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Green Energy & Environment 2 (2017) 204e217
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Review article

A review on photo-thermal catalytic conversion of carbon dioxide

Ee Teng Kho, Tze Hao Tan, Emma Lovell, Roong Jien Wong, Jason Scott*, Rose Amal*
Particles and Catalysis Research Group, School of Chemical Engineering, The University of New South Wales, Sydney 2052, New South Wales, Australia
Received 3 April 2017; revised 5 June 2017; accepted 5 June 2017
Available online 9 June 2017

Abstract

The conversion of carbon dioxide into value-added products is of great industrial and environmental interest. However, as carbon dioxide is
relatively stable, the input energy required for this conversion is a significant limiting factor in the system's performance. By utilising energy
from the sun, through a range of key routes, this limitation can be overcome. In this review, we present a comprehensive and critical overview of
the potential routes to harvest the sun's energy, primarily through solar-thermal technologies and plasmonic resonance effects. Focusing on the
localised heating approach, this review shortlists and compares viable catalysts for the photo-thermal catalytic conversion of carbon dioxide.
Further, the pathways and potential products of different carbon dioxide conversion routes are outlined with the reverse water gas shift,
methanation, and methanol synthesis being of key interest. Finally, the challenges in implementing such systems and the outlook to the future are
detailed.
© 2017, Institute of Process Engineering, Chinese Academy of Sciences. Publishing services by Elsevier B.V. on behalf of KeAi Communi-
cations Co., Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Keywords: Carbon dioxide conversion; Photo-thermal; Plasmonic catalysis; Solar thermal

1. Introduction An appealing solution to the persistent fuel demand and the

It is undeniable that the global energy demand has an ever-
growing thirst, driven primarily by our incessant craving for a
better quality of life and the consequent urbanisation and
economic growth. Despite rising environmental awareness and
establishment of policies that have facilitated the diversifica-
tion of energy sources to include more renewable alternatives,
fossil fuels will continue to dominate as a primary source of
energy [1]. One of the key consequences in having such a
dependence on carbon-based energy sources is increasing
carbon dioxide (CO2) emissions. Increasing emissions of this
greenhouse gas and its subsequent accumulation in the at-
mosphere, due to its relative inertness, has led to great con-
cerns regarding the ensuing irregularities in global weather
patterns and devastation caused to local ecosystems.
* Corresponding authors.
E-mail addresses: jason.scott@unsw.edu.au (J. Scott), r.amal@unsw.edu.au
(R. Amal).
inevitable CO2 emissions is to complete the carbon cycle via the
recycling of CO2 into synthetic fuels. This is possible through
the reduction of CO2. Nevertheless, one of the main hindrances
to such a process is its intense energy consumption. Despite the
overall exothermicity of reduction reactions, such as methana-
tion and methanol synthesis, the relative stability of a CO2
molecule necessitates energy provision to initiate its conver-
sion. The conventional industrial practice of deriving process
heat from fossil fuel incineration to fulfil the energy demand is
not ideal as it further contributes to CO2 release. Therefore, in
addition to studying effective pathways for CO2-to-fuel con-
versions, it is also crucial that a renewable energy feed source,
which is effective and suitable for such purpose, is accessible.
As the Earth's most abundant energy resource, the uti-
lisation of sunlight as an alternative energy supply has become
a popular field of scientific study. Several opportunities exist in
its application to provide for the demand of CO2 reduction
processes. While clean, solar energy-powered chemical pro-
cesses are more commonly associated with photocatalysis, the

