temperatures, which means that the cost travel via an external circuit to the cathode counter electrode where
of heat supply is signicantly raised. In other words, by following they perform the reduction reactions, via the formation of CO2 *
these thermochemical processes the energy costs are very high, radical anion. Still, recombination and corrosions of the photoin-
whereas, actual mitigation of the atmospheric CO2 does not take duced species are not avoided. Besides, electron-hole pairs travel
place [2426]. through the electrolyte and perform oxidation and reduction reac-
The electrocatalysis involves the use of electrodes and an exter- tions on the surface of the appropriate electrodes. It is found that
nal circuit. Specically, at the anode, water is oxidized to give O2 photoelectrolysis of water and photoreduction of CO2 happen at
and electrons. These electrons arrive at the cathode via an exter- the same time during the PEC process. Generally, PEC is performed
nal circuit and reduce CO2 to several products such as CO, CH3 OH in liquid phase solutions, either with homogeneous or with het-
etc. In the case that appropriate electrodes and catalysts are used, erogeneous catalysts. Contrariwise, in electrochemical reduction
high product yields are obtained. Besides, the reduction and oxi- of CO2 over the cathode material, the electrons and protons orig-
dation reactions are performed in different spaces and thus the inate from the anode material where water is oxidized via using
interference between the two kinds of reactions and their products electric energy. A major disadvantage of the PEC process is the
is totally avoided. From the opposing point of view, the electrodes inevitable degradation of the photoanode and the photocathode
may be easily deactivated, or they are not rather stable. Also, the due to their photoinstability. This disadvantage is usually cleared
competitive reaction, the water splitting, affects the CO2 reduc- by using non-corroding metallic layers on the surface of the semi-
tion efciency. Apparently, the combination of photovoltaics (PV) conductor which prevent the contact of the electrolyte and the
and electrocatalysis is proved to be friendlier for the environment semiconductor. Transition metal complexes of Ru, Re, bearing a
[24,2729]. large variety of geometries, have been used as homogeneous cat-
A. Nikokavoura, C. Trapalis / Applied Surface Science 391 (2017) 149174 153

alysts for the CO2 reduction. Non-oxide semiconductors, such as it was modied to form for example nanotube arrays or dispersions
p-GaP, n- and p- GaAs, n-Si, p-InP, GaP, CdS, SiC [28], p-CuInS2 [31] in zeolites [26]. Indeed, functionalized titanates have been recently
and oxide semiconductors such as WO3 , TiO2 , ZnO [28] are used as synthesized which exhibited rather high photocatalytic activities
cathode materials (heterogeneous photocatalysts) and reduce CO2 under visible light irradiation [37]. As Ti based photocatalysts are
to CH4 , CH3 OH, HCHO and HCOOH after several hours of illumina- extensively studied, in this review, non-Ti based photocatalysts, are
tion. In other cases, a molecular catalyst may be attached onto the studied as far as it concerns their structure, composition, physical
surface of the photocathodic semiconductor [32]. and chemical features, reactivity towards CO2 reduction and the
In a PEC cell, CO2 has been reduced either by using p-InP semi- reaction mechanisms where they participate. During the last few
conductor bearing a biological catalyst (enzyme) over its surface years, especially since 2012, a remarkable increase in the number of
or by using colloidal semiconductor suspensions [24,25,28]. Gas the published papers in the research eld of the CO2 photocatalytic
phase PEC CO2 reduction has also been studied by using a TiO2 reduction by non-TiO2 catalysts has been remarked, as shown in
covered photoanode where gaseous H2 O, under light irradiation, is Fig. 4. For that reason we believe that a wide scope review on this
converted into electrons and protons which reduce gaseous CO2 on subject would encourage researchers to continue their efforts in
a metal loaded carbon based electrode, with high electron conver- this exciting and promising scientic eld.
sion efciency [33]. PEC reduction of CO2 in gas-phase has several The in depth study of the non-TiO2 photocalysts for the CO2
advantages such as the enhanced solubility of CO2 and the eas- reduction is facilitated in case that they are categorized into several
ier recovery of the products. The use of inexpensive and versatile groups depending on their structure/chemical nature. Inorganic
nanocarbon materials, contributed to the enhancement of the reac- photocatalysts constitute the rst category which is consisted
tivity and selectivity of the CO2 reduction because they have not of the following sub-categories of single-metal oxides, mixed-
only conductive properties but they also facilitate the electron metal oxides, metal oxide composites, layered double hydroxides
mobility, the mass transfer, the dispersion of metal nanoparti- (LDHs) and salt composites. Carbonaceous photocatalysts consti-
cles (Pt, Fe) and the formation of active hydrogen species [34]. tute the second, more recent, category, which is composed of the
It has also been reported the study of a solar cell driven electro- sub-categories of graphene (GR), carbon nanotubes (CNTs) and
chemical process, where a two-electrode system, comprising of a g-C3 N4 composites. Lately, a third category that of hybrid organic-
copper wire (cathode) and a platinum wire (anode) are involved. inorganic photocatalytic materials appeared. In Table 1, the main
The CO2 reduction takes place on the cathode and CO2 exists as groups of non-TiO2 photocatalysts for the reduction of CO2 , as
dilute aqueous KHCO3 solution. The production of a mixture of well as the type of the irradiation and the experimental conditions
organic compounds, such CH3 OH, HCHO, HCOOH, CH4 , is competi- required, are depicted.
tive to the H2 O splitting that produces H2 . The reaction mechanism The very low sensitivity to solar irradiation which is the
involves the excitation of the solar cell by sunlight irradiation, the main disadvantage of TiO2 , was not bypassed for a large num-
photogeneration of electrons and holes, the oxidation of H2 O to O2 ber of inorganic photocatalysts such as the single-metal oxides
and H+ on the anode and the passing of the H+ through a cation and mixed-metal oxides. Contrariwise, metal oxide composites,
exchange membrane to the cathode where H radicals are formed. LDHs and salt composites absorb mainly in the visible part of
When two H radicals recombine, H2 is produced via a competitive the spectrum exhibiting rather high photocatalytic efciencies. On
reaction to CO2 reduction [35]. the other hand, almost all the carbonaceous and hybrid photo-
Sometimes there are advantages in combining the solar water catalytic materials absorb visible light and this fact contributes to
splitting process with reactions of CO2 reduction. In that way, their superiority. Additionally, they exhibit excellent electronic and
hydrogen, produced by the water splitting, may reduce the CO2 physicochemical properties which facilitate the mechanism of the
to CH3 OH or other useful materials. For example, an electrolysis photocatalytic CO2 reduction, often resulting in amazing photocat-
cell, with a photoelectrode which absorbs UV/visible light irradi- alytic efciencies. Besides, the facile synthetic processes, the low
ation (photons), generates electrons and holes which electrolyse cost and the abundance of the raw materials make the prepara-
water to produce O2 and H2 . Certainly, there are several factors tion of carbonaceous photocatalysts more attractive and maybe
that must be obeyed at the same time, the band-gap energy of the the most attractive candidates for the CO2 photocatalytic reduction
photoelectrode must be low enough in order to absorb visible light [38,39].
irradiation and high enough in order to generate electrons capable Generally, the most important factors that inuence the ef-
of performing water splitting. Besides, the photoelectrode must be ciency of the photocatalytic reduction of CO2 are the degree of
stable, inexpensive and resistant to corrosion. Oxides (TiO2 , CaTiO3 , visible light excitation, the charge excitation and transport, the
SrTiO3 ), composite oxides and double layered semiconductors have adsorption and activation of CO2 on the surface of the photocata-
been tested, but it is very challenging to satisfy all these demands lyst, the kinetics of the CO2 reduction and the possible undesirable
[24,29]. Alternatively, electricity can be generated via the usage of reactions tha may take place during the photocatalytic reduction
solar energy, such as photovoltaics (PV) then by the usage of that of CO2 , as shown in Fig. 5 [40].
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 3. Inorganic photocatalysts for CO2
there are several difculties that must be overcome, such as the reductionsemiconductors
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 Semiconductors are among the rst photocatalytic systems used
[32]. for the performance of solar driven reactions. They possess rel-
Among all the above methods used for the reduction of atively high stability and they ensure mobility of charge carriers
CO2 , the most promising one seems to be the photocatalytic enabling their transportation to the surface and letting the redox
reduction because it is simple, friendly for the environment, non- reaction begin. They are also inexpensive materials [41]. When
electricity/heat dependent and relatively costless. semiconductors absorb light irradiation consisting of photons with
The most widely used photocatalyst for the CO2 reduction is TiO2 energy equal or greater than their band gap, photoexcitation takes
semiconductor, then, titania based photocatalysts or titanates fol- place. Electrons are excited from the valence band (VB) to the con-
low [36]. The properties of TiO2 , such as the band-gap energy, were duction band (CB) of the semiconductor leaving an unoccupied
improved when it was loaded with metals or non-metals or when state (electron hole) in the valence band. Most of the times, elec-
154 A. Nikokavoura, C. Trapalis / Applied Surface Science 391 (2017) 149174

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 Solid-gas (catalyst-CO2 /H2 O, catalyst-CO2 /H2 ,
catalyst-CO2 /CH4 ) systems/Aqueous dispersions
Mixed-metal oxides UV/VIS Solid-gas (catalyst-CO2 /H2 O) systems/Aqueous dispersions
Metal oxide composites VIS (mainly) Solid-gas (catalyst-CO2 /H2 O) systems/Aqueous dispersions
Layered Double Hydroxides (LDHs) UV/VIS Solid-gas (catalyst-CO2 /H2 O, catalyst-CO2 /H2 )
systems/Aqueous dispersions
Salt composites UV/VIS (mainly) Aqueous/organic solutions

Carbonaceous photocatalysts
Composite photocatalysts based on graphene (GR) VIS Aqueous dispersions
Composite photocatalysts based on carbon nanotubes (CNTs) VIS Aqueous dispersions
g-C3 N4 and composite photocatalysts based on g-C3 N4 VIS Aqueous dispersions/Solid-gas (catalyst-CO2 /H2 O) systems

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


VIS Aqueous/organic solutions

trons and holes recombine to release the absorbed energy as heat


or rarely as light and thats the reason behind the very low pho- Because of the thermodynamical inertness of the CO2 molecule,
tocatalytic efciency. When they dont recombine, they migrate to the electrons reaching the semiconductor surface are not all capa-
the surface of the semiconductor where they are trapped by the ble of reducing CO2 . The reducing potential of a species is a measure
adsorbed reactants and the photocatalytic redox reactions begin. of its reducing power, and the higher (more negative) it is the
Conduction band electrons reduce adsorbed species on the surface more reductive the species is. Therefore, photoexcited electrons
of the catalyst. On the other hand, valence band holes are oxidants, must have higher reduction potentials (more negative) than water
evoking direct oxidation of the adsorbed species or indirect oxida- reduction producing H2 . Otherwise H2 will be produced from water
tion via surface-bound hydroxyl radicals formed by holes trapped reduction which is a competitive reaction to the CO2 reduction.
at the semiconductor surface [38,4245]. Band levels of some simple and widely used semiconductors are
CO2 is a very stable molecule as it constitutes the combustion shown in Fig. 6 [46].
nal product of all the carboneous fuels. The conversion process Furthermore, the reaction mechanism of CO2 reduction must
to potential fuels is endothermic and therefore demands very high have multiple stages during which electrons and protons are trans-
sums of energy [46]. ferred. In case of a single electron transfer to CO2 in order to produce
The photochemical reaction that takes place during the articial CO2 , the reduction potential is too high (E red = 1.9 V) making
photosynthesis is shown below: the progress of the photocatalytic reaction very difcult. If a pro-
ton is simultaneously transferred to the CO2 , the radical anion
CO2 + H2 O(orH2 ) + photocatalyst + h of CO2 * is produced, which is stabilized reducing the reduction
potential (E red = 1.23 V) and therefore making easier the progress
Carbonaceous products + O2 [16]
A. Nikokavoura, C. Trapalis / Applied Surface Science 391 (2017) 149174 155

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

2e + 2H+ H2 E red = 0.42 V(VvsNHE)[46, 47]


