Biomass Conversion and Biorefinery

https://doi.org/10.1007/s13399-022-02552-8

REVIEW ARTICLE

Biochemical conversion of ­CO2 in fuels and chemicals: status,

innovation, and industrial aspects
Rishi Gupta1 · Archana Mishra2 · Yeruva Thirupathaiah3 · Anuj Kumar Chandel4 

Received: 25 December 2021 / Revised: 26 February 2022 / Accepted: 3 March 2022

© The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature 2022

Abstract
Carbon dioxide levels in the earth atmosphere have been rising to alarming levels over the past few decades by human activ-
ity and thus caused global climate change due to the “greenhouse effect,” which in turn brought about adverse effects on the
planet. Major sources of carbon dioxide ­(CO2) emissions include fossil fuel combustion, land-use change, industrial processing,
respiration of various life forms, and decomposition of biomass. However, over the past 20 years, there has been a continuous
research effort on the reducing carbon dioxide levels, by converting into the syngas, methanol, dimethyl carbonate, epoxides,
polymers, and fine chemicals through chemical catalytic or biotransformation routes. Biological conversion including micro-
bial and/or enzymatic conversion holds high potential as an alternative to the energy-intensive chemical conversion of ­CO2.
Besides being the low energy process, bio-conversion of C ­ O2 offers several unique advantages such as an easy and improved
production at a high scale with a better conversion rate, the possibility of a diverse product range, and hyper-production by
genetic modifications with zero competition for land with food crops. To this end, products that use ­CO2 biotransformation
by the global biotech and chemical industry are only about 11.5 million tons annually, and it is a very small fraction of the
approximately 24 billion tons of annual C­ O2 emission. Hence, there is an enormous scope for generation of high end biorefiner-
ies through C
­ O2 bioconversion systems. Here, we review the various production sources of C ­ O2, the metabolic and enzymatic
­CO2 conversion pathways, and the commercialization potentiality of various green chemicals from ­CO2.

Keywords CO2 emissions · Biological conversion · Renewable fuels and energy · Environment management

1 Introduction
Natural events and anthropogenic activities have led to
the generation of high level of ­CO 2 emissions into the
environment. Since natural ­C O 2 emission events are
self-balancing, anthropogenic activities are considered
the main factor for this environmental change leading to
global warming and climate change. Fossil fuels burning
is the largest source (~ 85%) among all the anthropogenic
* Anuj Kumar Chandel
anuj10@usp.br; anuj.kumar.chandel@gmail.com
1 560  ppm (https://​w ww.​wefor ​u m.​o rg/​a genda/​2 020/​0 7/​
Material Characterization Laboratory, Anton Paar India Pvt.
Ltd, Udyog Vihar, Gurugram, Haryana 122016, India
2 tists). According to the study, if C
Macro Oceans Inc, San Francisco, CA, USA
3
Central Sericulture Research and Training Institute, Mysuru,
Karnataka 570008, India
4
Department of Biotechnology, Engineering School of Lorena
(EEL), University of São Paulo, Lorena 12.602.810, Brazil
activities (https://​o urwo​r ldin​d ata.​o rg/​C O2-​a nd-​o ther-​
green​house-​gas-​emiss​ions). As per stoichiometry, com-
bustion of 1 ton of fossil fuel carbon emits approximately
3.5 tons of ­C O 2 , which leads to the accumulation of
about ­1012 tons carbon in the environment [1]. It has been
reported that the ­CO2 concentration in the atmosphere at
Mauna Loa has increased from 277 to 408.5 ppm from
1750 to 2019 [2, 3]. Furthermore, BP’s Energy Outlook
2030 (2013) predicts that oil will still remain the most
dominant resource of energy in the years to come. It is
also forecasted that the global energy demand will grow
by 36% between 2011 and 2030 [4], and if the buildup
of ­CO 2 continues at current rates by 2060, it will cross
clima​te-​change-​incre​ased-​carbon-​dioxi​de-​emiss​ions-​scien​
­ O2 does reach double
the pre-industrial level, then there is up to an 18% chance
that temperature will rise to 4.5 °C above pre-industrial
levels (http://​u nfccc.​i nt/​resou​rce/​d ocs/​2 015/​c op21/​e ng/​
l09r01.​pdf n.d).