http://dx.doi.org/10.1016/j.gee.2017.06.003
2468-0257/© 2017, Institute of Process Engineering, Chinese Academy of Sciences. Publishing services by Elsevier B.V. on behalf of KeAi Communications Co.,
Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
 E.T. Kho et al. / Green Energy & Environment 2 (2017) 204e217
achievable conversion efficiencies at current stages of devel-
opment are often unfeasible for large-scale operations as
compared to the more industrially established thermal catal-
ysis. With solar irradiation comprising primarily both heat and
light energy, prospects for photo-thermal catalytic CO2
reduction thus seem favourable.
In the ensuing sections, the possibility of harnessing heat
and light from solar energy through solar thermal technologies
and plasmonic resonance effects is outlined. Additionally, the
application of such technologies for effective catalytic recy-
cling of CO2, with particular reference to the strength and
limitations of the differing routes, is reviewed. In addition to
discussing the potentials of different candidate materials for
simultaneously achieving successful solar absorption and CO2
reduction, the foreseen challenges ahead in the realisation of
such a process are also assessed.
2. Overview on photo-thermal catalysis
2.1. Motivation for photo-thermal catalysis
Thermal catalysis is one of the most common forms of
catalysis, with conventional industrial processes such as the
ammonia synthesis and reforming utilising heat input to
compensate for the endothermicity of these reactions. One of
the key reasons for industrial dependence on thermally driven
catalysis is the high efficiency and applicability for large scale
processes. Nevertheless, the large energy demand is often
provided for via the incineration of fossil fuels [2]. With
growing concerns regarding the depletion of non-renewable
fuel resources and rising awareness regarding environmental
footprints, harnessing solar energy to drive energetically
demanding catalytic processes is desirable. Aside from the
photovoltaic transformation of sunlight into electricity to
facilitate conversion, the direct activation of catalytic materials
through sunlight absorption is also possible. The work by
Honda and Fujishima [3] on the use of a titanium dioxide
semiconductor for water-splitting instigated a rapid expansion
in the field of photocatalytic research. However, despite the
energetically ideal concept of the direct translation of light into
chemical energy, the practical application of photocatalytic
technologies is greatly hindered by the lack of effective con-
versions, especially for industrially-scaled operations [4], with
the difference in efficiencies often several orders of magnitude
below the capabilities of thermal catalysis.
This subsequently inspired the concept of light-for-heat in
catalysis as an alternative to conventionally fossil fuel-
powered systems. What distinguishes such photo-thermal
catalysis from traditional thermal- or photo-catalysis is the
utilisation of both the light and heat components of solar ra-
diation, whereby heat is either obtained directly from or
initiated by the light absorption. This thus enables the uti-
lisation of a sustainable energy source (as with photocatalysis)
all the while attaining effective catalytic conversions typically
obtained for thermal catalysis.
The possible pathways to realising the concept are visualised
in Fig. 1. The ‘direct’ procurement of heat from solar radiation is
205
possible via the traditional concept of solar thermal heating.
Solar thermal heating operates based on the principle of utilising
a light-absorbing material or infrastructure to capture heat from
the visible or infrared spectrum of solar radiation. The trapped
heat will then result in an elevation in temperature, the extent to
which depends on the properties of the light-absorbing material
and infrastructure design.
Another pathway from which heat energy can be obtained
from sunlight is through the plasmon resonance phenomenon.
Although both these ‘direct’ and ‘indirect’ routes essentially
rely on vibration at a subatomic scale, the surface plasmon
resonance distinguishes itself from the conventional percep-
tion of heating. In addition to the conventional heat energy
production upon light absorption, this phenomenon allows the
formation of intense, localised hotspots due to the resonance
of surface plasmons of plasmonic materials upon exposure to
radiation of certain frequencies.
2.2. Heat-harvesting for photo-thermal catalysis
There exists a range of routes to harvest heat from the sun
for photo-thermal catalytic conversions. These routes are
examined in this section, specifically in the context of solar
thermal technologies and the plasmonic resonance effect.
Finally, a critical evaluation of the application of such heat-
harvesting approaches for carbon dioxide is presented.
2.2.1. Solar thermal technologies
The sensation of heat felt upon exposure to sunlight crudely
explains the concept of solar thermal heating. From residential
rooftop water heating systems to solar furnaces capable of
temperatures beyond 2300 K, records of solar thermal tech-
nology applications can be traced back to prehistoric times [5].
In heat exchanging applications for domestic purposes, tem-
perature requirements are not as stringent (e.g. water-heating),
e-
CO2
CxHyOz
Fig. 1. Sourcing heat from the sun for a photo-thermal catalytic system.
Heating of the catalyst bed can be achieved either through directing concen-
trated solar irradiation onto the catalyst material or relying primarily on the
localised plasmonic heating effects through surface plasmon excitation.
206 E.T. Kho et al. / Green Energy & Environment 2 (2017) 204e217
the basic infrastructure comprises a collector upon which solar
radiation is ‘gathered’ and reflected to a working fluid (either
gaseous, liquid or molten salts) to conduct and/or circulate the
absorbed energy. For higher temperature systems, the collector
usually is designed to allow for light-concentrating capabilities
for heat intensity amplification (Fig. 2). Depending on the
solar concentrating systems utilised, concentration ratios be-
tween the range of 30e100 (for a parabolic trough system to
achieve 500e700 K temperatures, Fig. 2a) and up to
5000e10,000 (in a double-concentration system consisting of
a heliostat field, a reflective tower and a ground receiver
capable of temperatures in excess of 1500 K, Fig. 2d) are
attainable [6].
To achieve effective heat trapping, two key qualities are
required by the absorbing material: high solar absorption and
low thermal emissivity. Materials with high solar absorption
enable more effective heat generation, whereas low thermal
emissivity is essential to minimise subsequent heat loss
through radiation. Therefore, in addition to the intuitive choice
of using a dark-coloured heat absorbing material, much effort
has been invested in the understanding of optical and thermal
properties of materials for constructing solar absorber coatings
such as paints, enamel, carbides, and cermets [7,8].
One of the main appeals of the technique of heat harvesting
is the extremely high temperatures attainable through the
concentration of solar energy. As mentioned previously, tem-
peratures beyond 1000 K are possible depending on the solar
concentrator configuration. Such capability is subsequently
(a)
Concentrator
Fig. 2. Main high temperature solar concentrator system categories: (a) parabolic trough, (b) central power tower, (c) parabolic dish, and (d) double concentration.
Adapted from Ref. [6].
(a)
PG
HX REFORMER
RECIEVER
FG
PG - Product gas
Fig. 3. Different configurations for a solar reactor: (left) reactor decoupled from solar receiver system, (middle) integrated tubular reactor/receiver, and (right)
catalytically active solar absorber. Adapted from Ref. [4].
taken advantage of for thermochemical conversions. These
processes involve a redox cycle in which firstly, high tem-
