Journal of Energy Chemistry 49 (2020) 96–123

Contents lists available at ScienceDirect

Journal of Energy Chemistry

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

Review

Current technology development for CO2 utilization into solar fuels

and chemicals: A review
Azeem Mustafa a,b, Bachirou Guene Lougou a,b,c,∗, Yong Shuai a,b,∗, Zhijiang Wang c,
Heping Tan a,b
a
Key Laboratory of Aerospace Thermophysics of MIIT, Harbin Institute of Technology, Harbin 150001, Heilongjiang, China
b
School of Energy Science and Engineering, Harbin Institute of Technology, Harbin 150001, Heilongjiang, China
c
MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin
Institute of Technology, Harbin 150001, Heilongjiang, China

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

Article history: The continuous consumption of fossil fuels causes two important impediments including emission of
Received 5 December 2019 large concentrations of CO2 resulting in global warming and alarming utilization of energy assets. The
Revised 9 January 2020
conversion of greenhouse gas CO2 into solar fuels can be an expedient accomplishment for the solution
Accepted 15 January 2020
of both problems, all together. CO2 reutilization into valuable fuels and chemicals is a great challenge
Available online 5 February 2020
of the current century. Owing to limitations in traditional approaches, there have been developed many
Keywords: novel technologies such as photochemical, biochemical, electrochemical, plasma-chemical and solar ther-
CO2 conversion mochemical. They are currently being used for CO2 capture, sequestration, and utilization to transform
Photochemical CO2 into valuable products such as syngas, methane, methanol, formic acid, as well as fossil fuel con-
Biochemical sumption reduction. This review summarizes different traditional and novel thermal technologies used in
Electrochemical CO2 conversion with detailed information about their working principle, types, currently adopted meth-
Plasma chemical
ods, developments, conversion rates, products formed, catalysts and operating conditions. Moreover, a
Solar thermochemical processes
comparison of these novel technologies in terms of distinctive key features such as conversion rate, yield,
use of earth metals, renewable energy, investment, and operating cost has been provided in order to have
a useful review for future research direction.
© 2020 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published
by Elsevier B.V. and Science Press. All rights reserved.

Azeem Mustafa is currently studying for a PhD degree Bachirou Guene Lougou is Assistant professor of the
from the School of Energy Science at Harbin Institute of School of Energy Science and Engineering at Harbin In-
Technology China. He received his B.Sc. and M.Sc. degrees stitute of Technology. He received his B.S. degree in
in Mechanical Engineering from University of Engineering Physical-Chemistry Science and M.S. degree in Energy
and Technology, Taxila in 2012 and Harbin University of Efficiency and Renewable Energies from the University
Science and Technology, China in 2018, respectively. His of Abomey-Calavi, Benin and Ph.D. degree in Power En-
research interest is conversion of carbon dioxide into so- gineering and Engineering Thermophysics in 2018 from
lar fuels. Harbin Institute of Technology, China. In 2018, he joined
the faculty of Harbin Institute of Technology, China. His
research focuses on Carbon-neutral energy and Hydrogen
storage systems, CO2 utilization, High-temperature solar
thermochemical energy conversion, Optimum design of
redox thermochemical reactor, and Synthesis of porous
catalyst /redox oxide materials. He is also interested in Advanced chemical energy
storage materials, Electrochemical energy conversion system, and Solar Photochem-
ical energy conversion system.

∗
Corresponding authors.
E-mail addresses: 15bf02043@hit.edu.cn (B.G. Lougou), shuaiyong@hit.edu.cn (Y. Shuai).

https://doi.org/10.1016/j.jechem.2020.01.023
2095-4956/© 2020 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.
 A. Mustafa, B.G. Lougou and Y. Shuai et al. / Journal of Energy Chemistry 49 (2020) 96–123
Dr. Yong Shuai is a full professor, Dean of School of En-
ergy Science and Engineering at Harbin Institute of Tech-
nology (HIT), China. He received his B.S. degree in 2001
and Ph.D. degree in 2006, from Harbin Institute of Tech-
nology, both in Engineering Thermophysics. In Oct. 2004,
he joined the faculty of Harbin Institute of Technology,
China. In April 2011- April 2012, he was a Visiting Sci-
entist with the Mechanical Engineering at Georgia Insti-
tute of Technology, Atlanta, USA. His current research in-
terests are in the areas of Micro/nanoscale energy con-
version and transfer, Thermal analysis of electronic equip-
ment and optical system, Numerical methods for radia-
tive heat transfer, Solar thermochemical energy conver-
sion, Sustainable Energy (especially solar thermal utilization), Energy Material, Fluid
Mechanics, Computational Fluid Dynamics (CFD), and Analyzing and testing tech-
niques in thermal and fluid science. He is also interested in Advanced chemical en-
ergy storage materials, and combined Solar Photo-Thermal-Electrochemical energy
storage system.
Zhijiang Wang is a professor of the School of Chemistry
and Chemical Engineering at Harbin Institute of Technol-
ogy, China. He received his B.S., M.S. and Ph.D. degrees
from Harbin Institute of Technology. He continued his
studies as a postdoctoral fellow at the University of Ox-
ford. His technological interests are in the synthesis and
characterization of high-quality nanoparticles and multi-
component nanostructures with controlled structure and
interface interactions, which could greatly enhance the
potential and broaden the application of nanomaterials in
the electrocatalysis including CO2 reduction and nitrogen
reduction reactions. His research topics presently include
understanding the mechanisms from the perspective of
electronic density of state.
Heping Tan is currently a full professor and director of
the Institute of Aerospace Thermophysics of Harbin In-
stitute of Technology. He graduated from Harbin Insti-
tute of Technology with a Master’s degree in 1980 and
obtained a doctorate degree from Poitiers University in
France in 1989. His research interest includes Numerical
heat transfer, Radiation heat transfer, Solar thermal uti-
lization, Analysis and suppression of stray light in space
optical system.
1. Introduction
The global energy infrastructure is transforming with poten-
tially substantial effects on energy trade and market because
world energy utilization has high implications for the socioeco-
nomic development of human beings [1,2]. The world has also
realized that necessary alterations will be much needed to meet
the increasing demand for energy. The current sources of fossil
fuel are insufficient to fulfill the global energy consumption, as
they will get double in the next thirty years and triple before
2100 [2]. As stated by [3], the economic break down in Europe
and North America reduced the energy consumption by 5% and
4.5%, respectively. The rates of energy consumption were vigorous
in many developing countries (>4%).
Although, the energy obtained from fossil fuel is very im-
portant because their burning yield impressive quantities of
energies/weight [4], but continuous consumption of fossil fuels
for industrial purposes is threating to the atmosphere as large
concentrations of CO2 are emitted into the environment. The
energy consumption exhibited an ascending trend from 1961 to
2010 [3]. The world is paying huge attention to the development
of renewable energy to meet the growing demand. The main
sources of renewable energy like wind, waves, sunlight, tides,
biomass, nuclear energy, and geothermal heat generate electricity
with almost zero emissions of CO2 .
The abundant CO2 can be treated as an asset by employing
appropriate technologies to convert CO2 into solar fuels and
chemicals. The recycling of CO2 can reduce global warming and
fossil fuel consumption [5]. There are many conversion technolo-
gies such as photochemical, biochemical, electrochemical, plasma
97
chemical and solar thermochemical which can transform CO2 into
valuable products.
Biochemical conversion depends on photosynthesis to trans-
form sunlight into biomass which can be further processed and
utilized. Other novel technologies like photochemical and solar
thermochemical depend on direct solar radiation. The former
technology depends upon photons energy and the latter uses
concentrated solar energy. Plasma and electrochemical rely on
electricity. The share of renewable energy in 2014 was 19.2% of
the overall global energy consumption and the predicted share
of renewable energy of the world’s electricity generation was
23.7% in 2015 [6]. Currently, it is at a stage that the wide-scale
utilization of renewable energy is the main issue for better storage
and convenient transportation of the electricity generated. Though
it is possible to store in batteries, it is inefficient as compared
to storage in chemicals and fuels [7]. These fuels - termed as
carbon neutral or solar fuels – provide extremely high volumetric
or gravimetric storage capacity, possess high energy densities and
are compatible with existing global fuel infrastructure.
The CO2 conversion reactions can be classified into fuel produc-
tion and chemical production. The former is regarded as a highly
suitable objective for the transformation of large amounts of CO2
because it has a large market size than the latter. Methanol is an
interesting chemical and is in the middle of these two classes be-
cause it is used as fuel and chemical in fuel cells and engines [8].
To accomplish the conversion of CO2 into valuable products, the
reactions employ co-reactants that are actually hydrogen donors.
Liquid products are better than gasses for most applications in the
current existing system. The direct oxidative and indirect oxidative
routes are two approaches that can be utilized to accomplish
this. The former approach is used to produce short-chain olefins
(C2 H2 , C3 H6 ), oxygenated products (CH3 OH, CH2 O, HCOOH) and
hydrocarbons. The latter approach yields syngas which can be
further processed into almost any kind of fuel or chemical. In
this approach, the H2 /CO should be controlled because it plays an
important role in the production of desired products.
Gaseous hydrogen has many serious disadvantages due to its
physicochemical characteristics as compared to liquid products [9].
Moreover, it is very costly to safely store, dispense and transport
gaseous hydrogen, while liquid products are already compatible
with the existing infrastructure. Hence, a shift from products
obtained from liquid fossil fuels (kerosene, gasoline, diesel) to a
sustainable and renewable liquid fuel is much needed. Methanol
is the quite simple chemical having one carbon, and hence can
be considered as a possible solution to meet these requirements.
Nevertheless, currently, it is generated from methane for economic
reasons; it can conveniently be acquired from many carbon sources
like biomass, landfill gas, biogas, and CO2 . That is why it has been
suggested as essential solar fuel for the aforementioned anthro-
pogenic cycle of carbon [10]. While finding the most suitable CO2
conversion approach having the potential of commercialization on
a wide scale, the efficient generation of solar fuel is very necessary
to be economically compatible with existing infrastructures. This
review has discussed traditional and novel approaches (used to
produce solar fuels) to cover all the fundamental aspects along
with the latest developments followed by future perspectives for
each CO2 conversion process. A clear understanding of the matter
has been presented by adding effects and mitigation of notorious
gas CO2 in the first section.
Fig. 1 describes the adopted methodology and structure of this
review. Initially, effects of carbon dioxide on atmosphere and its
mitigation are presented. Then a section on carbon capture and
utilization is included. Traditional thermal approaches and their
subsequent pros and cons are described in the third section of
this review. While in the fourth section of this review, photo-
chemical, biochemical, electrochemical, plasma chemical and solar
98 A. Mustafa, B.G. Lougou and Y. Shuai et al. / Journal of Energy Chemistry 49 (2020) 96–123

Effects of CO2 and its

mitigation Ethanol Formaldehyde Ethane

Approaches for CO2

conversion
Conventional thermal Products Obtained
Novel thermal
approaches Ethylene from CO2 Formic Acid
approaches
reduction

Pure CO2
Biochemical splitting
Carbon
Methanol Methane
Monoxide
Electrochemical Co-reactant

Fig. 3. Chemical products obtained from CO2 conversion.

Photochemical
Hydrogenation
reforming of
of CO2
methane
Plasma chemical
Comparison between
Solar
approaches for CO2
thermochemical
conversion
Fig. 1. Methodology of the review.
thermochemical are discussed in terms of their working princi-
ple, conversion rates, technological advancements, and formed
products. Finally, a comparison has been provided at the end to
demonstrate the importance of each conversion technology in
certain perspectives.
1.1. Effects of CO2 and its mitigation
The utilization of natural resources in industrial applications
has unprecedented contributions to the advancement and prosper-
ity of human beings in the past centuries. At present, to meet the
82% energy requirements per day, ten billion cubic meters of nat-
ural gas, twenty-two million tonnes of coal and eighty-five million
barrels of oil are consumed [10]. These natural resources (natural
gas, coal, and oil) are carbon-rich fossil fuels and their burning
leads to the emission of large concentrations (around 30 billion)
of greenhouse gas, mainly CO2 into the environment [11,12]. The
natural carbon cycle has been outpaced by these anthropogenic
emissions of CO2 and the concentrations of atmospheric CO2 have
increased from 280 ppm – before the industrial revolution – to
390 ppm in 2010 and by the end of this century, are expected to
Dry
be 570 ppm [13]. Due to the release of this increased amount of
CO2 , there are detrimental effects on the environment and climate
e.g. global warming, which is having multidimensional effects
on the earth’s ecosystem and consequently affect human beings
[14]. According to the report of the Climate Resilience Handbook,
numerous natural disasters – heat waves, hurricanes, wildfires,
and droughts – leading to a loss of 31 billion-dollar were recorded
in 2017 [15].
Therefore, it seems quite necessary to reduce the production
of CO2 and convert this greenhouse gas into useful chemicals for
environmental protection [17]. The conversion of main greenhouse
gas, CO2 into value-added products can solve the interlinked and
challenging problems of the modern age. Its conversion can not
only shift our dependence from conventional fossil fuels to newly
developed fuels (Fig. 2) but also tackle the issue of global warming
[18–20]. Probably, the generation of value-added products out of
CO2 can efficiently close the carbon loop.
It associates with the principle of green/sustainable chemistry
if the large anthropogenic concentrations of CO2 are reduced and
converted into industrially valuable feedstock for fuel produc-
tion (Fig. 3) and hence, sustained chemical industry and energy
economy can be established by developing cost-effective methods
and approaches for the mitigation of CO2 [21–23]. There are
several modern CO2 conversion technologies that are currently
into practice, e.g. biochemical, photochemical, electrochemical,
plasma-chemical and solar thermochemical and their advantages
and disadvantages along with their future prospects are principally
discussed in this review. However, CO2 capture, utilization, and
storage (CCUS) [8,24–30] - which are other applications of CO2 –
are also briefly discussed herein.

Fig. 2. GHG emissions by gas and economic sector-wise Production of GHG [16].
 A. Mustafa, B.G. Lougou and Y. Shuai et al. / Journal of Energy Chemistry 49 (2020) 96–123 99

CO2, O2, N2

CO2
Air Flue gases
Combustion CO2 separation
Fuel

Post-combustion capture CO2 dehydration

Compression
Separation
utilization

Gasification process
Fuel Combustion
and CO2 separation

O2 Air
CO2, O2, N2
Air Air separation

Pre-combustion capture

Combustion

O2
Recycle flue gases
Air separation
Air
Oxyfuel combustion capture

Fig. 4. Capturing process for CO2 [33].