13
Vol.:(0123456789)

Region-wise status of C ­ O2 emission in the world is shown
in Fig. 1. According to the report, Asia is the largest emit-
ter (53%), with China (27.2%) and India (6.8%) as the big-
gest contributor. China alone is responsible for generating
10 billion tons of C ­ O2 emission annually. North America
is the second largest continent in terms of ­CO2 emissions
contributing to almost 18% of global anthropogenic C ­ O2
emissions. In North America, the USA is the main contribu-
tor (14.6%) with annual production of approximately 5 giga
tons of C ­ O2. European Union Countries along with Russia
stands for approximately 17% C ­ O2 emissions (http://​unfccc.​
int/​resou​rce/​docs/​2015/​cop21/​eng/​l09r01.​pdf).
COPE 21 Climate Change Summit accepted the “Paris
Agreement” to mitigate greenhouse gas (GHG) emissions to
keep the worldwide temperature rise up to 1.5 °C (http://u​ nf-
ccc.​int/​resou​rce/​docs/​2015/​cop21/​eng/​l09r01.​pdf). Accord-
ing to IEA, this limit of temperature increase can only be
achieved by limiting the C ­ O2 levels by 15 giga tons annually,
but still, only 14% of C ­ O2 is captured annually [5]. This
means that there is a need for enormous efforts in this area.
In the quest for ­CO2 emission management, various carbon
capture and storage strategies (CCSS) have been investigated
in the last two or three decades. ­CO2 can serve as a major
carbon feedstock to be converted into chemicals and fuels,
and also its transformation to value-added products offers
the dual advantage of both decreasing the atmospheric C ­ O2
levels and subsequently efficiently exploiting it as potential
carbon resources [6]. In general, ­CO2 fixation is carried out
by physicochemical removal of ­CO2 from the atmosphere
and its subsequently catalytic conversion to chemicals and
fuels [7, 8]. However, microbial and enzymatic approaches
for ­CO2 fixation and transformation to high-value products
are gaining extensive interests [8–10]. These approaches
include gas fermentation, microbial electrosynthesis, and
enzymatic conversions [11, 12]. Biotechnological interven-
tions could be opened up further by exploring metabolic
pathways in genetically modified microorganisms and in
Fig. 1  Global ­CO2 emission sta-
tus (adapted from [https://​ourwo​
North America (18%)
rldin​data.​org/​CO2-​and-​other-​
green​house-​gas-​emiss​ions])
Africa (3.7%)
13
Biomass Conversion and Biorefinery
designer biocatalysts that would make the process of ­CO2
conversion more efficient into fuels and chemicals (Boot-
Handford et al. 2019; [8]. Various physicochemical routes
including thermal catalytic conversion, photocatalysis,
electrocatalysis, and/or photo-electrocatalysis have been
attempted for such catalytic conversion of C ­ O2 to various
products. Various catalytic metals, metal oxides and novel
nano-sized catalyst metal–organic frameworks (MOFs) have
been developed for thermal catalytic hydrogenation of ­CO2.
However, the high cost of fossil fuel used and the high value
of reactant hydrogen gas added in the thermal catalysis pro-
cess make this approach less competitive to produce meth-
ane or methanol [13]. While, in photocatalysis, the photon-
generated electrons induce hydrocarbon formation following
redox reaction to ­CO2, however, the process has low conver-
sion efficiency and poor selectivity of products, and most
importantly, it involves toxic and expensive metal elements,
which makes the process less favorable (Kocí et al. 2010;
[14]. Another C ­ O2 conversion approach involves the elec-
trocatalytic conversion of ­CO2 to store energy. The approach
involves use of an external electric field as an energy source
for the reduction of ­CO2 [15]. Compared with thermocataly-
sis, the electrocatalytic conversion is a much cost-effective
method,however, similar to other catalytic systems, product
selectivity is still the major concern [16]. Recently, photo-
electrocatalysis, which combines the advantages of photo-
catalysis and electrocatalysis, has started to gain interest for
the selective conversion of C ­ O2 under sunlight irradiation.
However, the process needs more efficient and environmen-
tally benign catalytic systems and efficient utilization of
solar energy to make the process cost competitive [17–19].
Carbon fixation by cyanobacteria and algae is of prac-
tical interest because they can grow on a large scale in a
short period of time and convert ­CO2 into various metabo-
lites more efficiently. Recent studies have demonstrated that
hybrid airlift photobioreactor systems found to be highly
efficient in the selection of suitable microalgae species on
Europe + Russia (17%)
Asia (53%)
South America (3.2%)
Oceana (1.3%)
Biomass Conversion and Biorefinery
mixotrophic culture mode and used to calculate carbon
dioxide bio-fixation rate to quantify the carbon removal
[20]. Algae have been considered a key player in carbon
bio-fixation in a mixotrophic mode of cultivation performs
photosynthesis by trapping solar energy and provides a com-
plete bio-circular approach for sustainable development for
generation of value-added products [21].
In the present review, we aim to explore the various
sources of atmospheric ­CO2 emissions, strategies to reduce
the ­CO2 levels, detailed understanding of the microbial con-
version of ­CO2, elucidation of enzymatic routes for a diverse
product portfolio from ­CO2, and commercial industrial set-
ups involved in C ­ O2 bioconversion. Though the utilization
of CO2 will never be the entirety of the solution, additional
strategies such as minimization of energy usage and shift-
ing towards on alternative renewable energy sources and
developing novel processes for converting C ­ O2 to produce
valuable chemicals could be an ideal solution.
2 Sources of ­CO2 emissions
Natural systems and anthropogenic activities are the two
main ­CO2 emission sources. The natural system includes
ocean sinks, earth, volcanic activities, and respiration activi-
ties; however, it is a complex system as the exact under-
standing of its ­CO2 adsorption and emission mechanisms
and methods to collect data are still uncertain. Among natu-
ral sources, oceans are the largest contributor with 42.84%
of ­CO2 emissions [22]. Since oceans have approximately
50 times more C ­ O2 than the atmosphere, they also perform
huge ­CO2 diffusion activities by which ­CO2 is released. It
has been reported that this process generates about 330 giga
tons of C ­ O2 emissions globally [22]. Respiration activities
by plants and animals contribute to 28.56% of total natural
emissions, which subsequently amounts to about 220 giga
tons of ­CO2 emissions [22]. Besides, plants and animals,
respiration by microorganisms, soil animals, and plant roots
are other important sources of natural C ­ O2 emission. These
soil emissions are also due to decomposition activities by the
microorganisms. In combination, soil accounts for annual
220 billion tons of ­CO2 emissions globally [22],US [23].
Additionally, volcanic ­CO2 emission due to volcanic erup-
tion can annually create about 0.15 to 0.26 billion tons of
­CO2 emissions (http://v​ olcan​ oes.u​ sgs.g​ ov/h​ azard​ s/g​ as/c​ lima​
te.​php). In addition to volcanic activities, earthquakes also
contribute significantly to atmospheric ­CO2 emission. There
are very few reports where C ­ O2 emissions from earthquakes
are reported. Recently, it has been reported that the Tohoku
earthquake liberated approximately 19.2 Petagram ­CO2-eq
[24], while total GHGs emission from the Wenchuan earth-
quake was nearly 1 Petagram C ­ O2-eq [25]. Nevertheless,
it is also noteworthy that the total natural system emission
roughly has the same order as its absorption. The ocean car-
bon sink alone is approximately 12.6 giga tons per year [26].
Besides natural causes, increasing industrialization
and soaring population levels have led to increasing
the ­C O 2 emissions worldwide and are responsible for
exerting extra pressure on the earth system. It has been
reported that anthropogenic GHG emissions account for
approximately up to 66.6% of the total global GHG emis-
sions. The main anthropogenic sources of ­CO2 emissions
include the use of fossil fuels, land-use change including
agricultural activities, and industrial processes (Table 1).
It has been reported that all these factors have now led to
reach the levels of ­CO2 emissions to a significantly dan-
gerous limit (Van [27, 28]. ­CO2 emissions from different
anthropogenic activities are discussed in the following
section (Table 1).
2.1 CO2 emissions through fossil fuel combustion
The burning of fossil fuels is primarily used to generate elec-
tricity, as a transportation fuel and driving force for several
manufacturing operations. However, its combustion leads
to a significant amount of ­CO2 generation. According to a
report, in 2016, fossil fuel caused 73.5% of total anthro-
pogenic GHG emissions with more than 32.5 billion tons
of ­CO2 emission (https://​www.​ipcc.​ch/​site/​assets/​uploa​ds/​
2019/​08/4).
Worldwide, coal, oil, and natural gas are the 3 main types
of fossil fuels that have been used extensively in various
sectors, and out of which, coal is the main source of ­CO2
emissions. It is calculated that each ton of coal can give
rise to 2.5 tons of ­CO2 equivalents emissions [29]. Among
various sectors, the use of fossil fuels in heat and electricity
generation alone has generated approximately 49.1% fuel
associated with GHG emissions. In 2016, 15.01 billion tons
of fossil fuels were used for electricity and heat generation,
which is 6.15% higher than in 2010 (https://​www.​wri.​org/​
resou​rces/​data-​visua​lizat​ions/​world-​green​house-​gas-​emiss​
ions). The sector is majorly dependent on coal as a fuel
source, which makes it a major carbon footprint contributor
(International Energy Agency 2012). The burning of fuels
for transportation is the second biggest reason for anthro-
pogenic carbon emissions. In 2016, the transportation sec-
tor emitted 7.87 billion tons of ­CO2. This sector not only
includes road transport, but also marine shipping, aviation,
and rail transport. Steady increase in the automobile indus-
try and transportation of goods are also the prominent com-
ponents of this sector. Among various modes of transport,
road transport alone accounts for 74.8% of C ­ O2 emission.
It is important to note that the levels of C ­ O2 emission from
the transportation of goods has even surpassed the total
emissions from the industrial sector. However, among vari-
ous types of transport, aviation is the most carbon-emitting
13