perature (> 1500 K) treatment of a metal oxide (e.g. CeO2
[9e11] and ZnO [12e14]) is performed to obtain its reduced
form. The ensuing step is then conducted at a slightly lower
temperature where the reduced metal oxide is exposed to re-
actants such as CO2 (or H2O) to promote their reduction.
Solar-aided reforming is another common conversion process
that has been tested in a solar reactor configuration [4,15e17].
A catalyst is usually utilised in order to lower the temperature
requirements for conversion (
1000 K). In this case, the
catalyst can either be located in a reactor decoupled from the
receiver or be included as part of the receiver where it is also
exposed to irradiation (Fig. 3).
2.2.2. Plasmonic resonance effect
As opposed to focusing on infrastructure design, as is the
case for solar thermal technologies, the plasmonic route places
greater attention on developing the light-absorbing material
itself. While both traditional photocatalysis and plasmonic
catalysis rely on light-source activation, their similarities stop
here. Conventional photocatalysis utilises light energy to
overcome the bandgap energy difference of a semiconductor,
subsequently generating active electrons and holes that are
capable of a myriad of redox reactions depending on the
reducing/oxidising potentials of the resulting charge carriers
(i.e. the positions of the conduction/valence bands). Plasmonic
catalysis, on the other hand, relies on the resonance of the
(b) (c) (d)
Reflective tower
R
Concentrator
Heliostats Heliostats
R - Receiver
(b) (c)
Tubular
PG reactor Catalytically
-active
absorber
PG
FG FG
FG - Feed gas HX - Heat exchanger
 E.T. Kho et al. / Green Energy & Environment 2 (2017) 204e217
oscillations of free electrons (i.e. plasmons) upon the absorp-
tion of incident electromagnetic radiation. Such resonance
occurs when the delocalised electrons are supplemented with
an energy wave, whose frequency corresponds to the charac-
teristic resonant frequency of the metal nanoparticle (Fig. 4).
The radiation frequency required for such excitation de-
pends on factors such as composition, shape, and size [19e24]
as illustrated in Fig. 5. The dependence of plasmonic response
on particle composition and morphology can be explained by
Mie theory, which has been readily exploited for theoretical
analyses of particle optical properties [25]. Mie theory states
that the total extinction cross-section of a particle depends on
its spherical volume, the dielectric constant of its surrounding
environment, and the dielectric function of the particle. Fac-
tors such as composition, shape, and size influence the
dielectric function of the particle. In polyhedral studies
(Fig. 5a), blue plasmonic shifts have been observed for par-
ticles with increasing number of facets, with spherical parti-
cles having the smallest plasmonic peak position [22]. In these
studies, it was also noted that polyhedral particles may exhibit
multiple surface plasmon resonances, leading to band broad-
ening and the emergence of new discrete peaks [20]. Similarly,
changing the composition of the particles through alloying can
promote the formation of plasmonic peaks, notably as a
mixture of the individual plasmonic components (Fig. 5b)
[23]. The dependency of plasmonic response on particle
composition and morphology permits the flexible tuning of
absorption wavelength based on the intended application.
In terms of material choices, gold, silver and copper are
amongst the most commonly studied metals for plasmonic
applications due to their strong plasmonic responses [26].
Whilst nanosized gold and silver are popular candidates, nickel
and copper have also garnered significant attention due to their
relatively cheaper costs. These metals also have the advantage
of having their plasmonic frequencies correspond to electro-
magnetic radiation residing within the visible-near infrared
region, which is in greater abundance within the solar spectrum
as compared to the ultraviolet light, upon which most effective
semiconductor photocatalysts are reliant on.
For the purpose of photo-thermal catalysis, plasmonic
resonance presents itself as an appealing alternative to con-
ventional heating for reactions that require elevated tempera-
tures. While the earlier studies into plasmonic-assisted
reactions were mainly dedicated to their photochemical as-
pects, it was not until 2007 when Cao et al. [27] first looked
E-field Metal
sphere
e- cloud
Fig. 4. Schematic of plasmon oscillation for a sphere, showing the displacement
of the conduction electron charge cloud relative to the nuclei. Reprinted with
permission from Ref. [18]. Copyright (2003) American Chemical Society.
207
into utilising thermoplasmonics for nanoscale material fabri-
cation. Ni pigments have long been used for solar thermal
heating despite not being previously deemed as plasmonic
nanoparticles [28,29]. In contrast to conventional heating,
where heat is provided externally, thermoplasmonics enables
rapid and localised heating within the vicinity of the plas-
monic nanoparticle [30].
In addition to the thermal energy supplement, reactant
molecules in the vicinity of a plasmonic nanoparticle can
experience an enhanced incident photon rate and/or photo-
generated hot electron formation (Fig. 6b and c [31]). Not to
be confused with thermoplasmonics, photogenerated hot
electrons have an athermal charge carrier distribution which
cannot be described using a Fermi-Dirac distribution. Instead,
their behaviours are more similar to electron-hole pairs in
semiconductors [32]. The injection of hot electrons may occur
directly from catalyst to reactant or through a semiconductor
support interface, similar to that of a dye-sensitised photo-
catalyst [33]. By acting as both the optical absorption and
catalytic sites, plasmonic photocatalysts have advantages over
semiconductors due to their higher electron density and af-
finity to reactants. Consequently, in contrast to conventional
photocatalysis, which typically provides yields in the micro-
mole (per gram catalyst per hour) range, plasmonic catalysts
are often capable of yields greater by orders of magnitude
[34e36].
2.2.3. Evaluating the relative strengths and weaknesses of
solar thermal vs. plasmonic technologies for photo-thermal
CO2 conversion
Aside from the capabilities and potential of the respective
solar energy-harvesting techniques discussed above, it is
important to acknowledge the relative limitations of the tech-
nologies for the design of a successful photo-thermal CO2 con-
version system that is practical for real world applications. While
laboratory-scale experiments often place a primary focus on
aspects such as conversions and yields, industrial considerations
such as scalability, cost effectiveness, and robustness of the
system also have to be taken into account for successfully
transferring novel technologies to commercial operations.
Solar thermal catalysis has the advantage of technical
maturity with tests carried out in commercial scale-receiver/
reactors since the 1980's [2,16,37,38]. While the tests have
delivered promising results, the robustness of catalyst mate-
rials under the typically high operating temperatures of solar
thermal catalytic reactors is frequently cited to be the short-
coming of such systems with catalyst disintegration via sin-
tering and/or the encapsulation of active phases being amongst
the most commonly reported issues [16,17,39e41]. These
occurrences largely stem from the fact that the high temper-
ature reaction conditions place severe stress on the lifetime of
a catalyst. Moreover, the need for a thermally resistant reactor
with high levels of technical precision, in addition to the large
footprint requirements, leads to exorbitant costs associated
with constructing solar thermal infrastructure.
On this basis, plasmonic catalysis appears to offer the
advantage as the intense heating occurs locally, within the
208 E.T. Kho et al. / Green Energy & Environment 2 (2017) 204e217

