Chemical Engineering Science 236 (2021) 116515

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Chemical Engineering Science

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

A comprehensive review on different approaches for CO2 utilization

and conversion pathways
A. Saravanan a, P. Senthil kumar b,⇑, Dai-Viet N. Vo c, S. Jeevanantham a, V. Bhuvaneswari a,
V. Anantha Narayanan a, P.R. Yaashikaa d, S. Swetha b, B. Reshma b
a
Department of Biotechnology, Rajalakshmi Engineering College, Chennai 602105, India
b
Department of Chemical Engineering, Sri Sivasubramaniya Nadar College of Engineering, Chennai 603110, India
c
Center of Excellence for Green Energy and Environmental Nanomaterials (CE@GrEEN), Nguyen Tat Thanh University, Ho Chi Minh City, Viet Nam
d
Department of Biotechnology, Saveetha School of Engineering, Chennai 602105, India

h i g h l i g h t s g r a p h i c a l a b s t r a c t

CO2 was used as an inexpensive

feedstock for various fuels and
chemicals production.

Explained various utilization
approaches and their mechanisms for
CO2 mitigation.

Discussed the various CO2 conversion
processes.

Current status and Scope for further
research on CO2 conversion has been
discussed.

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

Article history: Carbon dioxide (CO2) is a odourless and colourless gas which plays a noteworthy role in the climate and
Received 30 August 2020 weather changes. Different natural and anthropogenic activities induces CO2 emission in the environ-
Received in revised form 19 January 2021 ment. Though CO2 causes global warming, it acts as an essential element for photosynthesis process in
Accepted 6 February 2021
plants. CO2 can also be used as an inexpensive feedstock for the production of various fuels and chemi-
Available online 17 February 2021
cals. Many approaches like electrochemical, thermal, biochemical, chemo-enzymatic and photocatalytic
methods are available by means of which the harmful CO2 is captured from the environment. Similarly,
Keywords:
via different chemical, physical and biological processes, it can be converted into useful products like
Carbon dioxide (CO2)
CO2 emission
fuels and chemicals. This review mainly focuses on various utilization approaches and their mechanisms
CO2 utilization for CO2 mitigation. In addition, CO2 conversion processes like hydrogenation, esterification, methanation,
Conversion pathways reforming, and reverse water-gas shift (RWGS) reactions, their mechanisms and their current status along
Reforming with future perspectives were comprehensively discussed.
Chemical synthesis Ó 2021 Elsevier Ltd. All rights reserved.

1. Introduction industrialization and urbanization, energy consumption is likely to

The 20th century has witnessed an exponential increase in pop-
ulation and energy consumption. With the increase in the trends of
⇑ Corresponding author.
E-mail address: senthilkumarp@ssn.edu.in (P. Senthil kumar).
be higher in the 21st century. Fossil fuels, especially a coal - power
plant, contributes over 40% of the total CO2 emissions (Carapellucci
and Milazzo, 2003). Though the fossil fuels are considered to be the
key energy sources for many industrial processes in the recent
years, the combustion of petroleum-based resources rapidly
increases the CO2 levels and causes various harmful effects in the
environment. It is documented clearly that the level of CO2 was