Fig. 5. Main factors inuencing the photocatalytic efciency of the reduction of CO2
and strategies for its enhancement [40].
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 deter-
mines 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 unex-
ploited. 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.
Fig. 6. Band levels of simple semiconductors [46].
Besides, it is well accepted that noble metals (Au, Ag, Pd, Pt) dop-
ing contributes to the capture of CB electrons on the surface of
of the reaction. Generally, when protons and electrons are trans-
the photocatalysts and thus lowers the possibility of recombina-
ferred simultaneously in many small, rapid successive steps the CO2
tion of the photogenerated electrons/holes; additionally it reduces
photoreduction is facilitated [47,48]. Depending on the number of
the activation energy for the photocatalytic reduction of CO2 [50].
electrons used, the reaction product can be methane, methanol,
By the term doping is meant the assimilation of atoms or ions into
formaldehyde, carbon monoxide or formic acid. In Fig. 7 the pho-
the bulk of a semiconductor crystallite without altering its surface
toexcitation and electron transfer process for the production of CO
[38]. Doping must be performed at low concentrations in order to
is pictured [47]. The main reactions followed and values of reduc-
avoid recombination of holes and electrons which is fostered by
tion potentials at pH = 7 during the articial photosynthesis are
the presence of metal ions. Furthermore, dopants must not distort
shown below:
the semiconductor lattices, so it is very important for their con-
CO2 + 2e CO2 E red = 1.90 V(VvsNHE) centrations not to exceed the allowed limits during semiconductor
synthesis. If dopants are found in the appropriate proportion into
CO2 + 2e + 2H+ HCOOH E red = 0.61 V(VvsNHE) the semiconductor, their photoactivity is signicantly improved.
Photosensitizers, such as organic dyes or quantum dots (QDs), com-
bined with semiconductors, improve the photocatalytic efciency
CO2 + 2e + 2H+ CO + H2 O E red = 0.53 V(VvsNHE)
because they increase the absorption at the visible part of the
spectrum. When a semiconductor absorbs visible radiation, pho-
CO2 + 4e + 4H+ HCHO + H2 O E red = 0.48 V(VvsNHE)
toexcited electrons transit from the dye to the conduction band
and therefore facilitate the progress of the photocatalytic reac-
CO2 + 6e + 6H+ CH3 OH + H2 O E red = 0.38 V(VvsNHE) tion. Besides, the introduction of structural defects and the surface
plasmon resonance effect (SPR) increase the visible light excitation
CO2 + 8e + 8H+ CH4 + H2 O E red = 0.24 V(VvsNHE) [40,43,46,47].
156 A. Nikokavoura, C. Trapalis / Applied Surface Science 391 (2017) 149174

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 semiconduc-
tors interact adequately with each other. The result of this coupling
is the physical separation of charge carriers following their gen-
eration and the hampering of their recombination. Furthermore,
the semiconductor with the shorter band gap can act as a photo-
sensitizer 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 Fig. 8. Mechanism for the photoreduction of CO2 with H2 O over the ordered meso-
porous Fe doped CeO2 [59].
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 brush-like, ower-like, tree-like, dendritic and branched structures
of a semiconductor also increases its photocatalytic reactivity by [38,51,54].
increasing the number of reaction sites. Besides, the decrease of
the particle size leads to a considerable increase in the afnity of a 3.1. Single-metal oxides
semiconductor to adsorb CO2 and thus enhances the photocatalytic
efciency [46,52]. The rst photocatalytic systems, studied for the CO2 reduc-
Plenty of different morphologies of nanoparticles can be tion were the inorganic single-metal oxide semiconductors. The
achieved depending on reaction conditions during the semicon- photogenerated electrons are transferred from the VB to the CB,
ductor synthesis process. It has been shown that the morphological forming electron/hole pairs (e /h+ ) which further reduce/oxidize
and structural characteristics of a nanoparticle affect its photo- compounds adsorbed on the surface of the semiconductor [52]. The
catalytic reactivity. The separation of photoexcited electron-hole most popular semiconductor is TiO2 , pure or modied, alone or in
pairs and their transfer to the surface of a semiconductor is composites. TiO2 semiconductors exhibit some great advantages
essentially assisted when hierarchical heterostructures are used. such as high stability, low cost and reduced toxicity [55]. Addi-
Spherical nanoparticles (zero dimensional) have the advantage tionally, TiO2 exhibits enhanced photocatalytic efciencies during
of a high ratio surface/volume, so charge carriers have a short photocatalytic reactions such as water splitting, detoxication etc.
distance to traverse before reaching the surface. When different Nevertheless, TiO2 exhibits a major disadvantage which is the lim-
morphologies are combined, they may lead to the formation of a ited sensitivity to sunlight. Absorbing only the ultraviolet part of
hierarchical heterostructure with upgraded photocatalytic efcien- the electromagnetic solar radiation means that TiO2 absorbs only
cies. For example when spherical nanoparticles (ZnO and Al2 O3 ) 5% of the solar energy reaching the Earths surface [38,43]. In order
are combined with CdS nanowires, photocatalytic reactivity of the to extend the absorbance to the visible part of the spectrum sev-
hydrogen generation reaction is enhanced because of the resulting eral modications of TiO2 photocatalysts have been realized as well
high surface area and the efcient charge separation. Nanostruc- as a lot of other single-metal oxides, with lower values of band-
tures can also assume the form of wires, tubes and belts (one gap energy, have been prepared. Certainly, common single-metal
dimensional) differentiating themselves from the bulk semicon- oxides, such as WO3 , were found rather insufcient for the photo-
ductors. It has been found that as the length of a nanoparticle catalytic reduction of CO2 , due to their small value of band-gap
increases the same happens to its photocatalytic efciency. Besides, energy which favored the recombination of the photogenerated
hydrothermal and/or calcination processes usually improve the species and their low CB edge potential [56].
photocatalytic reactivity of heterostructures owing to increased
porosity, chemical or thermal stability. Other morphologies include 3.1.1. Solid-gas systems
the two dimensional structures with a platelet shape and the plac- 3.1.1.1. H2 O as the reducing agent. In many cases, the photocata-
ing of chemical particles on them. In this way, high surface area lyst in the solid state reacted with a gas mixture of the reactants.
and remarkable electric properties are ensured for the semiconduc- Pb3 O4 , BiOI, CeO2 reacted with a gas mixture of CO2 /H2 O, where
tor. Graphene or graphene-based composites are usually used as water was the reducing compound. In the case of hydrated Pb3 O4
platelet supports. Three dimensional mesoporous structures have (hematite), the enhanced number of water molecules on its sur-
also been mentioned. For example, In(OH)3 with mesoporous struc- face was crucial. It was found that the increased transfer of oxygen
ture exhibited almost 20 times higher photocatalytic efciency atoms from water molecules to the oxygen containing prod-
towards the reduction of CO2 (0.8 mol CH4/ g* h) than that of n- ucts, such as methanol, resulted in the increase in the amount
In(OH)3 (0.04 mol CH4/ g* h) [53]. The 3D mesoporous structures of products (2.6 mol CH3 OH/g* h/) [57]. Hierarchical structures
possess multidimensional domains at different levels and com- of BiOI produced CH4 (1.58 mol/g* 8 h) when they reacted with
plex/fascinating pore structures. In this case, the large number of H2 O, whereas the amount of the photocatalytic product was
multi-sized pores ensures the large specic area and the high rate almost the half (0.68 mol/g* 8 h) when BiOI was in the bulk form
of transfer for the species. Besides, the CO2 molecules easily dif- [58]. Mesoporous Fe/CeO2 produced increased amounts of CO
fuse into the reaction sites and the products are easily removed (74.3 mol/g* h) and CH4 (17.3 mol/g* h) because of the Fe dop-
from them. As a consequence, the photocatalytic reactivity of the ing which formed an extra dopant energy band and the enhanced
semiconductor is highly enhanced. Some typical three dimen- number of chemisorbed oxygen species on its surface, as depicted
sional structures (hierarchical nanostrucrures) are the urchin-like, in Fig. 8. The reaction mechanism involves the CO2 adsorption on
the surface of the catalyst followed by the reaction of CO2 with pho-
A. Nikokavoura, C. Trapalis / Applied Surface Science 391 (2017) 149174 157

togenerated electrons via the formation of free radicals CO2 * [59]. was further enhanced when the calcination process took place at
ZnO is the most widely studied single-metal oxide photocatalyst temperatures below 400 C [69].
for the reduction of CO2 . It consists the TiO2 analogue, possesses
similar values of bang-gap energy with that, it is a low-cost prod- 3.1.1.3. CH4 as the reducing agent. In the rare case that CH4 is the
uct and it has not been regarded as a very environmentally harmful reducing compound, the reaction mechanism involves the forma-
compound [6062]. In the early 90s, ZnO in a clathrate hydrate tion of free radicals CH3 * , H* , CO2* and the reaction among them
phase reacted with CO2 gas to nd that the presence of impurities to produce mainly oxygenated compounds such as formates and
such as S, Si and P atoms, lowered the excitation energy of elec- acetates. The solid photocatalyst (ZrO2 ) reacted with a gas mix-
trons and holes and therefore shifted the absorption of ZnO to the ture of CO2 and CH4 to form little amounts of CO (almost 1 mol
visible part of the spectrum [63]. Studies upon Cu and N doped CO/g* 6 h) [68]. In addition, calcinated ZnO immobilized on stainless
mesoporous ZnO materials showed that the higher value of sur- steel mesh reacted with a CO2 /CH4 gas mixture displaying satisfac-
face area of the samples prepared by the hydrothermal method tory conversion percentages of CO2 (11% after 5 h) [64,70]. Other
contributed to the increased photocatalytic activity compared to studies conrmed the effect of the amount of ZnO coated on mesh
those prepared by other methods (SC). The insertion of Cu into the on the photocatalytic activity, as it has impact on the active surface
mesoporous ZnO also controlled the selectivity and increased the of the catalyst [70]. In Fig. 9, SEM images of ZnO photocatalysts
photocatalytic activity since its dispersion and interaction with ZnO coated on mesh are shown [70]. Moreover, efcient photosensi-
was increased along with the absorption in the visible part of the tizers such as metallophthalocyanines (MPc), were added to ZnO
spectrum. Still, the optimum photocatalytic efciencies were not coated on stainless steel mesh in order to extend the absorbance of
rather impressive (1 mol CO/g* h) [60]. Sharifnia et al. synthesized ZnO into the visible part of the spectrum and thus enhance the pho-
calcinated ZnO immobilized on stainless steel mesh. Calcination tocatalytic activity (optimum conversion percentages of CO2 :23%
led to the decrease of ZnO particles size, resulting in specic sur- after 5 h) [71].
face area increase and agglomeration decrease. Calcination also
improved the absorbance of photocatalysts in the UVvis region 3.1.2. Aqueous dispersions
of the spectrum and shifted the absorbance slightly towards the The photocatalysts were dispersed in water or aqueous
visible area. Stainless steel mesh was selected as a support for ZnO, solutions and they reacted with CO2 in the gas phase. Inter-
owing to its large specic surface area, resistance to corrosions, esting heterostructures, consisted of common cations, such as
enhanced absorption of UV light irradiation and sufcient ventila- ZnTe/ZnO, synthesized by hydrothermal methods, produced dif-
tion for gases transport [64]. Eventually, the conversion percentage ferent amounts of CH4 , depending on the ZnO nanostructures
of CO2 to a group of oxygenated products, on the surface of the cal- (optimum efciency: 100 mol CH4 /g* 5 h). The formation of het-
cinated ZnO immobilized on stainless steel mesh was satisfactory erojunctions via an intimate interfacing of ZnTe and ZnO, enhanced
(9% after 5 h). Bartoszek et al. carried out experiments where moist- the rate of the electron transfer between ZnTe and ZnO compared
ened hematite photocatalysed the CO2 reduction when its surface to the recombination rate of the photogenerated species, and thus
came in contact with a mixture of CO2 -H2 O in gas phase, giving an increased the photocatalytic activity [72]. NiO dispersed in water
explanation on the origin of methane in the atmosphere of Mars, was found to be more efcient photocatalyst than other single-
which had puzzled scientists. The role of water was found to be very metal oxides dispersed in aqueous solutions, such as ZnO, WO3 ,
important; the higher the water on hematite surface, the higher Cu2 O, CuO. The enhanced photocatalytic activity of NiO (170 mol
was the formation of oxygenates (methanol, acetone, formalde- CH3 OH/g* h), was attributed to the surface defects. Namely, vacant
hyde, acetaldehyde). Generally, oxygenated molecules bearing two oxygen spaces on the NiO surface strengthened the interactions
or three carbon atoms, like acetone, might be produced via various with CO2 molecules and facilitated the transportation of the pho-
mechanisms which include photoinduced radical reactions (such togenerated species [73,74]. Additionally, Yahaya et al. concluded
as the recombination of radicals from methanol and aldehydes) that the CO2 photoreduction to CH3 OH does not proceed via a sin-
[57,65]. Recently, a 5% CdS/WO3 photocatalyst was synthesized gle mechanism, as happens in the case of the reduction of free CO2 .
and its photocatalytic activity for the CO2 reduction under vis- On the contrary, H2 CO3 formed by the CO2 dissolution in water
ible light irradiation was found 1.02 mol CH4 /g* h, actually not is responsible for the mechanisms such as the one in the H2 CO3
rather high. It was proved that CdS/WO3 heterostructure samples and carbonate ions reduction [57]. Peiqiang et al. demonstrated the
form a hierarchical Z-Scheme which contributes to the enhance- excellent photocatalytic property (1.8 mmol CH3 OH/L* m2* 6 h) of
ment of the photocatalytic activity, compared to that of the bare one dimensional wedged N/CuO owing to the N doping which con-
samples, owing to the efcient spatial separation of the photogen- tributed to a red shift at the absorption of light as it introduced an
erated electron/hole pairs. CdS nanoparticles were uniformly and intermediate band between the VB and the CB of CuO and increased
intimately dispersed on the surface of WO3 nanospheres and the the carrier mobility [75]. Aqueous suspensions of hydrous cuprous
reduction reactions of CO2 took place on the CdS surface whereas oxide (Cu2 Ox H2 O) exhibited satisfying photocatalytic efciency
the oxidation reactions took place on the WO3 surface [66]. (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
3.1.1.2. H2 as the reducing agent. When the photocatalyst in the the high density of electrons and therefore the preference for mul-
solid state reacted with a gas mixture of CO2 and H2 , the CO2 tielectron processes [44].
reduction proceeded via the dissociative adsorption of H2 on its sur-
face. Ga2 O3 produced CO (3.6 mol/g* 5 h) upon reacting with CO2 3.2. Mixed-metal oxides
molecules, whereas MgO and ZrO2 formed slightly higher amounts
of CO [67,68]. Calcinated ZnO immobilized on stainless steel mesh Mixed metal oxides, consisting of two or more kinds of met-
reacted with a CO2 /H2 gas mixture but the conversion percentage als and oxygen, have been widely used as photocatalysts for the
(3% after 5 h) was found to be lower compared to that obtained CO2 reduction. They possess semiconducting properties and their
when gas mixtures of CO2 /H2 O (9% after 5 h) or CO2 /CH4 (11% after aqueous suspensions, irradiated by visible light, have been mainly
5 h) were used [64]. Hydrogenation of CO2 on the surface of NiO, studied. In most cases water plays the role of the reducing agent,
via a dissociative hydrogen adsorption on oxygen rich sites (surface and it is oxidized to O2 and H+ ions. The latter, react directly with
defects), resulted in a boost to the photocatalytic activity, which CO2 molecules and photogenerated electrons or with CO2 * radi-
158 A. Nikokavoura, C. Trapalis / Applied Surface Science 391 (2017) 149174