2. Carbon capture and storage
The need to reduce emissions of CO2 from the environment
is shoving scientific community and technologists to explore and
develop new strategies that may be efficient for controlling and
reducing the atmospheric level of CO2 . The capture of CO2 from
flue gasses of industrial processes or power plants to prevent it
from getting into the atmosphere is a possible option (Fig. 4). This
captured CO2 can be utilized in different ways such as carbon
source in industrial processes or disposing of it in coal beds, oil
wells, and geological cavities, etc. The CO2 capture from flue gasses
released from continuous sources, that corresponds to 60% of the
total released CO2 , is a mature approach. Phases of solid or liquid
(membranes are also used) are utilized to capture CO2 [31,32].
There is continuous innovation in this area and new materials
with enhanced specific characteristics are being developed like
polymeric amines, hybrid materials, metallic organic structures
and functionalized silicates which are not only energetic but are
also economical [31].
It is considered one of the most significant technologies used
to decrease CO2 emissions and, in this technology, CO2 is removed
directly from utility or industrial plants and then subsequently
stored in a secure medium [34]. The main CCS rationale is to pro-
duce biofuels by reducing CO2 emissions and in connection with
this, subdue climate change [35]. In CCS technology, the CO2 stor-
age time period should be more than the predicted peak interval
of fossil fuel usage, like if CO2 reappears into the environment, it
should arise after the estimated peak interval of fossil fuel usage.
Currently, this technology is quite promising for CO2 mitigation
and is highly useful for large amounts of CO2 [36]. Owing to the
world’s big stock of low-priced fossil fuels, there is a high need to
explore new opportunities for CO2 capture from the combustion of
fossil fuel to avoid it from penetrating into the atmosphere. Large
concentrations of carbon can be obtained from several sources like
coal-fired and biomass plants. The former type of power plants is
regarded as dirty because they emit heavy concentrations of CO2 ,
so there is an urgent need to employ CCS technology in this type
of industry. Hence, excessive amounts of CO2 will be removed
from the atmosphere and a low-pollution source of energy will
be delivered to society, emphasizing the development of efficient,
economical and clean energy systems [33].
The chemical CO2 recycling from industrial and natural re-
sources into different products can be obtained by utilizing CSS
as a component of the reductive hydrogenative transformation
process. Fig. 5 presents a carbon transformation cycle into valuable
products.
2.1. Working of CCS technology
Many techniques can be utilized for CO2 capture: absorption
in a solid or liquid, gas phase sequestration and hybrid processes
[38,39]. However, three main sequestration processes can be
described as [40]:
• Process 1: this process incorporates the selective CO2 uptake
over a solid surface which is reproduced by extending the tem-
perature or decreasing the pressure to liberate the adsorbed
CO2 .
• Process 2: a liquid solvent is used in this process which absorbs
CO2 gas which subsequently forms a compound. The solvent is
taken to another section and when the heat is applied to this
solvent, it liberates CO2 . This solvent is further used to absorb
CO2 in the next cycle.
• Process 3: a permeable membrane is used to separate CO2
from flue gasses in this method.
100 A. Mustafa, B.G. Lougou and Y. Shuai et al. / Journal of Energy Chemistry 49 (2020) 96–123
Fig. 5. Production of methanol and other chemicals via carbon conversion cycle [37].
100 Conversion
Energy efficiency
80
Conversion (%)
60
40
20
0 0
0 1000 2000 3000 4000 5000
Temperature (K)
Fig. 6. Relation between energy efficiency and thermal conversion in terms of tem-
perature (reproduced from ref. [51]).
Pre-combustion, oxyfuel combustion, and post-combustion
mechanism can be used in capturing the process of CO2 and
shown in Fig. 6 [41–43].
2.1.1. Pre-combustion process for CO2 capture
In this technique, CO2 is captured from the stream of syngas
before the occurrence of combustion and power generation pro-
cesses. At this stage, carbon is separated from the coal before its
utilization in the stream of gas. Firstly, coal is partially oxidized
by means of gasification in the presence of air or oxygen to
produce the syngas which consists of H2 +CO and methane traces.
This syngas, after passing through several phases of gas purifier
is further moved through a reactor where CO is transformed
into CO2 which has high partial pressure and chemical potential
paving better ways for capture and sequestration techniques. The
complete removal of CO2 synthesis gas with larger amounts of
H2 can be used for combustion to generate electricity [44,45].
More energy can be harvested from the streams of combustible
gas by using heat recovery facilities. The captured CO2 can be
compressed, dried and finally separated by physical adsorption
which is a commercially adopted technique for separation. Physical
solvents are also employed in CO2 capture without incorporating
any chemical reaction but it mainly relies upon the solubility of
CO2 in the solvent. The solvent having large concentrations of CO2
can be revived by utilizing stripping or flash desorption. Flash
desorption incorporates the degassing of a solvent having large
concentrations of CO2 at high pressure through different phases
50
to decrease the pressure. At this stage, CO2 is separated and the
Energy effciency (%)
40 solvent restores its original shape. In stripping, after degassing,
the solvent is processed with inert gas for CO2 removal. Presently,
30
Purisol, Selexol, Rectisol, and Fluor are commercially available
20 technologies that capture CO2 by physical adsorption.
10
2.1.2. Post-combustion process for CO2 capture
Many technologies are utilized to separate CO2 from flue gasses
released from industrial processes. The commonly used tech-
nologies are cryogenic separation, adsorption on membranes and
solids, chemical and physical solvent. It is very costly to establish
a post-combustion system when there are large volumes of flue
gasses to be processed and it seems an important limitation of
this process. Other than this, more energy is required to separate
CO2 from solids and solvents after separation. These drawbacks
need serious attention before this process becomes an efficient
candidate for CO2 separation. This process needs an efficient
cooling system because CO2 captured through this process is
obtained from high-temperature flue gasses, low concentrations of
CO2 . This process is utilized in coal-fired stations where the fuel is
combusted in the presence of air to produce streams which in turn
drives large turbines to produce electricity. The main ingredients
of flue gasses are CO2 , O2 , impurities and moisture contents. The
impurities sometimes disturb the capturing process by damaging
the sorbents [40,45].
2.1.3. Oxyfuel combustion
Oxyfuel combustion is another method for CO2 capture and
includes the burning of coal in the presence of O2 rather than air.
The important products formed during the process of combustion
are water, CO2 , and SO2 , hence, CO2 separation is not essential.
CO2 capture can be carried out from flue gasses by condensation
of water accompanied by compression and storage. In 1982, this
method was developed for the generation of CO2 with maximum
purity for the effective removal of oil. Cryogenic air dissociation
unit provides the O2 during the early stages and appropriate
combustible conditions are maintained by mixing pure O2 with
flue gasses before combustion. The high release of SO2 by flue gas
may cause corrosion of the complete setup. This process is highly
 A. Mustafa, B.G. Lougou and Y. Shuai et al. / Journal of Energy Chemistry 49 (2020) 96–123
advantageous in terms of technical feasibility but the requirement
of large quantities of oxygen causes high cost [46,47].
2.2. Challenges
Despite many advantages such as industrial CO2 utilization,
carbon trading and development of efficient CO2 storage, there
are several gaps and uncertainties concerning the utilization and
development of this technology with regard to life cycle effects,
costs, storage permanence, and capacity. Furthermore, high costs
of implementation, inefficient framework and power penalties are
other hindrances when employing CCS technology.
Primarily, CCS technology is energy-intensive and costly. For
instance, the carbon capture technique itself, replacement and
supply of gas sequestration materials in energy consumption and
power generation and maintenance of overall process, all are quite
expensive. It is an unfortunate fact that the CO2 capture and
storage approach needs those areas which don’t commonly exist.
For instance, generally, if the distance between the CO2 source
and disposal site is about 80 km, the plant efficiency reduces by
20%. The average storage cost mainly depends on the network
scale and facilities location. An optimized network of CO2 pipeline
can minimize the cost of infrastructure and operation as pipeline
length and capacity influence the cost of the overall system. There
can’t be commercial-scale development of this technology until
the cost of implementation is reduced, which can further get
public acceptance and attract political attention.
Legislation in different countries restricts the emissions gen-
erated from industrial applications, effectively requiring several
industries to employ CCS technology. The collaboration between
different operators i.e. CCS storage and emission source can achieve
productive enforcement of CCS technology. For the proper imple-
mentation of CCS technology, the development of a strategy con-
cerning the long-term utilization of this technology is necessary.
3. Conversion of CO2 – conventional thermal approaches
Before the utilization of modern CO2 conversion technologies,
conventional thermal approaches were into practice and the main
difference between two was the use of ‘fuel’. The latter used fossil
fuels to provide the necessary thermal energy in order to carry
out their processes. In this section, an overview (along with their
pros and cons) of those conventional thermal approaches has been
provided. Industrial-scale conventional thermal approaches may
be divided into pure CO2 decomposition and conversion of CO2
along with a co-reactant – H2 , CH4 , and H2 O.
3.1. Pure CO2 decomposition
To date, the pure splitting of CO2 is mainly ineffective due to
high stability of CO2 molecule (the Gibbs free energy of formation
for C–O bond is −394 kJ/mol), thus, requires substantial thermal
energy along with a highly active catalyst and optimal conditions
for the occurrence of the chemical reaction. Moreover, thermo-
dynamically, both enthalpy and entropy are unfavorable for the
conversion [48–50]. The splitting reaction (R1) can be written as:
1
CO2 (g ) → CO(g )+ O2 (g ) H ◦ = −293 kJ/mol
2 3.2. Co-reactant-based CO2 conversion
However, there is no point of disregarding the CO2 splitting
because it needs high thermal energy to proceed, though, appar-
ently, it seems that for such high value of Ho that this conversion
is unattainable, but there are many industrial applications which
involve endothermic reactions and can support this conversion
e.g. steam reforming of methane (R2) which is highly endothermic
reaction and has worldwide use [48–50].
CH4 (g )+H2 O(g ) → CO(g )+3H2 (g ) H ◦ = +206.3 kJ/mol
101
Thermodynamically, very high values of temperature are
needed for the CO2 splitting. Consider the following Fig. 6 for this
sake.
Thermal conversion and equivalent energy efficiency in terms
of temperature were discussed by Ramses et al. [51]. They theo-
retically calculated these values and showed that the reaction is
not very efficient at 20 0 0 K, having reaction enthalpy 245 kJ/mol
and to heat up 1 mole of CO2 from 300 to 20 0 0 K 92 kJ/mol
will be needed. The production equilibrium of oxygen and carbon
monoxide changes from <1% at temperatures under 20 0 0 K up to
45%–80% at 30 0 0–350 0 K.
In the past, researches have been conducted for decomposition
and separation of CO2 into various chemicals – CO and O2 –
using different kinds of membranes. Experiments were conducted
by Naotsugu et al. and they utilized the yttria-stabilized zirco-
nia membrane to determine the CO2 splitting rate and oxygen
permeation rate using argon as sweep gas and also constituted
their equations [52]. They concluded that CO2 conversion can be
improved by using the reactor system of YSZ–membrane and they
obtained only 0.5% conversion of CO2 at a temperature of 1782 K
having CO2 flow rate ranges between 4 and 250 cm3 (STP)/min.
Bernard et al. studied the production of carbon monoxide by direct
decomposition of carbon dioxide [53]. Their process consisted of
a selective oxygen pumping mechanism having a semipermeable
membrane – made up of calcia – stabilized zirconia - to dissociate
the carbon dioxide equilibrium. This process produced CO in
large quantities by extracting the oxygen with the assistance of
membrane, however, the overall conversion was also very low in
their study, they converted 21.5 mol% of CO2 into CO at 1954 K
with equilibrium production of 1.2%. The efficiency of the pro-
cess was lowered by the material used in the membrane which
actually reduced the permeation rate of oxygen. The separation
and decomposition of CO2 by utilizing membranes made up of
solid oxide was investigated by Ren et al. [54]. In a membrane
reactor, these membranes were analyzed for CO2 decomposition
into carbon monoxide and oxygen. At a temperature of 1213 K,
only 10% of CO2 was converted in the reactor with a membrane
of solid oxide (SrCo0.5 FeO3 ) along with methane which acted as a
sweep gas. Moreover, a further 2% conversion was achieved when
CO2 and helium were diluted and fed to the lower chamber and
mix up of argon and methane was sent to the upper membrane
chamber for CO2 decomposition.
The feasibility of direct splitting of CO2 into chemicals (mostly
CO and O2 ) with the help of semipermeable membranes for oxygen
extraction has been demonstrated in these researches. It can be
concluded that the approaches presented in these studies not only
require high values of temperature but they exhibit very small con-
version rates and therefore, are not successful and efficient to be
considered on the industrial scale. Additionally, these approaches
lack efficient dissociation of oxygen and carbon monoxide which
becomes an explosive blend in the presence of high temperatures.
A concise summary of the early attempts describing several
approaches for CO2 splitting has been provided to have a complete
perspective of the topic because it has accomplished the basis
for the development of novel technologies, discussed in the next
portions.
(1)
As discussed in the previous section that thermal decompo-
sition of CO2 requires high energy values so the only practical
approach to convert CO2 involves the usage of a co-reactant.
From the perspective of thermodynamics, it is considerably
convenient to transform CO2 when it is coupled with a reactant
having higher values of Gibbs free energy, e.g. CH4 and H2 . Basi-
(2) cally, the inherent chemical energy of hydrogen carriers will be
102 A. Mustafa, B.G. Lougou and Y. Shuai et al. / Journal of Energy Chemistry 49 (2020) 96–123
utilized to support the CO2 conversion [49,50]. For CO2 conversion
into methanol and syngas, most of the conventional processes in-
volve reaction of CO2 with either H2 or CH4 with CO2 , respectively.
A brief introduction to these reactions has been included in the
next sections. Since the water is an inexpensive and ubiquitous
source of hydrogen – as compared to other hydrogen sources – so
the combined reaction of water with carbon dioxide is of interest
and does not have any conventional approach and their reforming
into valuable chemicals with the aid of renewable energy will sig-
nificantly impersonate the natural photosynthesis [55]. There are
many other hydrogen donors which may be considered in place
of CH4 , H2 , and H2 O e.g. glycerol. However, in the next sections
reforming of CO2 with methane and hydrogen is presented.
3.2.1. Dry reforming of methane
The process of converting CO2 in the presence of CH4 is named
as dry deforming of Methane (DRM), while, in steam reforming
of methane, CH4 reacts with water instead of CO2 . Fischer and
Tropsch studied DRM first time back in 1928 and it has been a
challenging issue for the engineering community ever since [56].
During world wars, there was a quest for developing alternative
chemicals and fuels due to the limited availability of fossil fuels
[57–59]. After the oil crisis of the 1970s, the scientific community
started paying attention to consuming natural gas – which is
abundant and cheap – for the development of alternative fuels
and chemicals in order to reduce the dependence on fossil fuels. In
the past decade, concerning environmental protection and climate
change, DRM has also been assumed as a way to mitigate the
CO2 concentration to produce value-added chemicals. The DRM
reaction (R3) is:
CO2 (g )+CH4 (g ) → 2CO(g )+2H2 (g ) H ◦ = +247.3 kJ/mol (3)
The dry reforming of methane is a complex process and re-
quires high temperature [60,61] values – 900 to 1200 K – and
some catalyst to proceed due to the high stability of CO2 molecule
and inert nature of CH4 , while on the other hand, steam reforming
of methane is a pretty straightforward process due to the presence
of water.
DRM, to date, is not widely utilized on the industrial scale as
a major drawback of this process is the formation and deposition
of soot which results in the early deactivation of the catalyst.
The inability to efficiently convert CO2 and requirement of high
temperature has sparked the development of new technologies
– biochemical, solar thermochemical and electrochemical, etc.
for CO2 conversion. Of course, the researches on the convenient