https://doi.org/10.1016/j.ces.2021.116515
0009-2509/Ó 2021 Elsevier Ltd. All rights reserved.
A. Saravanan, P. Senthil kumar, Dai-Viet N. Vo et al.
increased because of the industrialization and urbanization during
the middle of 19th century, causing the climate change or global
warming (Yaashikaa et al., 2019). Carbon dioxide contributes
nearly three-quarters of greenhouse gas emissions and so it is con-
sidered as the major gas responsible for the climate change (Nejat
et al., 2015; Artz et al., 2018). An increase in CO2 concentration in
the atmosphere has been contributed by many sectors such as
energy, transportation, manufacturing industries, fuel, electricity
and agriculture. The rise in the population also has an impact over
the CO2 emissions, particularly in China, India and US (Wu et al.,
2016). China, USA, India, Canada, Russia and Japan are the major
countries which have the highest energy consumption and green-
house gas emissions among other countries in the world (Jordaan
et al., 2017; Kijewska and Bluszcz, 2016; Nejat et al., 2015; Xu
et al., 2018).
In the current scenario, global warming and ocean acidification
are the two major problems attributed to the CO2 increase in the
environment. Ocean acidification due to the increase in the CO2
level leads to the changes in seawater chemistry and shows nega-
tive impacts on aquatic ecosystem and warm water stress, which
in turn results in the extinction of microbial species in the ocean
(Feely et al., 2004; Shirayama and Thornton, 2005). The effects of
global warming includes drought, flooding, destruction of plant
and animal species, rise in the sea level and increase in the fre-
quency of natural disasters such as hurricanes and cyclones
(Salameh, 2014). In spite of using carbon fuel and alternate energy
in the lower level, it is very difficult to reduce CO2 as a safer level in
the atmosphere. Therefore, CO2 should be caught and converted
into useful products or compounds. Further, CO2 emission is
remarkably associated with economic growth, development and
human life expectancy in the country (Wang et al., 2015). Hence,
decreasing CO2 emission developed as a new research interest
worldwide. Many scientists and researchers are engaged in this
goal of conversion of CO2 into beneficial products like value-
added chemicals, or as fuels which can be captured and stored as
an efficient energy source (Ansari and park, 2012).
The utilization of CO2 is broadly classified into two groups, the
direct usage of CO2 and conversion of CO2 into value-added chem-
icals. The value-added chemicals including methanol, urea, poly-
carbonate and dimethyl ether were formed either by the direct
utilization of CO2 or various transformation pathways using
microalgae (Huang and Tan, 2014). CO2 transformation into fuel
provides a unique advantage that can be a concurrent way for
removal of CO2 as well as its product, which may act as a substitute
for conventional transportation fuels (Hu et al., 2013). Some revo-
lutionary technologies have been developed for the industrial pur-
poses which involves the selective transformation of CO2 into
valuable products by the use of alternate organic compounds for
co-polymerization (Song, 2006). Carbon-dioxide capture and
sequestration (CCS) is one of the CO2 reducing techniques that
integrates numerous technologies concentrating on CO2 utiliza-
tion. It is an emerging technology that has a major role in the
development of low-carbon energy by reducing the CO2 released
from various power plants like coal fired and gas fired power
plants. CCS basically involves a three-step procedure of capturing,
transporting and storing of CO2 (Yang et al., 2008). If high CO2
emitting sources and industries adopt the strategy or implement
carbon capture and storage (CCS) technologies to efficiently man-
age the greenhouse gas, abundant CO2 will be made available as
a potential source for many applications. The center of attraction
of many researches is to make CCS technology cost effective as it
is not economically effective due to the high operating cost
involved in the stage of capturing CO2 (Herzog and Golomb,
2004). In future, there is a possibility that direct air capture will
be prominently used and the income generated from the product
formed by the CO2 utilization can be used to counterbalance the
2
Chemical Engineering Science 236 (2021) 116515
cost of CO2 capture. Due to the increasing concerns towards safety
of the underground, the ocean storage of CO2 and utilization
through CO2 captured from power plants is gaining attention glob-
ally (Huang and Tan, 2014).
CO2 is an inert gas, and has low Gibbs free energy and high oxi-
dation state; therefore, a CO2 conversion reaction requires higher
energy input and efficient catalysts to achieve more yields
(Damiani et al., 2012). Therefore, sufficient energy valuation for
each step in the conversion process has to be carried out to confirm
the efficiency of the system. This review explains various CO2 uti-
lization methods such as electrochemical, thermal, biochemical,
chemo-enzymatic and photochemical approaches to understand
about each system and to evaluate the products from the applica-
tion of these processes.
2. Sources of CO2 emission
Emissions due to the usage of fossil fuels like petrol, gasoline,
and diesel for transportation are the primary reasons for the
increased CO2 levels in the atmosphere (Fan et al., 2018). Avoiding
development like industrialization, urbanization and transporta-
tion for CO2 emission reduction is not possible because of the eco-
nomic development (GDP) of a country which particularly depends
on these sources (Wang et al., 2020a, 2020b). Global CO2 emissions
through the combustion of fuels were recorded to be around 32.8
billion tons (IEA, 2017). Overpopulation has stressed a demand
for easier transport, causing a dramatic surge in private transport.
Therefore, the introduction of public railway transport along dense
areas caused a considerable decrease in CO2 emissions (Gagatsi
et al., 2016; Tsumura et al., 2019). An interrelation between urban-
isation and economic improvement with direct correspondence to
the emissions was analysed using models in the G20 countries
(Arvin et al., 2015).
Electricity production is a basic need for any kind of an indus-
trial production and the burning of fossil fuels in thermal power
plant fulfils the necessity. Research and development (R&D) are
an integral part of any industry and a study shows that it greatly
improves the productivity, thereby leading to excess CO2 emissions
(Kahouli, 2018). Several industries play a part in emitting CO2, like,
in the case where a number of pharmaceutical companies’ out-
growth in China led to double the number of metric tons of CO2
produced due to their utilisation (Gao et al., 2019). Metallurgical
industries, another important growth sector requires a lot of heat
energy, to fulfil its requirements and thus is in the need of fuels.
The CO2 emitted from those kinds of industries in China was about
3.2 billion tons in 2015 and certain companies were found to have
a good emission reduction potential which has to be worked upon
(Lin and Xu, 2018). The emissions by the industrial sectors in
China, based on an average energy efficiency index were about
90%, which is significantly higher than their counterparts (Xia
et al., 2020b). Every industry is ultimately dependent on construc-
tion works to either build or upgrade them and therefore, construc-
tion companies are greatly needed. These construction companies
can also release a certain amount of CO2 during their processes (Shi
et al., 2015; Takayabu et al., 2019; Zhang et al., 2019b).
Carbon emission also occurs via deforestation as trees tend to
sequester CO2 inside their bark and upon chopping them, the
trapped carbon is again sent into the atmosphere. Agricultural soils
and cattles also release a significant amount of carbon emissions.
The inequality on CO2 emission through the Theil index via agricul-
tural practices was found to be increasing in Iran (Pakrooh et al.,
2020). In the period of 1990–2014 in Pakistan, it was observed that
the production through agriculture being carbon-based products
increased carbon emissions greatly and traditional farming prac-
tices also aided in this too (Waheed et al., 2018). Another way of
A. Saravanan, P. Senthil kumar, Dai-Viet N. Vo et al.
emitting CO2 is by forest fires which can arise due to man-made or
natural causes and it affects the productivity of the forests
(Sannigrahi et al., 2020). Brazil and Indonesia were found to con-
tain about 35% of all the sequestered carbon and deforestation
accounts for about 6–17% of all CO2 that is emitted through various
ways (Baccini et al., 2012). The higher levels of carbon emissions
due to destruction of forest lands for cultivation was observed
based on the theoretical models (Galinato and Galinato, 2016;
Machado et al., 2017).
The residential sector involves some fossil fuels, which are
burned for heat energy for consumption and other purposes. The
residential evolution of CO2 due to aggressive urbanisation in 64
cities in China was observed to be about 5.6 million tons (Bai
et al., 2019). It is estimated that the carbon emission by the resi-
dential sector of Thailand would be about 77 million tons and it
would be about 86 million tons in Vietnam in the future (Thuy
and Limmeechokchai, 2015). As the number of houses in an area
increases, it denotes that the economic opportunities are good,
leading to an increased income. This was observed in the house-
holds of many countries like China that the increase in the per cap-
ita income in the houses corresponded to an increase in the
residential carbon emissions (Zang et al., 2017). The amounts in
kg of CO2 emitted per person via direct and indirect modes for daily
purposes were found to be about 10 kg (Hirano et al., 2016). The
usage of water heaters constituted a significant part in power util-
isation and it was found in US that switching to alternate ways like
solar heaters could help in reducing the carbon emissions (Sanders
and Webber, 2015).
3. Environmental impacts of CO2
CO2 generally helps in maintaining the temperature by trapping
the heat that gets bounced off from the surface. Since the emission
rate is very high now, lots of heat energy gets trapped creating
harmful effects to the environment. It has been observed that the
increase in temperature now favours blue green algae to become
a dominant force due to higher N2 fixing capability in water bodies
causing eutrophication which affects the entire aquatic ecosystem
(Visser et al., 2016). These algae with the above-mentioned condi-
tions are also capable of producing toxins like microcystin which
upon consumption was found to cause liver damage (Gehringer
and Wannicke, 2014). The colonisation of certain species of aquatic
plants like the water primrose (Ludwigiahexapetala) is induced
upon by a 3 °C rise in temperature affecting the native diversity
(Gillard et al., 2017). About 1.5–2 °C rise is capable of raising heavy
metal contaminants by about 90%, which upon condensation seeps
into the underground reservoir and pollutes the water quality
(Wijesiri et al., 2020). An aquatic fungal decomposer (Limnephilus
sp.) was found to be at 50% of its total potential in decomposing
when exposed to a 6 °C increase which indicates the temperature’s
inhibitory effects on the aquatic food chain (Batista et al., 2012;
Sadatshojaie and Rahimpour, 2020).
Prolonged exposure to CO2 of about 700 ppm resulted in respi-
ratory muscle damage in the diaphragm and hormonal abnormal-
ities in rats (Martrette et al., 2017; Krauskopf et al., 2019). CO2
exposure is also associated with anxiety and stress, as a test of
about 20% carbon dioxide was able to push people with existing
panic related conditions to anxiety (Blechert et al., 2013). A short
term or acute contact with carbon dioxide has been found to alter
the blood pH slightly and affect the metabolic rates of Atlantic sal-
mons (Salmo salar) (Khan et al., 2018).
Another negative impact of increasing CO2 concentration in the
atmosphere is ocean acidification. The oceans pH is slightly basic
but upon the addition of carbon dioxide, it is getting more and
more acidic which is injurious to the underwater coral reefs. These
3
Chemical Engineering Science 236 (2021) 116515
coral reefs need calcium carbonate in their shells, but its concen-
tration is reduced due to CO2. It has been observed in Hudson
Bay, Canada that the partial pressure of CO2 was raised up to 165
matm due to the organic carbon present inside which gets con-
verted into carbon dioxide (Capelle et al., 2020). Upon treating
sea urchin with CO2 acidified water, its rate of food intake and
intestinal enzymatic activities were reduced (Zhan et al., 2020).
Similarly, mussels were treated with water at pH 7.4 leading to a
decrease in strength and stability. It also leads to proton accumu-
lation in the extracellular spaces of cells in them (Zhao et al., 2020).
The flora of the world is also not spared as the accumulation of
CO2 lead to various problems in the plant’s genotype and pheno-
type. FACE (Free-air CO2 enrichment) experiments were performed
to find out how plants react to higher than optimal levels of CO2
and it is noted that the rate of photosynthesis decreases upon
alternating the levels of CO2 every 1 min (Allen et al., 2020). Expo-
sure to elevated quantities of CO2 decreases the potential for tran-
spiration via the stomatal pores which led to a reduction in
essential mineral concentration in wheat (Houshmandfar et al.,
2015).
Climatic change to harsh environments for us is not so far as it
has been noted that for every degree rise in global warming, the
precipitation would be aggravated by a rate of about 6.5% denoting
the possibility of an abnormal heavy monsoon in China (Zhang and
Zhou, 2019). The extent of temperature increase, creates more
amount of water to get lost as vapour which would lead to drought
and bushfires (Wang et al., 2017b; Wilke et al., 2019). It has been
found that tropical diseases would be more effective upon the raise
in temperature as the virus inside a mosquito vector (Aedesaegypti)
takes comparatively a shorter incubation time and greater expo-
sure (Gloria-Soria et al., 2017). The presence of Vibrio sp. capable
of causing gastrointestinal disease was found to be elevated at
higher temperature of waterbodies in Netherlands (Schets et al.,
2011).
4. CO2 utilization approaches
The US Department of Energy’s (DOE) Carbon Sequestration
Program primarily focuses regions of research in the CO2 utiliza-
tion comprises of CO2 enhanced recovery of hydrocarbons, manu-
facture of chemicals, mineralization and polymerization process
(Damiani et al., 2012). These domains have great possibility to uti-
lize high capacities of CO2 to economical products. In spite of the
various products that can be obtained by CO2, there is an existence
of huge gap between CO2 generated and CO2 converted. Hence, bet-
ter solution for this issue is to reduce the use of fossil fuels at the
source for electricity and promote the use of renewable sources
like wind, solar, hydrothermal and geothermal energies. If these
renewable energies are used in combination with different CO2 uti-
lization strategies, it paves the way for reducing the atmospheric
CO2 to a significant extent. In the recent times, scientists have
started to take advantage of different approaches such as photocat-
alytic reduction of CO2, electrochemical and thermal approaches
for the CO2 utilization and transformation (Whipple and Kenis,
2010). The different approaches for CO2 utilization and conversion
into valuable chemicals are shown in Fig. 1. The advantages and
disadvantages of CO2 utilization approaches are listed in the
Table 1.
4.1. Electrochemical approach
CO2 is converted into various products such as CO, carboxylic
acid, alcohols and alkenes etc. (Chen et al., 2018). The basic config-
uration of the electrochemical reduction is shown in Fig. 2 which
consists of a cathode and an anode through which electricity is
A. Saravanan, P. Senthil kumar, Dai-Viet N. Vo et al.
Fig. 1. Different approaches for CO2 utilization and conversion.
applied in the electrolytic solution. The electrodes are separated by
the ion exchange membrane (Babita et al., 2011). The electro cata-
lyst must be highly selective and active in order to decrease the
activation energy needed for the conversion process (Yaashikaa
et al., 2019). Electrochemical reduction of CO2 produces various
beneficial products, among them hydrogen (H2) and formic acid
(HCOOH) are obtained in the presence of Ruthenium Carbonyl
complex as a catalyst. It has been shown that the heterocyclic
organic compound such as pyridine shows a significant effect on
promoting the electrochemical conversion of CO2 (Barton Cole
et al., 2010). It is reported that GCE (Glassy carbon working elec-
trode) modified by Pt@histamine –reduced graphene oxide with
KNO3 as an electrolyte produced a maximum of 2.96 mmol L1
of ethanol.
CO2 ðg Þ þ 6Hþ ðaqÞ þ 6e ! CH3 OHðaqÞ þ H2 OðlÞ
The histamine present in the electro-catalyst led to the forma-
tion of formic acid, which is an intermediate and by combination
with Pt nanoparticle, availability of the absorbed H atom was
increased which in in-turn produces high hydrogenated products
like methanol (Zarandi et al., 2019). Further, the selectivity of the
desired product can be increased by using appropriate electrolyte,
catalyst and potential applied to the process. In the electrochemi-
Table 1
Advantages and disadvantages of various CO2 utilization approaches.
Approaches Advantages
Electrochemical
No additional heat is required