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 ciency are achieved [7779]. Sun et al. studied the photocatalytic
paths, depending on the values of the reduction potential of the activity of ball-ower-like Bi2 WO6 , prepared by a hydrothermal
mixed-metal oxides. 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
3.2.1. Solid-gas systems H2 O on the basic sites of Bi2 WO6 . The highest photocatalytic activ-
3.2.1.1. H2 O as the reducing agent. Solid-gas systems where the ity (333 nmol CO/g* h) was observed in the condition with little H2 O
mixed-metal oxide photocatalyst is found in the solid state and vapor, owing to the increased crystallinity, reduced recombination
the reaction mixture of CO2 /H2 O is found in the gas phase have rate of photogenerated species and increased stability of basic sites
been studied in a small extend. Concisely, solid Zn2 GeO4 , KNbO3 , on the surface of the photocatalyst, whereas the regeneration of the
HNbO3 and Bi2 WO6 reacted with CO2 and H2 O vapor via the catalyst by water washing, was found to be rather effective [80].
oxidation of water molecules to O2 and H+ ions and the reduc-
tion of CO2 by the H+ ions and the photogenerated electrons, as
3.2.1.2. H2 as the reducing agent. Gas-solid systems, where the solid
it has already been referred when water plays the role of the
photocatalyst react with a gas mixture of CO2 and H2 via chemisorp-
reducing compound. Bulk Zn2 GeO4 , exhibited very small photocat-
tion of CO2 molecules onto its surface, have been sparsely studied.
alytic activity (<1 mol CH4 /g* h) whereas nanoribbons of Zn2 GeO4
Generally, the decisive step of the reaction mechanism is the CO2
were found to be much more reactive photocatalysts (1.5 mol
chemisorption, which is favored when the catalyst possesses basic
CH4 /g* h, 6 mol CH4 /g* 14 h). The superiority of the latter could be
sites which facilitate the absorption of CO2 by altering its linear con-
attributed to many factors, such as their enhanced specic surface
formation and assisting the reduction by hydrogen. As the degree of
area (28.27 m2 /g vs 0.75 m2 /g), their extremely good crystal quality,
CO2 absorption enhances, the photocatalytic activity increases too.
their increased lengths and ultrathin geometry which promote the
LiTaO3 exhibited low photocatalytic activity (0.42 mol CO/g* 24 h),
separation of photoinduced species, prevent the recombination of
signicantly lower than that of single-metal oxides such as Ga2 O3 ,
them and promote the rapid transportation of the charge carriers.
MgO and ZrO2 , which bear a larger number of basic sites on their
It was also demonstrated that the loading of Pt (1% wt) or RuO2 (1%
surface [81].
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 3.2.2. Aqueous dispersions
photocatalytic efciencies were observed for KNb3 O8 , HNb3 O8 and The following mixed-metal oxides: CaFe2 O4 , BiVO4 , LaCoO3 ,
Bi2 WO6 . Certainly in case that they did not have bulk structures NaBiO3 , NaNbO3 , KNbO3 , CuGaO2 , CuAlGaO4 , Bi2 WO6 and BaCeO3
and they formed nanobelts and nanoplates, their activities were were studied either in contact with small amounts of water,
importantly enhanced (3.58 mol CH4 /g* h, 1.71 mol CH4 /g* h and or dispersed in aqueous solutions. Aqueous suspensions of p-
1.1 mol CH4 /g* h, for HNbO3 , KNbO3 and Bi2 WO6 , respectively). type CaFe2 O4 , containing NaH2 PO2 and BaCO3 , saturated with
The formation of hydrogen bonds between water molecules and CO2 gas, produced mainly methanol and formaldehyde (2 mol
the H on the HNb3 O8 surface deters the recombination of pho- CH3 OH/g* 4 h and 3 mol HCHO/g* 4 h) via a direct mechanism
toinduced electrons and holes because they are trapped on the which did not involve the formation of CO2 * radicals. It was sug-
interlayer surface and therefore higher values of photocatalytic ef- gested that the photocatalytic reduction of CO2 took place at the
A. Nikokavoura, C. Trapalis / Applied Surface Science 391 (2017) 149174 159

interface constituted of solid CaFe2 O4 , solid BaCO3 and water where compartment O2 was evolved [90]. LaCoO3 displayed notable pho-
CO2 and CO3 2 were more reactive [82]. Aqueous NaOH suspen- tocatalytic efciency (40 mol HCOOH/g* h), which was found to be
sions of BiVO4 produced methanol or ethanol, depending on the tripled in case of the synergistic doping with C and Fe (130 mol
available amount of CO2 . The determinant role of the crystal struc- HCOOH/g* h) [91]. The modication of Bi2 WO6 microspheres with
ture to the photocatalytic activity was studied, to nd that in conducting polymers (PPy, PANI, PTh) increased the absorption in
monoclinic BiVO4 (30 mol ethanol/g* 80 min) there is a higher ten- the visible area of the spectrum, decreased the recombination rate
dency to form Bi O bonds with CO3 2 ions than in tetragonal of the photogenerated electron-hole pairs and facilitated the charge
BiVO4 (2 mol ethanol/g* 80 min) and thus the transfer of photo- transfer efciency, resulting in enhancement of the photocatalytic
generated electrons from vanadium to CO3 2 is facilitated. The activity by 2.8 times, compared to that of bare Bi2 WO6 . As the
important role of the NaOH solution was partly attributed to its CB of Bi2 WO6 is found too low for the CO2 photoreduction to gas
action as a hole scavenger which helps the separation of photoin- products such as CH4 and CO, the main products detected under
duced species, and to its ability to dissolve more CO2 than water visible light irradiation, were methanol (56.5 mol CH3 OH/g* 4 h)
[83]. Aqueous NaOH suspensions of lamellar BiVO4 exhibited satis- and ethanol (20.5 mol CH3 CH2 OH/g* 4 h) [92]. Various cocatalyst
fying photocatalytic activity in methanol (35 mol methanol/g* 6 h) nanoparticles (Ag, Au, Pt, CuO and RuO2 ) enhanced the photocat-
as in the current study, the available amount of CO2 was relatively alytic activity of perovskite-type BaCeO3 for the CO2 reduction,
lower than in case of monoclinic/tetragonal BiVO4 and the forma- under UV light irradiation. Especially, 0.3%Ag/BaCeO3 was found to
tion of one carbon atom products was favored [83,84]. A reaction be the more effective photocatalyst among the others, but generally
mechanism, which involves the oxidation of water molecules to O2 not rather effective (4 mol CH4 /g* 7 h). The cubic crystal structure
by the photogenerated holes and the reduction of CO2 to methanol of Ag nanoparticles found on the surface of BaCeO3 promoted the
by the photogenerated electrons on the surface of the lamellar close contact between Ag and BaCeO3 leading to the formation of
BiVO4 was proposed [84]. The effect of the preparation method an active center which lowered the activation energy of the reac-
of NaBiO3 to the photocatalytic reduction of CO2 was found to tion and facilitated the separation of the photogenerated species
be crucial when NaBiO3 nanopowders were synthesized through [93].
hydrothermal, sol-gel and dehydration methods. The diversica-
tion in the crystallinity, the specic surface area and the size 3.3. Metal oxide composites
and shape of the particles produced via each method resulted
in different photocatalytic activities. Namely, the photocatalytic The combination of two metal oxides in order to prepare
efciency of NaBiO3 samples synthesized by the sol-gel method photocatalysts with ameliorated photocatalytic efciency for the
was several times higher than those prepared by other methods, reduction of CO2 has also been attempted. NiO consists one of
owing to the smaller size of their crystallites, the higher value of the most widely studied metal oxides cocatalysts. In the crushing
specic area and the lower band gap energy (sol-gel: 0.6 mol majority, the reaction mixture, either in the gas or liquid phase,
CH3 OH/g* h, hydrothermal: 0.37 mol CH3 OH/g* h, dehydration: composed of CO2 and H2 O. The main products of the photocat-
0.037 mol CH3 OH/g * h) [85]. Not really hopeful photocatalytic alytic reduction of CO2 with H2 O, under visible light irradiation,
efciencies were observed for NaNbO3 and KNbO3 , by Shi et al. were CH3 OH  CH4 .
(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 3.3.1. Solid-gas systems
values of specic surface area of the samples and therefore they 3.3.1.1. H2 O as the reducing agent. Solid NiO/InTaO4 photocatalyst
could be easily improved [86]. Besides, Shi et al. demonstrated that has reacted with a gas mixture of gaseous CO2 and water vapors
NaNbO3 nanowires, prepared by a combination of hydrothermal in an optical ber photoreactor, composed of assembled optical
and heating processes, exhibited tenfold increase in the photocat- bers with pure silica core and a polymeric shield (optimal ef-
alytic activity (1600 ppm CH4 /g* 150 min) compared to that of bulk ciency: 21.0 mol CH3 OH/g* h at 75 C) [94] as well as in a monolith
NaNbO3 , prepared by SSR (140 ppm CH4 /g* 150 min) [87]. In sep- photoreactor with internal channels covered with a layer of the
arate studies, the effect of the crystal structure and Pt doping on catalyst, over a lower SiO2 sublayer (0.16 mol CH3 OH/g* h) [95].
the photocatalytic activity, were studied concurrently. The superi- On the other hand, multifunctional Pt (0.5%wt)/ZnAl2 O4 /ZnGaNO
ority of cubic Pt/NaNbO3 (1.3 mol CH4 /g* h and 4.2 mol CH4 /g* h) with mesoporous structure, small band-gap energy, enhanced gas
over the orthogonal Pt/NaNbO3 (0.5 mol CH4 /g* h and 1.5 mol adsorption capacity and basicity, owing to the presence of ZnAl2 O4 ,
CH4 /g* h) was obvious. Apparently, the transfer of the photogener- increased the light absorbance and assisted the fast migration of
ated electrons is facilitated in the cubic crystal lattice, owing to its the photogenerated species, resulting in satisfying photocatalytic
differentiated electronic structure [88]. Lekse et al. studied the pho- activity (38 mol CH4 /g* 8 h) [96].
tocatalytic 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 3.3.2. Aqueous dispersions
hexagonal, rhombohedral or randomly substituted rhombohydral The effect of the nature of the supporting materials (basic
structure and consist of alternating layers of octahedrally B metal or acidic) on the selectivity and the photocatalytic activity has
atoms spaced by two coordinated A metal atoms. Namely, CuGaO2 , been analyzed for CuO/ZnO supported on MgO (8 mol CH4 /g* h
even if it was doped with Fe, exhibited low photocatalytic activity and 0.8 mol C2 H6 /g* h). It was deduced that basic supporting
(9 ppm CO/g* h), as the only effect of Fe doping was the shifted the materials interact more thoroughly with the reactive site of the
absorption towards higher wavelengths (lower values of band-gap semiconductor and thus favor the formation of dimerized prod-
energy) [89]. On the contrary, aqueous acidic solution with Fe+2 ucts [97]. Potassium bicarbonate (0.2 M) aqueous suspensions of
ions (pH = 2.6) of cube-like shaped Pt/CuAlGaO4 , synthesized via NiO(1%wt)/InTaO samples, where NiO particles were randomly
the solid state fusion method, exhibited improved photocatalytic dispersed in InTaO4 agglomerates (12 m), exhibited mediocre
efciency (8 mol CH3 OH/g* h), when they were put in a novel twin photocatalytic activity (1.394 mol CH3 OH/g* h). NiO acted as an
reactor and reacted with a mixture of CO/CO2 . The singularity of the electron acceptor and so improved the photocatalytic activity com-
twin reactor was the division of H2 and O2 producing photocata- pared to that of bare InTaO4 samples. Methanol was produced
lysts into two compartments separated by a membrane. As a result, via 6 electron reduction processes where CO2 or H2 CO3 or CO3 2
in the one compartment H2 was generated and simultaneously etc. were reduced by InTaO4 because of the more negative reduc-
reacted with CO2 to produce mainly methanol, whereas in the other tion potential of the conduction band of InTaO4 compared to
160 A. Nikokavoura, C. Trapalis / Applied Surface Science 391 (2017) 149174