(a) 140 spheres pentagons triangles

120 X188K 50nm

Size (nm)
100

80

60

40
400 450 500 550 600 650 700
Peak Plasmon Resonance Wavelength (nm)

(b)
1.5
Ag:Au

1:4
Abs (1.0 cm)

1.0 1:3
1:2

1:1
0.5

1:0 1:0.5

0.0
300 400 500 600
Wavelength (nm)

Fig. 5. Influence of: (a) dimensions of silver nanoparticles over their peak absorption wavelength [23]; and (b) composition of silver-gold alloys over the spectral
absorption profiles of the nanoparticles [24]. Reprinted with permission from Ref. [24]. Copyright (2000) American Chemical Society.

(a) (b) (c) (d) (e) (f)

hv e- hv
e- e-
hv hv
e- e-
Light Light Light Light

h +
h +
Molecular
h + reactant
Catalyser
metal oxide
Reductor agent Plasmonic
nanoparticle

Fig. 6. Possible mechanisms for plasmonic catalysis: (a) thermoplasmonic temperature increase for heat transfer to reactant within vicinity; (b) nearby reactant
experiencing an apparent increase in incident photon rate (i.e. near field optical enhancement); (c) hot electron injection into nearby reactant; (d) plasmonic heat
generation resulting in enhanced electron-hole generation within a semiconductor for reactant molecule activation; (e) near field optical enhancement experienced
by semiconductor, leading to enhanced electron-hole generation; and (f) hot electron injection from a plasmonic nanoparticle into the neighbouring semiconductor,
which is then transferred into a reactant molecule nearby. Reproduced from Ref. [31] with permission from The Royal Society of Chemistry.
 E.T. Kho et al. / Green Energy & Environment 2 (2017) 204e217
vicinity of the active nanoparticles. As a result, the demand for
external heat supply to the system and overall thermal stress on
the infrastructure is much less for plasmonic-based catalytic
systems. In the case where heat is sourced from within the
plasmonic material itself, the robustness and stability of the
material properties affecting plasmonic efficiencies, such as
nanoparticle shape and size, over the course of prolonged usage
(and therefore continuous exposure to heat), becomes even
more crucial for maintaining consistent heating capabilities and
conversion performance. As demonstrated by the available
thermoplasmonic studies, strict requirements on the nano-
particles size (< 5 nm), high incident light intensity, and/or
extreme isolation of nanoparticles are currently the challenges
faced for plasmonic catalysis [42]. At such a relative stage of
infancy, most investigations remain invested in the development
and understanding of materials and are yet to venture into
feasibility studies for industrially scaled catalytic processes.
3. Overview of common CO2 conversion products and
pathways
Owing to the low CO2 conversion efficiency in CO2
reduction reactions via plasmonic catalysis, understanding
CO2 chemistry is critical for improving the conversion effi-
ciency. CO2 is an apolar molecule due to the linear configu-
ration of its two polar C]O bonds. Due to its relative
inertness, the resulting highly positive Gibbs free energy
means that its conversion is often not thermodynamically
favourable. Consequently, a catalyst is often required to acti-
vate the CO2.
Transforming CO2 into synthetic fuels can occur through
different pathways into a myriad of C-based products. In this
review, the focus will be placed upon its catalytic hydroge-
nation into CO, CH4, and CH3OH, which are often quintes-
sential building blocks for the downstream production of fuels
and chemical commodities.
3.1. Reverse water-gas shift reaction
The reduction of carbon dioxide into carbon monoxide (Eq.
(1)) is one of the more popular routes for CO2 conversion
studies mainly due to its low hydrogen consumption (as
compared to methanation) and high equilibrium conversion
rates [43]. Furthermore, the formation of CO forms an
important first step for the subsequent synthesis of carbon-
based chemicals and/or fuels [43e45].
CO2 þ H2 #CO þ H2 O DH ¼ þ 41 kJ=mol ð1Þ
The mechanisms suggested for reverse water-gas shift
(RWGS) reaction fall into two main categories: (i) the redox
pathway [46,47] and (ii) the formate decomposition mecha-
nism [48,49]. The redox mechanism is most often described
over a Cu-based catalyst, the metallic Cu0 atoms are partially
oxidised to form Cu2O and carbon monoxide (Eq. (2)) and the
oxidised copper is later reduced by the hydrogen present in the
system, reforming it to its metallic state accompanied by the
formation of a water molecule (Eq. (3)).
209
CO2ðgÞ þ 2Cu0ðsÞ #COðgÞ þ Cu2 OðsÞ ð2Þ
H2ðgÞ þ Cu2 OðsÞ #H2 OðgÞ þ 2Cu0ðsÞ ð3Þ
In contrast to the redox mechanism, the hydrogen mole-
cule does not actively interact with the carbon dioxide
molecule, the formate decomposition pathway suggests that
the hydrogen molecule first hydrogenates the carbon dioxide
into a formate intermediate. It is then from this intermediate
that the cleaving of the carbon-oxygen double bond occurs to
release a CO molecule [50]. The formate-mediated route is
also reported to occur for the methanation pathway (dis-
cussed in Section 3.2), but has often been debated regarding
the extent of its contribution toward product formation.
An investigation by Goguet et al. [51] is one such
example. Using a Pt/CeO2 catalyst for their in operando
spectrokinetic investigation, they proposed that the Pt metal
maintains the active (i.e. reduced) ceria surface via H2-
spillover. The resulting vacancies on the ceria surface then
bond with CO2 molecules to form surface carbonates, which
are the main intermediates that facilitate the final formation
of CO species.
3.2. Methanation
The production of methane from CO2 (Eq. (4)) is of great
interest in certain geographical locations due to the ease in
incorporating its distribution into existing infrastructure and
networks [52]. Furthermore, it serves as an attractive solution
for renewable energy storage with the added bonus of regu-
lating CO2 emissions.
CO2 þ 4H2 #CH4 þ 2H2 O DH ¼ 165 kJ=mol ð4Þ
In terms of the mechanistic pathway involved, claims from
both experimental and theoretical studies again falls into two
main domains: (i) direct hydrogenation of CO2 or (ii) CH4
formation via a CO intermediate [53], with majority of the
findings suggesting the latter process is the more probable
methanation route.
First proposed by Bahr, CH4 formation via the CO pathway
was supported by Peebles and Goodman in an investigation,
which compared the methanation of CO and CO2 over a
Ni(100) surface [54]. They found the activation energy and
reaction rate values for CH4 formation from CO2 and CH4
formation from CO were similar under identical reaction
conditions. Later studies utilising spectroscopic methods, such
as diffuse reflectance infrared spectroscopy (DRIFTS), and
Fourier-transformed infrared spectroscopy (FTIR) coupled
with mass spectroscopy, have observed both formate and CO
intermediates on the catalyst surface [55e57]. The ensuing
interpretations, however, have led to different conclusions.
Marwood et al. [55] proposed the formation of formate
through a carbonate species, which was subsequently hydro-
genated into an adsorbed CO species (COads) (illustrated in
Fig. 7), which has been suggested to be the rate determining
step [56]. In contrast, an in situ DRIFTS study (using Rh/g-
Al2O3) by Jacquemin et al. [57] reported instead that COads is
210 E.T. Kho et al. / Green Energy & Environment 2 (2017) 204e217