Table 1  Major ­CO2 emitting Source
sources and their various
contributing activities (adapted Fossil fuel combustion in transport sector
from:https://​ourwo​rldin​data.​org/​
CO2-​and-​other-​green​house-​gas-​
emiss​ions)
Industry processes
Electricity and heat
Agriculture
Chemicals
Land-use change
Manufacturing and construction
Other industry
transportation and therefore is one of the fastest-growing
­CO2 emission sources [30]. After the transportation sec-
tor, the manufacturing sector causes approximately 17% of
total GHG emissions. In 2016, the C ­ O2 generation due to
manufacturing and construction practice was approximately
6.1 billion tons (https://​www.​wri.​org/​resou​rces/​data-​visua​
lizat​ions/​world-​green​house-​gas-​emiss​ions). Besides, these
major contributors to anthropogenic emissions, burning of
fuels for other applications, and the emissions from other
miscellaneous applications also contribute to a sizeable
proportion. In 2016, they constituted approximately 12%
of the total fuel associated with GHG emissions ( https://​
www.​wri.​org/​resou​rces/​data-​visua​lizat​ions/​world-​g reen​
house-​gas-​emiss​ions).
2.2 CO2 emissions through land‑use changes
Land ecosystems are one of the major carbon stocks that
play a pivotal role in mitigating anthropogenic ­CO2 emis-
sions [31]. It has been observed that annually, land ecosys-
tem takes up almost one-fourth of the industrial C­ O2 emis-
sion globally [32]. However, attributing the man’s need for
food, fuel, and shelter led to an increase in deforestation
activities, and the growing population has further put huge
pressure on forest areas. As an estimate, from 1850 to 2000,
the land-use change has released approximately 396–690
giga tons of ­CO2 emission [33], while from 2000 to 2009,
it has contributed to almost 12.5% of total emissions [34].
Thus, land-use changes are one of the major contributors
for the ­CO2 emissions worldwide with the increased defor-
estation. Though converted agriculture land also acts as a
carbon sink but not as effective as forest land. Moreover,
13
Biomass Conversion and Biorefinery
CO2 emitting sectors
Road (16%)
Ship (2.25%)
Air (2.55)
Rail and pipeline (0.8%)
Cement (4.03%)
Iron and steel (4.98%)
Unallocated fuel burning (2.82%)
Residential building (14.67%)
Commercial building (8.88%)
Agriculture (1.21%)
Fisheries (1.07%)
2.42%
Burning (2.42%)
Crop land (1.88%)
Forest land (2.96%)
7.27%
6.72%
deforestation also leads to soil disturbance with increased
rates of decompositions, which subsequently emits C ­ O 2.
According to the IPCC Special Report, land-use change
activities are responsible for approximately of 13% C ­ O 2,
44% ­CH4, and 82% ­N2O emissions from anthropogenic
activities worldwide during 2007–2016 (https://​www.​wri.​
org/​resou​rces/​data-​visua​lizat​ions/​world-​g reen​house-​gas-​
emiss​ions).
2.3 CO2 emissions through industrial processes
Approximately, 36% of total anthropogenic ­CO 2 emis-
sions in the year 2016 came from the industrial sector out
of which manufacturing has accounted for the maximum
share. In 2016, among various industries, iron and steel
generate maximum anthropogenic ­CO2 emission (9.6%)
followed by chemical industries (4.84%) and cement indus-
tries (4.04%) (World steel Association. [35]. ­CO2 emis-
sions from the industrial sector are due to the excessive
use of fossil fuels and/or chemical reactions that occurred
during the production process. Fuels are used to produce
various chemical products which subsequently lead to
­CO2 emissions. Production of ammonia and hydrogen are
among the most C ­ O2 emission-intensive processes with
fossil fuels as their raw materials. Similarly, plastic and
lubricants use petrochemicals as their raw material, which
on combustion generates a high amount of C ­ O2. Chemi-
cal combustions are the main process in the iron-steel and
cement processing industries. To convert cast-iron to steel,
the iron is oxidized, which converts the carbon into ­CO2.
As an estimate, for the preparation of 1-ton steel, almost 2
tons of C
­ O2 is produced (World steel Association 2011).
Biomass Conversion and Biorefinery