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 pho-
tocatalsyts 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 sur-
face. 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* radi-
cals, 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 short-
ened. Regarding the addition of NiO, it has been conrmed that Fig. 10. Proposed mechanism for the photocatalytic reduction of CO2 on the surface
it is an efcient cocatalyst because it acts as an electron accep- of Ni/Ni3 (BO3 )2 /NiO, under visible light irradiation [102].
tor and thus prevents the electron-hole recombination. However,
the mismatching of the conduction bands of InTaO4 and NiO pre-
vents the electron transfer from InTaO4 to NiO. Liu et al. used
a Ni@NiO core-shell structure where the metallic Ni layer facil- Fermi level of Ni, to produce CH4 . The formation of CH4 was favored
itated the transportation of photoinduced electrons from InTaO4 as the Fermi level of Ni constitutes an electron rich region where
valence band to the NiO surface and thus enhanced the photocat- the performance of reactions requiring a large number of electrons
alytic efciency. The morphological analysis of Ni@NiO/N-InTaO4 is promoted [102].
showed that nanoparticles of the cocatalyst (Ni@NiO) were ran-
domly 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 3.4. Layered double hydroxides (LDHs)
(130 mol CH3 OH/g* h) and Ni@NiO/N-InTaO4 was the most ef-
cient photocatalyst (170 mol CH3 OH/g* h). That was expected Layered double hydroxides (LDHs) are thought to be compounds
because N doping effectively decreased the band gap, enhanced with the layered structure of brucite (Mg(OH)2 ), with a hexago-
the absorbance of visible light irradiation. Besides, Ni@NiO core- nal crystal structure. They are constituted of positively charged
shell structure, due its higher electronegativity compared to that sheets with the general type [MII 1-x MIII x (OH)2 ]x+ which indicates
of Ta, assisted the migration of electrons from the InTaO4 sur- that some trivalent cations have taken the place of the divalent
face to the NiO nanoparticles, where the reduction of the carbon cations. Anions are placed between two cationic layers in order
source (CO2 , H2 CO3 and CO3 2 ) began [99]. Aqueous potassium to ensure the neutral charge of the LDH. Besides, water is present
bicarbonate suspensions of NiO/InNbO4 and Co3 O4 /InNbO4 exhib- between the cationic layers. It is conrmed that the mass of water
ited similar but rather low photocatalytic activities (1.6 mol present in a LDH is almost 50% of the total mass of cations forming
CH3 OH/g* h and 1.5 mol CH3 OH/g* h, respectively). Still, they were the positively charged layers. MII can be one of the following met-
slightly higher than those of pure InNbO4 [100]. More recent stud- als: Mg, Mn, Fe, Co, Ni, Cu, Zn, MIII can be one of the followings Al,
ies on the photocatalytic activity of aqueous KHCO3 suspensions of Cr, Mn, Fe, Ga and the value of x usually varies between 0.170.33.
NiO/InVO4 demonstrated that the generation of little holes (sur- Intercalated anions can be the followings: CO3 2 , SO4 2 , NO3 ,
face defects) on the InVO4 surface after the deposition of NiO, Cl , OH . LDHs are efcient photocatalysts for the CO2 reduction
resulted in the formation of more active sites and thus higher because they exhibit a great sorption capacity for CO2 in the space
photocatalytic activity (1.102 mol/g* h for InVO4 vs 1.526 mol between the cationic sheets. On the other hand, Teramura et al.
CH3 OH/g* h for NiO/InVO4 ). Additionally, the photocatalytic ef- and Tanaka et al. demonstrated that simple mixtures of the same
ciency was enhanced because NiO/InVO4 absorbs more intensely metal hydroxides exhibit signicantly lower photocatalytic activ-
in the visible part of the spectrum, owing to the formation of a sub- ity. This fact indicates that the unique structure of LDHs facilitates
band on the upper end of the VB [101]. Studies of the photocatalytic the CO2 dissolution in the LDH interlayers and therefore its reac-
activity of aqueous suspensions of Ni/Ni3 (BO3 )2 /NiO nanoparticles tion with surrounded water molecules to produce CO and O2 via the
(0.41 mol CH4 /g*h, 4 mol CH4 /g*10 h) demonstrated that it is formation of photogenerated pairs of electrons and holes. Besides,
importantly enhanced compared to that of Ni3 (BO3 )2 (0.14 mol the choice of the cations present in the LDH inuences its semi-
CH4 /g*h, 1.5 mol CH4 /g*10 h) and Ni3 (BO3 )2 /NiO (0.16 mol conductor properties, the kind of the products (usually CO and/or
CH4 /g* h, 1.6 mol CH4 /g*10 h), owing to the presence of Ni which CH3 OH) and therefore its photocatalytic activitiy. LDHs constitute
facilitated the separation of the photogenerated species and delay the only layered materials with photocatalytic properties which are
their recombination. Namely, the reaction mechanism of CO2 formed by positively charged sheets, in contrast to the montmo-
reduction on the surface of Ni/Ni3 (BO3 )2 /NiO heterostructures rillonites, smectites and kaolinites which are formed by negatively
(shown in Fig. 10), involved (a) the transfer of the photogenerated charged layers. In fact LDHs exhibit higher sorption capacity for CO2
electrons from the CB of NiO to the CB of Ni3 (BO3 )2 and then to than montmorillonites and similar to that of zeolites [103,104]. The
the Fermi level of Ni, (b) the transfer of the photogenerated holes evaluation of the photocatalytic activity of LDHs was performed in
from the VB of Ni3 (BO3 )2 to the VB of NiO where they oxidize solid-gas systems, where the solid catalyst reacted with a gaseous
water molecules to O2 and H+ ions and c) the reduction of CO2 mixture of CO2 /H2 O or CO2 /H2 , as well as in aqueous suspensions,
molecules by H+ ions and photogenerated electrons found on the under UV irradiation.
A. Nikokavoura, C. Trapalis / Applied Surface Science 391 (2017) 149174 161

3.4.1. Solid-gas systems ing agents, such as 2-propanol, Na2 S etc., were added. ZnS and CdS
In solid-gas systems, the reaction mechanism involves the dif- based photocatalysts were the most studied ones.
fusion of CO2 molecules in the internal and the interlayer space of
the LDH, resulting in the formation of hydrogen carbonate species, 3.5.1. Aqueous/organic dispersions
which is a reaction intermediate. 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
3.4.1.1. H2 O as the reducing agent. Katsumata et al. studied the pho-
the polarity of the solvent. In non polar solvents, CO2 * free radi-
tocatalytic activity of Pd or Pt or Au dopped Zn-Cr LDHs which
cal is not solvated, so it is adsorbed on the surface of the catalyst,
was found satisfying (Pt (0.1%wt)/Zn-Cr LDH 7.8 mol CO/g* 3 h,
where CO and H2 O are produced, via double protonation reactions.
Pd (0.1%wt)/Zn-Cr LDH-4.3 mol CO/g* 3 h and Au (0.7%wt)/Zn-
In polar solvents CO2 * free radical is stabilized by solvation and
Cr LDH-3.8 mol CO/g* 3 h). It was also demonstrated that the
then HCOO is produced via protonation and reduction reactions.
undopped Zn-Cr LDHs exhibited very low photocatalytic activity,
Besides, the presence of thiols bound to Cd+2 ions, on the sur-
indicating the crucial role of Pt, Pd and Au which hinder the recom-
face of CdS, led to the enhanced formation of HCOO , owing to
bination of the photogenerated species and facilitate the progress
the decrease of the amount of adsorbed CO2 * free radical. Still,
of the photocatalytic reactions which proceed via the involvement
thiol modied CdS, in DCM, exhibited low photocatalytic activ-
of two electrons and produce CO [105].
ity (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
3.4.1.2. H2 as the reducing agent. As mentioned above, the selectiv- obtained by the study of Ru/ZnS suspensions in several solvents, as
ity of the photocatalytic reduction of CO2 was strongly depended on shown in Fig. 12. During the use of non polar solvents, the pho-
the LDH composition. Namely, Zn-GaIII , Zn-AlIII , Zn-Cu-GaIII and Zn- tocatalytic activity was reduced, whereas the amount of CO was
Cu-AlIII LDHs (shown in Fig. 11) produced CO and/or CH3 OH. It was increased, as mentioned above. Contrariwise, in polar solvents and
reported that the presence of Cu in the LDH structure enhanced the especially in water, the photocatalytic activity was enhanced, as
production of CH3 OH, owing to the Cu-CO2 interactions. The latter well as the production of HCOOH, resulting in remarkable photo-
promote the reaction among CO2 molecules, H+ ions and photogen- catalytic efciencies ZnS (0.8 mmol HCOOH/dm3* h and 0.2 mmol
erated electrons, as CO2 molecules bind to Cu sites in the form of CO/dm3* h, 1.2 mmol HCOOH/dm3* 5 h and 0.4 mmol CO/dm3* 5 h).
hydrogen carbonate species. Besides, the insertion of Cu atoms in The high polarity of the solvent, the great ability of Ru nanopar-
the LDH structure lowers the band-gap energy and thus enhances ticles to absorb CO2 , to act as electron donors and to reduce the
the photocatalytic activity. Characteristically, Zn-Cu-AlIII and Zn- activation energy surely contributed to these hopeful results [112].
Cu-GaIII LDHs produced 0.31 mol CH3 OH/g* h and 0.49 mol Yanagida et al. demonstrated that the surface characteristics of ZnS
CH3 OH/g* h, respectively. In the second case, Cu atoms were found nanocrystallites (such as sulfur vacancies), which originate from
not only in the interlayer space but also inside the cationic lay- their preparation method, affected the selectivity and activity of
ers, contributing to the faster diffusion of CO2 molecules which the photocatalytic CO2 reduction [113]. The addition of Cd2+ ions on
form the hydrogen carbonate species. Still, the photocatalytic activ- the surface of CdS, leads to the formation of surface defects and the
ities were very low [103,106,107]. Au/Zn-GaIII and Ag/Zn-GaIII LDHs increase in the number of active sites on the surface of the catalyst.
bearing Au or Ag nanoparticles on their surface, produced CH3 OH For that reason, Cd2+ /CdS suspension in DMF (and triethanolamine
and CO (0.201 mol CO/g* h and 0.03 mol CH3 OH/g* h, 0.102 mol as electron donor) produced satisfying amounts of CO (30 mol
CO/g* h and 0.118 mol CH3 OH/g* h, respectively). Specically, in CO/g * 30 min), which nally formed condensed organic products
Ag/Zn-GaIII LDH, Ag nanoparticles are electron donors owing to the (benzophenone, acetophenone and benzyl halides) via the forma-
Surface Plasmonic Resonance (SPR) effect and the methanol yield tion of a Cd2+ OCOCO2 intermediate complex [114].
was higher, whereas, in Au/Zn-GaIII LDH, Au nanoparticles act as The use of supporting materials for the enhancement of the
electron traps and CO yield was extremely limited at the expense photocatalytic activity of ZnS and CdS salts gave remarkable
of methanol [108]. 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
3.4.2. Aqueous dispersions
of supported ZnS with excess of Zn+2 ions led to the opti-
The photocatalytic efciencies of the aqueous dispersions of
mum photocatalytic activity (10.3 mmol/g* 4 h). It is therefore
LDHs were found to be increased in comparison with those of
deducted that the use of porous supporting materials, the addi-
the solid-state systems. Cu-M-Al (M = Mg, Zn, Ni) LDHs exhibited
tion of excess of metal ions on the surface of the catalyst
remarkable photocatalytic activity, especially Cu-Ni-Al LDH, owing
and the presence of a reducing agent in the reaction mix-
to its lowered band-gap energy and its increased specic surface
ture, combined together, result in the optimal photocatalytic
area (210 mol CH3 OH/g* h) [109]. In other study, Ni-Al LDH did
efciencies [115]. Several studies were performed in aqueous
not produce CH3 OH, besides it exhibited lowered photocatalytic
suspensions of ZnS and CdS, supported on MMT, with CTA
activity (20 mol CO/g* 8 h), obviously due to the absence of Cu
stabilizer which prevents the agglomeration of salt nanoparti-
[110].
cles. They exhibited noteworthy photocatalytic production of H2
(indeed by water splitting!)(CdS/MMT/CTA: 220 mol H2 /g* 25 h,
3.5. Salts composites 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
Salts have been extensively used as photocatalysts for the CO2 CH4 /g* 25 h). The reaction mechanism for hydrogen production,
reduction, in order to overcome several disadvantages of metalox- involves the oxidation of water molecules to O2 and H+ ions, the
ides, such as the high values of band-gap energy. In most cases, formation of H* free radicals via the reaction of H+ with photo-
their photocatalytic activity was studied in aqueous or organic sus- generated electrons and nally the reaction between two radicals
pensions, under visible light irradiation. The role of the solvent was H* to produce H2 . CH4 is formed either, via the reaction of CO2
crucial and determined the selectivity of the reaction. The forma- with H2 , or via the reaction of CH3 * free radicals (originating
tion of CO2 * free radicals constituted the common intermediate from CTA dissociation) with H* free radicals [116118]. The dif-
step of all the photocatalytic reactions, where often several reduc- ferent amount of ZnS nanoparticles on the surface of MMT (4.2,
162 A. Nikokavoura, C. Trapalis / Applied Surface Science 391 (2017) 149174