a product of the direct dissociation of CO2 without mentioning
the detection (and role) of formate species.
Experimental measurements coupled with computational
methods have also been used to probe the role of intermediate
species during CO2 hydrogenation on nickel. While it was
acknowledged that both formate and CO are present under the
reaction conditions commonly applied in the mechanistic
studies of CO2 methanation, Vesselli et al. [58] demonstrated
that formate was purely a spectator species and that the reaction
proceeded via the direct hydrogenation of the CeO bond of
CO2. This conclusion arose mainly from the findings that
formate has high reaction barriers for further hydrogenation for
its transformation into CO. This agrees with the findings by
Marwood et al. [55] who, despite proposing a different
methanation pathway, also reported the relative stability of the
formed formate species, and further lends credibility to the
argument of Goguet et al. [51] (discussed above) on the for-
mation of CO not being dominated by the formate route. Ren
et al. [59] performed density functional theory (DFT) calcula-
tions for the three mechanisms listed in Fig. 8 on the Ni(111)
surface with the energy involved in each step of the three paths
being illustrated in Fig. 9. A conclusion similar to Vesseli et al.'s
was reached that a comparison of the energy barriers involved
- 2HM
(HCO3)S
CO2 H
H22OO
- -
(HCOO )I (HCOO )S
- where the symbol * indicates an adsorbed species.
(OH )S
(CO)M
+6HM
CH4+H2O
Fig. 7. Proposed CO2 methanation mechanism involving the formation of
formate through a carbonate species. S ¼ support, M ¼ metal, I ¼ metal-
support interface [55].
in the rate determining steps of each route revealed the mech-
anism involving CO without direct participation of the formate
species being the most energetically plausible.
3.3. Methanol synthesis
One of the most apparent advantages methanol has over
products such as CO and CH4 is its liquid state at normal at-
mospheric temperature and pressure. This is desirable as it
provides a practical alternative for energy storage and trans-
port. Furthermore, much like CO, it can also serve as an
important starting constituent for olefins and aromatics
[60e63]. One of the major challenges for the methanol syn-
thesis process (Eq. (5)) is it is usually less selective than
methane and CO under low-pressure conditions. High pres-
sures (50e100 bars) are often required to suppress CO for-
mation via the RWGS pathway (Eq. (1)) [64].
CO2 þ 3H2 #CH3 OH þ H2 O DH ¼  49 kJ=mol ð5Þ
Similar to the Sabatier case, arguments on the CO2 to
methanol reaction pathway are dominated by the formate route
and the CO route factions. The pathway suggested for the
latter case proposes that CO2 first undergoes RWGS-like hy-
drogenation before the CO formed is sequentially hydroge-
nated into formyl (HCO), formaldehyde (H2CO), methoxy
(H3CO), and finally methanol [65]. The study by Grabow and
Mavrikakis [63] suggested the formate pathway being more
likely, whereby the hydrogenation of CO2 into methanol oc-
curs via the following sequence: CO2* / HCOO* /
HCOOH* / CH3O2* / CH2O* / CH3O* / CH3OH*
A mechanistic study by Studt et al. [66], which compared
CO2 to methanol pathways on different Cu-based catalysts,
shed further light on the debate regarding the importance of
differences in catalyst composition impacting on the resulting
mechanism experienced by the CO2 molecules. In addition to
the known effects of variation in reaction conditions (e.g. feed
gas composition, temperature, and pressure), their calculations
demonstrated that the promoting effect of Zn in a CueZnO
containing catalyst was not only kinetically-based, but also
stemmed from a deviation in the reaction mechanism due to
the different sites at which the key reactions occur.

(a) (b) (c)

H2+2* 2H* H2+2* 2H* H2+2* 2H*
CO2+* CO2* CO2+* CO2* CO2+* CO2*
CO2*+H * HCOO* CO2*+* CO*+O* CO2*+2H* C(OH)2*+2*
HCOO* CO*+OH* CO*+* C*+O* C(OH)2*+H* CH2O*+OH*
CO*+2H* CH*+OH* +H* +H* +H* +H* CH2O*+H* CH2*+OH*
C* CH* CH2* CH3* CH4+*
+H* +H*
+H* +H* +H* CH2* CH3* CH4+*
CH* CH2* CH3* CH4+* +H* +H*
O* OH* H2O* H2O+*
OH*+H* H2O* H2O+*
OH*+H* H2O* H2O+*

Fig. 8. CO2 methanation mechanism: (a) via CO involving the formate species; (b) via CO without the participation of the formate species; and (c) direct hy-
drogenation of CO2 without the participation of a CO intermediate [59].