Table 2  List of microbes assimilating ­CO2 for subsequent conversion to various value-added products
Biological system Organism Pathway Source Product Reference

Archaea Methanobrevibacter HP/HB CO2 Methane and thermo- [68]

aboriphilus stable enzymes
Methanospirillum sp. HP/HB CO2 Methane and thermo- [68]
stable enzymes
Methanothermobacter HP/HB CO2 Methane and thermo- [68]
thermautotrophicus stable enzymes
Pyrococcus furiosus Modified genetically to CO2 and ­H2 3-Hydroxypropionic [75]
harbor genes for HP/ acid
HB cycle
Cyanobacteria Synechococcus elon- CBB pathway CO2 Sucrose [58]
gates
Synechococcus elonga- CBB and Glycolytic CO2 2,3-Butanediol [57]
tus PCC 7942 pathway
Synechocystis elongates Over expression of CO2 Sucrose [211]
PCC7942 cscB gene
Synechocystis PCC6803 Expression of pdc and CO2 Ethanol [212]
cdhII
Synechocystis sp. Wood-Ljungdahl CO2 and H2O Ethanol or hydrocarbon [60]
pathway fuels
Synechocystis sp. Wood-Ljungdahl CO2 Bioethanol http://​www.​algen​
pathway ol.​com/ direct-
to-ethanol/the-
technology
Firmicutes Bacillus sp. SS105 CBB CO2 FAME [213]
Clostridium thermocel- Wood-Ljungdahl CO2 Acetate, ethanol, [68]
lum pathway butanol, caproate,
caprylate
C. aceticum Wood-Ljungdahl Industrial waste gases Acetone [80]
pathway
C. carboxidivorans Wood-Ljungdahl Industrial waste gases Acetone [80]
pathway
Clostridium acetobu- Wood-Ljungdahl CO2 Acetone and butanol [81]
tylicum pathway
Clostridium autoetha- Wood-Ljungdahl CO2 Acetate, ethanol, [68]
nogenum pathway butanol, caproate,
caprylate
Clostridium carboxidi- Wood-Ljungdahl H2/CO2 (3:1) Ethanol [79]
vorans pathway
Clostridium ljungdahlii Genetically modified Syngas Butanol [80]
pathways
Clostridium ljungdahlii Wood-Ljungdahl Industrial waste gases Acetone [80]
pathway
Clostridium ljungdahlii Wood-Ljungdahl Syngas Ethanol [214]
pathway
Acetobacterium woodii Wood-Ljungdahl H2:CO2 (67:33) Acetate [215]
pathway