conversion of green-house gas CO2 with the aid of CH4 and mod-
ification of catalyst to prevent coking issue and early deactivation
are in progress [62–68].
3.2.2. Hydrogenation of CO2
3.2.2.1. Production of methanol. The formation of methanol by se-
lective hydrogenation of carbon dioxide is a widely adopted pro-
cess on the industrial scale across the globe and by this method,
approximately, 70 M metric tonnes are produced annually. The
chemical reactions for methanol production are given below [11]:
CO2 (g )+H2 (g ) → CO(g )+H2 O(g ) H ◦ = +40.9 kJ/mol
CO(g )+2H2 (g ) → CH3 OH(g ) H ◦ = −90.8 kJ/mol
CO2 (g )+3H2 (g ) → CH3 OH(g )+H2 O H ◦ = −49.9 kJ/mol (6)
The production of H2 O as a by-product in the methanol for-
mation process is the main drawback of this process because,
when initiating the conversion of methanol from synthesis gas,
the one-third of the hydrogen is transformed into water. More-
over, the formation of methanol from selective hydrogenation is
not a thermodynamically suitable reaction as compared to the
production of methanol from synthesis gas [69,70].
Regardless of the problems associated, the formation of
methanol through the reaction of CO2 and H2 is the most effective
industrial-scale traditional approach for the transformation of CO2
into valuable chemicals.
Recently, the hydrogenation of CO2 to yield C2+ chemicals has
acquired a growing interest. The C2+ species can be regarded as en-
try platform chemicals for current value chains and therefore are
more advantageous over C1 compounds. For instance, C2 –C4 can
be utilized to enhance the calorific value of biogas and natural gas
by means of injection into distribution grids. C2 –C4 (light olefins)
are useful base substances for polymer production [71]. Under
atmospheric conditions, C5+ alkanes possess high energy densities
and are more suitable with the present liquid-fuel distribution.
Thus, they are the appealing forerunner of jet fuels. Corresponding
to methanol, higher alcohols are considered as clean fuels and an
alternative forerunner for small-chain olefins due to their elevated
octane numbers, volatile aromatic vapors and low NOx emissions
[72]. The hydrogenation of CO2 to hydrocarbons generally includes
CO generation at first through reverse water-gas shift (RWSG)
reaction accompanied by hydrogenation of the CO intermediates.
The RWSG is a key reaction in the hydrogenation of CO2 and
converts carbon dioxide into highly active carbon monoxide by
introducing hydrogen. This produced carbon monoxide can be
hydrogenated to alcohols and hydrocarbons [73].
The major hindrance in the hydrogenation of CO2 to produce
C2+ chemicals is the high coupling of C–C. Nevertheless, the encour-
aging discussion carried out in different available research articles,
C2+ product selectivity and time-yields has not sufficiently been
achieved. No large-scale adoption has yet accomplished. Moreover,
interactions between promotors, support and active phase are still
under discussion. More theoretical and experimental investigations
are required to improve the design of catalysts to enhance the
number of active sites and their subsequent activity [74].
3.2.2.2. Methanation of CO2 . Sabatier Reaction (R7) is an important
catalytic process whereby methane is produced by reacting H2
with CO2 in the presence of (some) catalyst and is commer-
cially an interesting process. Many excellent investigations about
the catalytic conversion of CO2 with H2 have been carried out
[29,39,75,76].
CO2 (g )+4H2 (g ) → CH4 (g )+2H2 O H ◦ = −252.9 kJ/mol (7)
Syngas and compressed natural gas are one of those many ap-
plications which are formed by the methanation of carbon dioxide.
Thermodynamically, the methanation of carbon dioxide is quite a
favorable reaction, however, this reaction has considerable kinetic
limitations because the methanation of carbon dioxide is an eight-
electron process and thus, an adequate catalyst becomes crucial
to proceed the chemical reaction [77]. This process does not have
much commercial significance to date, because 95% of hydrogen
is produced through SMR and carbon capture and utilization are
(4) costly. Methanation of carbon dioxide will be commercially more
advantageous and beneficial if carbon dioxide has been taken from
streams of wastes or inexpensive facilities and hydrogen from
(5) renewable energy sources.
3.2.2.3. Other products. Other than the products described in
above sections, there are products such as ethylene, formaldehyde,
and ethanol which can be produced through conventional thermal
conversion of CO2 . However, the process efficiency for these prod-
ucts is not notable, hence, different novel technologies are used for
 A. Mustafa, B.G. Lougou and Y. Shuai et al. / Journal of Energy Chemistry 49 (2020) 96–123
the production of these chemicals. For example, photoelectrochem-
ical technology is preferably used for the production of ethanol,
photochemical reduction is employed to obtain formaldehydes and
microwave plasma is utilized for the production of ethylene. The
production of different products entirely depends on reactions
conditions and the types of catalysts.
4. Novel approaches for CO2 conversion
4.1. Photochemical conversion
The irradiations of solar light are utilized for the reduction of
CO2 in photochemical transformation of CO2 and it is a sustainable
and emerging approach which has acquired huge attention as
it needs low temperature, small amounts of input energy and
considerable pressure and does not have negative impact on the
atmosphere and environment [3,78]. On the other hand, other con-
version approaches – biological, electrochemical, etc. – are costly
and need high values of input energy and temperature. Because of
these benefits, this approach is being employed to overcome the
current environmental issues and energy needs [79–81].
To date, photocatalytic activity and selectivity of products for
CO2 reduction are low. For the enhancement of CO2 reduction
via photochemical conversion with high selectivity and efficiency,
many kinds of researches [82,83] were conducted in the past
and there have been developed a number of approaches for
the improvement of CO2 adsorption kinetics, separation and
charge transfer. Few approaches are for improvement of band-gap
[84], defect control [85], development of catalyst [86], surface
sensitization [87], and modification of pore texture [88]. Engi-
neering processes can be utilized for efficiency enhancement of
photocatalysis. This technique can pave the method for photo-
reactor designing by changing the variables such intensity of light,
selectivity, temperature and product yield [89].
Type of catalyst bed (fixed or fluidized), operation (batch,
continuous) and phase types are three important frameworks that
are involved in the reactions of photocatalytic CO2 reforming.
For effective reduction of CO2 into valuable products, the catalyst
must have specificity in order to avoid the conversion of H2 O into
H2 and it must reduce the energy of activation that is termed
‘potential’ in electrochemical technology (Section 4.4). The uniform
photocatalytic CO2 transformation system mainly comprises of
electron relay, light absorber, the donor of electron and a molec-
ular catalyst [89,90] and the efficiency of such systems can be
quantified by the following terms:
• Turnover number: it corresponds to the total reductions
accomplished by a catalyst during its lifetime.
P ductor and hence restricted by the active sites of the
TN =
C
Where P is products obtained after CO2 reduction and C denotes
catalyst.
• Photochemical quantum yield: it is denoted by  and is the
determination of incident photons in a molar fraction which
are converted into products from CO2 reformation.
 = MP × N
Where MP denotes mole products / absorbed photons and N is
number of electrons needed for conversion.
• Catalytic selectivity: it is the ratio between the product’s
molar ratio after CO2 reduction and hydrogen.
P to go through the reduction or oxidation of the reactants and
CS =
H2
103
Photochemical
Transformation
Photosensitizer
Formic Acid
Electron Donor CO2
Methane
Catalyst
Fig. 7. The photochemical CO2 reduction mechanism [89].
Any catalyst that produces formate and CO from CO2 transfor-
mation has the thermodynamic capability of transforming proton
into hydrogen. The value of CS can be utilized for the quantifica-
tion of efficiency of CO2 transformation with respect to hydrogen
production at particular experimental provisions. Synthetic refine-
ments of the catalysts give an opportunity to modify the relative
reactivity with the assistance of steric and inductive effects [90].
4.1.1. Types of photocatalytic process
CO2 reduction to useful chemicals via photochemical trans-
formation is an effective approach as it does not need additional
energy for conversion and also does not affect the surroundings.
The process (Fig. 7) of photochemical reduction of CO2 through
solar energy is mainly of two types: homogeneous and hetero-
geneous photocatalytic processes. The reactants and the catalyst
are in the identical state of matter in the former process while in
the latter process both are in different phases. The steps for CO2
reduction via heterogeneous photocatalysis are given below.
Step 1 It is the step of light-harvesting in which solar radiations
are absorbed by the semiconductor. For the process of
photocatalytic reduction of CO2 , the energy obtained
from solar radiation must be the same or more than the
bandgap energy of that semiconductor. There should be
a complete utilization of solar radiations that strike the
catalyst to avoid loss of protons and efficiency enhance-
ment. This step is highly dependent on the structure and
morphology of the catalyst utilized for the photocatalysis.
Step 2 The holes and protons are generated in the conductance
and valance band, respectively, as a result of the excitation
of electrons in valance band to conductance band. Taper-
ing the gap between bands can enhance this excitation.
Step 3 The electrons proceed to the outer area of the semicon-
(1a) catalyst.
Step 4 The recombining of holes and electrons takes place at
this stage.
Step 5 There occurs recombination of the surface due to the
recombination in the 4th step.
Step 6 The reduction and oxidation reactions take place by using
the electrons and holes produced in the previous step.
(2a) Semi-conductors are generally used in a heterogeneous pro-
cess where the thermodynamics reactions are carried out by the
solar energy for the production of chemical fuels of high energy
[91,92]. CO2 photoreduction to methanol and formaldehyde using
semi-conductors GaP, TiO2 , WO, CdS and ZnO was under research
back in 1979 [92]. The holes and electrons that get to the surface
of semiconductors are restricted by the active sites of the catalyst
(3a) these reduction or oxidation reactions actually transform the CO2 .
104 A. Mustafa, B.G. Lougou and Y. Shuai et al. / Journal of Energy Chemistry 49 (2020) 96–123
Once the holes and electrons are formed the feasibility of (prod-
uct) production is high [2,93]. Similar to the process of natural
photosynthesis, solar energy can be stored in molecular bonds.
Photoreactors are utilized for energy storage whereby heat and
mass transfer and reduction process take place.
Homogenous photocatalysis is not widely applicable due to
the reaction’s recombination – it should be prevented to avoid
energy loss – and side reactions. Moreover, different other process
cycles may get terminated due to the degradation of catalyst in
homogenous photocatalysis.
4.1.2. Use of metal complexes for photochemical reduction of CO2
For efficient reduction of CO2 , many metal complexes are
being utilized due to their several obtainable redox states and
permitting the multielectron CO2 reduction. Some examples are
nickel cyclam [94], rhenium mono(bipyridyl) tricarbonyl [95],
carbine isoquinoline [96], nickel S2 N2 -type tetradentate [97],
ruthenium mono(bipyridyl) [98], ruthenium bis(bipyridyl) di-
carbonyl [99], manganese monon (bipyridyl) tricarbonyl [100],
osmium mono(bipyridyl) dicarbonyl [101], rhodium bis(bipyridyl)
[102] etc. These metal complexes with catalysts are used in
heterogeneous systems and in these systems, the reactions are
initiated by lowering the catalyst to generate a complex metal
with low valency which further reacts with CO2 . Photosensitizer
provides the electron for the generation of reduced catalysts. The
most commonly used metal complexes for the photochemical
conversion of CO2 are Ruthenium and (I) and Ruthenium (II).
The main benefits of utilizing Re (I) complexes are high
product selectivity and high efficiency of reduction. Their uti-
lization as a catalyst in photochemical reactions only yields the
CO and also restricts the generation of hydrogen. In the 1980s,
these complexes were utilized as a catalyst in photochemical
systems. It was concluded in [103] that when the combination
of DMF-triethanolamine solution and Re(I) complexes yielded
high selectivity and production of CO and the stability of the
photocatalysis as well CO2 reduction can be enhanced by the ad-
dition of chloride and bromide in that solution. The CO2 reduction
found to be less along with the generation of formate complexes
when chloride and bromide were not added. The function of
Triethanolamine as a reductant was significant.
The Ru (II) can be demonstrated as trans(Cl)-Ru(bpy)(CO)2 Cl2 ,
cis-[Ru(bpy)2 (CO)X]n + , [Ru (tpy)(bpy)X]n + and as a catalyst in CO2
reduction, Ruthenium (II) complexes are of great interest and re-
ceived remarkable attention. They absorb visible light and dissoci-
ation of CO ligand occurs when Ru complexes come in contact with
UV light, hence, photosensitizers are required for Ru (II) photocata-
lyst [104]. Ru (II) catalysts particularly convert CO2 into CO and for-
mate in the aqueous mixture and generate hydrogen as a reduction
by-product [105] while Re (I) complexes exclusively generate CO.
Co (II) complexes also act as a catalyst in photochemistry
and there two types are [CO (macrocycle)]2+ and [CO(NN̂)n]2+ .
In photocatalytic reactions, they are utilized to reduce CO2 into
CO and H2 . The capability of the photocatalytic process is highly
influenced by the intramolecular bonding of hydrogen, redox
potential, and macrocycle in [CO (macrocycle)]2+ complexes. In [CO
(NN̂)n]2+ complexes, the photocatalytic activity is extended by
the presence of NN̂ in the solution process [106]. Other than the
above-mentioned metal complexes, Ir (III) and Ni (II) complexes
are also being used [107,108].
4.1.3. Photoreactors
For the development of solar fuels by CO2 reduction, there
is an increasing interest to develop and improve the mechanism
and methods for the transformation of solar energy. The design
modification of photoreactors is a new topic of interest due to its
direct effect on the efficiency of CO2 transformation.
Photoreactor
Slurry Fixed bed
Membrane
1- Thin film
1- Internally illuminated 1- Fixed bed
2- Horizontal
2- Externally illuminated 2- Slurry
3- Optical fiber
4- Packed bed
5- Cylindrical
6- Monolith
Fig. 8. Different types of photoreactors.
The design of photoreactor mainly relies on light source, con-
struction material of photoreactor and heat exchange because the
performance of photoreactor is directly affected by these factors.
A crucial step for efficiency determination of photoreactor is as a
light source. In the photocatalytic process, the range of wavelength
and intensity are measured by the light source. The photoreactor
must have great capability for photon segregation [109]. The ma-
terials utilized for the construction of photoreactors are of many
types but mainly are stainless steel, quartz, and Pyrex. Quartz is
preferred over other materials for transmission of light due to
its transparency range in the ultraviolet region. Heat exchange is
also an important parameter for the designing of photoreactor
since light is the main ingredient of photoreactors so, mixing and
flow characteristics must be carefully designed for the appropriate
contact between reactants and the catalysts.
Depending upon the phase of reactants and catalysts, the pho-
toreactors have two types: two phase or three-phase. The phase
of the catalyst may be liquid or gas in two-phase photoreactors,
on the other hand, three-phase photoreactors usually employ
reactants in gas or liquid phase with a catalyst in the solid phase.
The further classification of photoreactors is shown in the Fig. 8.
4.1.4. Electron donor
The commonly used donors of the electron in the photo-
chemical conversion of CO2 are amines like triethanolamine
and triethylamine, dihydro-1H-benzo[d]imidazole derivatives and
ascorbate, etc. In the oxidation reaction of one-electron, a single
proton is discharged by these donors to suppress the back trans-
port of electron from the single-electron reduction stage of the
photosensitizer to single-electron oxidation species of the donor
of the electron. That discharged proton has a powerful reductive
capability to reduce catalyst, photosensitizer and the intermediates
produced. The electron donors serve as oxidative species with
two-electron in the photocatalytic system [110].
4.1.5. Catalyst
The function of a catalyst is to receive and accumulate the
electron which is emitted from the photosensitizer for the ac-
tivation of CO2 by means of bonding. A catalyst must have the
ability to stifle the evolvement of hydrogen when it converges
with CO2 conversion reactions [111]. The presence of intermediates
and catalysts under the conditions of photo-irradiation is quite
necessary for the excitation of the photocatalytic process [112].
The utilization of pure catalysts, as well as their doping, is an
important area of research. Several materials in its original form
don’t perform efficiently but when they are doped with other
materials, they exhibit good conversion rates. For instance, TiO2
catalyst can’t efficiently convert CO2 and has poor selectivity due
to inadequate charge recombination and band gap (Fig. 9). But
 A. Mustafa, B.G. Lougou and Y. Shuai et al. / Journal of Energy Chemistry 49 (2020) 96–123 105