350
TS1 292.3
300
250
Relative energy kJ/mol
200
150
TS1 113.1
100
TS1 93.7
C(OH)2 74.5
50
0
CO2(+H) 0
-50 HCOO -42.5
CO+O -75.6
-100
-150
Fig. 9. Potential energy diagram for different CO2 methanation mechanisms. Path 1, 2, and 3 correspond to the pathways listed in Fig. 8aec, respectively [59].
TS ¼ transition state.
4. Available candidates and opportunities in catalyst
materials selection
Materials that have been studied for CO2 hydrogenation is
listed in Table 1. One of the most common families of mate-
rials used for general catalysis is the metal family. For CO2
conversion, transition metals such as platinum [67,68], copper
[63,65,66,69,70], cobalt [71,72], ruthenium [56,73,74],
rhodium [75e79], and nickel [53,79e85] are amongst those
found to be active for CO2 hydrogenation. Aside from being
applied singly, the alloying of different metals to form a
bimetallic catalyst has also been exploited to manipulate a
catalyst's electronic properties [86e91]. One of the primary
aims of doing so is to affect product selectivity. For example,
on combining platinum and cobalt a greater tendency toward
CO production was reported [89] whereas varying the
composition of a cobalt-iron bimetallic catalyst influenced the
resulting alkane/alcohol selectivity [91]. More recently, a
nickel-gallium catalyst [90] was developed and shown to be
capable of higher selectivity toward methanol production.
Due to the effect of particle size on catalyst activity, nano-
scaled metal catalyst size is often obtained and/or maintained
by its dispersion upon a support material. Rather than acting
simply as an inert host, such supports are often capable of
exerting significant influence over the resulting surface chem-
istry of a catalyst. For the purpose of CO2 conversion, one of the
most useful traits of a support is its ability to encourage the
adsorption and even the activation of the CO2 reactant. Such
observations have been reported for conventionally popular
oxide-type supports. While ZnO is one of the most studied oxide
supports for (thermal) CO2 catalysis, due to its synergistic effects
with copper catalysts [51] [92e94], investigations on surface
defect-rich oxides such as TiO2 [43,95e97], CeO2 [86,98,99],
Ga2O3 [100,101], In2O3 [102e105], and their combinations
[65,106e108] have also been gaining momentum. Similar CO2
activation capabilities were found for carbide materials such as
titanium carbide [109,110] and molybdenum carbides
[111e113], where CO2 conversions were also obtained despite
E.T. Kho et al. / Green Energy & Environment 2 (2017) 204e217 211
Path 1
Path 2
TS2 264.3
Path 3
TS3 211.2
TS2 173.2 TS3 177.0
TS5 160.3
TS2 161.8 TS6 140.4
TS4 128.5
TS3 119.2 TS5 108.6
TS4 99.1
TS6 74.6
C+O 50.0
TS4 33.3 CH2 37.2 TS5 42.8
CH2+OH 57.1
CH2O+OH 47.5
CH+OH 30.9 CH3 3.0
CH2 22.9
CH4 -18.4
CH -34.9 CH3 -28.6
CO+OH -44.4 CH4 -38.3
CH3 -62.8
CH4 -104.1
Reaction coordinate
the absence of metals. Nevertheless, when coupled with metals
such as copper, nickel, or gold, a significant enhancement in
activity (with varying results in product selectivity) have been
observed [109]. Such synergism is often attributed to the inter-
action between the metal catalyst and the oxide or carbide sur-
face via occurrences such as creation of active centres at the
metal-support interface [43,108,114], promoted CO2 adsorp-
tion upon the oxide or carbide surface [106,115] and charge
redistribution at the metal-support interface.
Aside from the conversion aspects, there is also an opportunity
to adapt solar energy absorbing functionalities to these active
catalyst materials. For example, amongst the metals active for
CO2 reduction, Cu, Ni, and Au nanoparticles exhibit plasmonic
absorption that lies within the solar spectrum [30,116e121]. The
concept of plasmonic CO2 catalysis has, in fact, been demon-
strated in the works of Navarrete et al. [122] and Wang et al. [123];
the former presenting a proof-of-concept Cu/ZnO-impregnated
aerogel-containing microreactor for self-heating CO2 reduction
and the latter detailing a study on the effectiveness of laser-
induced heating on Au/ZnO for a similar application.
Aside from the dependence on the metal component, there
also exist prospects for the non-metallic (support) materials to
contribute to the harvesting of solar energy. Transition metal
oxides, such as those mentioned above, are semiconductors that
are capable of light energy absorption due to their unique band
structures. Therefore, as described by Baffou and Quidant [31],
in addition to thermoplasmonic effects, the combination of an
active, plasmonic metal catalyst with a semiconducting material
can result in enhanced charge carrier generation (due to ther-
moplasmonics or optical near-field enhancement) or hot electron
injection into the semiconductor (Fig. 5def). Such interactions
upon light illumination have been evidenced in various works
on both catalytic and mechanistic studies [124e130].
Additionally, it is not uncommon for metal/metal oxide-type
materials to be used as selective absorber coatings for solar
thermal collectors. The coupling of aluminium oxide with
metals such as cobalt [131,132], silver [133], platinum [134],
molybdenum [135,136], and most prevalently, nickel
Table 1

212
Catalyst materials reported for CO2 hydrogenation reactions and their respective performance.
Catalyst Reaction conditions Products Performance Ref
3 1
1 wt% Pt/TiO2  Fixed bed flow  CO (~50%)  2.03e6.48  10 mol s g1
cat (573 K) [43]
1
 573e873 K  Remaining composition  TOF ¼ 0.423e2.716 mol s (573 K)
not explicitly mentioned
 Fixed bed flow  CO e major product  TOF ¼ 0.44e2.716 s1 (573 K) [95]
 576e873 K  < 10% CH4 production
 Other products present but not
explicitly mentioned
Pt, Ni, Pd, Co on g-alumina  Batch reactor with FTIR attachment  CO  1.62e4.18  103 min1 g1
cat [86]
 CH4
Ni/Al2O3  Fixed bed  CH4  0e80% conversion [81]
 473e773 K, atmospheric pressure  CO
 Fixed bed  CH4  0e75% [82]

E.T. Kho et al. / Green Energy & Environment 2 (2017) 204e217

 523e773 K  CO
Ni/Ni(Al)Ox  523e773 K  CH4  Approx. 90% CO2 conversion [83]
 5e20 bar  Trace CO
 Trace C2H6
NiO/SBA-15  Fixed bed  CO  0e50% CO2 conversion [147]
 673e1173 K  CH4  TOF ¼ 0e12 min1
 Fixed bed  CH4  80e100% CO2 conversion [148]
 573e723 K  CO
2 wt% Pt/CeO2  Fixed bed  Pure CO products  13.7 ± 0.2% CO2 conversion [51]
 In operando DRIFT-MS system (498 K)
Co/CeO2 (K-promoted)  Packed-bed  CO  13e38% CO2 conversion [98]
 673e873 K  CH4
 Atmospheric pressure
Pt, Ni, Pd, Co on CeO2  Batch reactor with FTIR attachment  CO  2.88e12.51  103 min1 g1
cat [86]
 CH4
NixCe0.75Zr0.25xO2  673e823 K  CO  0.5e1.1 mmol g1
cat min
1
(673 K) [44]
1 1
 1 atm  CH4  5.8e20 mmol gcat min (823 K)
Ni/CZb  423e673 K  CH4  70e80% CO2 conversion [84]
 CO  2.16e2.41 mol CO2 g1
Ni s
1