Easy to scale-up

Recycled electrolyte reduces the total electrolyte
consumption

Renewable energy source can be utilized

High selectivity

Long term stable operation
Thermal
Produce a high yield
Photocatalytic
Do not require additional energy

Environment friendly

Economically feasible
Biochemical
Toxic tolerance

Higher selectivity

Require low pressure and temperature
Chemo-
Produce bulk chemicals
enzymatic
Chemical Engineering Science 236 (2021) 116515
cal reaction, electrodes play an important role. The electrodes are
generally composed of catalyst layer and the substrate layer to
transport the reactant gas CO2 and the product. Therefore, the
overall reactor performance is maximized by improving the elec-
trode configuration. In spite of its importance only few studies
have been carried out in improving the electrode performance.
The study conducted by Hori et al. showed the limitation of planar
electrode due to mass transfer limitation which arise because of
the poor solubility of CO2. It has been reported that the use of
gas diffusion electrode as cathode in combination with improved
catalyst deposition layer lead to improvements in the electrode
performance (Hori et al., 1994; Malkhandi and Yeo, 2019). Many
studies have been carried out by utilizing copper sulfide com-
pounds as catalyst in the CO2 electrochemical reduction process
due to their distinctive electrochemical properties (Yuan and
Hao, 2013; Garcia-Muelas et al., 2018; Yeo et al., 2018). Further,
selective production of formate is achieved by sulfur modified cop-
per catalyst where S acts as a main promoter (Chen et al., 2019a,
2019b). Previously formate was obtained at 0.96 V in 0.1 M
KHCO3 with Faradaic efficiency (FE) of 88% (He et al., 2015) using
Pb electrode. With the use of Sn electrode (Detweiler et al., 2014)
it is recorded that the FE can be increased up to 91% at 1.19 V.
The production of acetate with 96.5% FE and 96% selectivity at
1.15 V facilitated by the electro catalytic system built by POM
[SiW9V3O40]7 (SiW9V3) and metal indium results higher conver-
sion of CO2 (Zha et al., 2020).
Energy consumption for the electrochemical process is given by
V ð1þ /Þn
E¼ ð2Þ
1:641FE
where V is the voltage of the cell, a is element denoting the auxil-
iary energy needed, FE is the Faradaic efficiency and n is the count
of electrons (Sridhar et al., 2011). The important parameter which
describes the efficiency of this approach is the energetic efficiency,
current density, faradaic efficiency, the catalyst stability and the
process cost. A study conducted by Jhong et al. demonstrated the
ð1Þ
plot between current density versus energetic and faradaic efficien-
cies in the reduction of CO2 for the various products. It is concluded
that many of them showed the characteristics of high faradaic or
high energetic efficiency and high current density. But optimizing
these parameters remains a major challenge. For instance, in C1-
C2 fuel production which includes ethanol and methanol, it has
been showed that it has high FE and CD but has low EE (less than
22%) (Jhong et al., 2013a).
Disadvantages References

Lifespan of catalyst is low (Agarwal et al., 2011; Zhu, 2019)

Economically not feasible

Required more electric energy

Required high temperature (Hu et al., 2013; Galadima and

Stability of the catalyst is low Muraza, 2019)

Low product selectivity (Alper and Orhan, 2017; Gao et al.,

Produce a less yield 2020)

Time consuming process (Appel et al., 2013; Yaashikaa et al.,

Require high cost 2019)