Methane production (P mol/g cat )

Methane production (P mol/g cat )
16
14 10
12 8
10
6
8 Ni-TiO2 (1.0 mol%)
6 Ni-TiO2 (0.5 mol%) 4 Ni-TiO2 (1.0 mol%)
Ni-TiO2 (0.1 mol%) Ni-TiO2 (0.5 mol%)
4
TiO2 2 Ni-TiO2 (0.1 mol%)
2 TiO2
0 0
0 10 20 30 40 50 60 70 120 130 140 150 160 170 180 190
Reaction time (min) Reaction time (min)

Methane production (P mol/g cat )

Ni-TiO2 (1.0 mol%)
8 Ni-TiO2 (0.5 mol%)
Ni-TiO2 (0.1 mol%)
TiO2
6

0
0 10 20 30 40 50 60
Reaction time (min)

Fig. 9. Reduction of CO2 by only TiO2 and with different amounts of nickel [114].

Photocatalysts
Surface Surface un-
supported modified
catalyst catalyst

Non-oxide Oxide Non-oxide Oxide

catalyst catalyst catalyst catalyst

Sensitized Sensitized

Flexible Flexible
substrate substrate

Metal doped Metal doped

Non-Metal Non-metal
doped doped

Fig. 10. Categorization of photocatalysts for CO2 conversion.

when it is doped with Ni, the production of methane increases and hard to comprehend. Broadly, there are three stages for use of
significantly because Ni narrows down the bandgap of TiO2 [113]. semiconductors in photocatalytic CO2 reduction, (1) production of
But when it is doped with Ni, the production of methane charge-carriers (2) dissociation and migration of pair of electron
increases significantly because Ni narrows down the bandgap and hole and (3) redox reaction. The working of photocatalytic
of TiO2 [113]. Generally, photocatalytic CO2 conversion primarily CO2 conversion using semiconductor has also been described in
depends on the catalyst type (Fig. 10) and catalytic systems can be Section 4.1.1. The use of several kinds of semiconductors in pho-
classified into three main classes: semiconductor, hybrid systems, tocatalytic CO2 conversion has been reported and titanium dioxide
and complexes of transition metals. Each catalytic system has a has been extensively used [3]. A semiconductor will act as a
distinct reaction route and produces a particular product. catalyst if its band edge is more negative compared to the CO2
reduction potential for a specific product [115]. While the VB po-
4.1.5.1. Catalysts based on semiconductors. The use of semiconduc- tential should be positive with regard to water oxidation potential.
tors in photocatalytic CO2 conversion is a complex mechanism The heterosturucturing approach is the most efficient pathway
106 A. Mustafa, B.G. Lougou and Y. Shuai et al. / Journal of Energy Chemistry 49 (2020) 96–123
to increase the semiconductor catalytic performance in photo-
catalytic CO2 conversion. Several heterostructuring approaches
like sensitization, co-catalyst system, charge-carrier transfer and
indirect Z-scheme acquired a lot of attention due to their ability
to enhance the performance of the semiconductor [116].
4.1.5.2. Hybrid system. This is another type of catalytic system
that received huge attention for photocatalytic CO2 conversion. In
some studies, photocatalysts plus semiconductors with different
Z-scheme and sensitizer are categorized as hybrid systems. The
unique integration of semiconductors and TMC with enzymes to
perform the catalytic conversion is of practical interest because
the enzyme has a strong ability of catalysis offering high efficiency
and selectivity [117]. In this catalytic system, electrons required for
CO2 reduction are provided by sensitizers which can possibly be a
metal complex or semiconductor. The hybrid system utilizing the
suitable enzyme experiences efficient production of multi-electron
transport products like methane, methanol, formaldehyde and
formic acid [118]. It is observed that the nature of the donor
and the shape and size of CdS affects the catalytic activity of the
hybrid system. Many efforts have been devoted to investigating
the integration of photoactive materials and enzymes.
4.1.5.3. Catalysts based on transition metal complex (TMC). This type
of catalyst is frequently used in photocatalytic CO2 conversion be-
cause they have long-lasting excited states and strong capability
of absorbing most part of the solar radiation [119]. Moreover,
their light absorption capability and photocatalytic activity can
be changed by altering their structures. It should be noted that
photocatalytic CO2 conversion using transitional metal complex
(TMC) is strongly influenced by reactivity and structures of the
(metal) complex. Mostly, three major steps are involved in con-
version when the reductive quenching route is employed. Firstly,
photocatalyst absorbs the energy of light to generate excited states
through metal-to-ligand charge transfer [120]. The metal complex
works as both photosensitizer and catalyst. Secondly, excited states
will go through a reductive quenching reaction with the donor to
form a reduced complex that can be re-oxidized to photocatalyst
[121]. There are several kinds of metal complexes reported that
can be photodegraded by light radiation [122].
The poor chemical stability is the major barrier in commercial-
scale use of these metal complexes. Additionally, TMC commonly
doesn’t facilitate multiple electron-reactions because excitation
(done) by a photon can only yield a single electron [120].
4.1.5.4. Single-atom catalysts. Single-atom catalysts (SACs) having
dispersed metal active centers have recently acquired growing
attention for a large class of catalytic reactions. They exhibit
extraordinary performance in CO2 conversion, and their distinctive
structures are attractive for intermediates transfer, production of
required products, and activation of CO2 molecule. Recent improve-
ments in computational modeling, characterization techniques, and
synthetic methodologies have aided the development of numerous
single-atom catalysts. SACs mostly demonstrate remarkable perfor-
mance in a number of industrially crucial chemical reactions like
photochemical, thermochemical and electrochemical conversions.
A SAC design has special electronic and geometric characteristics
which facilitate hundred percent atom usage. The SACs reactivity
is highly useful in chemo-selective hydrogenation of nitroarenes.
Recent research investigations have widely extended the space
engaged by commonly used SACs. The early examples of SACs
were oxide-facilitated noble metal SACs [123] and then single
transition metal atoms grouped to N-doped carbon [124]. The
SACs preparing technologies incorporate those approaches that can
utilize materials with significant densities of surface single-atoms.
The recent rapid development indicates that such SACs will be
developed which will be robust having high activity, selectivity
and stability for industrially crucial reactions [125].
4.1.6. Photosensitizer
The redox photosensitizers perform a significant role in several
photocatalytic reactions, accumulating photons for mediation of a
hole or electron to catalyst from a donor. An efficient photosensi-
tizer should have strong optical absorption capability at extensive
wavelength ranges, mainly in the visible region and long lifetime
to react with the electron acceptor or donor. Ru (II) complexes -
[Ru(NN̂)3 ]2+ - are the most extensively employed photosensitizer
in different reduction-oxidation reactions e.g. photocatalytic CO2
transformation, production of O2 or H2 from H2 O [126]. The disso-
ciation of NN̂ in the reduction reaction is the major disadvantage
of using these complexes in the photocatalytic system. Neverthe-
less, the dissociated species can work like a catalyst for carbon
dioxide conversion but the process takes place in the absence
of catalyst which causes the dispersal of the product. Recently,
Osmium (II) complexes are being employed because they are
powerful electron donors and have strong absorption capability at
large wavelengths close to the visible region. The other used PS
are cyclometalated Ir (III), Os (II) diamine, Re(I) carbonyl diamine,
and Ru (II) diamine [89].
4.1.7. Future perspective
It is evident from the above information that promising de-
velopment has been accomplished towards the photocatalytic CO2
transformation. However, the currently used approaches are not
sufficient to date and more efforts are needed to enhance the ef-
ficiencies of the solar-fuel conversion. Based on the photocatalysis
process, there is a very small number of examples of chemical
systems that operate efficiently. The photon efficiency of those ma-
terials which are used in this technology and achievable conversion
rates are insufficient. Additionally, photoreactors frequently induce
operational inefficiencies in the overall system and consequently
practical applications of photoreactors are limited. In this tech-
nology, the development of visible-light-sensitive photocatalysts
which play an important role in the recycling of large concentra-
tions of CO2 is the immediate need. The ultimate objective is to
use solar radiation as the only input source of energy to achieve
a high CO2 reduction rate. Because visible light contains most part
of the energy of the solar spectrum, it behooves researchers to
regard photocatalysts as sunlight sensitive [2,127]. The researches
may be conducted for the better designing of co-catalysts to
control and enhance the product selectivity and uniform sensiti-
zation of co-catalysts of the complete nanotube arrangement for
improved conversion rates. The photocatalytic CO2 reduction may
become a crucial stepping stone for the production of solar fuels,
however, much development needs to be acquired before it could
be adopted efficiently on an industrial scale. It can be said that
game-changing reduction rates have not yet been attained and this
approach has a long path to go to attain its full potential to effec-
tively compete with other approaches for solar-fuel conversion.
4.2. Biochemical conversion
The conversion of solar energy into chemicals through natural
photosynthesis for the generation of biofuels is another pathway
and it is an attractive route to transform CO2 into fuels and
chemicals via biological conversion (Fig. 11). Photosynthesis can
contribute significantly to CO2 conversion from several industrial
sources like chemical industries and power plants etc. since they
can be employed in a renewable and sustainable manner. Bio-fuels,
food and valuable chemicals can be generated by the direct or
indirect conversion of biomass. Importantly, biomass has many
hydrogen elements and metals of alkali when being a resource of
 A. Mustafa, B.G. Lougou and Y. Shuai et al. / Journal of Energy Chemistry 49 (2020) 96–123
Alternative fuel consumption (%)
20
15 Biofuel
Natural gas
10
Hydrogen
5 vivo mechanism, tremendous efforts have been devoted by the
0 Formate is a chemical of high importance and used for the
2000 2010 2020 2030 2040 2050
Years
Fig. 11. Projection of biofuel utilization as energy source [33].
energy, the conversion of biomass involves the same mechanism
as gasification and liquefication. If the conversion of biomass is
carried out with a process of coal chemical generation, it can
accomplish synergies from the perspective of energy matching
and element supplement which will be helpful in the reduction
of fossil fuel usage as well as improvement of energy efficiency.
Additionally, the emission of CO2 will be cut down by the use of a
biological system [128].
4.2.1. Enzymatic conversion of CO2
Naturally, the CO2 fixation into organic components is not only
the beginning of biological evolution but it is also a life prereq-
uisite. For efficient biological evolution, six major pathways are
adopted by cells and these pathways provide encouraging reaction
mechanisms for CO2 conversion. For the fixation of CO2 , lyases,
oxidoreductases, and synthases contribute significantly to alter
the direction and accelerate the reaction in all six pathways. The
physicochemical microenvironments are created by cells to stabi-
lize these complex metabolic processes (six pathways) which also
avoid the deactivation of enzymes. The vitro-based CO2 conversion
whereby an enzyme may offer an efficient route to develop CO2
capture, separation, and utilization is of practical interest [129].
The direct use of a single enzyme (synthases, lyases or oxi-
doreductases) for the accomplishment of CO2 conversion/fixation
reaction for the catalytic conversion of CO2 in vitro is quite a
feasible approach for CO2 capture, separation, and utilization. The
use of Synthases in vitro application is not suitable because it
involves CoA-substrates and the obtained products are useless and
invaluable in our daily lives. On the other hand, he lyases and oxi-
doreductases are obtained from particular organisms and their use
help in the successful synthetization of notable materials, fuels,
and chemicals such as methane, formate, bicarbonate, and CO.
4.2.1.1. Transformation of CO2 by oxidoreductases. The transfer of
electrons from one molecule to another is catalyzed by oxidore-
ductase and the objective of using this enzyme is to obtain carbon-
based energy sources by reducing the oxidation state of the carbon.
CO is also undoubtedly an important fuel and chemical and
considered as the important feedstock for several synthetic mech-
anisms like Cativa, Fischer-Tropsch and Monsanto processes. It also
has high fuel value and can readily be transformed into methanol.
Naturally, [NiFe] CODH catalyzes the conversion between CO2 and
CO and there are centers of Ni and Fe on the active faces of [NiFe]
CODH. The [3Fe–4S] cluster connects and positions these centers
so that they remain close to each other. In the mechanism of CO2
reduction via [NiFe] CODH, reduced metal (Ni) is formed by the
transfer of an electron, accompanied by a chemical stage in which
bonding between Ni center and CO2 establishes to generate Ni-C
bond. Subsequently, a hydrogen bond is formed between histidine
residue and oxygen atoms. The water loss from Fe1 causes the
production of CO2 complex whereby O1 is bound to Fe1 and lysine
107
residue, generates a hydrogen bond. NiII CO species are formed due
to the loss of water and the splitting of the C–O1 bond. NiII CO
species quickly liberate CO and absorbs water for the completion
of the catalytic cycle. In enzymatic conversion, the binding and
catalysis of CO2 incorporates the proper location of residues and
activation by the [NiFe] centers and due to this phenomenon in
researchers to establish efficient vitro-based CO2 conversion
production of hydrogen and methanol, fuel cells and formic acid.
In vivo-based CO2 fixation, the catalysis carried out by Fate DH
with the NADH cofactor can convert CO2 into formate and it is
simply the transfer of hydride from the C4 atom to C atom carbon
dioxide. To facilitate this transfer, both NADH and CO2 are placed
in close proximity. NAD+ along with a bipolar arrangement is
left after the production of formate and is basically the reductive
acetyl-CoA route [129–131].
4.2.1.2. Transformation of CO2 by lyases. Unlike oxidation or hy-
drolysis, the splitting of the chemical bond is catalyzed by lyases
and then a new structure or double bond is formed. The catalysis
of Michael addition (a reverse reaction) using lyase enzyme is
normally present in cells and carboxylation of molecules along
with CO2 yields Valuable products. In nature, carbonic anhydrase
(CA) is commonly found in algae, mammals, plants, and bacteria
and plays an important role in the interconversion of CO2 and
bicarbonates. Additionally, it maintains the balance of acid-base
in blood and other cells of the body. For example, [Zn] CA is used
for CO2 hydration and in this mechanism, the active sites of the
metal CA comprised of Zn2+ ion are integrated with hydroxide and
histidine residues. The formation of hydroxide ligand takes place
when water is deprotonated by interacting with a weak base. This
hydroxide ligand then goes through a nucleophilic attack on the C
atom to produce bicarbonates and the molecules of bicarbonates
are stabilized by H-bonding. A catalyst could be regenerated by
the displacement of bicarbonate due to water. The specific location
of CO2 in the hydrophobic section, water activation because of
binding to Zn2+ and sites of H-boding are the key factors of this
method. Other than the turnover frequency of metal CA, it is as
strong as ~106 s−1 . In capture and separation of CO2 , carbonic
anhydrase has shown great potential due to its high efficiency
of catalysis and CA has been used, so far, for three approaches:
absorption, precipitation and membrane separation [129,132].
There exist many other kinds of lyases - other than CA - in cells
that have been used to catalyze the carboxylation of unprocessed
material accompanied by CO2 in vitro. The main objective of
using these lyases (decarboxylases) is to turn toxic materials into
hydrophilic and reduce their affinity for lipophilic biological com-
pounds. It would be interesting to note that these decarboxylases
are not enzymes included in those six major pathways and are
considered as enzymes for catalysis of the decarboxylation process.
In the past, researches have been conducted on the investigations
of decarboxylases since substrate carboxylation with CO2 can
reversibly be catalyzed by these lyases [129,132].
4.2.1.3. Transformation of CO2 by microbes. Different microbes such
as cyanobacteria and algae have the ability to assimilate CO2 . The
different inbuilt properties of these microbes like stability, toler-
ance capacity and production of metabolites are generally not suit-
able for CO2 transformation so their phenotype characteristics are
enhanced to make them suitable for the conversion process. The
details of a few common microbes are added in the next section.
Cyanobacteria are beneficial organisms for several industrial-
scale applications and have great potential because they are nat-
urally convertible, require simple nutrients and exhibit rapid cell
growth. They can be used for biofuel generation since they have
108 A. Mustafa, B.G. Lougou and Y. Shuai et al. / Journal of Energy Chemistry 49 (2020) 96–123
Table 1. Algae and their capacity of CO2 conversion.
Type of algae Conversion of CO2
(μmol/(g h))
Aphanothece microscopic Nageli 136–1364
Chlorella emersonii 7–73
Chlorella Kessleri 16–155
Chlorella sp. 66–663
Chlorella sp. 109–1086
Chlorella vulgaris 591–5909
Chlorella vulgaris 335–3352
Chlorella sp. 125–1246
Euglena gracilis 36–362
Microcystis aeruginosa 49–493
Nannochloris sp 57–569
Scenedesmus obliquus 19–188
Scenedesmus sp. 39–387
Scenedesmus obliquus 52–521
Spirulina sp. 36–358
natural diversity and can be grown at different locations, even not
suitable for agriculture. The transportation costs can be reduced by
producing biofuel at places close to the location of fuel consump-
tion [133]. Cyanobacteria are found very helpful for the reduction
of CO2 concentration and enhancement of oxygen contents. Gen-
erally, they are accountable for 20%–30% photosynthetic activity.
Engineered cyanobacteria are utilized to produce ethanol, and iso-
prene. In cyanobacteria, carbon utilization is mainly carried out by
RuBisco, though, its affinity is low for CO2 but has higher survival
rates due to the activity of carbonic anhydrase. The fixing CO2
efficiency of algae is low but their biomass production is higher as
compared to cyanobacteria. The RuBisco enzyme can be genetically
engineered to increase its affinity and biomass yield [89].
4.2.2. Transformation of CO2 by algae
Microalgae can be utilized to capture CO2 from different
sources such as industrial processes, atmosphere, and soluble
carbonates, therefore, they can be used for economically and
technically feasible productions of biofuels (Table 1). For biodiesel,
microalgae are considered the most attractive alternative source
and many current studies and efforts are carried out on microalgae
due to rich contents of oil and high growth rate.
Sugars, oils and bioactive composites are also contained by al-
gae. Other than fuels, the improvement in technologies for efficient
algal biodiesel generation is also suitable for biogas, bioethanol,
biohydrogen and biomass-to-liquid technologies employing fast-
growing microalgae. Additionally, other useful products e.g., animal
feed, biopolymers, and proteins can be generated during this pro-
cess. Due to the small harvesting cycle, multiple harvests with
more yields can be produced from algae. Moreover, the cultivation
of algal can be carried out on non-arable or marginal land with
the use of wastewater [149].
4.2.3. Future perspective
Biochemical processing of CO2 has been an emerging technol-
ogy to mitigate global warming and produce chemicals and fuels.
Based on the natural CO2 metabolic mechanism, two types of
enzymes are being used successfully for CO2 transformation into
value-added products. There have been reported several methods
for efficiency enhancement of enzyme-based catalytic processes.
Although a lot of work has been done, significant technical ad-
vances and investigations are required to employ enzymes for
CO2 conversion on large-scale. The enzymes which are being
used nowadays can’t be successfully used on a commercial scale
because they are expensive and possess high sensitivities with
respect to the environment. Some developed techniques and their
scaling up to commercial level is highly needed. Enzymatic trans-
formation of CO2 involves reactions that are cofactor dependent,
Carbon Monoxide
Reference (CO)
[134]
(HCOOH) or formate
[135] (HCOO-)
[136]
Electrochemical reduction of CO2
[137] (H2C2O4) or (C2O42-)
[138]
[139]
[140]
[141]
Methanol (CH3OH)
[142]
[143] Formaldehyde
[144] (CH2O)
[145]
[146]
[147] Methane (CH4)
[148]
Ethanol
(CH3CH2OH)
Ethylene
(CH2CH2)
Fig. 12. Products generated by electrochemical transformation of CO2 .
the price of these cofactors is high plus their availability is less
which restricts their utilization on large-scale applications. Hence,
more researches should be devoted to not only excavate new low
input energy consuming and inexpensive techniques for the effec-
tive reuse and regeneration of co-factor but enzymatic reactions
pathways without using cofactors may also be developed.
Nevertheless, biofuel resource has huge inherent potential, the
large-scale production of algae for the generation of biofuels is
still in progress. The identification and development of economical
methods for the growth of oil-rich algae and reduction of cost us-
ing integrated bio-refineries to generate biogas, biodiesel, electrical
power and animal feed can significantly improve the potential of
this technology. Moreover, the use of nutrients from industrial
wastewater and municipal sewage to minimize the consumption
of fertilizers for algae growth, determination of area-efficient
methods for CO2 capture and development of energy-efficient
and inexpensive harvesting techniques can play an extremely
important role to make this technology commercially viable and
meet the energy demands.
4.3. Electrochemical conversion
The electrochemical conversion of CO2 has gained great at-
tention due to its various advantages. This process is controlled
through reaction temperature and electrode potentials and the
overall consumption can be reduced because electrolytes can
be completely recycled. Additionally, this conversion process is
modular, compact, on-demand and can easily be scaled up for
different applications and electricity required to drive the system
can be acquired without producing new CO2 [150].
However, there are challenges, as well. For instance, slow
kinetics of CO2 reduction and small energy efficiencies even at
higher electrode potential. The electrochemical reduction process
also consumes high energies. The electrocatalysts exhibit poor per-
formance in terms of stability and catalytic activity. The reaction
mechanisms for electro-reduction of CO2 are very complicated
even if catalysts are used and generally, catalysts being used
are not much active. Depending upon the reaction medium and
material of the catalysts, the electrochemical transformation of
CO2 yields different kinds of products (Fig. 12) via two, four, six
and eight electron reduction routes in electrode configurations.
The products that can be produced via electrochemical transfor-
 A. Mustafa, B.G. Lougou and Y. Shuai et al. / Journal of Energy Chemistry 49 (2020) 96–123
Types of
electrolysis Cell
(SPCEC)
(SOEC) Alkaline
Solid
Solid oxide electrolysis
proton conducting
electrolysis cell cell
electrolysis cell
Fig. 13. Types of the electrolysis cell.
mation of CO2 are influenced by the materials of electrode and
catalysts, pressure and concentration of CO2 , reaction medium and
temperature, pH, buffer strength and electrolyte solution [17].
The design of the electrochemical cell is an essential aspect
that has an impact on the process of CO2 reduction, ascertain
Faradaic efficiency, stability, and current density. Electrolysis cells
are mainly of three types (Figs. 13 and 14); SOEC and SPCEC are
used for the combined/pure and combined transformation of H2 O
and CO2 , respectively. While water splitting is carried out in the
third type of cell. Since the first report on CO2 reduction in 1980,
different cell designs have been proposed for efficient reduction.
Currently, reactor vessels can be generally categorized into H-type
cells, microfluid cells, SOEC, DEMS cells, and polymer electrolyte
membrane flow cell.
4.3.1. Catalysts
As discussed in section 4.1.1, the function of a catalyst is to pro-
ceed with the selective production of the desired product and to
connect and activate CO2 to minimize the high overpotentials. The
choice of catalyst is highly important for the selective production
of different products on a commercial scale. In CO2 electro-
reduction, elements of transition metal and related compounds are
commonly used as electrocatalyst due to the presence of active
electrons and vacant orbits which energetically assist the bonding
between CO2 and metal. Four distinct streams of metal catalysts
are significantly used for the electrochemical transformation of
CO2 .
At ambient temperature and pressure, copper catalysts have a
unique capability of CO2 reduction into hydrocarbons. Modification
of Cu surfaces has exhibited an increase in selectivity for hydrocar-
bon production and reduction of overpotential. Cu electrode coated
with Cu nanoparticles has also shown impressive selectivity for
hydrocarbon production [151]. Formic acid with higher Faradaic ef-
ficiency can be produced by using metals for hydrogen production
e.g. Pb, Hg. MOF catalysts, metal oxides, and alloys significantly
contribute to the production of HCOOH. Methanol is a valuable
chemical due to its many applications. It can be produced by
reduction of CO2 through different processes such as heterogenous
(more successful) and electrochemical methods (low faradic effi-
ciencies) [152]. Carbon monoxide can be generated efficiently on
several metal electrodes and syngas can be formed when it com-
bines with H2 through the Fischer-Tropsch process. The negative
potential for CO production is higher than H2 so most researches
focus on enhanced CO production using more developed systems.
The use of nanoparticles is also efficient for CO productions [153].
4.3.2. Components of an electrochemical reduction system
4.3.2.1. Electrolyte. Although electrolytes strongly affect every
electrochemical system, few studies to date have paid attention to
the effects of its composition [153]. The heterogeneous process for
the electrochemical transformation of CO2 generally uses aqueous
electrolytes which are composed of anions (bicarbonate, hydroxide,
and halide) and cations (Sodium+, Potassium+). These salts are
frequently utilized because they possess high conductivities in
109
water, and proton needed for proton transfer in the electrochem-
ical process is offered by the water present in the electrolytes
[153]. The selection of electrolyte strongly affects the efficiency
of CO2 reduction, current density, and product selectivity. For the
same electrolyte, the selection of anion will affect the pH of the
solution at the Cu electrode which in turn, will strongly influence
the amounts of products generated. Similarly, the selection of
cation for bicarbonates (electrolyte) will influence the production
distribution on the Cu electrode. The buffering capacity of anion
and size of cation also have impact on pH and overpotential (the
difference in voltages of electrodes between thermodynamic and
actual world values to proceed a reaction), respectively [154,155].
4.3.2.2. Electrode. Electrodes also play an important role in each
heterogeneous electrochemical reduction of CO2 . An electrode is
composed of the catalyst layer and baking substrate of performing
multiple functions like reactant gas delivery to the catalysts, trans-
fer of product produced from catalyst to electrolyte membrane.
Enhancing electrode and reactor performance requires optimiza-
tion of such processes which depend on the intricate structure
of the electrode. The use of electrodes made up of planar metals
(Cu, AU, Ni, Sn, Ag, Ti, etc.) is restricted due to lower CO2 concen-
trations and surface area because of insufficient CO2 solubility in
aqueous electrolytes [156].
4.3.2.3. Gas adsorbent material. Conjugated microporous Polymer
(CMP) is widely used for adsorption of gas and capacity appli-
cations owing to their micro-porosity associated with the large
surface zone. The application of the above-mentioned polymers in
CO2 reduction is another area of advancement and few references
are available about their employment as terminals. The feasible
congregate of the multipurpose cathode is to provoke the impor-
tance to generate efficiency, selectivity, and effectiveness of the
electrocatalytic CO2 transformation. Desired morphology, sufficient
surface territory, prevalent usefulness, and sane pore-estimate
dispersion are the important variables for the transportation of
electron and mass and energy of substance response. Metal-
organic frameworks in comparison with other permeable materials
exhibit exceptional sizes of the tunable pore, multifunctionality,
and permeable structure which strengthen them to compete with
other permeable materials in different applications. Additionally,
their design is helpful for the definite and direct legitimization of
the associated structure-property relationship which is considered
an important aspect of materials enhancement. The exceptional
advancement of these MOFs has gained attention from many areas
and they are animating the progress of wave of frequent exuber-
ance applications. The extraordinary limit of gas storing of MOFs
at a different range of temperatures has resulted in their rapid de-
velopment, making enormous adsorbents highly useful in energy
components, power offices, vehicles, and gas tank [89,157,158].
4.3.3. CO2 conversion by microbial electrolysis
The products that are formed as a result of electrochemical
CO2 transformation are largely C1 species such as CO and HCOOH.
Although several electrocatalysts can be utilized to achieve the
coupling of C–C which is a difficult job to accomplish, microbial
electrolysis is preferably being used for this sake [159]. It is a
novel approach for transforming renewable sources of energy
such as solar and wind energy into useful chemicals and fuels
from CO2 . In this approach, microbes are used to convert CO2
into organic species with electrons (obtained from cathode). For
the development of microbial electrolysis, microbes and materials
of the electrode are considered important factors. Mixed and
pure cultures are two types, utilized for CO2 transformation in
microbial electrolysis. The mixed consortium is mainly separated
from sludge or wastewater, etc. and yields acetate which is a
110 A. Mustafa, B.G. Lougou and Y. Shuai et al. / Journal of Energy Chemistry 49 (2020) 96–123