 C2H6
 Fixed bed  CH4  Best activity at 76% CO2 conversion [149]
 Atmospheric pressure  CO
 673e753 K  C2H6
Ni/Ce0.72Zr0.28O2  Fixed bed  CH4  0.71e2.07 mol CO2 g1
Ni s
1
[85]
 423e673 K  41.1e85.2% CO2 conversion
NieRh/CZb  Fixed bed  CH4  78% CO2 conversion [84]
 423e673 K  CO  2.37 mol CO2 g1
Ni s
1

 C2H6
In2O3  Packed bed  CO  6e35% CO2 conversion [102]
 473e923 K
Ce2O3-promoted In2O3  Fixed bed  CO  0.39e19.98% CO2 conversion [107]
 523e773 K
CeO2-promoted Ga2O3  Fixed bed  CO  2.58e10.99% CO2 conversion [106]
 523e773 K
BaZrO3 (Y, Zn, Ce-doped)  Fixed bed  CO (97% selectivity)  37.5% (for BaZr0.8Y0.16Zn0.04O3) [150]
 873 K
 Atmospheric pressure
FeO nanoparticles  Fixed bed  CO  30e35% CO2 conversion [151]
 873 K  Other products not mentioned
Pt, Pd, Ni, Fe, or Cu on LaeZrO2  Electric-field assisted thermal reaction  CO ( 96% selectivity)  18.5e40.6% CO2 conversion [152]
 Fixed bed  CH4
 423 K with 3 mA input current
La1xSrxCoO3d  RWGS-CL systema  CO  110.8 mmol min1 g1 average CO generation rate [153]
 1123 K (during CO2 feed)
La0.75Sr0.25Co(1y)FeYO3  RWGS-CL systema  CO  40e80 mmol min1 g1 [154]
 823 K
TiC  Fixed bed reactor  CO  0.59% CO2 conversion [155]
 573 K  TOF ¼ 2.1 min1
 Atmospheric pressure

E.T. Kho et al. / Green Energy & Environment 2 (2017) 204e217

ZrC  Fixed bed reactor  CO  0.46% CO2 conversion [155]
 573 K  TOF ¼ 8.9 min1
 Atmospheric pressure
NbC  Fixed bed reactor  CO  2.09% CO2 conversion [155]
 573 K  CH4  TOF ¼ 61.1 min1
 Atmospheric pressure
TaC  Fixed bed reactor  CO  1.73% CO2 conversion [155]
 573 K  TOF ¼ 52.8 min1
 Atmospheric pressure
Mo2C  Fixed bed reactor  CH4  4.67% CO2 [155]
 573 K  CO  TOF ¼ 66.5 min1
 Atmospheric pressure
WC  Fixed bed reactor  CO  3.30% CO2 conversion [155]
 573 K  CH4  TOF ¼ 59.1 min1
 Atmospheric pressure
Cu, Ni, or Co on Mo2C  473e575 K  CO  4e31% conversion [112]
 2 MPa  CH3OH
 C2H5OH
 CH3OCH3
 CH4
 C2H6
 C3H8 and others
Au/TiC  Batch reactor attached to UHV chamber  CO (major product)  10e14  1015 produced molecules cm2 s1 [109]
 0.5 atm CO2:4.5 atm H2  CH4
 CH3OH
a
RWGS-CL: reverse water-gas shift chemical looping.
b
CZ: ceria-zirconia.