Produce a less yield

Need specialized bioreactor

Require high temperature which affects (Yong et al., 2015; Long et al., 2017)
enzyme activity
4
A. Saravanan, P. Senthil kumar, Dai-Viet N. Vo et al.
Fig. 2. Electrochemical CO2 utilization and conversion.
4.2. Thermal approach
Nowadays, CO2 capture and utilization have been the prime
concern for scientists as well as industries due to its harmful
effects to the environment. Therefore, researchers have developed
various techniques by which the captured CO2 could be converted
into various value-added chemical feedstocks, fuels, etc. (Galadima
and Muraza, 2019). Carbon monoxide (CO) was formed by the uti-
lization of CO2 and hydrogen through reverse water-gas shift
(RWGS) reaction (Chen et al., 2004). The produced CO through
RWGS was employed in various industries including steel fabrica-
tion, pharmaceutical and biotechnology based industries (Roy
et al., 2018). The RWGS reaction is endothermic, and operates at
the high temperature (550–750 °C) and low pressure (0–5 bar).
CO2 þ H2 ! CO þ H2 O DH ¼ þ41 kJ=mol
Based on the conditions of the reaction, it can be directed in
both forward and backward with slight change in the temperature
and pressure (Kho et al., 2017; Agarwal et al., 2015). Unlike RWGS
reaction, the dry reforming process produces syngas (CO and H2)
by utilizing CO2, natural gas and coal without the production of
water. The reaction occurs in the dry reforming process is given by:
CO2 þ H2 ! CO þ H2 O
The produced syngas was further transformed into hydrocar-
bons and chemical feed stocks. Syngas can also be produced by
bi-reforming process that is the combination of steam methane
reforming and dry reforming reaction. The bi-reforming reaction
is given as
CH4 þ H2 O ! CO þ 3H2
CO2 þ CH4 ! 2CO þ 2H2
Tri-reforming is another reforming process that combines these
two reforming methods (steam methane and dry reforming) and
partial oxidation of methane. The unique capability of this method
is to manipulate the CO and H2 ratio in the product to yield a vari-
ety of hydrocarbons (Agarwal et al., 2015). It is believed that poten-
tially methanol can replace the fossil fuels in the near future.
Conversion of CO2 to methanol renewably serves as a superior
method to neutralize the atmospheric CO2 concentration. The pro-
cess is denoted by,
Chemical Engineering Science 236 (2021) 116515
CO þ 2H2 ! CH3 OH ð7Þ
The methanol synthesis reaction is exothermic in nature that
was carried out at the temperature ranges of 210–290 °C and
50–80 bar pressure (Agarwal et al., 2015). Further, methanol can
be transformed to dimethyl ether through olefin or gasoline tech-
nology. Synthesis of Urea is another method for CO2 utilization and
reduction. It is a two-step process was given below,
2NH3 þ CO2 $ H2 N  COONH4 ð8Þ
H2 N  COONH4 $ ðNH2 Þ2 CO þ H2 O ð9Þ
Formation of carbamate from the liquid ammonia and gaseous
CO2 is explained in Eq. (8). Carbamate was further decomposed
into urea with water as byproduct. The decomposition of carba-
ð3Þ mate into urea was explained in Eq. (9). The synthesized urea will
be utilized for various fertilizers and polymers such as urea-
formaldehyde synthesis (Quadreilli et al., 2011). Although, these
methods serve as the better way for the CO2 utilization, it possess
certain disadvantage that majority of these approaches will further
increases the release of CO2 (Kho et al., 2017).
ð4Þ 4.3. Biochemical approach
Photo catalytic, electro catalytic reactions are the most widely
employed method for the conversion of CO2. In spite of several dis-
advantages such as low yield, requirement of high pressure and
temperature, bio catalytic approaches can be utilized due to their
efficiency and toxicity tolerance (Appel et al., 2013). Biochemical
conversion is the utilization of enzymes or microbial catalyst for
ð5Þ
the transformation of carbohydrates into simple sugars (Cadham
et al., 2016). It has higher selectivity and need low process and
ð6Þ
temperature. Photosynthesis is a process that fixes carbon, natu-
rally by the conversion of CO2, water and sunlight to organic com-
pounds. The ability of the biotic system to synthesize fuel from the
biomass is exploited for the conversion of CO2. Plants and prokary-
otic organism convert atmospheric CO2 into biomass through the
Pentose phosphate pathway, where fructose 1, 6-bisphosphate
and 1, 5-ribulosebisphosphate is released as intermediate products
(Aresta and Dibenedetto, 2007).
Similarly, other biochemical pathways involved in the CO2 con-
version are acetyl- CoA pathway, Reductive citric acid pathway and
5
A. Saravanan, P. Senthil kumar, Dai-Viet N. Vo et al.
Fuchs-Holo cycle (He et al., 2013; Hunt et al., 2010). Currently,
major research area includes genetic engineering of algal metabo-
lism in order to improve the oil production (Miller et al., 2010;
Morgan-Kiss et al., 2006). Cyanobacteria are the other choice for
the direct utilization of CO2, which produce different value added
chemicals such as ethanol (Dexter and Fu, 2009), isobutanol
(Atsumi et al., 2009), Isoprene (Lindberg et al., 2010), ethylene
(Ungerer et al., 2012) and alkanes. The genetically engineered
cyanobacteria Synecchococcus elongates produce 26.5 mg/L of iso-
propanol (Berla et al., 2013; Markley et al., 2014; Nozzi et al.,
2017). Acetogenic bacteria convert CO2 into Acetyl-CoA by reduc-
tive Acetyl-CoA pathway and further directed towards the produc-
tion of acetic acid (Phillips et al., 2017). Methanogens are the
microorganisms they produce methane by directly utilizing elec-
trons generated during CO2 utilization and reduction process.
Methanobacterium paulstre, Methanothermobacter marburgensis
and Methanocaldococcus jannaschii are the examples of methano-
gens (Cheng et al., 2009). High cost and need of specialized biore-
actor is the major limitation of this process, hence it is not being
used in industries (Gross et al., 2012). Another disadvantage with
this approach is the fact that the nutrients that are supplied to
the microbial culture in large scale in turn creates an additional
hit on the food shortage issue prevailing in many countries.
Although this approach has these issues, it could be made effective
on modifying the microbes to utilise a substrate that is present in
significant quantities or we can use the substrates that are the by-
products or wastes generated from the food industry like in the
case of corn steep liquor. Thus, the future of this approach is
mainly involved in the techniques of synthetic biology where
genetic manipulation of the organism can alter the biochemical
pathway to produce desired product in large quantities
(Darensbourg, 2010).
4.4. Chemo-enzymatic approach
Chemo-enzymatic is the process that combines biocatalytic
reaction for the synthesis of bulk chemicals. The enzymatic method
has several advantages such as higher selectivity, yield and the
reactions doesn’t require variable conditions. In the current situa-
tion, production of such chemical with high stereo selectivity is
important (Biermann et al., 2016). Diagrammatic representation
of chemo-enzymatic approaches for CO2 utilization and conversion
is shown in Fig. 3. Chemo-enzymatic approaches were applied in
Fig. 3. Chemo-enzymatic CO2 utilization and conversion.
6
Chemical Engineering Science 236 (2021) 116515
the industries in order to capture CO2 released from the power
plant (Yong et al., 2015; Long et al., 2017). CO2 is converted to
CO by [NiFe] Carbon monoxide dehydrogenase, which further con-
verted into different value added products such as hydrocarbons,
methanol and acetic acid (Parkin et al., 2007). Reduction of
carbon-dioxide with enzyme to form formate, formic acid and
methanol has been widely studied (Spinner and Mustain, 2011).
CO2 can be converted to formate, by Formate Dehydrogenase iso-
lated from the organism Syntrophobacter fumaroxidans (Reda
et al., 2008). High efficiency of about 93% in the production of for-
mate is observed, when the photo generated electrons were used.
The conversion of CO2 to formate takes place by the following reac-
tions (Shi et al., 2017),
CO2 þ Hþ þ 2e ! HCOO ð10Þ
CO2 þ 2Hþ þ 2e ! CO þ H2 O ð11Þ
It is being recorded that methanol, which is one of the impor-
tant chemical feedstock can be produced by the chemo-
enzymatic method of CO2 utilization. By combining the electro-
chemical method with this chemo-enzymatic process, Faradic effi-
ciency of (FE) of 10% was achieved (Schlager et al., 2016). Electron
source such as NADPH+/NADP couple is the limiting factor in the
conversion of CO2 to methanol. In order to overcome the limitation,
other renewable form of energy can be utilized for its reduction
process (Aresta and Dibenedetto, 2007). CO2 can also be converted
into methane by the use of enzyme nitrogenase. Yang et al. Studied
using nitrogenase for methane production, from that it was noted
that 1 nmol of nitrogenase can yield 21 nmol of methane at opti-
mum conditions (Yang et al., 2012).
Carbonic anhydrase (CA) is another enzyme which has a higher
reaction rate for CO2 conversion when compared with other
enzymes. CA catalyzes the conversion of CO2 into bicarbonate
(HCO 3 ). The reaction for bicarbonate synthesis was given below,
CO2 þ H2 O ! HCO3 þ Hþ ð12Þ
Besides utilizing CO2, CA is also involved in the process of CO2
capture and CO2 sequestration. But this reaction requires high tem-
perature, which affects the activity of the enzyme. These disadvan-
tages can be overcome by immobilization of the enzyme onto
beads or other matrix materials. Therefore, this process can aid
both CO2 capture and utilization leading to the production of valu-
able products economically (Gil et al., 2015).
Michael addition is the reaction that is catalyzed by the enzyme
called lyase, which involves in the breaking of the chemical bonds.
This enzyme can be exploited for the carboxylation of molecules to
form useful chemical products (Shi et al., 2015). There are four
types of carboxylation reaction: (i) Carboxylation of epoxides, (ii)
Carboxylation of aromatics, (iii) Carboxylation of hetero aromatics
and (iv) Carboxylation of aliphatic Substrates. Many researches
have been made in usage of multi-enzyme system for the conver-
sion of CO2 to isobutyraldehyde (Atsumi et al., 2009), sugars
(Cazelles et al., 2013) and L-Lactic acid.
4.5. Photocatalytic approach
Photocatalytic conversion of CO2 is one of the emerging area in
the research. This technique utilizes the light irradiation for the
reduction of CO2. Photocatalyst is the light sensitive catalyst
involved in the conversion of CO2 into useful products (Yaashikaa
et al., 2019). This is a better technique than other approaches such
as electrochemical, thermal in terms of energy efficiency and sus-
tainability. However, it is very low product selectivity, so many
researches targeted to improve it. The photocatalytic approach
for CO2 utilization and conversion into different value added prod-
A. Saravanan, P. Senthil kumar, Dai-Viet N. Vo et al.
Fig. 4. Photocatalytic CO2 utilization and conversion.
ucts is shown in Fig. 4. The two advancements aimed to increase
the photocatalytic approach are developing new forms of catalyst
and photoreactor (Tahir and Amin, 2017). There are two classes
in photocatalytic approach such as homogeneous and heteroge-
neous (Xiang et al., 2015). Semiconductors are utilized in the
heterogeneous photocatalytic reactions. The process of conversion
of CO2 into fuels by means of solar irradiation is sustainable as it
doesn’t require additional energy. Metal oxides have been utilized
for many purposes such as water treatment and other valuable
process. Here, methane is produced through photocatalytic CO2
conversion using different metal oxides as catalyst such as
W18O49 (Xi et al., 2012), HNb3O8 (Li et al., 2012), Bi2WO6 (Zhou
et al., 2011), TiO2 (Koci et al., 2009) and Zn2GeO4 (Liu et al.,
2010). As like methane, various useful products including CO, for-
mic acid, formaldehyde and ethanol were produced by utilizing
various metal oxides catalysts such as CuGaO2, LiNbO3, BiVO4,
ZnO, TiO2 and WO3 (Lekse et al., 2012).
It is reported that the use of metal sulphides has the better abil-
ity to absorb the solar energy and hence has the highest yield. ZnS
was used as catalyst for the production of methanol and methane
from CO2 (Koci et al., 2009). However, metal phosphide semicon-
ductors were used extensively in the methanol production, they
requires high potential for higher yield. For example, methanol is
synthesized with the faradaic efficiency of 100% of CO2 where p-
type GaP is utilized a catalyst (Barton et al., 2008). In order to pro-
vide the electron for the CO2, doping metal on semiconductor is
carried out. Carbon doped TiO2 was used as a catalyst for the con-
version of CO2 into formic acid.
Methane was produced with the help of Dye-sensitized TiO2
with 1% by weight of Pt. Another advanced approach in the CO2
conversion is the usage of Quantum dot-sensitized photocatalyst.
The maximum CO2 conversion rate was observed in the PbS QDs-
sensitized Cu-TiO2 (Wang et al., 2011). Phthalocyanine sensitized
photocatalyst was also used as catalyst due to its higher chemical
stability and semi-conductivity. Substrate based photocatalyst
were also developed as they offer high surface area. The substrate
that has been used includes polyethylene terphthalate (PET) and
polyethylene (PE). The PET supported TiO2 was utilized as sub-
strate based catalyst to convert CO2 into CO in the presence of a
light source (Jensen et al., 2011). The different types of value added
products produced through various CO2 utilization approaches and
the catalysts involved for the conversion process is presented in
the Table 2.
7
Chemical Engineering Science 236 (2021) 116515
4.6. Direct air capture of CO2 (DAC CO2)
Direct air capture (DAC) is one of the CO2 reduction technolo-
gies by which CO2 was directly captured from the environment
such as air released from the biomass power plant and cement
industries. It can reduce the level of atmospheric CO2 by removing
those using chemical media. Functionalised sorbent materials and
alkaline solution are the most commonly used chemical medium
for CO2 capture in the DAC process. After adsorption, it could be
stripped from the chemical medium by applying heat energy
(steam), then the CO2 steam could be dehydrated, compressed
and the concentrated CO2 was stored for future use. The concen-
trated CO2 can be used as source for carbonated beverages and
the converted form of CO2 can also be utilized as zero-net carbon
gasoline and synthetic jet fuel. DAC is not an alternative technol-
ogy for traditional CO2 reduction methodologies, but it can elimi-
nates the cost required for CO2 capture in CCS process and also
used to manage the CO2 emission from different sources. Though
DAC has the above mentioned advantages, it’s still in the initial
stage of development in the Europe and United States. In future,
large-scale DAC process might be implemented once it connected
with the policy inducement or economical case uses (Sanz-Pérez
et al., 2016; Beuttler et al., 2019).
5. CO2 conversion process
5.1. Hydrogenation
Since the influence of these emissions on the various aspects of
our biosphere is constantly increasing, we are in need of different
strategies to lessen the burden on our planet and one such method
is to convert the carbon dioxide in our atmosphere into valuable
products and by-products like methanol, dimethyl ether, formic
acid, etc. CO2 hydrogenation to methanol is a useful methodology
as it is used as biofuels, solvents or sources for synthesis of certain
chemicals. The hydrogenation process itself can be made more eco-
friendly through the use of hydrogen obtained from the electrolytic
splitting of water instead of using the methane reforming process
to produce it. In the electrolysis or water splitting process, water
could be decomposed into hydrogen (H2) and oxygen (O2) gas
using electricity with the potential difference of 1.23 V. Thus, the
produced green hydrogen can be effectively utilized as hydrogen
A. Saravanan, P. Senthil kumar, Dai-Viet N. Vo et al. Chemical Engineering Science 236 (2021) 116515