Fig. 14. Working principles of SOEC and SPCEC [51].

base for the formation of hydrogen, formate, and methane. In the Table 2. Metals and their end products.
case of a mixed consortium, there is no issue of cell apoptosis Metals End product
and the need for sterile conditions [160]. In microbial electrolysis,
Ru CH3 OH
cathodes are made up of carbon-based materials and cathode Ag, Au CO
improvements like surface chemistry and area are in progress to Zn CO + HCOOH
optimize microbial electrolysis. This approach has good potential Cu CH4 , H2 , C2 H2 , CO, HCOOH subjected to the conditions
for CO2 transformation and researches is being conducted for Cd, ln, Pb, Sn HCOOH + CO

its development. The development of efficient and inexpensive

cathodes can enhance the effectivity of this system. Table 3. Catalysis of electrodes by different metals with aqueous and nonaqueous
electrolytes.
4.3.4. CO2 conversion by photoelectrochemical cell Metal End result
An emerging technology for CO2 conversion is photoelectro-
Aqueous electrolyte Nonaqueous
chemical cell (PEC). It combines electrocatalysis and photocatalysis
electrolyte
approaches because there are distinct areas of interest of photo-
electric synergistic reduction of CO2 with water. Firstly, the usage sp metals (ln, Sn, Cd, Zn, Cu, CO
Ag, Au)
of solar energy can primarily lower the connected voltage, in this
sp metals (Hg, ln, Sn, Pb) Formate Oxalate
way decreasing the power consumption, and other than this, the d metals (Pt, Pd) CO also HCOOH, HCHO, CO including Ni
load of external predisposition voltage can steer the detachment CH3OH and HC
of holes and electrons (photogenerated), which is a basic advance- d metals (Fe, Cr, Mo, Ti, Nb) Oxalate and CO
d metals (Ru) HC, formaldehyde,
ment deciding the productivity of photocatalysis. Most of the time,
alcohols
the methods frequently embraced for the H2 O portion have been
misused for the conversion of CO2 . The CO2 initiations are con-
Table 4. Electrodes working with aqueous and non-aqueous electrolytes.
voluted as compared to water in many cases. The CO2 reduction
using photogenerated electrons can be an aggressive approach Metal End result
with H2 O reduction, in this route making necessary for these two Aqueous electrolyte
technologies vary sufficiently. The CO2 reduction yields more en- Zn, Au, Ag CO
tangled products than the reduction of H2 O which only produces Cu Hydrocarbons, aldehydes alcohols
H2 . The route of the photoelectrochemical transformation of CO2 to ln, Sn, Hg, Pb Formate
Al, Ga, Group VIII (except Pd) Weak performance
attractive chemicals emphasizes CO2 conversion from early inves-
Non-aqueous electrolyte
tigations to ongoing revelations, underscoring the refinements on Cu, Ag, Au, Sn, ln, Zn CO and CO3 2−
the latest pathways in major comprehension of the structural ef- Ni, Pd, Pt CO only
fects of the cocatalysts and semiconductors on photoelectrochem- Pb, Tl, Hg Oxalate
Al, Ga, Group VIII (except Ni, Pd, Pt) CO and Oxalic
ical CO2 reduction and several products arrangements [161,162].