13
 Biomass Conversion and Biorefinery

Table 2  (continued)
Biological system Organism Pathway Source Product Reference

Proteobacteria Acidithiobacillus CBB and rTCA​ CO2 Bioplastic [216]

thiooxidans
Citrobacter amalonati- HP/HB CO2, H2, sucrose Succinate [217]
cus
Cupriavidus eutrophus CBB and rTCA​ CO2:O2:H2 (1:2:7) PHA [218]
B-10646
Desulfobacter hydrog- CBB and rTCA​ CO2 Bioplastic [216]
enophilus
E. coli Reductive glycine CO2 Glycine and serine [104–106]
pathway
E. coli rTCA cycle CO2 Malate [109]
E. coli Reverse action of for- CO2 Formic acid production [110]
mate hydrogenlyase
E. coli CBB cycle CO2 Cell growth [111]
Ideonella dechloratans CBB and rTCA​ CO2:O2:H2 (1:2:7) PHB [219]
R. eutropha Harboring heterogene- CO2 Diesel range methyl [94]
ous fatty acid synthe- ketone
sis genes
R. eutropha A photoelectric device CO2 Isobutanol and [95]
3-methyl-1-butanol
R. eutropha Molybdenum-based CO2 Polyhydroxybutyrates, [96]
catalyst surface butanol, farnescene,
display and other long-chain
alkenes
Ralstonia eutropha CBB and rTCA​ CO2 Bioplastic [216]
Rhodobacter capsulatus CBB and rTCA​ CO2 Bioplastic [216]
Rhodopseudomonas NifA, encoding tran- Light-driven ­CO2 Methane [65]
palustris scription activator of reduction
nitrogenase
Thiomicrospira denitri- CBB and rTCA​ CO2 Bioplastic [216]
ficans
Xanthobacter flavus CBB and rTCA​ CO2 Bioplastic [216]
Actinobacillus suc- HP/HB Biogas Succinic acid and [98]
cinogenes methane
A. succinogenes HP/HB Lignocellulosic hydro- Succinic acid [99]
lysate
Yeast S. cerevisiae Reductive glycine CO2 Glycine and serine [107]
pathway
S. cerevisiae Coexpression of cbbM, CO2/xylose/maltose Ethanol [220]
sPRK, GroEL, and
GroES
*
 CBB Calvin-Benson-Bassham, rTCA​reductive TCA, DC/HB dicarboxylate/4-hydroxybutyrate, HP/HB 3-hydroxypropionate/4-hydroxybutyrate

Typically, in the cement industry, limestone is transformed
chemically at elevated temperature; almost 0.9 tons of ­CO2
is liberated to prepare 1 ton of cement [36].
3 CO2 conversion through microbial routes
Microbial conversion of ­CO2 is one of the crucial strat-
egies for C
­ O 2 mitigation and its conversion various to
value-added products (Table 2). The approach holds high