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 lyst. Colloids of ZnS exhibited impressive photocatalytic activity
the extent of the agglomeration and the uniform distribution and (optimum: 2300 mol oxalic ions/dm3* 48 h in pH = 14), whereas
therefore the photocatalytic activity (optimal efciency for the ZnS that of CdS was much lower (136 mol formic ions/dm3* 42 h in
(3.1%wt)/MMT: 300 mol H2 /g* 24 h, 28 mol CH4 /g* 24 h, 3 mol pH = 6) [121127]. Ni dopping of ZnS aimed to leverage the abil-
CO/g* 24 h) [119]. The prominent role of the geometric features ity of Ni+2 ions to trap the photogenerated electrons and thus
of a photoreactor was also studied in aqueous ZnS/MMT suspen- to reduce the probability of recombination of the photogener-
sions. Between two stirred batch annular reactors the one whose ated species. Besides, it was expected that the double use of
geometry secured the optimum mixing of the reactants, exhib- methanol, as solvent and as sacrice compound and the hydrother-
ited almost 23 times higher photocatalytic efciency (380 mol mal preparation method of Ni/ZnS would improve signicantly the
H2 /g* h, 30 mol CH4 /g* h, 4 mol CO/g* h and 3.2 mol CH3 OH/g* h photocatalytic efciency. Indeed, methanolic suspensios of Ni/ZnS
versus 140 mol H2 /g* h, 8 mol CH4 /g, 0.5 mol CO/g* h and were more efcient (121.4 mol methyl formate/g* 24 h) than bare
1.6 mol CH3 OH/g* h) [120]. ZnS (87.6 mol methyl formate/g* 24 h), but the difference was not
A lot of studies have been carried out in colloids of CdS and ZnS,
so dramatic [128]. Contrariwise, the formation of heterojunction
containing sacrice compounds-electron donors (Na2 S, NaH2 PO2 structures between CdS and Bi2 S3 , promoted the separation of pho-
etc.) or other compounds that determine the selectivity of the
togenerated species, enhanced their lifetime, increased the specic
photocatalytic reaction. For example, the addition of TMACl in
surface area and the absorption in the visible part of the spectrum
the reaction mixture contributed to the production of dimer-
and therefore signicantly enhanced the photocatalytic activity of
ized products, such as ions of acetic acid or oxalic acid, owing their aqueous suspensions (613 mol CH3 OH/g* 5 h for CdS/Bi2 S3
to the formation of an aprotic layer on the surface of the cata-
A. Nikokavoura, C. Trapalis / Applied Surface Science 391 (2017) 149174 163

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 activ-
ity (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 satis-
fying 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
Fig. 13. Redox potential values (eV vs NHE) of GR and several common semicon-
preparation process of the photocatalyst and its selectivity/activity, ductors [140].
to nd that when CdIn2 S4 was synthesized from thiouria, the pho-
tocatalytic activity was doubled compared to that exhibited in
case that l-cystein was the staring material [133]. Aqueous alka- 4. Carbonaceous photocatalysts for CO2 reduction
line solutions of CuInS2 and Zn-doped CuInS2 with highly ordered
nanoarray structure, where the role of Zn was to reduce the recom- The interest about carbonaceous photocatalysts i.e. compos-
bination rate of photogenerated species and the contact resistance, ite photocatalysts based on carbon (graphite, active carbon, black
were also found to be conspicuous photocatalysts for the CO2 carbon bers, carbon nanotubes, graphene and g-C3 N4 ), that usu-
reduction (0.012 M CH3 OH/h and 0.032 M CH3 OH/3 h) [134]. ally contain compounds with semiconducting properties, has been
In special occasions, H2 was added to the aqueous reaction mix- expressed recently. In the large majority of the studies, their photo-
tures in order to enhance the photocatalytic activity. For example, catalytic activity for the CO2 reduction was evaluated during their
aqueous suspensions of the salt based photocatalyst reacted with a reaction with H2 O, via the oxidation of water molecules and the for-
gas mixture of CO2 /H2 . Namely, AgBr photocatalysts supported on mation of free radicals CO2 * [139,140]. As far as the carbon-based
paligorskite have been prepared, in order to enhance their photo- 2D layered materials, such as graphene and g-C3 N4 , are concerned,
catalytic activity, owing to the increased surface area and porosity it is evidenced that their supporting properties, their adsorption
and the negatively charged paligorskite surface. Besides, palig- afnity for CO2 , the light utilization and the graphene/g-C3 N4 cou-
orskite has an increased gas absorption capacity for CO and H2 and pling determine their photocatalytic efciency [39].
it exhibits high stability towards the effect of visible light irradia-
tion. Eventually, even if the photocatalytic efciency of the aqueous 4.1. Composite photocatalysts based on graphene (GR)
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 GR is already known as an electron transfer medium with large
CH4 /g* h and 12 mol CH4 /g* 10 h), it remained moderate [135]. specic surface area high chemical stability, excellent electronic
Also, moderate photocatalytic activity was performed by aque- conductivity and good optical tranmittance, widely used in photo-
ous suspensions of Cux Agy Inz Znk Sm with RuO2 or Rh1.32 Cr0.66 O3 as catalysis. Heteroatom (O, N, B, P and S) doped GR exhibits improved
cocatalysts (optimum activity: 21.1 mol CH3 OH/g* h) but after the conductive and optical properties and it favors the formation of het-
addition of H2 , the activity was found to be almost ve times higher erojunctions which facilitate charge generation and transportation
(118.5 mol CH3 OH/g* h for RuO2 /Cu0.30 Ag0.07 In0.34 Zn1.31 S2 ). It and therefore enhance its photocatalytic activity [141,142]. Fur-
was reported that H2 reacts with the photogenerated holes to form thermore, graphene (GR) has been chemically modied in order to
H* free radicals that facilitate the production of CH3 OH and hinder obtain superior photocatalytic properties and it has been widely
its oxidation [136]. Furthermore, anomalous spherical nanoparti- used in composite photocatalysts of the type semiconductor/GR.
cles of Co/MoS2 , synthesized by hydrothermal method, were used Owing to the existence of Fermi level and the even distribution of
for the photoelectrocatalytic reduction of CO2 to CH3 OH under vis- semiconductor nanoparticles on their surface, they have exhibited
ible light (35 mmol/L). The Co-doped MoS2 exhibited enhanced signicant photocatalytic activity. Fermi level is found lower than
photocatalytic activity compared to MoS2 , owing to the upward the CB of most semiconductors (less negative value of reduction
shift of the CB and VB redox potentials, as well as the enhanced potential), resulting in the transfer of photogenerated electrons
specic surface area and the increased number of active sites [137]. 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 photo-
generated electrons is elongated and the photocatalytic reactions
are facilitated. In case that Fermi level of GR is found higher than the
3.5.2. Solid-gas system CB of the semiconductor (more negative value of reduction poten-
The only study that refers to the evaluation of the photocatalytic tial), the photogenerated electrons cant be transferred from the
activity of a salt in a solid-gas system, did not lead to encouraging semiconductor to GR, thus, the presence of a photosensetizer is
results. CoTe reacted with a gas mixture of CO2 and H2 O to pro- required (Fig. 13). Photosensitizers are sensitized by the absorp-
duce very low amounts of CH4 (1.8 mol CH4 /g* h and 4.97 mol tion of photons and they produce electrons which follow the path
CH4 /g* 8 h). In this case the reaction mechanism proceeded via the photosensitizer-GR-semiconductor-reactants quickly owing to
formation of a variety of free radicals such as H* , CO2 * , CO* , C* , the high conductivity and the unique at structure of GR. There-
CH3 * , CH* and CH2 * [138]. fore the mean free path of electrons is elongated, resulting in
164 A. Nikokavoura, C. Trapalis / Applied Surface Science 391 (2017) 149174

Fig. 14. Schematic diagram of the synthetic process of Cu2 O/RGO photocatalysts Fig. 15. Schematic scheme of the proposed photocatalytic CO2 reduction on the
[139]. surface of ZnO/RGO photocatalyst [147].

reduction of the recombination rate between the photogenerated [147]. On the other hand, WO3 /RGO composite exhibited a very
species and enhancement of the photocatalytic activity. Besides, low photocatalytic activity (0.1 mol CH4 /g* h) as a result of the
owing to the formation of metal-carbon or metal-oxygen-carbon lowering of its oxidizing power (shift of the VB towards lower
bonds between GR and semiconductors, the band gap energy values of oxidation potential) compared to that of WO3 , after the
diminishes and thus the photocatalyst absorbs in the visible part addition of RGO [148]. The best photocatalytic activity among
of the spectrtum. Generally, Semiconductor/GR photocatalysts the GR based photocatalysts was exhibited by hexamolybdate
exhibit higher photocatalytic activity compared to bare semicon- clusters Cs2 Mo6 Bri 8 Bra 6 /GO and (TBA)2 Mo6 Bri 8 Bra 6 /GO diluted in
ductors as the synergistic effect plays an important role. For that a mixture of H2 O/DMF (1644 mol CH3OH/g* 24 h and 1294 mol
reason, the preparation of Semiconductor/GR composites con- CH3 OH/g* 24 h, respectively versus 439 mol CH3 OH/g* 24 h for
stitutes an ambitious goal for the scientic community. The main bare GO). In this case, the excitation of Mo6 units via the absorption
preparation processes followed for Semiconductor/GR photocat- of visible light, facilitated the transfer of electrons to the CB of
alysts are hydro/solvothermal, solution mixing and in situ growth GO where the reduction of CO2 to methanol takes place. Besides,
methods, which apparently affect their structure, morphology, size owing to the high mobility of charged species and its increased
and photocatalytic activity [39,140,143]. For example, the com- specic surface area, GO enhances the photocatalytic activity
bination of a facile one-step green synthesis, the presence of synergistically [149]. The photocatalytic efciency of aqueous
metal-oxygen-carbon bonds and the two dimensionality (2D) of suspensions of carbon nanoparticles, bare or bearing metals (such
GR and GRO nanostructured composites, such as (BiO)2 CO3 /GR and as Au) on their surface, which act as electron acceptors, was also
(BiO)2 CO3 /GRO, resulted in high photocatalytic activities owing to evaluated [150]. CdS nanorods/RGO composites photocatalytically
their large surface areas and effective charge separation and trans- reduced CO2 to CH4 under visible light irradiation (2.51 mol CH4
fer [144]. g* h). The enhanced photocatalytic efciency, compared to that
of bare CdS nanorods, was attributed to the electron acceptor
4.1.1. Aqueous/organic suspensions properties of RGO and to the strong adsorption and activation of
ZnO/RGO, Cu2 O/RGO, BiVO4 /RGO, WO3 /RGO, Cs2 Mo6 CO2 molecules by RGO, through - conjugation interactions. The
Bri 8 Bra 6 /GO and (TBA)2 Mo6 Bri 8 Bra 6 /GO consist characteristic content of RGO was 0.5% wt, thus its role was that of an efcient
examples of composite photocatalysts based on GR. Aqueous and economic cocatalyst compared to noble metal Pt which did
alkaline suspensions of Cu2 O/RGO and BiVO4 /RGO exhibited not actually enhance the photocatalytic activity in a higher degree
similar photocatalytic activities in CH3 OH (41.5 mol/g* 10 h) [151,152].
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 4.2. Composite photocatalysts based on carbon nanotubes (CNTs)
by GO and Cu(AC)2 , as shown in Fig. 14, contributed to the aqueous suspensions
uniform distribution of Cu2 O nanoparticles on the RGO surface.
During the photocatalytic reduction of CO2 , the photogenerated CNTs have been used for the amelioration of the photocatalytic
electrons were transferred from the CB of Cu2 O to the surface activity of carbonaceous composites, such as AgBr/CNT and plas-
of RGO which provided electrons to CO2 molecules [139]. It monic Ag/AgBr/CNT, because they constitute supporting materials
was established that ZnO/GO nanocomposites, synthesized by and they possess enhanced ability for storing electrons which are
a solvothermal method, exhibit enhanced adsorption ability on used for the CO2 reduction. Aqueous suspensions of AgBr/CNT with
CO2 compared to that of bare ZnO and GO, therefore they could KHCO3 produced signicant amounts of CH4 , CH3 OH, CH3 CH2 OH
form promising photocatalysts for the reduction of CO2 [146]. and CO (156, 94, 16 and 39 mol/g* 5 h, respectively). CNTs play the
2D ZnO/RGO composites consisting of wrinkled GO sheets with role of an electron sink, which gathers the photogenerated elec-
nicely distributed ZnO nanoparticles on their surface exhibited trons originating from the CB of AgBr and thus facilitates the CO2
remarkable photocatalytic activity (ZnO(10%wt)/RGO:263.1 mol reduction mechanism, as shown in Fig. 16. It was also reported that
CH3 OH/g* 3 h), 5fold higher than that of bare ZnO (52.4 mol as the length of CNTs was increased, the photocatalytic activity
CH3 OH/g* 3 h). The strong interaction between ZnO and RGO was also increased, owing to the hindering of the recombination
resulted in inhibition of the fast recombination of the photo- of the photogenerated species and the binding of Ag+ ions on the
generated holes and electrons and thus enhancement of the CNTs surface. Besides, the effect of several carbonaceous support-
photocatalytic activity. In Fig. 15 is clearly demonstrated that ing materials, such as GP, EG, AC and GP, and the effect of pH of the
GR acts in a similar way with RGO in the Cu2 O/RGO composite aqueous suspension on the photocatalytic activity, was studied. It
A. Nikokavoura, C. Trapalis / Applied Surface Science 391 (2017) 149174 165