4.3.5. Impact of different factors on product selectivity

Product selectivity can be mainly determined by the reduction
route and process kinematic which results in the generation of
different chemicals. The electrons are obtained by CO2 either from
cathode or medium in the course of early phases of electrochemi-
cal reduction of CO2 . As a result, an intermediate is formed which
is absorbed by the cathode for the production of desired products.
The nature and type of reaction route influence the electrode
potential, catalyst, electrolyte solution, pH and concentration of
CO2 [163].
The bonding accomplished between carbon and adsorbed an-
ion, increased the electron transfer from anion to carbon dioxide,
hence, initiating the conversion of CO2 when electrode composed
of copper mesh was placed in the solution. The stronger halide
anion adsorption to the electrode help achieve the highest CO2
conversion. The use of cations like cesium and rubidium also
enhances the electrochemical reduction of CO2 to CO. The use
of different metals (for electrodes) and their corresponding end
products are shown in the following Tables 2–5 [164].
It is found highly suitable to employ an electrode made up
of single metal for the electrochemical reduction of CO2 [165]. In
Table 3, the use of particular metals and end products is given.
The different other electrocatalyst materials are also used for the
 A. Mustafa, B.G. Lougou and Y. Shuai et al. / Journal of Energy Chemistry 49 (2020) 96–123 111

Table 5. A summary of experimental conditions, catalytic materials and main products.

Catalyst Type of electrolyte Composition of electrolyte Current density (mA cm−2 ) Pressure/ temperature Main product Reference

Ag Solution + CO2 gas 18% mole EMIMBF4 in water − Ambient/ RT CO (96%) [166]
Pd, Ag and Zn Solution + CO2 gas 10 mM KHCO3 ~200 Ambient/ RT CO (> 90%) [167]
Ag foil CO2 Saturated solution 0.1 M KHCO3 4 (−1.02 V vs RHE) Ambient/ RT CO (90%) [168]
An-Cu CO2 Saturated solution 0.1 M KHCO3 20 (−1.08 V vs. RHE) Ambient/ RT C2 H4 (38.1%) [169]
Cu/Ag CO2 Saturated solution 0.05 M CS2 CO3 − Ambient/ RT C1 and C2 /CO [170]
CoPc CO2 gas Solution + CO2 gas 1 M KOH 150 Ambient/ RT CO (95%) [171]
Graphite/Cu/ C Solution + CO2 gas 7 M KOH ~100 (−0.55 V vs. RHE) Ambient/ RT C2 H4 (70%) [172]
NPs/PTFE
Cu2 O/ZnO Solution + CO2 gas 0.5 M KHCO3 − Ambient/ RT CH3 OH (25.6%) [173]
ln/Pb CO2 Saturated solution 1 M NaHCO3 40 Ambient/RT HCOOH (80%) [174]
Cu NPs CO2 Saturated solution 0.1–0.5 KHCO3 (−1.8 V vs. Ag/AgCl). 1–9 atm /RT C2 H4 + CH4 (45%) [175]
RuPd/Sn CO2 gas Solution + CO2 gas 1 M KOH + 0.5 M KCL ~100 (−0.55 V vs. RHE) Ambient/ RT HCOOH (89%) [176]
CuNp Solution + CO2 gas 1 M KOH ~200 (−0.7 V vs. RHE) Ambient/ RT C2 H4 (46%) [177]
Cu nanocube CO2 Saturated solution 0.25 M KHCO3 68 (−0.96 V vs. RHE) Ambient/ RT C2 (over 60%) [178]
NS-C CO2 Saturated solution 0.1 M KHCO3 2.86 (−0.49 V vs. RHE) Ambient/ RT CO (92%) [179]
Ni/YSZ H2 O - CO mixtures or CO2 –H2 YSZ electrolyte tubes − 750 °C CO [180]

production of specific products with maximum current efficiencies.
The poor water solubility (at STP) restricts the utilization of CO2
in an aqueous solution.
Only small CO2 quantities are available on the surface of the
electrode to procced the reaction. However, this problem can be
overcome by using pressurized CO2 . Metals like ln or Pb generate
more CO while Pb and Cu increase the production of formic acid
at pH 4.0 [164].
4.3.6. Future perspectives
To date, enormous rewards and potential have been accom-
plished by electrochemical CO2 reduction. But this approach is
not mature enough for the production of low carbon fuels on
an industrial scale due to various technological challenges like
high overpotential, the generation of entangled products, material
instability of electrodes, high consumption of energy, small Faradic
efficiencies, kinetic barriers and low CO2 solubility in aqueous
solution. Generally, the biggest challenge is the poor performance
of electrocatalysts because of insufficient stability of catalysts, poor
catalyst activity, and product selectivity. There is no electrocatalyst
available to date for CO2 conversion on a large-scale. Hence, stable
catalysts having high selectivity and catalytic activity should be
developed on priority bases. New approaches and methods for
the activation of CO2 molecule at small values of overpotentials
are needed to effectively transform CO2 into valuable chemicals
and fuels. The novel electrodes should be developed which enable
electrolysis at suitable current densities. Novel electrodes allowing
electrolysis at current densities near to water electrolyzers (which
are commercially available) should be developed, for which elec-
trodes composed of solid oxide become suitable options. Moreover,
it is needed to better understand the mechanistic role of metal
oxides in order to generate the possibility of electrode design with
different compositions. It can be concluded that efforts should be
devoted to the development of durable catalysts as well as opti-
mization of system design should be carried out. Several research
directions in the future may include improvement in stability and
catalytic activity by exploring new electrocatalysts, optimization of
reactors, electrodes and system design for large-scale applications.
4.4. Plasma technology
Many efforts have been devoted to the development of energy-
efficient methods and technologies to convert CO2 in value-added
products. Plasma technology is one of these emerging technologies
which are gaining a lot of interest. Plasma is actually a (partially)
ionized gas and consists of electrons and numerous neutral species
such as different kinds of ions, radicals, molecules, and excited
species. The plasma is an extensively reactive chemical due to
the interaction of the above-mentioned species with each other
[181,182]. The high potential of this technology for the conversion
of CO2 has a huge potential due to the existence of energetic elec-
trons in a plasma. Plasma is generated when gas is broken down
by employing electric power to it, i.e., the generation of positive
ions and electron. Electrons have low weights as compared to
other plasma species and most energy obtained by electrons is
from the electric field. They have higher energies and don’t con-
sume their energy so expeditiously in collision with other species.
Thus, these high energy electrons have the ability to activate the
inert gas by means of excitation, dissociation and ionization and
the species generated by this route, will easily go through other
reactions, producing new molecules. Hence the gas (CO2 ) does
not need to be heated completely. By this approach, endothermic
reactions e.g. DRM or CO2 splitting can take place at moderate
reaction conditions with significant energy consumption. It is not
energy efficient to generate plasma by using electrical power [183].
Microwave plasmas (MW), gliding arc (GA), and dielectric
barrier discharges (DBD) are the most commonly used plasma for
CO2 transformation. Microwave plasma was reported to be most
efficient but under peculiar conditions, which would be appeal-
ing for commercialization, produces a drastic drop in efficiency
[183,184]. The energy efficiency of GA plasma is also comparatively
high at atmospheric pressure. Its energy efficiency was 60% for
conversion of up to 16% (DRM) and 43% for conversion of 18%
(CO2 splitting). DBD plasma is not much energy efficient (2%–10%),
but as indicated for different other applications, energy efficiency
can be improved using a packing of dielectric in the reactor.
Furthermore, its design is very simple and works at atmospheric
pressure, which is highly useful for upscaling. It has already been
shown for the generation of ozone on large-scale and therefore, it
has huge potential for commercialization.
Plasma is also considered the fourth state of matter because
matter converts into solid, liquid, gas and finally plasma and Irving
Langmuir first introduced this term in 1928. Plasma is an ionized
state of matter having at least one unbound electron, making
ions with positive charges. Practically, the degree of ionization of
plasma varies from 100% (completely ionized) to 10−6 (partially
ionized). The presence of excited species in plasma leads to light
emission. Plasmas can be found in many applications such as
microelectronics, material science, environmental and medical.
They are also used as sources of light due to their ability of
emitting light. Other than natural plasma, it can be classified into
fusion plasmas (high temperature) which are actually completely
ionized and gas dischargers (weakly ionized). Another classifica-
tion can be made on the basis of thermal equilibrium. The plasma
temperature can be determined by energies of several species
112 A. Mustafa, B.G. Lougou and Y. Shuai et al. / Journal of Energy Chemistry 49 (2020) 96–123
present in plasma and their different kinds of motion (rotational,
translational and vibrational) [51].
4.4.1. Different plasma technologies for methane – carbon dioxide
reforming
Plasma utilized for methane – carbon dioxide reforming can be
categorized into thermodynamically equilibrium (thermal plasma)
and thermodynamically non-equilibrium plasmas (cold plasma). In
cold plasma, the electrons as compared to other species possess
more kinetic energies and plasma average temperature used to
be very close to room temperature. The temperature of electrons
and other species is approximately the same (having a range of
10 0 0 K). Since electron density is higher in thermal plasma, be-
cause of the large number of collisions between other species and
electrons, the energy of electron obtained from the electric field
consumes in the heating of other species to reach thermodynamic
equilibrium in both electrons and other species. Thermal plasma
has thermo-chemical and electron-induced chemical reactions.
4.4.2. Reforming of methane-carbon dioxide by cold plasma
Cold plasmas are generally heterogeneous inside the discharge
space resulting in small reaction region which restricts treatment
and conversion capacity. The catalytic process is introduced in
the reforming of methane-carbon dioxide by cold plasma in order
to increase the rate of conversion. In cold plasmas, a catalyst
can be introduced either by placing it (catalyst) in the discharge
space or at the end of discharge space [185]. Different types of
plasmas have been used to reform methane-carbon dioxide and
their characteristics have been included below. At the end of the
section, Table 7 is added which presents a comparison in terms of
conversion rate and products obtained between types of plasma.
4.4.2.1. Microwave discharge. The reactor of microwave plasms in-
corporates waveguides, microwave generator and resonance cavity
placed into a quartz tube whereby chemical reactions are carried
out to produce plasma. This plasma generally operates at a wide
range of pressure and frequencies (GHz). MW discharge exhibits
excellent discharge uniformity and has greater discharger space
as compared to other cold plasmas at atmospheric pressure. The
temperature of particle and electron is approximately 20 0 0 K and
0.4–0.6 eV, respectively in MW discharge [186]. The reforming of
methane-carbon dioxide through MW discharge yields acetylene,
synthesis gas and ethylene. The excessive amount of methane in
feed leads to more hydrocarbons in the conversion process. The
reforming of methane-carbon dioxide through MW discharge. The
chemical reaction is induced by the high temperature of the gas
and the high energy of electrons. Despite all, the equipment used
in MW discharge is bulky and complex and it is problematic to
acquire large equipment favorable for industrial demands.
4.4.2.2. Corona discharge. It is heterogeneous discharge and pro-
duced at atmospheric pressure having a high intensity of electric
field for the decomposition or ionization of feed gas. Corona
discharge incorporates two (irregular) electrode; high curvature
and low curvature (shown in Fig. 15). This discharge is formed as
the electric break down occurs in the vicinity of high -curvature
electrode when the applied voltage surpasses the given limit.
The temperature of gas and electron is approximately 400 K and
3.5–5 eV, respectively in corona discharge [187]. The high density
of electrons (1015–1019 m-3 ) mostly surrounds the high-curvature
electrode. In corona discharge, reaction volume is restricted by
localized breakdown which makes this discharge difficult to obtain
a high treatment capacity in the reforming of methane-carbon
dioxide by this discharge.
Line
electrode
Power
Tube
supply
electrode
Discharge
region
Fig. 15. Schematic diagram of the corona discharge reactor [185].
4.4.2.3. Gliding arc discharge. There are several diverging elec-
trodes made up of metals in the reactor and arc discharge is
produced when high voltage is exerted on the electrode (Fig. 16).
Lesueur et al. patented the principle of this discharge in 1988
and it was further improved by Czernichowski et al. [188]. This
discharge is eminent by arc flame and primarily produces on
the nearest gap, that arc is further extended and its root slides
along the surface of the electrode by drawing of the rapid flow
of employed gas until quenches plasmas downstream. Based upon
the flow rate of gas and discharge power, the GAD can be classified
into cold or thermal plasma [189].
4.4.2.4. Dielectric barrier discharge (DBD). It was first discussed
by Siemens and is also known as silent discharge [190,191]. It is
mainly used to produce ozone and typically incorporates planar
electrodes which are positioned parallelly having a gap of few
millimeters and one of these electrodes has a dielectric cover
which prevents the generation of arc and spark (Fig. 17).
The material of dielectric could be ceramics, glass, polymer,
quartz or any material of small dielectric loss and high strength of
breakdown [187]. At atmospheric pressure, DBD is also a heteroge-
neous discharge and needs alternating voltages for operation. The
temperature of gas and electron is approximately in hundreds K
and 1–10 eV, respectively in DBD [192]. This discharge was utilized
for the reforming of methane-carbon dioxide by many researchers
(Table 6). DBD shows lower conversion rates in most situations
and syngas selectivity are low and products are normally complex.
The reaction performances are not impressive even if the com-
bination of plasma and catalyst is used. The intrinsic features of
DBD cause more production of hydrocarbons in the reforming of
methane-carbon dioxide. In the filar channel, the CH4 molecules
are easily decomposed into radicals of CHx with high density and
energy of the electron. These radicals quickly leave the channel
and move into other region (free-discharge zone) where they
interact to produce hydrocarbons [185].
4.4.2.5. Atmospheric pressure glow discharge (APGD). This discharge
is like an arc and produced by employing some hundred volts
between electrodes [193] using a ballast circuit to prevent the
conversion of glow into the arc (Fig. 18).
 A. Mustafa, B.G. Lougou and Y. Shuai et al. / Journal of Energy Chemistry 49 (2020) 96–123 113

Mixing
chamber

Electric heat
Pure methane
tube
cylinder

Control B
Pure carbon panel
dioxide cylinder Electric
thermocouple

Nozzle

Voltage regulator

Teflon plate

AC power
supply Transformer
Quartz
encloser
Electric
Electrode thermocouple

Mass flow
meter

FT-IR

Hydrogen sensor

Outlet

Fig. 16. Setup of gliding arc discharge [185].

Table 6. Different types of plasma along with their features.

Types of plasma Catalyst H2 /CO2 Conversion of CO2 (%) Major products Reference

DBD CuO/ZnO/Al2 O3 3:1 13.3 methane, methanol [196]

DBD Ni/zeolite 4:1 96 CO, methane [197]
packed-bed DBD Ni-Cex Zr1- x O2 4:1 78 methane [198]
DBD Cu/g-Al2 O3 ,Mn/g-Al2 O3 and Cu-Mn/g-Al2 O3 – 7.5 CO, H2 O, and CH4 [199]
DBD – 1:9–9:1 2–7 CO, H2 O and CH4 [200]
MW discharge – 1:1 – CO, acetylene, methanol, ethylene, [201]
RF discharge – 4:1 26 CO and H2 O, as well as CH4 [202]
MW – 3:1 82 CO, H2 O, C2 H4 [203]
MW Ni/TiO2 1:9 23 CO [204]
Surface discharge – 1:1 15 CO [205]

The ‘glow’ demonstrates that the discharge plasma is luminous
contrary to the dark discharge [181]. Glow discharge can work over
a long range of pressure. The electron density is 1018 –1019 m−3
and the temperature of gas and electron is approximately in
20 0 0 K and 1–2 eV, respectively in APGD [194,195]. The efficiency
of energy conversion through the jet of cold plasma is increased
considerably as compared to other types of cold plasmas. This
is obliged to the mode of plasma utilized and design configu-
rations of reactors. An AC jet of cold plasma with a frequency
of 20 kHz has high plasma temperature and density of electron
as compared to DBD and corona discharge. Such high values of
plasma temperature cause catalyst heat up and consequently
increase the synergistic effect of catalyst and plasma, similarly,
high density of electron directly enhances the reforming reaction.
APGD is a promising form of plasma for methane-carbon dioxide
reforming attributable to high density and energy of electron plus
appropriate plasma temperature. However, the enlargement of this
process on a commercial scale is one of the notable challenges.
4.4.3. Thermal plasma
It is a uniform and continuous plasma produced in the path-
way of an electric arc. It is characterized by a high density of elec-
tron (1019 –1020 m−3 ), a high temperature of electron and has dis-
tinct chemical and thermal effects. It has numerous applications
and is widely adopted on the industrial scale [63]. It has several
types, shown below (Fig. 19). Thermal plasma has a high poten-
tial for reforming of methane-carbon dioxide due to chemically
reactive elements and high temperature. In comparison with the
114 A. Mustafa, B.G. Lougou and Y. Shuai et al. / Journal of Energy Chemistry 49 (2020) 96–123

Table 7. Different plasmas with percentage of obtained products at different power.