13
Biomass Conversion and Biorefinery
potential as an alternative to the energy-intensive chemi-
cal conversion of C ­ O 2 [37]. Besides, being low energy
process, microbial conversion of ­CO2 offers several advan-
tages such as easy production at a high scale, high produc-
tivity, high conversion rate, low source specificity, diverse
product range, the possibility of hyper-production by
genetic modifications, and zero competition for land with
food crops [38]. Amelioration in biofuels titers by micro-
organisms seems possible by manipulating the metabolic
intermediates that are recognized in the cellular glycolysis
pathway. A vast number of native microorganisms have a
distinct genetic system that is capable of the synthesis of
green chemicals and fuels [39]. However, the production
of these petroleum substitutes from the microorganisms
is still uncompetitive and requires genetic manipulation
for industrial use. Metabolic engineering has played a key
role in the improvement of ­CO2 utilizing microorganisms.
Metabolic engineering-based innovations will be pivotal to
engineer the superior strains that would make the process
of conversion of ­CO2 more efficient at an industrial scale.
3.1 CO2 fixation pathways in photosynthetic
microbes
There can be several pathways for the ­CO 2 fixation in
microbes; however, so far, seven ­C O 2 fixation path-
ways have been proposed. These include Calvin-Ben-
son-Bassham (CBB) cycle, the reductive tricarboxylic
acid (rTCA) cycle, the reductive glycine pathway, the
reductive acetyl-CoA (Wood-Ljungdahl) pathway, the
3-hydroxyproppionate bicycle, the 3-hydroxypropionate/4-
hydroxybutyrate cycle (HP/HB), and the dicarboxylate/4-
hydroxybutyrate (DC/HB) cycle (Fig. 2). CBB cycle is
used by algae, proteobacteria, cyanobacteria, and most
plants and is quite similar to pentose phosphate pathway
with RuBisCO as its key enzyme [40]. In this pathway,
ribulose-5-phosphate on uptake of ­CO2 molecules forms
3-phosphoglycerate, while in the case of the Wood-Ljun-
gdahl pathway [41] and the reductive glycine pathway
[42, 43], ­CO2 is reduced directly by CO dehydrogenase,
formate dehydrogenase, and formylmethanofuran dehy-
drogenase. This pathway has been reported to be active
in a variety of organisms, including proteobacteria, spiro-
chaetes, and planctomycetes [40]. Interestingly, DC/HB
cycle, HP/HB cycle, 3-HP bicycle, and rTCA cycle all
have evolved around common intermediates, viz., acetyl-
CoA and succinyl-CoA, and also have several common
reactions in their cycles. However, each cycle is present in
the specific microbial group, and their C
­ O2 uptake mecha-
nism also varies. DC/HB cycle assimilates one mole of
bicarbonate and one mole C ­ O2 with pyruvate synthase,
PEP carboxylase, and 4-hydroxybutyryl-CoA dehydratase
as key enzymes [44]. So far, the presence of this cycle
has been reported only in anaerobes and facultative aer-
obes such as Thermoproteales [45] and Desulfurococca-
les [46] and Pyrolobus fumarii [47]. Both HP/HB cycle
[48, 49] and 3-HP bicycle [50, 51] employ acetyl-CoA/
propionyl-CoA carboxylase to assimilate two moles of
bicarbonate,however, 4-hydroxybutyryl-CoA dehydratase
is the main enzyme in the HP/HB cycle [44] and in 3-HP
bicycle are propionyl-CoA synthase [52] and malonyl-CoA
reductase [53], and HP/HB cycle has only been reported
in aerobic Crenarchaeota, and 3-HP bicycle has shown
its presence in green non-sulfur bacteria only [40]. rTCA
cycle, which is reversal of TCA cycle, fixes two moles of
­CO2, and it is reported in green sulfur bacteria, aquificae
bacteria, and proteobacteria [44]. Besides, in these natural
pathways, efforts are also been made to elucidate artificial
­CO2 fixation pathways in microbes. One such synthetic
pathway is the crotonyl-CoA/ethylmalonyl-CoA/hydroxy-
butyryl-CoA (CE TCH) cycle. The pathway consists of 17
enzymes from 9 different organisms with crotonyl-CoA
carboxylase/reductase as its key enzyme. This enzyme
has shown a higher reaction rate than RuBisCO at 40%
less energy expenditure than CBB [54, 55]. In another
study, Bar-Even et al. suggested two synthetic pathways of
malonyl-CoA-oxaloacetate-glyoxylate (MOG) assimilat-
ing two bicarbonate molecules to produce glyoxylate. In
principle MOG mimics the natural ­CO2 fixation pathway
of C4 plants; however, it employs methylmalonyl-CoA
carboxytransferase enzyme, due to which the cycle com-
plete without losing the carbon. Moreover, the pathway
is suggested to have better specificity, kinetics, and ATP
efficiency than the CBB cycle [56].
Cyanobacteria, the autotrophic photosynthetic bacte-
ria, can fix C
­ O2 by photosynthesis and can be genetically
manipulated (especially for Synechocystis and Synecho-
coccus) to convert C ­ O2 into various products [57]. The
main strategies for the genetic manipulation of cyanobac-
teria are improvement in the efficiency of RuBisCO, reduc-
tion of photorespiration, directed pathway design, and
hyperexpression of key enzymes to increase carbon flux
[25, 58, 59]. Kanno and coworkers modified the glycolytic
pathway and CBB cycle in Synechococcus elongatus PCC
7942 for enhanced C ­ O2 fixation. The study demonstrated
an amplified conversion of Ru5P to R15P for increased
production of 2,3-butanediol in dark by deletion of a reg-
ulatory gene (cp12) of the CBB cycle [59]. In another
study, S. elongates were engineered to export ­CO2 in the
form of sucrose, which was subsequently consumed by
the Halomonas boliviensis to produce PHB [60]. Another
example is the genetic manipulation of Synechocystis sp.
to produce bioethanol by Algenol Biofuels., USA (http://​
www.​a lgen​o l.​c om/ direct-to-ethanol/the-technology).
Similarly, Joule Unlimited Technologies Inc., MA, USA,
13