Table 2
List of catalysts used for the production of valuable products through CO2 utilization and conversion approaches.

S. No Catalysts Products Approaches References

1 Sulfur modified copper Formate Electrochemical (Chen et al., 2019a, 2019b)
2 Formate Dehydrogenase Formate Chemo-Enzymatic (Reda et al., 2008)
3 Pd/HZSM-5 Dimethyl ether Hydrogenation (Chu et al., 2017)
4 Nitrogenase Methane Chemo-Enzymatic (Yang et al., 2012)
5 Carbonic anhydrase Bicarbonate (HCO
3) Chemo-Enzymatic (Yong et al., 2015)
6 CuInS2 thin film Methanol Photoelectrochemical (Yuan and Hao, 2013)
7 Indium Acetate and Formate Electrochemical (Zha et al., 2020)
8 Nickel (Ni) Methane Thermal (Reforming) (Zhang et al., 2020b)
9 W18O49 Photocatalytic (Xi et al., 2012)
10 TiO2 Methane & Methanol Photocatalytic (Koci et al., 2009)
11 HNb3O8 nanobelt Methane Photocatalytic (Li et al., 2012)
12 Bi2WO6 nanoplate Methane Photocatalytic (Zhou et al., 2011)
13 Zn2GeO4 nanoribbon Methane Photocatalytic (Liu et al., 2010)
14 Cu/ZnO/Al2O3 Carbon monoxide Reverse water gas shift (RWGS) (Zhuang et al., 2019)
15 ZnS Methanol and Methane Photocatalytic (Koci et al., 2009)
16 p-type GaP Methanol Photoelectrochemical (Barton et al., 2008)
17 PET supported TiO2 Carbon monoxide Photocatalytic (Jensen et al., 2011)
18 Zeolite membrane Methanol Hydrogenation (Raso et al., 2020)
19 CuZnZr/ferrierite hybrid Dimethyl ether (DME) Hydrogenation (Sheng et al., 2020)
20 RuCl3xH2O Formate Hydrogenation (Jaleel et al., 2019)
21 Au/Al2O3 Formate Hydrogenation (Filonenko et al., 2016)

2020b). Ru/MgAl catalyst with non-thermal plasma treatment

Fig. 5. Hydrogen production through electrolysis of water.
fuel. Hydrogen production through electrolysis of water is depicted
in Fig. 5. The general reaction for water splitting or electrolysis of
water is given as follows:
2H2 O ! 2 H2 + O2
The general reaction for the hydrogenation process is given as
follows:
CO2 þ 3H2 ! CH3 OH þ H2 O
The selectivity of this reaction was improved in different ways.
The usage of a zeolite membrane in this process was found to yield
methanol more than that of the possible amount in traditional
reactors due to their issue of thermodynamic equilibrium (Raso
et al., 2020). Similarly, a combination of copper-cerium-
zirconium solid solution and copper oxide prepared at 450 °C
caused the conversion of CO2 to about 71.8% methanol due to the
formation of H+ and HCOO ions in higher quantities (Wang
et al., 2020a, 2020b). Another effective 10Cu/ZnCr-3.5 catalyst pro-
duced a yield of 4.7 mmol/gcat/h of methanol and if CO was added,
it avoided the reverse water gas reaction favouring the production
of methane (Xiong et al., 2019). Cu/AlCeO catalyst prepared
through co precipitation was able to make the surface of the cata-
lyst more basic helping the hydrogenation process to form metha-
nol with STY (space time yield) of 11.9 mmol h1 g1 (Li et al.,
exhibited an excellent CO2 conversion rate of about 85% by having
comparatively lower activation energy of 21 kJ mol1 than the
other thermal processes (Xu et al., 2020).
Platinum doped on monovalent graphene catalyst was used to
adsorb CO2 to facilitate the addition of hydrogen to it and the lower
activation energy range of about 0.56–2.8 eV demonstrates its fea-
sibility (Yan et al., 2020). Not only methanol, there can be several
pathways in this hydrogenation process which leads to different
products like in the case of dimethyl ether, which can be used as
a replacement for propane in Liquefied Petroleum Gas (LPG) and
it is also preferred as a diesel fuel nowadays. The mechanism caus-
ing this direct conversion is given in Eq. (15).
CuZnZr=FER
2CO2 þ 6H2 ƒƒƒƒƒƒƒ! CH3 OCH3 þ 3H2 O ð15Þ
In the above process, the carbon dioxide adsorbed on the cata-
lyst surface tends to get converted into two essential intermedi-
ates, i.e., carbonate and formate finally leading to the formation
of methoxy groups and thereby dimethyl ether (Sheng et al.,
2020). Another direct dimethyl ether synthesis can be done by
the power to liquid approach, where electricity helps in H2 produc-
tion and when this is used to hydrogenate carbon dioxide, the total
ð13Þ conversion was expected to be about 82% via simulation software
like Matlab R2017b (Michailos et al., 2019). Similarly, formates
were also produced through this process as they have various pur-
poses in the printing, and dyeing industries. On the usage of a
ð14Þ RuCl3xH2O catalyst with a melamine polymer, about 0.42 M of for-
mate could be produced, as a bicarbonate ion is first formed which
then converts to formate (Jaleel et al., 2019). Au/Al2O3 catalysts
were able to hydrogenate CO2 with reaction rates of about
100 h1 of the product formate formed through the following reac-
tion (Filonenko et al., 2016).
Au=Al2 O3 &Et3 N=THF