Type of plasma Feed flux CH4 / Power Conversion Selectivity (%) H2 /CO SE References
(mL/min) CO2 (W) (%) (kJ/mol)

CH4 CO2 CO H2 Acetylene Ethylene

(C2 H2 ) (C2 H4 )
Cold plasmas
MW discharge 200 3/2 30 70.8 68.8 75 – 17.8 4.1 1.5 307 [206]
DC Corona Discharge 60 1/2 63 94.1 77.9 97.1 69.4 – – 0.6 1134 [207]
Corona discharge 43 1/1 46.3 62.4 47.8 66.8 70 15.8 1.5 1.2 1798 [208]
Gliding arc discharge 1000 1/1 190 40 31 62 50 12 – 0.9 608 [209]
DBD and Ni/Al2 O3 30 1/1 130 55.71 33.48 60.9 51.92 10.12 – 1.0 10,385 [210]
DBD 20 1/1 107.4 72.8 44.4 82 70 – – 1.0 7289 [211]
Cold plasma jet and Ni/Al2 O3 8300 4/6 770 60.06 40.35 96.79 96.87 – – 1.0 134 [212]
Thermal plasmas
Bioanode thermal plasma 73,300 4/6 18,000 78.71 64.80 96.79 28.85 / / 0.8 274 [213]
Single anode thermal plasma (H2 ) 21,700 4/6 8500 87.98 84.34 82.27 43.48 / / 0.7 520 [214]
Single anode thermal plasma 33,300 4/6 9600 92.32 82.19 90.15 75.43 / / 0.7 290 [215]
(N2 + Al2 O3 )

High voltage Mixer

electrode
Cold plasma
Product jet reactor
Power
supply

Power
supply Grounded
electrode
CH4 CO2 N2
Catalyst bed

Cool trap

Fig. 18. APGD schematic diagram of the experimental setup [185].

Thermal plasma

Quartz tube
Alternating Radiofrequency
Direct current High frequency
current arc inductively
arc torch capactive torch
torch coupled torch

Fig. 19. Types of thermal plasmas.

Gas
Feed
distributor
Fig. 17. Schematic diagram of the reactor of BDB [185].
aforementioned cold plasmas, reforming of methane-carbon diox-
ide using single-anode TM shows many advantages in terms of
conversion efficiency, selectivity, by-products, and treatment ca-
pacity.
Moreover, in thermal plasma input gas is directly injected into
the plasma jet instead of the discharge region between the two
electrodes. The conversion efficiency and treatment capacity can
be increased if feed gasses are directly added in the discharge
region as plasma producing gas (Fig. 20).
The literature cited in this review (Table 6) shows that thermal
plasmas exhibit higher selectivity, conversion, treatment capacity,
and specific energy. It is quite appropriate to develop this process
for industrial applications.
4.4.4. Hydrogenation of CO2
Owing to the expensive hydrogen, there is limited research on
hydrogenation of CO2 through plasma. Economically viable and
sustainable production of H2 is essential for approaches depending
on the utilization of H2 as co-reactant. However, CO2 hydrogena-
tion through plasma has recently attained a lot of attention.
It can be concluded that CO2 hydrogenation through plasma ex-
hibits poor performance, even if we compare it with CO2 splitting
and DRM. To date, this approach is not much successful because
the combination of hydrogen and carbon dioxide is not favorable
for the production of methanol in the single-step process.
4.4.5. Future perspectives
Different plasma approaches for CO2 transformation have been
discussed in the above sections. Plasma technology has a high
potential for CO2 processing due to high temperature, enthalpy
content, electron density, and treatment capacity. However, there
are several challenges that restrict its wide-scale applications.
 A. Mustafa, B.G. Lougou and Y. Shuai et al. / Journal of Energy Chemistry 49 (2020) 96–123
1.0
CO2
0.9 CH4
Conversion
0.8
0.7
0.6
0.5
0.15 0.20 0.25 0.30
Փ (m3/h/kW)
1.00
0.95
Conversion
CO2
CH4
0.90
0.85
0.80
0.12 0.13 0.14 0.15
Փ (m3/h/kW)
Fig. 20. Experiments performed by ref. [185] to compare the conversion and selectivity for thermal plasma.
A standardized framework is highly needed in data reporting to
enable data comparison inside and outside the plasma technology.
The important standard here is to compare the energy efficiency
and conversions. As far as conversions are concerned, it needs
clear data for diluting agents when utilized, because these agents
significantly affect the plasma process. Moreover, the impact of
gas expansion in plasma operation, which is neglected, but can
tremendously affect data accuracy e.g., the conversions acquired
via GC measurements. Regarding energy efficiency, at first, there
should be no interpretation space about the reported power
(whether it is measured or applied power) and through which
approach this power is acquired. Secondly, there should be an aim
to ascertain the important products along with their selectivities,
to measure the energy efficiency depending upon the reaction en-
thalpy including fuel generating efficiencies. Thirdly, the literature
on power supplies and corresponding efficiencies and optimization
is urgently needed to compare conversion efficiencies (solar to
fuel). Generally, for materials testing for plasma catalysis, reporting
data as well as a framework for experimentation are quite essen-
tial for the development of plasma technology which will highly
assist the plasma community and CO2 transformation community.
Energy efficiency in terms of SEI, it is obvious that mostly
employed SEIs are extremely high, especially when used with
catalysts. To achieve highly efficient energy conversions, low
SEIs (0.1–5 eV) should be targeted. Additionally, because plasma
technology is more susceptible to feed impurities, more inves-
tigations and researches are required towards the impact of gas
compositions on the chemical (noxious by-products, distribution
of products) and physical side.
4.5. Solar thermochemical conversion
Traditional industrial processes rely on hydrocarbons for pro-
ducing fuels and metals and they are highly carbon and energy-
intensive. The depletion of fossil fuels and environmental changes
has led to the development of solar industrial processes. The con-
centrated solar approach provides the opportunity of transforming
solar radiation into electrical, chemical and thermal forms. On the
115
1.0
0.9
0.8
Selectivity
CO
0.7 H2
0.6
0.5
0.4
0.35 0.15 0.20 0.25 0.30 0.35
Փ (m3/h/kW)
1.00
0.95
0.90
Selectivity
H2
0.85 CO
0.80
0.75
0.70
0.16 0.12 0.13 0.14 0.15 0.16
Փ (m3/h/kW)
other hand, the conventionally concentrated approach incorporates
the utilization of solar energy to drive many chemical reactions
[216] in several applications. Solar thermochemical operations
utilize solar energy to drive highly endothermic reactions.
Attempts were directed to switch dependency from fossil fuels
to hydrogen economy after the fuel crisis of 1973. Consequently,
studies on thermochemical decomposition of water to produce
hydrogen were initiated. The oil embargo and high prices of oil
ensured the momentum of investigations on thermochemical
processes for the next decade. However, the number of researches
declined up to the year 20 0 0 due to the stable oil market. With
an emphasis on environmental changes, solar thermochemical
processes again received attention in the mid of the year 20 0 0
and the investigations have been increasing.
4.5.1. Working principle
With the help of solar energy, CO2 can be reduced in many
ways. The most efficient method is the direct uses of sunlight
because it does not require any additional energy and has no
negative impact on the atmosphere [57]. The further two types of
this method are thermal conversion and quantum conversion. In
the former type, firstly solar radiation is absorbed and then work
is extracted. The latter type includes extraction of work directly
from the semiconductor or any other compound which are used
as light absorber [58]. As mentioned before, concentrated solar
energy in the solar thermochemical process is utilized as high-
temperature heat to drive high endothermic reactions. Thermal
dissociation of CO2 which involves only a single step requires high
temperatures and separation techniques to prevent the formation
of an explosive mixture (CO and O2 ) [58,59]. In the multi-step
thermochemical conversion of CO2 , metal oxides are used.
Multi-step CO2 dissociation employing metal oxides in redox
reactions detour the issue of separation and additionally, they
permit operation even at moderate temperatures. In the first step
(endothermic), solar thermal reduction of MOox to M or MOred is
carried out and the second step (exothermic) involves oxidation of
MOred with CO2 to produce CO (Fig. 21), enabling the MOox to be
116 A. Mustafa, B.G. Lougou and Y. Shuai et al. / Journal of Energy Chemistry 49 (2020) 96–123
Fig. 21. Multi-step CO2 dissociation [51].
used again in the first step [217]. M denotes metal e.g., Zn, Fe or
Ce.
The direct utilization of sunlight in solar thermochemical tech-
nology is the main advantage. The concentrating solar technique is
currently used for electricity generation and can be combined with
high-temperature reactors to generate solar fuels on a wide-scale
at a cheap cost and to attain high solar-to-fuel efficiencies [58].
Currently, solar flux ratios (>2 MW m−2 ) can be attained using
a solar dish and tower systems. A comprehensive review related
to solar concentrating approaches can be found in [218]. The
solar thermochemical cycles have the ability to achieve a greater
efficiency compared to those methods which utilize energy vector
or a small portion of the solar-spectrum and are simpler in design
[62,64]. This ability is due to the phenomenon that solar-based
thermal processes work at high temperatures and use the com-
plete solar spectrum and offer a thermodynamically suitable way
to produce solar fuels [51].
4.5.2. Categorization of solar thermochemical processes
In Fig. 22, different types of solar thermochemical processes
are given. Broadly, this process has two types: the production of
industrial products and fuel generation. Many industrial products
(aluminum, zinc, lime, carbon nanotubes) can be produced by
solar thermochemical systems and it has a high potential.
The up-gradation of carbonaceous feed yields synthesis gas and
solar fuels such as hydrogen can be generated by solar thermolysis
incorporated in a thermochemical cycle. Synthesis gas can also be
produced by the combined splitting of water and carbon dioxide
in the thermochemical cycle. The water, accompanied by process
heat, is directly dissociated at high temperatures (190 0–40 0 0 K)
in solar thermolysis. Solar energy can be utilized for gasification
and reforming of methane, biomass, and coal that incarnate solar
energy in the produced gasses. Thermochemical cycles are actually
a chain of chemical reactions that decompose carbon dioxide
and water to generate carbon monoxide or hydrogen respec-
tively. Contrary to solar thermolysis, the chemical reactions in the
thermochemical cycle are carried out at low temperatures (800–
2100 K). Thermochemical cycles are categorized as metal oxide
reduction-oxidation based cycles and multi-step cycles. In metal
oxide-based cycles, hydrogen and oxygen are produced by periodic
oxidation and reduction of redox materials. Depending upon the
material, this type of thermochemical cycle can be further catego-
rized into volatile and non-volatile cycles. While multi-step cycles
involve compounds of chlorine, bromine, and sulfur, etc., and these
elements undergo a chain of reactions to decompose water for
oxygen and hydrogen production in different steps of the reaction.
Based on the electrolysis, further classification of multi-step cycles
is hybrid or pure thermal cycles.
4.5.3. Reactors
Reactors in solar thermochemical technology are of extreme
importance and have attained a lot of research interest [219,220].
There are two general types of reactors utilized for experimenta-
tion of solar thermochemical systems: directly or indirectly heated.
The reactants are heated by the direct solar radiation in the former
type, while the non-transparent surface is used to receive the solar
energy and then this heat is transferred to the reactants in the
latter type. Depending upon the working principle, these reactors
have further types and few reactors have been tested in pilot-scale
plants and laboratories. Further classifications of directly heated
reactors are volumetric reactors and in this type of reactors,
catalytic absorber directly absorbs the solar energy and further
transport it to feed gas. Depending upon the absorber, honeycomb,
structured and foam are other types of volumetric reactors. Com-
paratively, foam-based reactors have a much better mechanism
of heat transfer which avoids flow instabilities during working at
high temperatures and these reactors exhibit more porosity that
permits solar energy to enter deeper in the material [221].
The indirectly heated reactors incorporate molten salts, sodium,
solid particles or air as heat transfer medium. For methane re-
forming, solid particles were used at NREL. The reactor used in
this process works at 1870–2120 K and generates some carbon. In
the Asterix project [222,223], the air was used as the heat transfer
medium, this mechanism allows reforming design independent
of solar considerations and the influence of any variable such
as clouds can be reduced by using thermal storage. MoSTAR for
methane reforming has been developed in Japan and primarily
used to obviate the cloud effects [224]. After successfully em-
ploying at laboratory scale, they are extending it to use on five
kilowatts dish concentrator. In another project, molten salts were
used to perform the solar reforming of methane in CoMETHy [225].
On the other hand, there is a main challenge of coking in
other reactors. Carbon particles increase radiative heat transfer
in the aerosol reactor. Another advantage is working at a high
temperature which means higher conversion rates that directs to
more products and also avoids catalyst material [226]. The attack
of CO2 on reactor walls can be avoided by maintaining the ratio
of methane to carbon dioxide (>1). Tubular reformers with the
different number of coils have been used for methane reforming
in Australia. The prime focus of these reformers was to conduct
methane reforming at relatively low temperatures (820–970 K).
The process at low temperature reduces heat deficiencies from the
reactor by using the maximum amount of solar energy. Table 8
presents the reactor performance and test conditions for different
experimental setups.
4.5.4. Metal oxide redox pairs
There are many renowned redox cycles which can dissociate
H2 O and CO2 and have theoretical efficiencies more than 40%.
Generally, volatile and non-volatile are two-cycle classes consid-
ered for metal oxides. Doping techniques are frequently used in
both types of non-volatile cycles to improve their physical, ther-
modynamic and kinetic characteristics. The commonly employed
oxide pairs with reaction schemes are summarized in Table 9.
4.5.4.1. Perovskites. Perovskites are represented by the high yield
of oxygen at relatively high temperatures and they also incorporate
energy-demanding reduction-oxidation. Their redox properties are
determined by the cation which is present at the M site. It is
 A. Mustafa, B.G. Lougou and Y. Shuai et al. / Journal of Energy Chemistry 49 (2020) 96–123 117

Solar
thermochemical
process
Syngas/
Industrial
Hydrogen
applications
production

Recycling of
waste and
utilization
Solar Hydrocarbon Thermochemical
thermolysis feed cycles
Carbide,
Nitrides

Metal oxide Multistep cycles

Ammonia
Gaseous feed Solid feed
production

Carbon Sulphur Iodine

Methane Hybrid cycles Pure thermal
nanotubes

Solar processes Thermal Calcium

Reforming
materials decomposition Hybrid sulphur bromine cycle
Copper chloride
cycles

Lime Steam
production reforming

Dry reforming

Fig. 22. Different types of solar-based thermochemical processes.

Table 8. Different types of reactors with their test conditions and obtained conversions.

Type of reactor T (K) P (bar) Qsolar (kW) Reforming element Conversion (%) Efficiency (%) Reference

Volumetric 970–1130 3.5 300 CO2 80 – [227,228]

Volumetric 1173 15 400 Steam 80 80 [229–231]
Tubular reformer 1120 20 25, 500, 1200 Steam/CO2 – – [232,233]
Volumetric 1473 1 150 CO2 70 85 [234,235]
Volumetric 1473 4–9 40 CO2 97 79 [236,237]
Volumetric 1033 8.5 220 Steam – – [238–240]
Tubular receiver 1273 7.8 170 Steam 93 – [222,223]
Sodium reflex 958–1098 2–6 1.5–7.8 CO2 50–70 – [241,242]
Aerosol 2073 – 10 CO2 70 – [226]
Tubular absorber 1193 1 5 CO2 90 26 [224]

Table 9. Commonly used redox pairs [243].