Fig. 2  Existing ­CO2 fixation pathways in microbes including a
the Calvin-Benson-Bassham (CBB) cycle, b the reductive glycine
pathway, c the reductive TCA (rTCA) cycle, d the dicarboxylate/4-
engineered cyanobacteria (Synechocystis sp.) to produce
ethanol or hydrocarbon fuels from C
­ O2 and H
­ 2O directly in
a single-step process [61]. Besides cyanobacteria, purple
non-sulfur bacteria (Rhodospirillum rubrum, Rhodobac-
ter sphaeroides, R. capsulatus, Rhodovulum viride), and
anoxygenic phototrophic purple sulfur bacteria (Thiodic-
tyon syntrophicum) [62, 63] have also been studied for
simultaneous ­CO 2 capture and H ­ 2S removal from flue
gases and wastewater [52, 64, 65]. In a report, Fixen and
colleagues demonstrated ­CO2 assimilation to methane by
13
Biomass Conversion and Biorefinery
hydroxybutyrate (DC/HB) cycle, e the Wood-Ljungdahl pathway, f
the 3-hydroxypropionate/4-hydroxybutyrate cycle (HP/HB cycle),
and g the 3-hydroxyproppionate (3-HP) bicycle
Rhodopseudomonas palustris using nitrogenase transcrip-
tion activator (NifA) [66].
3.2 CO2 fixation pathways in other microbes
Besides the photosynthetic microbes, the C
­ O2 fixating capa-
bilities of non-photosynthetic microorganisms have also
been investigated. Archaea belonging to phyla Euryarchae-
ota and Crenarchaeota and bacteria belonging to phyla Pro-
teobacteria, Actinobacter, Aquificae, Chlorobi, Firmicutes,
Biomass Conversion and Biorefinery
Chloroflexi, and Thermodesulfobacteria are among non-
photosynthetic ­CO2 fixating microorganisms. Most of the
microbes in Euryarchaeota are C ­ O2-type hydrogenotrophic
methanogens, i.e., capable of methane production using C ­ O2
and ­H2 as substrate molecules. Examples of these methano-
genic archaea are Methanobrevibacter aboriphilus, Metha-
nothermobacter marburgensis, Methanosarcina barkeri, and
Methanothermobacter thermautotrophicus [67]. Methano-
gens have the potential of bioremediating and sequestering
­CO2 at the same time along with the production of methane
as an alternative fuel source [68, 69]. While Crenarchaeota
are facultatively aerobic or strictly anaerobic, hyperthermo-
philic archaebacteria including Cenarchaeales, Desulfuro-
coccales, Sulfolobales, and Thermoproteales [70–75] and
some members of these archaea are reported to assimilate
­CO2 by HP/HB cycle [48]. In a study, the hyperthermophilic
archaeon Pyrococcus furiosus has been modified geneti-
cally to harbor genes for HP/HB cycle from Metallosphaera
sedula to produce 3-hydroxypropionic acid (3-HP) from ­CO2
and ­H2 [76].
Acetogenic mixotrophs, such as Clostridium sp., also has
the potential to capture C­ O2 and its onward use as a feed-
stock to produce industrial products, viz., acetate, acetone,
butanol, caprylate, caproate, ethanol, lactate, methanol, and
valerate, using different pathways [77–79]. Ramachandriya
et al. [80] reported 23% sequestration of C
­ O2 using Clostrid-
ium carboxidivorans from a supply of H ­ 2/CO2 (3:1) along
with a 66.5% theoretical yield of ethanol. In another report,
a genetically modified strain of C. ljungdahlii has been used
for butanol production from syngas [81]. Similarly, using the
engineered strains of C. ljungdahlii, C. carboxidivorans, and
C. aceticum, a German company, Evonics, has developed a
acetone fermentation process employing ­CO2 from indus-
trial flue gases [81]. Recently, Papoutsakis and colleagues
engineered C. acetobutylicum for ­CO2 fixation by integrating
eleven genes of the Wood-Ljungdahl pathway from C. ljun-
gdahlii [82]. Besides, acetogens such as A. woodi, Blautia
products, Butyribacterium methylotrophicum, C. autoetha-
nogenum, Moorella thermoacetica, Eubacterium limosum,
and Thermoanaerobacter kivi can also be used for assimi-
lating ­CO2 through non-photosynthetic and anaerobic route
[71, 72, 83, 84].
Moreover, Proteobacteria have also shown the capability
of sequestering ­CO2 employing various pathways. Among
them, α-Proteobacteria such as R. capsulatus, Rhodobacter
sphaeroides, Oligotropha carboxidovorans, and Xantho-
bacter flavus capture ­CO2 by Calvin cycle [85, 86], while
some β-proteobacteria (Herbaspirillum autotrophicum) and
γ-proteobacteria (Acidithiobacillus ferrooxidans, A. thioox-
idans, and Hydrogenovibrio marinus) also used Calvin cycle
to assimilate ­CO2 [49, 85, 87, 88]. Other Proteobacteria such
as Desulfobacter hydrogenophilus and Thiomicrospira deni-
trificans have been reported to employ the rTCA cycle for
autotrophic CO2 fixation [89, 90]. Ralstonia eutropha, a
β-proteobacteria, has been modified genetically to convert
­CO2 into industrially useful products [91–93]. Also, it has
been reported to synthesize PHAs and produce medicinal
compounds via diverse carbon utilization pathways [89,
90, 94]. A native beta-oxidation pathway knockout strain
of R. eutropha, which is harboring heterogeneous fatty acid
synthesis genes, has demonstrated production of methyl
ketone at a concentration of 50–65 mg/L [95]. In another
study, the strain of R. eutropha has been used to develop
a photoelectric device capable of using hydrogen to drive
­CO2 fixation for the production of 3-methyl-1-butanol and
isobutanol [96]. Similarly, a molybdenum-based catalyst dis-
playing R. eutropha has been used to develop an integrated
microbial electrocatalytic system to produce butanol, poly-
hydroxybutyrates, farnescene, and other long-chain alkenes
[97]. Besides R. eutropha, Actinobacillus succinogenes, a
rumen derived Proteobacteria, is also been used as a poten-
tial candidate for genetic modification to capture C ­ O2 and
subsequent conversion to useful commodities. A. succino-
genes is the best-known natural succinate producer and also
a capnophile, which requires high amount of ­CO2 for the
increased production of Succinic acid [98]. Gunnarsson and
coworkers demonstrated production of succinic acid and
methane from A. succinogenes using biogas as carbon source
[99]. In another study, Li and colleagues used lignocellulosic
hydrolysate for large-scale succinic acid production from A.
succinogenes [100]. Later, Jajesniak and group genetically
modified the A. succinogenes strain to elucidate its carbon
metabolism and nutritional requirements [101]. Moreover,
attempts have also been made for in situ recovery of succinic
acid without salt production [102].
3.3 CO2 fixation using genetic engineered microbes
In addition to the above-described microbes, attempts have
also been made to develop genetically modified Escherichia
coli and S. cerevisiae strain for ­CO2 fixation for the production
of a wide array of chemicals [59, 65, 79, 103, 104]. There are
several reports on the heterotrophic expression of reductive
glycine pathway for ­CO2 assimilation and its conversion to cel-
lular glycine and serine in both E. coli [105–107] and S. cer-
evisiae [108]. While Mattozi and colleagues incorporated four
subgroups of 3-HP bicycle separately in different E. coli strains
and demonstrated that all the recombinant strains have devel-
oped the capability to assimilate C ­ O2 [109], in another report,
Guo and coworkers have demonstrated enhanced malate pro-
duction by incorporating the rTCA cycle into the periplasm of
E. coli [110]. Moreover, scientists at the University of Dundee
(UK) genetically modified the E. coli strain for efficient carbon
capture and formic acid production [111]. Recently, Gleizer
and colleagues developed a fully autotrophic E. coli strain
capable of growing solely on C ­ O2 by incorporating a complete
13