ƒ! HCOO :Et 3 NHþ
H2 þ CO2 ƒƒƒƒƒƒƒƒƒƒƒ ð16Þ
5.2. Esterification
The formation of a fruity smelling compound otherwise known
as esters using alcohols and acids is a general reaction and the
usage of CO2 in it provides numerous advantages like in the case
of an esterification of fatty acids with ethanol using an
Amberlyst-15 catalyst, supercritical CO2 (carbon dioxide exists as
8
A. Saravanan, P. Senthil kumar, Dai-Viet N. Vo et al.
a fluid above its critical temperature and pressure), increased the
conversion to CoA esters by about 50% (Melfi et al., 2019). Simi-
larly, this supercritical CO2 when used along with montmorillonite
K10 catalyst aided in increasing the conversion of levulinic acid
to ethyl levulinate by about 9% and it also helped the catalyst to
withhold its potency for 4 reuses (Da Silva Junior et al., 2020).
Rosin is a resin obtained from pine trees and when it is hydro-
genated to yield glycerol esters, the addition of subcritical CO2 low-
ered the activation energy of the reaction acting as an acid catalyst
ensuring the possibility for comparatively less stringent conditions
than normal (Zhang et al., 2017). A decrease of about 6 kJ mol1
activation energy in the presence of SC CO2 for the same rosin
esterification reaction along with the lowering of the change in
enthalpy (DH°) were also observed (Zhou et al., 2018). In the case
of the production of flavour esters from fatty acids using lipase
enzyme, the usage of supercritical CO2 was found to activate or
deactivate the enzyme based on the conditions set and this fluid
as a medium helps the fatty acids to bind with the enzyme better
(Dias et al., 2018). Similarly, lipase obtained from Pseudomonas
cepacia was treated with both sub and supercritical CO2 and the
latter increased its esterification activity due to certain changes
in their secondary and tertiary structure of proteins (Chen et al.,
2013). Diethyl carbonate is an ester that can be used as a fuel addi-
tive and an electrolyte for batteries. An amount of 0.056 mmol h1-
of product was obtained from ethanol and CO2 and the presence of
CO2 increased the yield of dimethyl carbonate than traditional
reactions.
2CH3 OH þ CO2 ! CH3 OCðOÞOCH3 þ H2 O ð17Þ
Dimethyl carbonate, which can also be used as a fuel additive,
was produced from carbon dioxide at 7.3 MPa and 80 °C 
100 °C produced a yield of about 97% dimethyl carbonate from dis-
tillation (Wang et al., 2017a).
5.3. Oxidation and reduction
The following reaction indicates the catalytic conversion of
ethylene to ethylene oxide and it has been observed that about
2.8 tons of CO2 was utilized with the operating temperatures used
being even lesser than 400 °C (Mobley et al., 2017).
C 2 H4 þ CO2 ! C 2 H4 O þ CO ð18Þ
Since, nickel is an important element extracted from ores,
extraction of Ni from nickel laterite by first reducing it and then
by oxidation using carbon dioxide at 1100 °C obtained a good qual-
ity ferronickel with 37.2% nickel grade (Hang et al., 2020). Using a
LaFexCo1xO3 perovskite oxide, CO2 was used to oxidise methane
where the reaction involved the partial splitting of carbon dioxide
to CO with a selectivity of about 52% and the provision of Fe to this
reaction promoted both the conversion and separation reactions
(Shen et al., 2020). FeOx/TiO2 catalyst is capable of a chemical loop-
ing reaction (a redox reaction of ethane to ethylene conversion and
CO2 to CO conversion) producing CO of about 2 mmol/g of CO2 at
reaction conditions of 700 °C (Jeong et al., 2020). The treatment
of supercritical CO2 to metals like steels are involved in several
thermal related industries and we can see that the oxidation of
these metals, which is not feasible was reduced when the CO2 pres-
sure was provided at 5 MPa (Bidabadi et al., 2019). In all the ther-
mal process, evolution of carbon dioxide after combustion is a huge
disadvantage and so there are several methods used to tackle that.
A simulation study of a model for amine combustion indicated that
for a run time of about 7500 h/year, it could capture 408 tCO2 /h as
they have included the degradation of solvents along with it
(Leonard et al., 2015). Similarly, amine degradation to other
products thermally doesn’t happen easily as they are thermally
stable, but upon the addition of 0.7 CO2 /mol DEEA, N,
9
Chemical Engineering Science 236 (2021) 116515
N-Diethylethanolamine, its rate of degradation was found to be
increased (Gao et al., 2014). When Calcium carbonate is treated
at conditions lower than 1000 °C, CaO are particles formed which
when mixed with Al3+ ions enable the conversion of CO2 to CO2 3
as they act as a catalyst to the sintering reaction (Beruto et al.,
2012). About 95% conversion of carbon dioxide into CO was
achieved using thermal plasma by first pre activating CO2 to O2
which then helps in the following carbon oxidation process
(Li et al., 2019).
SnO produced from SnO2 was able to catalyze the conversion of
carbon dioxide and water to hydrogen and CO with the CO2 reduc-
tion requiring comparatively increased temperatures (Abanades,
2012). When iron oxide (Fe3O4) was subjected to redox reactions
with carbon dioxide, about 99% yield of syngas (CO and H2) was
obtained at 1600 K with increased pressure and decreased temper-
ature favouring the reaction (Bachirou et al., 2016). The obtained
syngas can be converted into various fuels and other products.
Another process of producing it is by the Zn/ZnO redox reactions
with the final product of syngas and ZnO at operating conditions
of 2030 K and ZnO is sent back to the reactants (Loutzenhiser
and Steinfeld, 2011). The heat requirements for the redox reactions
involving Zr-CeO2 is comparatively lower than perovskites in the
syngas production process and so the overall efficiency was higher
than the other catalyst with no need for temperatures to be beyond
1600 °C (Muhich et al., 2018). CoFe2O4 produced via sol-gel
method was capable of producing syngas of about 139 mmol of
CO/g at 1000 °C which was higher than other Co ferrite materials
(Takalkar et al., 2019).
5.4. Methanation
The conversion of CO2 into methane holds various uses as in the
case of fuel Cells and it is an important intermediate which can
then get converted into syngas, which is also a fuel for even inter-
nal combustion engines (Sun et al., 2020). Upon adding different
concentrations of Ni (wt.%) to MgO catalyst, the conversion of
CO2 was revealed to be about 87% at a range of 533–648 K with
Nickel helping out in more hydrogen to be adsorbed onto the sur-
face favouring increased conversion based on the amount added
(Loder et al., 2020). The methanation kinetics were analysed using
three different modelled reactors out of which the bubbling
fluidized-bed reactor required the least amount of catalyst
(34 kg) at a flow rate of 166.5 Nm3/h than the other fixed bed reac-
tors for converting carbon dioxide by about 90% (Italiano et al.,
2019; Ngo et al., 2020). Since this process is an exothermic in nat-
ure, a plasma activated reactor for methanation was proposed with
a safety insulation ensuring no excessive loss of the evolved heat
and the observed temperature of 350 °C ensured reduced power
consumptions for the plasma-based reactor with about 73% effi-
ciency (Biset-Peiro et al., 2020). C12A7 also called as Mayenites
when used with Ruthenium along with a hydroxide ion had lower
activation energy of 70.9 kJ mol1at 225 °C than other ions or mod-
ified catalysts because this OH allows for the production of car-
bonates which then gets converted to formates and thereby to an
intermediate necessary for methane formation (Wu et al., 2020).
Ni/CeO2 prepared through a sol gel method was found to have
an activity that is 2–48 times greater than conventional Ni/CeO2
catalysts with a conversion of about 80% and this was due to the
formation of an aldehyde intermediate (Ye et al., 2020). Another
approach using Ni/Ce combination was to support them through
reduced graphene oxides. This provided a good product yield of
about 83% and conversion of about 84% and this was because of
that graphene’s increased surface area, allowing the proper attach-
ment of the metal (Hu et al., 2019). This CO2 methanation process
when performed in a fluidized bed reactor using a NiMgW catalyst
indicated that the product yield lowered when the feed inlet rate
A. Saravanan, P. Senthil kumar, Dai-Viet N. Vo et al.
and the particle sphericity and diameter became higher (Jia et al.,
2019). In the case of Ni/SiO2-Al2O3 catalyst, the addition of Mn
was proven to be helpful as it aids in the reduction process and
in adsorbing carbon dioxide even at lower temperatures than nor-
mal (Vrijburg et al., 2020). The impregnation of nickel nanoparti-
cles onto a chromium terephthalate MIL-101 was utilized for
methane production, which yielded a XCO2 of about 56% at
320 °C. The reason for this production was because of using an
increased H2 proportion in the CO2:H2 ratio (Mihet et al., 2019).
The use of plasma to deposit particles as a thin film was utilized
on CoOx catalysts and it was seen that the oxidative state of Cobalt