Type Cycle Symbol Reaction scheme

SnO2 (s ) → SnO(g )
Volatile Tin Oxide SnO2
ZnO(s ) → ZnO(g )
Zinc Oxide ZnO
Mx Fe3−x O4 → xMO + (3 − x )FeO
Non-volatile (stoichiometric) Ferrite Mx Fe3- x O4 Fe3 O4 → FeO
Iron oxide Fe3 O4 Fe3 O4 +3Al2 O3 → 3FeAl2 O4
Hercynite Fe3 O4 +3Al2 O3
ABO3 → ABO3−δ
Non-volatile (stoichiometric) Perovskite ABO3 CeO2 → CeO2−δ
Ceria CeO2 Mx Ce1−x O2 → Mx Ce1−x O2−δ
Doped Ceria Mx Ce1- x O2
118 A. Mustafa, B.G. Lougou and Y. Shuai et al. / Journal of Energy Chemistry 49 (2020) 96–123
Fig. 23. Classification of two-step cycles.
a category of nonstoichiometric oxides and denoted by ABO3- δ .
These oxides are commonly unexplored for the metal reduction in
thermochemical cycles. A and B are cation sites on which dopants
can be replaced and hence, material configurations are signifi-
cantly larger in perovskites compared to ceria. A thermodynamic
study involving the extraction of entropies and enthalpies and
data evaluation of oxygen non-stoichiometry has demonstrated
that LSM perovskites denoted as La1- x Srx MnO3- δ can enhance the
capacity of oxygen exchange than pure ceria [244]. As shown by
experiments, though reduction extents are significantly greater,
oxidation is thermodynamically less feasible leading to incomplete
oxidation. Nonetheless, overall CO production from the decom-
position of CO2 remains substantially higher compared to ceria.
McDaniel et al. explored a more favorable and promising type of
perovskites. They doped Sr2+ and LaAlO3- δ with Mn on A and B
sites, respectively [245]. They conducted oxidization at 1273 K,
reduction at 1253 K and produced six and nine times more CO
and H2 , respectively than ceria (Fig. 23). La1- x Srx FeO3- δ for looping
applications has been studied by [246]. They produced syngas
by using methane in the reduction process which lowered the
temperatures (10 0 0–1273 K). Large amounts of hydrogen were
produced when a mixture of La0.3 Sr0.7 FeO3- δ and 5% NiO were
used. To date, Lanthanum manganites – which uses Mn4+ /Mn3+
ions for redox reactions – is the family of perovskites which are
extensively considered and studied [244,247–250]. These materials
of perovskite exhibit low oxidation performance and need large
quantities of oxidizing gas that significantly increases heat losses
[251,252]. Few perovskites material possesses high molar mass as
compared to ceria and heat capacity [244,253]. For a specific tem-
perature difference in two steps, the high heat capacity of these
perovskites results in a high loss in terms of sensible heat. These
studies demonstrate that, based on different doping schemes,
many perovskites can be developed which can efficiently increase
the yield of desired products at low temperatures. The develop-
ment of such materials which can be transformed below 1273 K
can be a turning point for the production of solar fuels [254].
4.5.4.2. Ceria. Flamant and Abanades conducted an experiment
in which CeO2 was reduced to Ce2 O3 at 2273 K. They observed
extensive sublimation (higher than 50%) [255]. Based on their
experiments, Haile and Chueh developed a cycle to reduce CeO2
into CeO2- δ which operates at low temperatures for stoichiometric
reduction [256]. Chueh et al. tested and established a solar reactor
based on ceria-materials and successfully demonstrated the cycle
viability under real solar conditions [257]. Panlener et al. investi-
gated defect chemistry of ceria and oxygen non-stoichiometry at
high temperatures. They concluded that iron oxide-based cycles
have a high capability of oxygen exchange compared to ceria and
sintering is not as such intricate due to a high melting point
[258,259]. Hence, it is not essential to dissolve or support them
in more strong structures. The decomposition of water and carbon
dioxide was experimentally demonstrated in [260], producing
syngas by changing the molar ratio of water and carbon dioxide
in the reactor. In pure ceria, ionic and electronic conductivities
directly affect diffusion rates [261,262].
Heat transfer limits the reaction extents in reduction more
than surface kinetics or oxygen diffusion. CO2 oxidation rates
depend on surface area and are highly rapid than Fe-based ma-
terials of smaller lengths [260,262,263]. Haile and Chueh studied
the cyclical stability and found that grain growth and sintering
decrease the yield significantly in early (100) cycles, however, the
production rates of hydrogen and stability of hydrogen/oxygen was
remarkable for the next 400 cycles [264]. Although ceria has an
attraction in terms of stability and kinetics, its storage capacity
is low than other materials. In Fig. 24(a), production of oxygen
due to CeO2 reduction with respect to Poxygen and temperature
are demonstrated. The reduction is generally 1/8 of Co-Fe at
T = 1473 K, x = 0.15, Poxygen = 10−10 bar is shown in Fig. 24(b).
Efficient heat restoration is necessary for this cycle to achieve
economic feasibility and solar-to-fuel efficiency [265].
4.5.4.3. Ferrites. Replacement of transitional metal in the lattice
of magnetite can enhance the oxygen storage-capacity than pure
magnetite. An increase of metal concentration in the lattice can in-
crease the reduction extent at given conditions. Ferrites have been
studied thermodynamically and tested experimentally using metal
cations CoFe2 O4 [266], ZnFe2 O4 [267], MnFe2 O4 [268], NiFe2 O4
[269], Mn0.5 Zn0.5 Fe2 O4 [270] and Ni0.5 Mn0 .5Fe2O4 [271] etc. on
A site [272]. The testing of ferrite-powders has determined the
impact of different parameters on the production of hydrogen and
oxygen and the temperature values suitable for cyclic operations
[273]. The major drawback is a high reduction temperature (1500–
1700 K) which results in oxide sintering. Much attention has been
devoted to addressing this issue by utilizing redox reagent at
elevated temperatures. Ferrites are relatively more stabilized when
dissolved in chemically inert materials to avoid melting and sin-
tering. Kodama et al. conducted experiments incorporating Co and
Ni ferrite with ZrO2 or YSZ [22,48]. The production of hydrogen
 A. Mustafa, B.G. Lougou and Y. Shuai et al. / Journal of Energy Chemistry 49 (2020) 96–123 119

1.4 1.2
(a) (b)
1.2 1.0

Production of CO
Porduction of H2
1.0
CeO2 0.8 CeO2
0.8 SLMA3
0.6 SLMA3
SLMA2
0.6 SLMA1
SLMA2
0.4 SLMA3
0.4
0.2 0.2
0.0 0.0
0 200 400 600 800 0 200 400 600 800
Time (s) Time (s)

Fig. 24. Rates of H2 (a) and CO (b) production in terms of time for different perovskites.
SLMA1: Sr0.6 La0.4 Mn0.6 Al0.4 O3-δ ; SLMA2: Sr0.4 La0.6 Mn0.6 Al0. 4O3- δ ; SLMA3: Sr0.4 La0.6 Mn0.4 Al0.6 O3- δ [245].

Table 10. Comparison of different technologies used for CO2 conversion.

Technology Use of earth metals Renewable energy Turnkey process Conversion and yields Products Investment cost Operating cost Flexibility

Traditional Yes – No High Yes Yes High Low

Photochemical Yes Direct Yes Low Yes Low Low Low
Biochemical No Direct No Medium Yes H/L High Low
Electrochemical Yes Indirect No High Yes Low Low Medium
Plasma chemical No Indirect Yes High Yes High Low High
Solar Thermochemical Yes Direct Yes High No High Low High
∗
The reference [3,51,111,112,127,181,183,243,273] has been considered for establishing this table.

was high than Fe–YSZ process, as demonstrated by Allendorf et al.
[274].
Relating to the composition of materials, it can be said that fer-
rite containing Mn and Zn demonstrates problems related to phase
stability and volatilization, respectively [275]. The robust ferrites
are CoFe2 O4 and NiFe2 O4 which operate efficiently and reliably
and at real-world conditions. Concerning to reaction mechanism,
data obtained from mass-spectrometers and thermogravimetric
analyzers have been utilized by several research groups for the
establishment of kinetic models and their subsequent extraction
[276–278]. Interestingly, the latest studies have only converged
commonly practiced patterns. Thermal decomposition of carbon
dioxide and water using ferrites is fast compared to their typical
reduction and hence consumes less time.
4.5.5. Future perspectives
Solar thermochemistry has evolved as a feasible route that
uses concentrated solar energy and is currently being used on a
commercial scale for power generation. Even though significant
progress has been achieved in the solar thermochemical trans-
formation of CO2 utilizing metal oxides, a lack of basic research
to investigate the performance of metal oxides subjected to high
temperatures in redox cycles has impeded the development of
new materials. Basic problems coupled with surface chemistry,
production methods of material, oxygen transport, the impact of
thermochemical cycling on constituents and structural changes
still require efficient solutions. Moreover, thermal losses in the
reactor largely limit the cycling rates and efficiency which results
in the poor transfer of radiative and conductive heat across the
structures of metal oxides.
It is thermodynamically favorable to convert CO2 through redox
reactions but the conclusive factor determining the commercial
feasibility is solar-to-fuel efficiency and currently, efficiencies more
than 10% still need experimentation with scalable and robust solar
reactors. It is essential to discover new materials that have large
capabilities of oxygen exchange at average temperatures and their
execution in solar reactors. Furthermore, material stability and fast
chemical kinetics over hundreds of cycles should be demonstrated
for every material considered. This is an important factor to
get market acceptance because materials should stay active for
hundreds of cycles to hamper high costs associating with repeated
replacements. Commercial-scale usage of this technology is again
determined by exploring earth-abundant materials that can work
at lower temperatures to attain high system efficiency.
5. Summary
It is evident from the above discussion that, irrespective of
maturity, commercialization and other detrimental aspects, all
the current approaches have particular advantages. Table 10 has
been included to demonstrate the comparison between all these
technologies.
The rare utilization of earth-abundant metals is one of the dis-
tinct disadvantages of almost all the current adopted technologies,
in terms of cost and sustainability. A great challenge for all the
aforementioned approaches to become more efficient is to use eas-
ily accessible inexpensive materials. The discussion about depen-
dence on renewable energy (directly or indirectly) is subtle. The
direct utilization of renewable energy gives an edge to photochem-
ical, biochemical and solar thermochemical over other technologies
that use indirect renewable energy. There is no extra step of energy
conversion in photochemical, biochemical and solar thermochem-
ical approaches and hence energy losses are prevented. In plasma
and electrochemical conversions, the efficiency of renewable gener-
ation of electricity determines the overall energy efficiency of these
approaches. However, it also shows that these approaches (plasma
and electrochemical) can depend on other sources of renewable
energy such as wave, hydro, tidal and wind power, enhancing their
employability, because they can be operated anywhere without the
availability of solar energy. The combined use of photo and bio-
chemical technologies with artificial lighting is also an indirect
source of renewable energy. The wide-scale employability of these
sources is a challenge for easy transport and efficient storage of
the electricity generated. Thus, a stabilized grid is required which
needs those technologies which flexibly follow the periodic and
sometimes inconsistent supply of electricity. Approaches that can
harness this type of energy and transform it into carbon-free fuels
could be crucial for the future infrastructure of energy. Most tech-
nologies (except biochemical and photochemical) exhibit high con-
version rates and productions and solar to fuel efficiencies of these
120 A. Mustafa, B.G. Lougou and Y. Shuai et al. / Journal of Energy Chemistry 49 (2020) 96–123
approaches are demonstrated in Table 10. Another aspect is the
separation of products when all the feed is transformed. Based on
the process, electrochemical and solar thermochemical CO2 trans-
formations are the only two approaches capable of producing sep-
arated products. For instance, pure splitting of CO2 yields CO and
oxygen streams. It is a notable advantage because their separa-
tion (carbon dioxide and oxygen) is highly energy-intensive. Al-
though, it is expected that the use of membranes will provide a
convenient and energy-efficient way of separation. The products in
plasma technology are in one feed and their separation is possibly
the biggest drawback of plasma technology. The research on this
topic needs more attention.
The direct oxidative route to generate more valuable products
is highly favorable instead of current involving indirect method,
which first generates carbon monoxide and hydrogen and then
these chemicals are further processed. All the technologies -
except solar thermochemical - are capable of producing many
valuable chemicals directly, though the amounts of chemicals are
extremely low. It requires insights and research to achieve more
yields from these technologies.
Currently, the costs of investment and operation are low for
most approaches. Excepting, biochemical technology (where both
investment and operating costs are high depending upon the type
of bioreactor) and solar thermochemical technology which has a
high cost of investment due to the mechanism of solar energy
concentration.
6. Conclusions
The conversion of CO2 into fuels and chemicals is an alternate
approach to overcome both fuel shortages and climate change.
Several CO2 conversion technologies: photochemical, biochemi-
cal, electrochemical, plasma-chemical and solar thermochemical
have been undertaken to evaluate their performances for CO2
conversion into value-added products. All these technologies
have some challenges in their practical application for CO2 cap-
ture and transformation. The materials and procedures for the
generation of industrial feedstock and solar fuels are disparate
and can’t easily interrelate. The photochemical transformation
of CO2 seems to be an emerging approach and though, it has
a complex reduction mechanism, the objective is to reduce the
steps experienced during the reduction process. A few possible
ways to overcome this issue are the selection of proper semi-
conductors with a developed hybrid structure, band edges and
morphology designing. Electrochemical reduction of CO2 is also
a promising technology whereby the catalyst is viewed as an
important factor in regulating yield, reaction rates, and selectivity.
Metal electrodes can be scaled down quite easily with low Faradic
efficiency, high overpotential, and low current densities. The use
of microbes in biological technology is continuously expanding for
CO2 conversion into value-added fuel and chemicals and several
microbial species have been found which efficiently contribute
to the conversion process. Different organisms can be genetically
modified to increase the yield and efficiency of the biochemical
process. The productivity of biochemical processes can be en-
hanced by optimal selection of microbes, physiological parameters,
and structure of bioreactor. Plasma-chemical is also extensively
being used for the transformation of CO2 through the cold plasma
and thermal plasma. The latter type of plasma is considered the
best option for reforming of CH4 –CO2 because of highly reactive
elements and temperature and has many advantages over cold
plasma in terms of selectivity, efficiency, treatment capacity, and
by-products. The direct oxidative generation of oxygenates through
plasma-chemical conversion seems to be very promising and need
more investigations. Solar thermochemical technology has under-
taken many leaps forward and appeared as a feasible path to use
concentrated solar energy. The direct utilization of solar energy
makes this technology highly useful and advantageous over other
conversion processes. Concentrated solar energy is currently being
employed commercially for power generation applications and
reduction of CO2 and H2 O into CO and H2 . Liquid hydrocarbons
can be produced by further processing the syngas. Though solar
thermochemical splitting of carbon dioxide and water through
metal oxides are thermodynamically convenient, higher ηsolar-to-fuel
still requires experimentation with powerful solar reactors.
Declaration of Competing Interests
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgments
This work was supported by the National Natural Science
Foundation of China (51522601; 51950410590), China Postdoc-
toral Science Foundation Fund (2019M651284), and Fundamental
Research Funds for the Central Universities (HIT.NSRIF.2020054).
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