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].

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 neg-
ative 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 con-
stituent 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 oxida-
tion) take place. In this way, the separation of the photogenerated
Fig. 17. Overview of the photocatalytic reduction of CO2 with g-C3 N4 [157]. species is promoted but the total redox ability of the photocatalyst
is lowered. In case of the Z-Scheme mechanism, the photogenerated
was demonstrated that the use of GP and CNTs led to the opti- species are not transferred between the conduction bands and the
mum photocatalytic efciencies because of their excellent electric valence bands of the two constituents and thus the redox ability of
conductivity [153,154]. the composite photocatalyst is maintained [39,155,160,161]. The
suggested charge separation and Z-Scheme mechanisms, for the
4.3. g-C3 N4 and composite photocatalysts based on g-C3 N4 photocatalytic reaction of WO3 /g-C3 N4 composites, are presented
in Fig. 18 [155].
g-C3 N4 constitutes the most studied carbonaceous photocata-
lyst 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 band- 4.3.1. Solid-gas systems-H2 O as the reducing agent
gap energy (2.67 eV), which contribute to its high reducing power Outstanding photocatalytic activity (3.48 mmol CO/g* 7 h) was
and the ability of absorbing in the visible part of the spectrum, exhibited by mesoporous cubic structured g-C3 N4 , owing to its 3D
respectively. Besides, because of the formation of strong covalent structure and high specic surface area which enabled the activa-
bonds between carbon and nitrogen atoms, g-C3 N4 is stable under tion of H2 O and CO2 molecules and the effective diffusion of CO2 in
irradiation, in alkaline or acidic solutions, and it is synthesized via the interior space of the catalyst [162]. In other study, 2D ordered
simple and economic methods, such as the termal polycondensa- layers of g-C3 N4 with Pt nanoparticles distributed on their sur-
tion of melamine at high temperatures (450 C) [155158]. During face (Pt (1% wt)/g-C3 N4 ), synthesized from urea, exhibited higher
the last years, improved synthetic processes leading to g-C3 N4 photocatalytic activity compared to that of bare g-C3 N4 because
materials with high crystallinity and drastic modications of g- Pt facilitated the transfer of the photogenerated species (0.06 umol
C3 N4 surface (such as the introduction of heteromolecule dopants) CH4 /g* h, 0.06 umol CH3 OH/g* h, 0.02 umol HCHO/g* h and 0.12 umol
leading to the red shift of the optical absorption range and the CH4 /g* 7 h, 0.10 umol CH3 OH/g* 7 h, 0.022 umol HCHO/g* 7 h). Cer-
formation of heterostructures in g-C3 N4 , have been performed for tainly, in case that the Pt percentage surpassed a certain value
the enhancement of the overall photocatalytic activity towards the (1%), the efciency was reduced, due to the re-formation of CO2
CO2 reduction [159]. Its photocatalytic activity has been studied and H2 O, via the reaction of O2 with CH3 OH and HCHO [163]. Ran-
in gas-solid systems, in which the solid catalyst reacted with a domly ordered nanosheets of S/g-C3 N4 produced greater amounts
gas mixture of CO2 /H2 O, as well as in aqueous suspensions. Still, of methanol (1.12 umol CH3 OH/g* 3 h) than pure g-C3 N4 (0.81
the basic disadvantage of g-C3 N4 is its moderately low oxidizing umol CH3 OH/g* 3 h), because S/g-C3 N4 absorbs higher amounts of
166 A. Nikokavoura, C. Trapalis / Applied Surface Science 391 (2017) 149174

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 C3 N4 (0.26 mol CH3 OH/g* h). It was inferred that HCO3 , formed
generate structural defects that enhance the photocatalytic ef- when CO2 was adsorbed on the g-C3 N4 surface, through acid-base
cieny [164]. Halogens of Ag were deposited on the surface of interactions with amino groups, in the presence of H2 O, was more
protonated g-C3 N4 [AgX(X = Cl Br)/pCN], via a method which active than CO2 [168].
involved deposition/precipitation processes with the aid of ultra- It was reported that in aqueous suspensions of WO3 (0.5%wt
sounds. During the reduction of AgX, Ag atoms displayed surface Au)/g-C3 N4 , WO3 (0.5%wt Ag)/g-C3 N4 and SnO2-x (42.2%wt)/g-C3 N4
plasma resonance effect. The enhanced photocatalytic activity of composite photocatalysts, which reacted with CO2 in the gas
Ag/AgBr(30%wt)/pCN (10.9 mol CH4 /g* 10 h) compared to that of phase, the Z-Scheme mechanism was followed. Layered struc-
the pure constituents was attributed to the surface plasma res- tured Au or Ag/WO3 /g-C3 N4 composites, prepared via a planetary
onance effect and to the formation of a heterojunction between mill process, mainly produced methanol (2500 nmol/g* 24 h and
pCN and AgBr, into the hybrid photocatalyst. It was also reported 1750 nmol/g* 24 h, respectively), whereas SnO2-x /g-C3 N4 compos-
that the charge separation was more effective in Ag/AgBr/pCN ites, prepared by a simple calcination method, principally produced
than in Ag/AgCl/pCN, and this was attributed to the right com- CO (16 CO/g* h). Ag or Au nanoparticles in WO3 /g-C3 N4 compos-
bination of the redox potentials of pCN and AgBr compared to ites participated in the reduction of CO2 , whereas the addition of
the combination of redox potentials of pCN and AgCl [165]. The SnO2-x on the g-C3 N4 surface enhanced the specic surface area
preparation of RGO/pCN photocatalysts via the combination of a and the absorption of visible light of the composite. In both cases,
dispersion method with ultrasounds, accumulation by electrostatic it was demonstrated that in heterojunctions, where the Z-Scheme
forces and - interactions and a reductive process with NaBH4 , mechanism is followed, an excellent mixing of the constituents is
led to the formation of 2D compounds with intimate contact in required, otherwise, the photocatalytic activity appears very low,
width of the heterojunction connection. The latter contributed to because the mechanism cant be evolved. Therefore, it is proved that
the rise of the photocatalytic activity of the hybrids (13.93 mol the enhanced photocatalytic efciency is ascribed to the effective
CH4 /g* 10 h), compared to that of pure RGO and pCN. It was also separation of the photogenerated species, between WO3 and g-
reported that RGO constituted an excellent accumulation center C3 N4 and the retention of the high oxidizing and reducing power of
for electrons that aided the reduction of CO2 to CH4 . Still, the high WO3 and g-C3 N4 , respectively [155,169]. Effective heterojunctions
excess of RGO (>15%) occupied the active catalytic centers at pCN between the constituents of g-C3 N4 /r-P (PCN-x), Pt (0.5%wt) In2 O3
and thus the effective absorption of visible light and the number (10%wt)/g-C3 N4 and ZnO/g-C3 N4 composites, led to high photo-
of photogenerated electrons from pCN to RGO, were reduced. The catalytic efciencies (295 mol CH4 /g* h, 159.2 ppm CH4 /g* 4 h and
reaction mechanism involved the transportation of the photogen- 30 mol CO/g* h, respectively). It was reported that in these three
erated electrons from the VB of pCN to the CB and then to the cases, a charge separation mechanism was followed. The main
Fermi level of RGO for the reduction of CO2 to CO2 * as shown in advantage of PCN-x composites, prepared by a solid state anneal-
Fig. 19 [166]. For the rst time, it was demonstrated by Yu and Peng ing method, is that they are composed of economic and non-toxic
et al. that g-C3 N4 /ZnO composites reduced CO2 to CH3 OH (0.6 mol materials which absorb visible light. g-C3 N4 nanosheets folded
CH3 OH/g* h) via a direct Z-Scheme mechanism (and not the con- on the edges of r-P surface formed effective heterojunctions that
ventional charge separation mechanism) favored by the intimate facilitated the interfacing of g-C3 N4 and r-P and consequently
interfacial contact between the g-C3 N4 and ZnO phases [167]. 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
4.3.2. Aqueous suspensions ZnO/g-C3 N4 composites, synthesized by an impregnation method,
Amine-functionalized g-C3 N4 , prepared via heating urea at with chemical bonds between ZnO and g-C3 N4 , exhibited enhanced
500 C and treatment by monoethanolamine solution, exhibited photocatalytic activity. In both cases, the photogenerated electrons
higher CO2 adsorption capacity and thus enhanced photocat- are transferred from the CB of g-C3 N4 to the CB of the second con-
alytic activity for CO2 reduction under uv/visible light (0.34 mol stituent and the reduction of CO2 molecules by the accumulated
CH4 /g* h and 0.28 mol CH3 OH/g* h) compared to that of bare g- electrons takes place [171,172].
A. Nikokavoura, C. Trapalis / Applied Surface Science 391 (2017) 149174 167