was involved more in the methanation process and out of those,
CoO could manage an excellent CO2 conversion of 73%
(Kierzkowska-Pawlak et al., 2019).
5.5. Reforming
The reaction of carbon dioxide with methane to produce syn-
thesis gas is known as dry reforming and if water is added along
with the process, it is called as bi-reforming. The different types
of reforming processes including dry reforming, bi-reforming and
tri-reforming processes for CO2 utilization and conversion are
shown in Fig. 6. The formed syngas can be converted into different
kinds of organic products like methanol, and synthetic fuels. ZrO2/
Al2O3 along with nickel and cobalt which has been co-precipitated
has been used as a catalyst after calcination for this reforming pro-
cess and the addition of 0.2% Rh ensured an excellent carbon diox-
ide conversion of about 71% with only 3.8% of cake accumulation
onto the catalyst (Al-Fatesh et al., 2018). Reforming along with
steam in a gliding arc reactor utilizing plasma was found to
increase the formation of hydrogen in the product stream due to
the formation of hydroxide radicals. This process could lower the
production of soot since it does not involve thermal stimulus
(Xia et al., 2020a). Ni/SiO2 catalysts were prepared and calcined
at different temperatures for using in the reforming process and
the calcination temperature of 600 °C provided the best CO2 con-
version of 3.2 mmol g1 Ni s
1
due to the optimal medium sizes of
the Ni nanoparticles on the catalyst surface (Zhang et al., 2019a).
CNiCe (a nickel-based CeO2 added catalyst) was availed for the
dry reforming reaction with the conversion first lowering to 52%
due to sintering of nickel, which later increased to about 79%
because of the reduction of NiO (Zhang et al., 2020b). The presence
of just nickel as a catalyst alone would not help in reforming as
Fig. 6. Different types of CO2 reforming processes.
10
Chemical Engineering Science 236 (2021) 116515
when Ni gets reduced during the reaction, it will cause the
methane to get converted to carbon which has a negative impact
on the CO2 conversion process. So, calcined ilmenite with NiO
was used in order to avoid the negative impact and the time taken
for the syngas production was 5 min for 5% NiO added (Sun et al.,
2019). Ni with a silica coating supported on carbon fibers having
5% by weight of Ni was utilized for the methane reforming process
with an excellent methane conversion of about 90% and this com-
bination was found to make the sintering resistance higher for the
Ni particles (Wei et al., 2020). Activated carbon catalysts with dif-
ferent additions like Ce, Co and W were tried out in different pro-
portions using the multi RSM (Response Surface Methodology) and
the results show that Ce and Co contributed positively to the car-
bon dioxide conversion but W caused both the reactant conver-
sions to lower (Li et al., 2020a).
A membrane made up of ceramic-carbonate which was found to
have an excellent permeation capability of oxygen and CO2 was
used for the oxy reforming reaction and this was capable of pro-
ducing a continuous amount of syngas for even up to 300 h at
875 °C with alterable H2/CO ratios (Fabián-Anguiano et al., 2019).
Ni-0.35C/Al2O3 catalyst along with glucose was prepared and the
glucose degraded to products such as methane and H2. These prod-
ucts helped in reducing the nickel particles easily which is neces-
sary for the reaction without the application of any extra thermal
energy, especially for the reduction process (Zhao et al., 2019).
Ni-Fe-Al oxide catalyst was used for the chemical looping reform-
ing of methane and it achieved an 88% selectivity of carbon monox-
ide and a methane conversion of about 98% for up to 20 runs. This
combination could also avoid the deposition of carbon on the cat-
alyst to a good extent (Kim et al., 2020).
5.6. Reverse water-gas shift (RWGS) reaction
Reverse water-gas shift reaction, is a way of producing CO and
water when carbon dioxide is treated with H2. Hence, this method
is an efficient carbon mitigation strategy with an additional provi-
sion to obtain water. A stainless steel of the type 316 having a noz-
zle diameter of about 20 lm was used as a catalyst for the RWGS
reaction resulting in a conversion of about 80% at 1000 K with the
temperature being directly proportional to the yield (Thompson
et al., 2020). Zeolite-based Mo catalysts were tried out for this
RWGS reaction and they achieved a good CO selectivity value of
about 99% with the addition of Cu helping out in the Mo reduction
process, facilitating a better conversion of about 18% at a temper-
ature of 773 K (Okemoto et al., 2020). Normal Mo particle size is
comparatively large making it less effective for the RWGS reaction
because of its low catalytic activity and this was changed by car-
burising it to change it into Mo2C. Therefore, the prepared Mo2C
particles have a diameter of just 0.5 nm and are capable of provid-
ing a greater product selectivity of about 99% aided by the addition
of nitrogen which changed its basicity (Ma et al., 2020). Tungsten
chloride catalysts were added along with Na or K and by lowering
the activation energy, they increase the amount of CO2 adsorption
on for the RWGS reaction. Therefore, a product yield of about 26%
was obtained at 350 °C for the WC catalyst with added potassium
(Morse et al., 2019). Saponite clay with different metal elements
like Cu, Co and Ni was tried out with the Ni-Cu combination having
no deposition of carbon on the catalyst or sintering and it provided
increased selectivity towards the RWGS reaction and mostly avoids
methane formation (Nityashree et al., 2019). Cu/CeO2 nanospheres
as catalysts for the RWGS reaction were analysed and it showed
that the presence of O2 vacant sites on the surface aided most of
the CO2 to get adsorbed and get converted into necessary interme-
diates like formates, carbonates important for it to convert into CO
and water (Zhang et al., 2020a). Two vanadium carbide catalysts
with one (V8C7) having a deficiency in the number of C atoms were
A. Saravanan, P. Senthil kumar, Dai-Viet N. Vo et al.
utilised for the RWGS study. From the study, it was observed that
the catalyst with the C vacancy adsorbed more amount of CO2 and
lowered the energy barrier for the carbon dioxide dissociation to
the product by about 1 eV (Pajares et al., 2020). The use of 5%
Co/CeO2 mesoporous catalyst for the RWGS reaction was found
to be efficient for a run of about 10 h at 600 °C due to the excellent
interaction between the Co and the ceria having a large surface
area ensuring good catalytic activity (Wang and Liu, 2018). Iron
supported on alumina was an extremely selective catalyst for
RWGS reaction and exhibited high CO selectivity and fast catalytic
CO formation (Sengupta et al., 2019). A conversion of about 50% at
a temperature of 500 °C was achieved when 0.5% Ru was added to
Cu/ZnO/Al2O3 catalyst. The yield of CO was actually twice the nor-
mal because of the Ru addition which had become Ru-Cu nanopar-
ticles and it was completely towards the formation of CO (Zhuang
et al., 2019). MgO nanocrystals prepared using surfactants were
doped with different concentrations of Ni and 7% Ni addition pro-
vided the best catalytic activity even after a run for 50 h at 600 °C
and any much higher addition of Ni than this affected the final
yield (Ranjbar et al., 2018).
6. Difficulties in CO2 utilization and conversion
The challenges involved in the CO2 utilization include (i) Cost
required for the capture of CO2 in CCS technique, (ii) energy
requirements and (iii) market scale up (Spinner et al., 2012). There-
fore, the source of the CO2 must be considered as a major factor, as
that influences the cost involved in its capture and utilization
(Chen et al., 2018). As discussed, CO2 is converted into beneficial
products by the use of different approaches. Due to certain practi-
cal difficulties, electrochemical conversion is not applied majorly
in industries even in the present due to optimization of the Fara-
daic efficiency (FE), Energetic Efficiency (EE) and Current Density
(CD) which are required to succeed in this approach (Jhong et al.,
2013). The mineralization of CO2 is not feasible due to the technical
challenges (Galadima and Muraza, 2019). However, the normal
weathering process is made to use by mining minerals like olivines
which can convert the atmospheric carbon to bicarbonates and
later into limestone’s through the in situ in dunite massifs
approach or to fill ground olivine in deserted deep opencast mines.
In this approach excess heat was generated during the reaction
process that can be collected as steam having high enthalpy. For
the effective result the high enthalpy steam should be applied only
to a large volume of olivine, because for the same operation in a
smaller scale, the heat losses will be more. Author Schuiling pro-
vides a solution for the above-mentioned problem through a con-
vective system which is similar to the geothermal system. For
the convective system, the grounded olivine is to be filled in half