213
214 E.T. Kho et al. / Green Energy & Environment 2 (2017) 204e217
[137e141] has been previously reported. The popularity of the
nickel-alumina composite stems from its solar absorption
properties e it possesses the ideal combination of high absor-
bance (for effective energy absorption) and low thermal emis-
sivity (to minimise losses through thermal radiation) [138]. The
possibility of utilising the spectrum-selective characteristics of
such a combination of materials for solar thermal catalysis has
been revealed to be attainable through the CAESAR (CAtalyt-
ically Enhanced Solar Absorption Receiver) project [142].
CAESAR was applied to the CO2 reforming of methane using a
catalyst material (in the form of a catalyst foam), which acted as
a receiver upon which the concentrated solar radiation was re-
flected to. Carbide materials also exhibit great potential for such
an application. Carbides that have been tested for selective solar
absorbance purposes include hafnium, tantalum, and titanium
carbides [143e145]. Although studies specifically on carbides
active for CO2 reduction (e.g. Ti- and Mo-carbides) are less
common than that of alumina, the carbide family of refractory
materials has the distinctive advantage of high thermal resis-
tance [146]. This is an important attribute for fabricating a
catalyst/absorber foam with greater durability as the loss of
structural integrity is frequently cited as the mode of failure for
alumina-based catalyst foams [16,17].
5. Challenges in the execution of catalytic photo-thermal
CO2 reduction
An ideal catalyst possesses the following qualities: high
activity, selectivity, and stability. To design a photo-thermal
catalyst whereby heat generation is supplemented, partially
if not completely, from its solar absorption capabilities,
additional considerations have to be taken into account for the
material's heat generation efficiencies.
For example, the issue of material stability becomes even
more substantial in the case of plasmonic catalysis as plas-
monic absorption and the resulting effects are greatly affected
by both the size and shape of the nanoparticles [20,21,156]. It
is also known that nanoparticles tend to succumb to events
such as sintering and loss of nanostructured morphology upon
extensive exposure to heat. Therefore, the control of such
properties of a material becomes one of the key steps to ensure
the practical applicability and robustness of the phenomenon.
The design of photo-thermal materials often calls for a
composite component to facilitate optimisation of the solar
heat generation performance and catalytic conversion capa-
bilities. In this case, the effect each component has on the
other also must be taken into account. For instance, in the case
of Au/TiO2 both the metal and support are capable of light-
activation, Tan et al. [157] used in situ spectroscopic studies
to illustrate a difference in the preferred pathway (for ethanol
oxidation) upon introducing a light source to a thermal reac-
tion. In addition, on utilising light sources with different
wavelength ranges (ultraviolet and visible), variations in the
origins of the active electrons and their subsequent transfer
routes were observed, which consequently altered the reaction
outcome. The study highlighted the importance of under-
standing the pathways associated with photo-thermal CO2
reactions to gain better insights into catalyst performance
especially in terms of product selectivity.
Complementary to material design and fabrication, the
experimental setup for photo-thermal catalysis requires careful
consideration, as conventional systems used for gas-solid het-
erogeneous catalysis (e.g. enclosed plug-flow tube reactors) are
often not suited to light-based applications. Existing solar ther-
mal reactors, such as the one designed by Palumbo et al.
(Fig. 10), can be modified for photo-thermal catalyses under
concentrated solar irradiation [158]. In their study, Meng et al.
[159] retrofitted a water splitting rig for tandem hydrogen gen-
eration and photo-thermal CO2 reduction using a xenon arc lamp
(20 mW/cm2) as the illumination source. Nonetheless, the main
drawback of these designs is the lack of a secondary heating
system for deconvoluting photothermal heating and photo-
induced charge transfer effects. To achieve this, both Westrich
et al. and Tan et al. utilised external heating elements to heat up
the catalyst bed from the base while exposing the top to
continuous illumination [160,161]. Alternatively, Upadhye et al.
[162] adapted a commercially available reactor (Harrick Sci-
entific, HVC-MRA-5), which was originally designed for in-situ
spectroscopy analyses, to study the impact of visible light illu-
mination on CO2 reduction by oxide-supported Au catalysts. In
these studies, the secondary heating systems were capable of
generating temperatures up to 400e600  C, which allows for the
study of non-illuminated (i.e. dark) thermal catalysis, while
thermal heating from the irradiation sources was minimised
through the use of specific bandwidth sources and/or filters.
While the focus thus far has been placed on the reduction of
CO2 to fuels, it must be kept in mind that hydrogen plays an
equally important role in the reaction. This then brings us to
the issue of a suitable hydrogen source. Despite the increasing
abundance of CO2, hydrogen is not as readily available and
requires additional steps for its production. In terms of current
approaches, the steam reforming of methane remains as the
primary route for its large-scale production. However, despite
its effectiveness, steam reforming is an energy intensive pro-
cess often powered by fossil fuels. This will then further
contribute to CO2 emissions and defeat the original intention
of utilising hydrogen for CO2 recycling.
Aside from natural gas, water is another appealing hydrogen
source. In order to overcome the energy intensive water split-
ting process for effective mass hydrogen (and oxygen) pro-
duction, three potential solutions are frequently proposed:
photocatalytic water splitting [163,164], photoelectrochemical
water splitting [165] and solar powered electrocatalytic water
splitting [166]. Hydrogen can be produced by photocatalysis
via the direct utilisation of solar energy. Reviews detailing the
studies and applications of sustainable photocatalysts to ach-
ieve cost-effective photocatalytic water splitting are readily
available [164,167]. Recent developments in photocatalysis
include the introduction of carbon-based nanostructures
coupled with existing semiconductors or as standalone photo-
catalysts [163,164,168e170]. While exhibiting potential, sep-
aration of the hydrogen and oxygen gas products remains a
major bottleneck for coupling this technology with photo-
thermal CO2 recycling.
 E.T. Kho et al. / Green Energy & Environment 2 (2017) 204e217
(a) 5
9
(b)
6
7
10
2 1
4
3 8
Illumination Source
(b) (d)
Infrared Filter
Catalyst Bed
Inlet Outlet
Heat Source
Fig. 10. Potential reactor configurations for coupling and/or decoupling of heat and light in photo-thermal catalytic studies: (a) Palumbo et al. [158]; (b) Meng et al.
[159]; (c) Westrich et al. (Adapted with permission from Ref. [160]. Copyright (2011) American Chemical Society.); (d) Tan et al. (Adapted with permission from Ref.
[161]. Copyright (2016) American Chemical Society.); and (e) Upadhye et al. (Reproduced from Ref. [162] with permission from The Royal Society of Chemistry.).
Another potentially sustainable hydrogen generation tech-
nology is photoelectrochemical water splitting which is essen-
tially a short-circuited solar-powered electrochemical cell.
Photoelectrochemical water splitting utilises semiconductor-
based electrodes, which are capable of splitting water into
hydrogen and oxygen upon photoexcitation. Nevertheless, the
viability of this solution for large-scale application is often
challenged by its low solar energy to electricity conversion. To
date, electrocatalysis coupled with matured photovoltaic tech-
nology is thought to be the most feasible system for mass pro-
ducing hydrogen as a feed for CO2 recycling. The conversion
record is currently held at 40% efficiency with the use of a triple
junction solar cell [171]. The feasibility of such solar-powered
electrocatalytic water splitting has, in fact, been evidenced by
Jia et al. [166], whose work demonstrated a solar-to-hydrogen
conversion capability of more than 30%.
6. Conclusion and outlook
Solar-powered fuel production that consumes CO2 as
feedstock is an ideal concept that shows great potential for
simultaneous CO2 mitigation and renewable fuel production.
While the thermal catalytic reduction of CO2 has been rela-
tively well-studied, the effects of coupling the catalytic pro-
cess with light requires further work and understanding in
order to gain a better comprehension of the process chemistry
and mechanisms involved.
Although solar thermal technologies and plasmonic catal-
ysis have mostly been discussed individually, they do not have
to be mutually exclusive. Concurrent use of both technologies
may, in fact, complement the shortcomings of each technique.
For example, the utilisation of plasmonic materials in a solar
thermal reactor may be used to reduce the amount of solar
concentration required from the collector, thus reducing the
215
(c)
(e)
severe requirements on the solar reactor infrastructure while
reducing the sole dependence on thermoplasmonic heat gen-
eration to achieve a sufficient temperature.
To accomplish the realisation of photo-thermal CO2 catal-
ysis, one of the key factors is successful integration of multiple
disciplines of study: solar absorbing infrastructure design;
materials development; the sourcing of renewable hydrogen;
effective CO2 capture; and an understanding of CO2 conver-
sion pathways. Furthermore, surveys on influential factors,
such as solar irradiation consistency, space availability, and the
integration of synthetic fuel production with the existing dis-
tribution network and infrastructure will also be necessary to
assess the suitability of photo-thermal CO2 reduction pro-
cesses for different geographical locations.
Conflict of interest
The authors declare no conflict of interest.
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