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 synergisti-
cally 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, moder-
ate 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 mod-
ied 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].
Fig. 20. Possible reaction mechanism for the Co-ZIF-9 cocatalysed photoreduction
of CO2 employing CdS as the light harvester [179].
5. Hybrid organic-inorganic materials-zeolitic imidazolate
frameworks-(ZIFs)
Co-ZIF-9/CdS, the photocatalytic activity of hybrids consisting of
The special structure of ZIFs, resembling to that of zeolites, ZIF nanoparticles distributed on the surface of a material with
ensures their enhanced chemical and thermal stability, the high semiconducting properties was studied for Co-ZIF-9/g-C3 N4 and
values of specic surface area and the high absorption ability for ZIF-8/ZnGeO4 composites too. The highest photocatalytic efcien-
CO2 . Namely, ZIFs form tetrahedral networks by several transition cies were achieved in aprotic solvents such as MeCN, DMF, THF
metals such as Cu, Zn and Co which are linked via imidazolate and DMSO, owing to the Lewis acid-base interactions that facil-
connections. The interaction between the imidazolate connec- itated the solvation of CO2 . It was reported that the activities
tions plays a decisive role in the chemical modication and the of Co-ZIF-9/g-C3 N4 and ZIF-8/ZnGeO4 (20.8 mol CO/g* 2 h and
specication of their structure. Thus, owing to their special fea- 2.44 mol CH3 OH/g* 10 h, respectively) were increased compared
tures, recently, ZIFs were studied as catalysts or as cocatalysts of a to those of bare g-C3 N4 and ZnGeO4 . Thus, the synergistic effect
molecular catalyst for the CO2 photocatalytic reduction. The pho- of the enhanced capability of ZIFs for CO2 adsorption, the crys-
tocatalytic activity of ZIFs was evaluated in aqueous, organic or tallinity and the even distribution of the semiconducting material
mixtures of aqueous and organic solutions. Emphasis was given on the surface of ZIF, resulted in efcient photocatalytic hybrids
to the role of solvents-it was demonstrated that the optimum [177,180,181].
efciencies of ZIFs were exhibited when aprotic solvents were
used, because they facilitated the more sufcient solvation of CO2 6. Comparison and assessment of the activities of the main
[174177]. photocatalytic systems/categories of catalysts
Aqueous solutions of orthorhombic structured Cu(II)-ZIFs,
prepared by hydrothermal methods, exhibited extraordinary pho- It was made comprehensible that an ideal photosynthetic sys-
tocatalytic activity (1712 mol CH3 OH/g* 5 h), owing to synergistic tem for the CO2 reduction must absorb effectively the solar
effect of the orthorhombic structure and the small band-gap irradiation and produce large amounts of photogenerated species
energy [174]. Wang et al. studied the use of a Co containing ZIF which do not recombine rapidly, but they are transferred to the
(Co-ZIF-9) as cocatalyst for the photocatalytic reduction of CO2 active centers of the catalyst, where they react with CO2 molecules.
together with a photosensitizer compound based on Ru. It was The most preferred photocatalysts possess low band-gap energy
reported that the presence of Ru increased the cost of the photo- and thus they absorb in the visible part of the spectrum in order
catalytic system furthermore, it wasnt stable enough [178]. Later to achieve their excitation. As it was previously reported, in the
on, the same authors studied ZIFs (Co-ZIF-9) as cocatalysts in large majority of the studies, water was the reducing agent and
combination with a semiconductor (CdS). Co-ZIF-9/CdS solutions the reaction mechanism involved its oxidation by the photogen-
in a mixture of H2 O/acetonitrile, with bpy and TEOA, as elec- erated holes to produce oxygen and H+ ions and the formation of
tron mediating/donors systems, respectively, exhibited almost 45 free radicals CO2 * intermediates [7679]. Alternatively, but more
times higher photocatalytic activity (50.4 mol CO/g* h and 11.1 rarely, H2 was used as reducing agent and the photocatalytic reac-
H2 mol/g* h), compared to that of pure CdS. The accumulation tion proceeded via the dissociative adsorption of H2 molecules on
of the photogenerated electrons of CdS at the active centers of the surface of the catalyst followed by the reaction with adsorbed
Co-ZIF-9 and their reaction with the adsorbed CO2 molecules, CO2 molecules or free radicals CO2 * [64,6769]. CH4 was the least
led to a signicant enhancement of the photocatalytic efciency. used reducing compound and in this case, the reaction mecha-
Namely, it was deduced that the adsorption and diffusion of nism involved the formation of free radicals such as CH2 * , CH3 *
the reactants was performed on the catalytic centers of Co-ZIF- etc. [64,68,70].
9 and that the electron transfer from the CB of CdS, after the Attempts have been performed in order to compare the pho-
photoexcitation, was the rate determining step of the photocat- tocatalytic activities for the CO2 reduction of the main categories
alytic reaction. Besides, it was found that the role of imidazolate of photocatalysts. Concisely, metal or non-metal dopped semicon-
based ligand in the Co-ZIF-9 structure was crucial by affect- ductors with rather low band-gap energy, materials with special
ing positively the adsorption and activation of CO2 and thus its morphology and/or heterojunctions formed between their com-
conversion to CO. The effect of temperature and solvent in the ponents, were found to be more efcient photocatalysts. The
photocatalytic production of CO was also studied. It was demon- comparison between photocatalysts that belong to the same or dif-
strated that the temperature enhancement resulted in desorption ferent group is realized provided that it is understood that some
of CO2 from the reaction system at temperatures higher than factors such as the reaction medium, the kind of reducing com-
40 C, whereas a certain amount of H2 O present in the reaction pound, the physical state of the photocatalytic system, the kind and
mixture is essential in order to achieve CO selectivity. A possi- the special features of the photoreactor are different, and thus they
ble reaction mechanism is depicted in Fig. 20 [179]. Except of affect the activity and the selectivity of the photocatalytic reaction.
168 A. Nikokavoura, C. Trapalis / Applied Surface Science 391 (2017) 149174

Table 2
Selected metal oxides reported for CO2 reduction.

Photocatalyst description Efciency Type of irradiation Experimental conditions Ref. (year)

Single-metal oxides
hydrated Pb3 O4 (hematite) 2.6 mol CH3 OH/g* h UV Solid-gas (catalyst-CO2 /H2 O) system [57] (2011)
Hierarchical structures of 1.58 CH4 mol/g* 8 h) Simulated sunlight Solid-gas (catalyst-CO2 /H2 O) system [58] (2014)
BiOI
Mesoporous Fe/CeO2 74.3 mol CO/g* h, 17.3 Simulated sunlight Solid-gas (catalyst-CO2 /H2 O) system [59] (2014)
CH4 mol/g* h
Cu/ZnO 1 mol CO/g* h VIS Solid-gas (catalyst-CO2 /H2 O) system [60] (2013)
ZnO immobilized on 9% after 5 h UV Solid-gas (catalyst-CO2 /H2 O) system [64] (2013)
stainless steel mesh
CdS(5%)/WO3 1.02 mol CH4 /g* h VIS Solid-gas (catalyst-CO2 /H2 O) system [66] (2015)
Ga2 O3 3.6 CO mol/g* 5 h UVVIS Solid-gas (catalyst-CO2 /H2 ) system [67] (2010)
ZnO immobilized on 3% after 5 h UV Solid-gas (catalyst-CO2 /H2 O) system [64] (2013)
stainless steel mesh
ZrO2 1 mol CO/g* 6 h high-pressure Hg-lamps or Solid-gas (catalyst-CO2 /CH4 ) system [68] (1980)
sunlight
ZnO immobilized on 11% after 5 h UV Solid-gas (catalyst-CO2 /CH4 ) system [64] (2013)
stainless steel mesh
MPc/ZnO immobilized on 23% after 5 h VIS Solid-gas (catalyst-CO2 /CH4 ) system [71] (2014)
stainless steel mesh
ZnTe/ZnO 100 mol CH4 /g* 5 h VIS Aqueous dispersions [72] (2015)
NiO 170 mol CH3 OH/g* h UV Aqueous dispersions [73] (2004)
1D wedged N/CuO 1.8 mmol CH3 OH/L* m2* 6 h VIS Aqueous dispersions [75] (2014)
Cu2 Ox H2 O 24 mol CH3 OH/L* 20 mg UVVIS Aqueous dispersions [44] (1989)
(200 W medium pressure
mercury lamp)

Mixed-metal oxides
Zn2 GeO4 nanoribbons 1.5 mol CH4 /g* h Solar irradiation Solid-gas (catalyst-CO2 /H2 O) system [76] (2010)
Pt and RuO2 /Zn2 GeO4 25 mol CH4 /g* h Solar irradiation Solid-gas (catalyst-CO2 /H2 O) system [76] (2010)
nanoribbon
KNbO3 nanobelts 1.71 mol CH4 /g* h UV Solid-gas (catalyst-CO2 /H2 O) system [77] (2012)
HNbO3 nanobelts 3.58 mol CH4 /g* h UV Solid-gas (catalyst-CO2 /H2 O) system [77] (2012)
Bi2 WO6 nanoplates 1.1 mol CH4 /g* h VIS Solid-gas (catalyst-CO2 /H2 O) system [79] (2011)
ball-ower-like Bi2 WO6 333 nmol CO/g* h VIS Solid-gas (catalyst-CO2 /H2 O) system [80] (2014)
LiTaO3 0.42 mol CO/g* 24 h UV Solid-gas (catalyst-CO2 /H2 ) system [81] (2010)
CaFe2 O4 2 mol CH3 OH/g* 4 h, 3 mol UV Aqueous dispersions containing NaH2 PO2 and BaCO3 [82] (1994)
HCHO/g* 4 h
monoclinic BiVO4 30 mol ethanol/g* 80 min VIS Aqueous NaOH dispersions [83] (2009)
tetragonal BiVO4 2 mol ethanol/g* 80 min VIS Aqueous NaOH dispersions [83] (2009)
lamellar BiVO4 35 mol CH3 OH/g* 6 h VIS Aqueous NaOH dispersions [84] (2012)
NaBiO3 0.6 mol CH3 OH/g* h (sol-gel) VIS Aqueous dispersions [85] (2014)
0.37 mol CH3 OH/g* h
(hydrothermal)
NaNbO3 2.3 ppm CH4 /h UV Aqueous dispersions [86] (2012)
NaNbO3 nanowires 1600 ppm CH4 /g* 150 min UV Aqueous dispersions [87] (2011)
KNbO3 7 ppm CH4 /h UV Aqueous dispersions [86] (2012)
Cubic Pt/NaNbO3 1.3 mol CH4 /g* h UV Aqueous dispersions [88] (2012)
Orthogonal Pt/NaNbO3 0.5 mol CH4 /g* h UV Aqueous dispersions [88] (2012)
Fe/CuGaO2 , 9 ppm CO/g* h UV Aqueous dispersions [89] (2012)
cube-like shaped 8 mol CH3 OH/g* h VIS Aqueous acidic dispersions with Fe+2 ions [90] (2013)
Pt/CuAlGaO4
C/Fe/LaCoO3 130 mol HCOOH/g* h VIS Aqueous dispersions [91] (2009)
Bi2 WO6 microspheres with 56.5 mol CH3 OH/g* 4 h, VIS Aqueous dispersions [92] (2015)
conducting polymers (PPy, 20.5 mol ethanol/g* 4 h
PANI, PTh)
0.3%Ag/BaCeO3 4 mol CH4 /g* 7 h UV Aqueous dispersions [93] (2015)

Metal oxide composites


NiO/InTaO4 21.0 mol CH3 OH/g* h (optical Simulated solar irradiation Solid-gas (catalyst-CO2 /H2 O) system [94] (2010)
ber reactor)
NiO/InTaO4 0.16 mol CH3 OH/g* h VIS Solid-gas (catalyst-CO2 /H2 O) system [95] (2011)
Mesoporous Pt 38 mol CH4 /g* 8 h VIS Solid-gas (catalyst-CO2 /H2 O) system [96] (2012)
(0.5%wt)/ZnAl2 O4 /ZnGaNO
CuO/ZnO (10%) supported on 8 mol CH4 /g* h, UVVIS (mercury arc Aqueous KHCO3 dispersions [97] (1999)
MgO 0.8 mol C2 H6 /g* h lamp source (250 mW))
NiO(1%wt)/InTaO 1.394 mol CH3 OH/g* h VIS Aqueous KHCO3 dispersions [98] (2007)
NiO/InTaO4 2.8 mol CH3 OH/g* h Simulated solar irradiation Aqueous dispersions [94] (2010)
(quartz reactor)
Ni@NiO/N-InTaO4 170 mol CH3 OH/g* h VIS Aqueous dispersions [99] (2011)
NiO/InNbO4 1.6 mol CH3 OH/g* h VIS Aqueous KHCO3 dispersions [100] (2012)
Co3 O4 /InNbO4 1.5 mol CH3 OH/g* h VIS Aqueous KHCO3 dispersions [100] (2012)
NiO/InVO4 1.526 mol CH3 OH/g* h VIS Aqueous KHCO3 dispersions [101] (2015)
Ni/Ni3 (BO3 )2 /NiO 0.41 mol CH4 /g*h UV Aqueous dispersions [102] (2015)
A. Nikokavoura, C. Trapalis / Applied Surface Science 391 (2017) 149174 169

Table 3
Selected LDHs reported for CO2 reduction.

Photocatalyst description Efciency Type of irradiation Experimental conditions Ref. (year)

Layered Double Hydroxides (LDHs)


Pt (0.1%wt)/Zn-Cr LDH 7.8 mol CO/g* 3 h UV Solid-gas (catalyst-CO2 /H2 O) system [105] (2013)
Pd (0.1%wt)/Zn-Cr LDH 4.3 mol CO/g* 3 h UV Solid-gas (catalyst-CO2 /H2 O) system [105] (2013)
Au (0.7%wt)/Zn-Cr LDH 3.8 mol CO/g* 3 h UV Solid-gas (catalyst-CO2 /H2 O) system [105] (2013)
Au/Zn-GaIII LDH 0.201 mol CO/g* h,0.03 mol CH3 OH/g* h VIS Solid-gas (catalyst-CO2 /H2 ) system [108] (2014)
Ag/Zn-GaIII LDH 0.102 mol CO/g* h, 0.118 mol CH3 OH/g* h VIS Solid-gas (catalyst-CO2 /H2 ) system [108] (2014)
Zn-Cu-AlIII LDH 0.31 mol CH3 OH/g* h UV Solid-gas (catalyst-CO2 /H2 ) system [107] (2014)
Zn-Cu-GaIII LDH 0.49 mol CH3 OH/g* h UV Solid-gas (catalyst-CO2 /H2 ) system [107] (2014)
Cu-Ni-Al LDH 210 mol CH3 OH/g* h VIS Aqueous dispersions [109] (2015)
Ni-Al LDH 20 mol CO/g* 8 h UV Aqueous dispersions [110] (2015)

Table 4
Selected LDHs photocatalysts reported for CO2 reduction.