of the deserted deep opencast mines and covered it by backfill
and then at the bottom side the collected high enthalpy steam
and CO2 were injected. Thereby, the CO2 level in the atmosphere
might be reduced. This approach can be optimised and also has
the potential to be cost effective (Schuiling, 2006). The common
difficulties involved in the biochemical conversion, includes nutri-
ent delivery, collection of products and maintenance of culture. It
is suggested that organism can be genetically engineered in order
to overcome these difficulties. However, multiple copies of the
genomes lead to genetic knockout. Further, pretreatment is
required and productivity is less when compared to that of
thermo-chemical process. Additionally, they require long process-
ing time, high reaction time and involves difficulties in down-
stream processing steps (Singh et al., 2015). The thermal
approach requires harsh operating conditions such as high pres-
sure and high temperature. Limitations of the thermal approach
11
Chemical Engineering Science 236 (2021) 116515
includes catalyst instability at the elevated temperature, syngas
production, and low selectivity and cost (Galadima et al., 2011).
In the above two approaches, selectivity is low and it is difficult
to use high performance catalyst. Although selectivity is higher in
chemo-enzymatic conversion of CO2, there are certain disadvan-
tages such as high cost, recycling of catalysts, undesirable interac-
tions in co-immobilization and unavailability of ion type cofactors
(Shi et al., 2015). Photocatalytic conversion process requires high
capital, energy for the utilization of semiconductors with a broad
band gap. The major limitations in the substrate based photocata-
lyst are degradation of the polymer, formation of volatile products
and difficulty in separating the catalyst from the product. Catalysts
involved in the conversion require optimization and treatments,
which can further add up to the cost (Kumar et al., 2012). The con-
version of CO2 into long chain hydrocarbons is difficult (Hu et al.,
2013). In addition, there is a limitation in the kinetics of the con-
version of CO2 (Kumar et al., 2012). Most of these technologies
are still in their development or pre-commercial stage, which
cause a problem with scale-up (Cadham et al., 2016). CO2 utiliza-
tion is less supported than the conventional energy sources and
it is not yet commercialized (Huang et al., 2014).
7. Current status and future perspectives
Energy utilization is primarily contributed by the fossil fuels
such as coal, petroleum and natural gas. With the increase in global
economic development, there is an increase in the level of CO2 in
the atmosphere. It is reported that the resources are getting
exploited significantly higher than the amount that is actually
needed and hence more waste is generated leading to the increase
in the greenhouse gas emissions. Therefore, it is highly essential to
implement major changes in the energy system. The challenges
involved in the utilization of CO2 as the energy source are majorly
around economic viability. As carbon dioxide is not a high value
product such as ethylene or syngas, it has fewer industrial applica-
tions, and therefore less profitable. A crucial problem that affects
the thermal conversion of CO2 is the associated operational and
cost difficulties. Designing of new reactors will provide the chance
to implement large-scale CO2 utilization. Future studies can also be
focused on combining the usage of associated thermo stable
catalytic-mechanism in order to enhance the selectivity. In the pre-
sent, the photocatalytic conversion of CO2 was carried out in the
presence of artificial source of light. Research in this field is tar-
geted towards the utilization of the solar energy for the CO2 con-
version and in the minimization of the band gap energy by the
process of doping the semiconductors. The success rate of both of
these methods will rely upon the research based on the integration
of areas such as solar absorbing infrastructure, efficient system for
the capture of CO2 and basic understanding about the techniques.
In the last 50 years, numerous studies have been contributed in the
field of electrochemical conversion of CO2. In order to improve the
efficiency, further studies can be carried out to improve the cata-
lyst lifetime, increase the tolerance for impurities and in the design
of specialized reactors. The present biochemical approaches have
low selectivity and low product yield. The exploitation of the
diverse population of autotrophic microorganism and utilization
of the other techniques such as metabolic engineering, next gener-
ation sequencing and genetic manipulation to attain the desirable
results will significantly contribute to the successful biochemical
conversion of CO2. Biochemical conversion of CO2 can possibly find
its applications in the chemical, petrochemical, agricultural, envi-
ronmental and pharmaceutical industries. Chemo-enzymatic
approach towards the utilization of CO2 is a promising technique
in order to achieve high selection and product yield. The possible
work in this area may be around the disadvantages involved in
A. Saravanan, P. Senthil kumar, Dai-Viet N. Vo et al.
these techniques. The existing enzymes are highly expensive and
studies have been carried out to increase its activity and stability.
Research in identifying the problems in industrial application and
scaling them up is desired. Further, the design of the enzymes by
computational methods can be used to create novel enzymes that
can yield the desired results. New inventions and research in the
field of CO2 capture, utilization and sequestration are present
throughout the world. Contribution in implementing the tech-
niques can be made by researchers, governments and people in
order to move towards the goal of sustainability.
8. Conclusion
CO2 utilization and conversion present both difficulties as well
as chances to attain sustainability and mitigate the energy
demand. This review explains the different approaches and the
conversion strategies of CO2 into value-added products and their
challenges. Electrochemical and photocatalytic approaches have
gained importance in the research field due to their high selectiv-
ity, yield and efficiency. The use of micro-organisms and metabolic
engineering is also gaining attention in the recent times. A green
approach for CO2 capture, sequestration and conversion is the
chemo-enzymatic approach. The integration of these several
approaches leading to better conversion is appreciable as it can
complement the shortcomings of the individual techniques. Even
though, fossil fuel will be the major energy source in this decade,
it is highly necessary to focus on CO2 utilization as a source for fuel
or energy production and chemical feedstock. Because, burning of
fossil fuel for different purposes such as transportation, heat and
electricity, releases huge amounts of CO2 in the atmosphere. More
research is needed on the fundamentals, and techniques in the
areas such as catalytic chemistry, reaction kinetics and optimiza-
tion steps. Future research can be focused on the energy saving,
space saving, easy to scale up and cost-effective CO2 conversion
techniques. The evaluation of energy, economics and environment
is important in designing a system for CO2 conversion. It is also
reported that the conversion of CO2 into feedstock chemicals is
ineffective when compared to the production of high energy prod-
ucts such as methanol and dimethylether in terms of utilization of
captured CO2. In spite of these advantages, CO2 utilization and con-
version have a limited market potential since both the cost of pro-
duction and cost of CO2-cycled energy products are considerably
high when compared to conventional energy products. The major
barrier in the market for CO2 cycled products is the quality param-
eters set for these products which is due to policy issues. Hence the
government can come up with new policies for relaxing certain
constraints for these products and also can give incentives to
industries to support CO2 utilisation and commercialisation. In
the near future, the depletion of fossil fuels would cause a great
energy demand and this would create a proper situation for these
CO2 cycled products to fulfil the demand for energy.
CRediT authorship contribution statement
A. Saravanan: Writing - review & editing, Data curation, Formal
analysis. P. Senthil kumar: Conceptualization, Validation, Supervi-
sion. Dai-Viet N. Vo: Conceptualization, Validation. S. Jeevanan-
tham: Resources, Visualization. V. Bhuvaneswari: Investigation,
Formal analysis. V. Anantha Narayanan: Resources, Visualization.
P.R. Yaashikaa: Resources, Formal analysis, Visualization. S.
Swetha: Resources, Formal analysis. B. Reshma: Resources, Formal
analysis.
12
Chemical Engineering Science 236 (2021) 116515
Declaration of Competing Interest
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.
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