Photocatalyst description Efciency Type of irradiation Experimental conditions Ref. (year)

Salt composites
thiol modied CdS 0.5 mol HCOO /g* 7 h, 0.45 mol UV-VIS DCM and propanol (hole [111] (1998)
CO/g* 7 h, 0.5 mol H2 /g* 7 h, 0.5 mol (500 W high scavenger)
CH3 COCH3 /g* 7 h pressure mercury
arc lamp)
Cd2+ /CdS 30 mol CO/g * 30 min VIS DMF and triethanolamine (as [114] (1998)
electron donor)
CdS/MMT/CTA 220 mol H2 /g* 25 h, 30 mol UV Aqueous NaOH solutions [116] (2011)
CH4 /g* 25 h
CdS 136 mol formic ions/dm3* 42 h UVVIS Aqueous colloids [121] (1998)
(pH = 6)
CdS/Bi2 S3 613 mol CH3 OH/g* 5 h VIS Basic aqueous dispersions [129] (2011)
Ru/ZnS 0.8 mmol HCOOH/dm3* h, 0.2 mmol UV Aqueous solutions [112] (2015)
CO/dm3* h, 1.2 mmol HCOOH/dm3* 5 h,
0.4 mmol CO/dm3* 5 h
Zn+2 /ZnS(13%)/SiO2 10.3 mmol HCOO /g* 4 h UV 2,5-DHF [115] (1997)
ZnS (3.1%wt)/MMT 300 mol H2 /g* 24 h, 28 mol UV Aqueous NaOH solutions [119] (2014)
CH4 /g* 24 h, 3 mol CO/g* 24 h
ZnS/MMT/CTA 210 mol H2 /g* 25 h, 40 mol UV Aqueous NaOH solutions [118] (2013)
CH4 /g* 25 h
ZnS/MMT 380 mol H2 /g* h, 30 mol CH4 /g* h, UV Aqueous solutions [120] (2011)
4 mol CO/g* h, 3.2 mol CH3 OH/g* h
ZnS 2300 mol oxalic ions/dm3* 48 h UVVIS Aqueous colloids [121] (1998)
(pH = 14)
Ni (0.3%wt)/ZnS 121.4 mol methyl formate/g* 24 h UV Methanolic dispersions [128] (2013)
Fe+2 ions (103 M) 2.5 mol HCHO/g* 30 min UV Aqueous solutions [131] (1994)
Cu2 O/SiC 191 mol CH3 OH/g* 5 h VIS Anoxic aqueous solutions with [132] (2011)
NaOH and Na2 SO3
Cubic CdIn2 S4 5258 mol formic methylester/g* 10 h VIS Methanolic solutions [133] (2014)
Highly ordered nanoarray 0.012 M CH3 OH/h VIS Aqueous alkaline solutions [134] (2014)
structured Zn/CuInS2
AgBr/paligorskite 8 mol CH4 /g* h VIS Aqueous dispersions (H2 [135] (2012)
added)
RuO2 /Cu0.30 Ag0.07 In0.34 Zn1.31 S2 118.5 mol CH3 OH/g* h VIS Aqueous dispersions (H2 [136] (2011)
added)
CoTe 1.8 mol CH4 /g* h VIS Solid-gas (catalyst-CO2 /H2 O) [138] (2014)
system

The photocatalytic efciencies of the most important metal oxides reduction often took place under visible irradiation, apparently
(Table 2), LDHs (Table 3), salt composites (Table 4), carbonaceous owing to the decreased band gap energy values.
materials and ZIFs (Table 5), the kind of irradiation and the specic Studies on the photocatalytic efciency of the mixed-metal
experimental conditions are depicted. oxides have shown that in most cases, their aqueous suspensions
As far as it concerns the single-metal oxides, the most widely were used and that the most remarkable results were displayed
used photocatalytic systems were the solid-gas phase systems, in by the ordered monoclinic BiVO4 (35 mol CH3 OH/g* 6 h) and Fe/C
which water vapor played the role of the reducing compound and doped LaCoO3 (130 mol HCOOH/g* h), where the synergistic effect
the catalyst was found in the solid state. The optimal photocatalytic between Fe and C contributed signicantly to the enhancement of
activity was exhibited by Fe/CeO2 (74.3 mol CO/g* h) [5765]. Dur- the activity [44,75,8289,91]. Solid gas systems, where the reaction
ing the study of the aqueous suspensions of the single-metal oxide mixture consisted of H2 O and CO2 , exhibited satisfactory photo-
catalyst, the highest photocatalytic activity was expressed by NiO catalytic efciencies, such that of RuO2 (1%wt)/Pt(1%wt)/ZnGeO4
(170 mol CH3 OH/g* h), and it was increased in comparison with (25 mol CH4 /g* h, 100 mol/CH4 /g* 16 h) [7679], whereas solid-
that of Fe/CeO2 in the solid-gas phase system [44,7275]. UV irra- gas systems where H2 was the reducing agent, didnt produce
diation was frequently used, apparently owing to the increased satisfying amounts of products [81]. Almost half of the mixed-metal
band gap energy values of the semiconducting materials. On the oxides were irradiated with UV light whereas the other halves were
other hand, in case of doped single-metal oxides, the photocatalytic irradiated with visible light.
170 A. Nikokavoura, C. Trapalis / Applied Surface Science 391 (2017) 149174

Table 5
Selected carbonaceous materials and ZIFs reported for CO2 reduction.

Photocatalyst description Efciency Type of irradiation Experimental conditions Ref. (year)

Carbonaceous photocatalysts
Composite photocatalysts based on graphene (GR)
Cu2 O/RGO 41.5 mol/g* 10 h Simulated sunlight Aqueous NaOH solutions [139] (2014)
BiVO4 /RGO 51.5 umol ethanol/g* 10 h Simulated sunlight Aqueous NaOH solutions [145] (2015)
ZnO(10%wt)/RGO 263.1 mol CH3 OH/g* 3 h UVVIS Anoxic aqueous alkaline solutions [147] (2015)
WO3 /RGO 0.1 mol CH4 /g* h VIS Aqueous dispersions [148] (2013)
Cs2 Mo6 Bri 8 Bra 6 /GO 1644 mol CH3 OH/g* 24 h VIS H2 O/DMF [149] (2015)
CdS nanorods/RGO 2.51 mol CH4 /g* h VIS Aqueous acidic dispersions [152] (2014)

Composite photocatalysts based on carbon nanotubes (CNTs)


Ag/AgBr/CNT 30 mol CH4 /g* 5 h, 16 mol VIS Aqueous suspensions with KHCO3 [153] (2013)
CH3 OH/g* 5 h, 3 mol ethanol/g* 5 h,
8 mol CO/g* 5 h (pH = 8)
AgBr/CNT 156 mol CH4 /g* 5 h, 94 mol VIS Aqueous suspensions with KHCO3 [154] (2014)
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 VIS Solid-gas (catalyst-CO2 /H2 O) system [162] (2014)
Pt (1% wt)/g-C3 N4 0.06 umol CH4 /g* h, 0.06 umol VIS Solid-gas (catalyst-CO2 /H2 O) system [163] (2014)
CH3 OH/g* h, 0.02 umol HCHO/g* h
S/g-C3 N4 1.12 umol CH3 OH/g* 3 h VIS Solid-gas (catalyst-CO2 /H2 O) system [164] (2015)
Ag/AgBr(30%wt)/pCN 10.9 mol CH4 /g* 10 h VIS Solid-gas (catalyst-CO2 /H2 O) system [165] (2015)
RGO/pCN 13.93 mol CH4 /g* 10 h VIS Solid-gas (catalyst-CO2 /H2 O) system [166] (2015)
Amine-functionalized g-C3 N4 0.34 mol CH4 /g* h, 0.28 mol VIS Aqueous acidic dispersions [168] (2015)
CH3 OH/g* h
Au/WO3 /g-C3 N4 2500 nmol CH3 OH/g* 24 h VIS Aqueous dispersions [155] (2014)
Ag/WO3 /g-C3 N4 1750 nmol CH3 OH/g* 24 h VIS Aqueous dispersions [155] (2014)
SnO2-x (42.2%wt)/g-C3 N4 16 mol CH3 OH/g* h Simulated sunlight Aqueous dispersions [169] (2015)
g-C3 N4 /r-P (PCN-x) 295 mol CH4 /g* h VIS Aqueous dispersions [170] (2013)
Pt (0.5%wt) In2 O3 (10%wt)/g-C3 N4 159.2 ppm CH4 /g* 4 h VIS Aqueous dispersions [171] (2014)
ZnO/g-C3 N4 30 mol CO/g* h Simulated sunlight Aqueous dispersions [172] (2015)
CdMoO4 /g-C3 N4 18 mol CO/g* h, 6 mol CH3 OH/g* h VIS Aqueous dispersions [173] (2015)
g-C3 N4 -BAx 56.3 mol CO/g* 4 h, 12.5 mol H2 /g* 4 h VIS H2 O/acetonitrile, containing [157] (2015)
Co(bpy)3 +2 and TEOA

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


Orthorhombic Cu(II)-ZIFs 1712 mol CH3 OH/g* 5 h VIS Aqueous solutions [174] (2013)
Co-ZIF-9/CdS 50.4 mol CO/g* h, 11.1 H2 mol/g* h VIS H2 O/acetonitrile, with bpy and TEOA [179] (2015)
Co-ZIF-9/g-C3 N4 20.8 mol CO/g* 2 h VIS Aprotic solvents (MeCN, DMF, THF, [180] (2014)
DMSO)
ZIF-8/ZnGeO4 2.44 mol CH3 OH/g* 10 h VIS Aqueous dispersions [181] (2013)

The mixing of metal oxides in metal-oxide composites resulted nature on the selectivity was conrmed, whereas extremely high
in the amelioration of their optical properties and thus the effective photocatalytic activities were mentioned, higher than those of
photoexcitation of their VB electrons under visible irradiation. Also, metal oxides and LDHs. Among the higher photocatalytic ef-
metal oxide composites were studied in depth as far as it concerns ciencies are those of Zn+2 /ZnS(13%wt)/SiO2 in 2,5-DHF (10.3 mmol
their photocatalytic activity towards CO2 reduction with H2 O in formats/4 h), aqueous suspensions of ZnS (3.1%wt)/MMT/CTA
solid-gas systems as well as in aqueous suspensions. N/InTaO4 was (300 mol H2 /g* h), colloids of ZnS (2300 mol oxalates/dm3 ) and
found to be the more efcient photocatalyst in a solid-gas reac- methanolic solutions of CdIn2 S4 (5258 mol methyl formate/10 h)
tion system (125 mol CH3 OH/g* h and 250 mol CH3 OH/g* 2 h) [111138]. Except of the ZnS based salt composites which mainly
whereas Ni@NiO/N-InTaO4 dispersed in aqueous solution exhibited absorb UV irradiation, the majority of salt composites absorb visible
particularly high photocatalytic efciency (170 mol CH3 OH/g* h light and this fact makes them appealing photocatalysts for the CO2
and 310 mol CH3 OH/g* 2 h) owing to the presence of Ni, NiO which reduction when they are dissolved in aqueous or organic mediums.
acted as electron donors [94102]. The most recently studied group of photocatalysts for the
The high absorption capacity for CO2 of LDHs constitutes the CO2 reduction is that of carbonaceous catalysts which exhibited
basic factor that contributes to the very high photocatalytic activ- very encouraging results. Except of their stability, carbonaceous
ities. It is reported that the main products are CH3 OH and CO, materials, based on GR, CNTs or g-C3 N4 , usually combined with
and the presence of Cu determines the selectivity of the reac- inorganic semiconductors, have exhibited outstanding photocat-
tion for methanol [103,104]. Aqueous suspensions of Cu-Ni-Al alytic activities [139,140]. In case of the composite carbonaceous
LDH exhibited the highest photocatalytic efciencies in CH3 OH photocatalysts, the enhanced photocatalytic activities were
(210 mol/g* h and 620 mol/g* 3 h) [102], whereas solid-gas sys- attributed to the generation of effective heterojunctions between
tems where the reaction mixture was H2 O/CO2 or H2 /CO2 , didnt their components (charge separation mechanism or Z-Scheme).
exhibit signicant photocatalytic activities (from 0.2 mol to The photocatalytic activity of carbonaceous photocatalysts has
20 mol product/g* h) [103,106108]. The percentage of UV light been studied either in aqueous/organic suspensions or in gas-
absorbing LDHs is higher than that of visible light absorbing ones, solid systems where the gaseous reaction mixture consisted of
owing to their high values of band-gap energy. H2 O and CO2 . Aqueous suspensions of BiVO4 /RGO (51.5 mol
The photocatalytic activity of salt composites was studied ethanol/g* 10 h), ZnO(10%wt)/RGO (263.1 mol CH3 OH/g* 3 h) and
mainly in their aqueous or organic solutions, where usually com- solutions of Cs2 Mo6 Bri 8 Bra 6 /GO (1644 mol CH3 OH/g* 24 h) in
mon reducing agents were added. Besides, the effect of the solvents H2 O/DMF exhibited the most enhanced activities among the GR
A. Nikokavoura, C. Trapalis / Applied Surface Science 391 (2017) 149174 171

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