CBB cycle into E. coli [112]. Interestingly, the US scientists
have created a novel enzyme, formolase, to convert formalde-
hyde into dihydroxyacetone, which opens up the avenues for
the development of a novel C ­ O2-assimilation pathway that on
incorporating into E. coli’s can be used for the direct conver-
sion of ­CO2 into ethanol as fuel (https://​sites.​google.​com/​view/​
lidst​rom-​lab/​resea​rch/​formo​lase-​enzyme-​engin​eering?​authu​
ser=0).
3.4 CO2 fixation using microbial electrosynthesis
CO2 capture and conversion using microbial electrosynthe-
sis are another potential approach. Microbial electrosynthesis
from ­CO2 relies on the electron uptake capability of microor-
ganisms from the cathode directly or using reduced mediators
or regenerated equivalent from the electrode as an electron
source. The initial proof of C
­ O2 reduction via microbial elec-
trosynthesis was demonstrated by Nevin and colleagues, where
Sporomusa ovata reduced the C ­ O2 by directly consuming the
electrons out of graphite electrodes and generated acetate
[113]. In another report, Zhang and coworkers brought about
2.3-fold higher acetate production with the use of nickel nan-
oparticle coated carbon cathode by S. ovata in MEC setup
[114, 115]. Similarly, Jourdin and colleagues reported a higher
acetate production with the use of nanoweb carbon cathode
owing to an increase in surface area for microbial adherence
[116]. Other pure cultures of acetogenic electrotrophs, such as
A. woodii, C. aceticum, C. ljungdahlii, S. sphaeroides, and S.
silvacetica, have also been employed to produce acetate [117].
The product formation in microbial electrosynthesis is greatly
depending upon the cathode material. A maximum of 80%
improvement in acetate production has been obtained by modi-
fied cathode material such as carbon nanotube (CNT)-cotton,
chitosan, Au-nanoparticles (Au-NPs), 3-aminopropyltrieth-
oxysilane, Pd-NPs, Ni-NPs, and polyaniline [114]. Besides
acetate [114, 118, 119], this approach has also been used to
produce several other value-added products, such as butanol
[120], formate [121], methane [118, 122], oxobutyrate [117],
and ­H2 [118].
4 Enzymatic conversion of ­CO2
4.1 Conversion of CO2 by carbonic anhydrase
Carbonic anhydrase (CA) is one of the most prominent
enzyme systems to capture ­CO2. It can directly convert
­C O 2 to bicarbonate ­(HCO 3 − ) in a two steps reaction
involving a nucleophilic attack and active site regenera-
tion [123]. This conversion process can assist three dif-
ferent processes, viz., mineralization, membrane, and
absorption, in ­CO2 capture, sequestration, and utilization
[124]. For instance, the CA-induced enzymatic conversion
13
Biomass Conversion and Biorefinery
of ­CO2 may involve chemisorption of ­CO2 with regener-
able alkaline aqueous solvents to significantly increase the
­CO2absorption rate and facilitate lower heat of desorption
[124].
Though the use of calcium has shown its immense
potential in a variety of processes, however, the stringency
of reaction conditions, for instance, process temperature
(up to 125  °C), is the major hindrance in their fullest
exploitation [124]. Several approaches have been adopted
to overcome these limitations by the researchers (Daigle
and Desrochers 2009,[125, 126]. Additionally, Migliar-
dini and colleagues developed a thermostable CA from
Sulfurihydrogenibium yellowstonense, which on immo-
bilization over polyurethane foam revealed efficient ­CO2
capture and carbonate conversion. In another approach,
Alvizo and group employed site-directed mutagenesis to
develop mutants of Desulfovibrio vulgaris with improved
thermotolerance (up to 107 °C) [127]. Interestingly, to
increase the selectivity of RuBisCO enzyme towards ­CO2,
Lin and coworkers attempted to overexpress CA in Chlo-
rella sorokiniana and C. vulgaris, which when used in
photobioreactors exhibited a remarkable increase in their
­CO2 capture capability with improved protein and biomass
production [128].
4.2 Conversion of CO2 by formate dehydrogenase
Formic acid (formate), the main product of formate dehy-
drogenase assisted conversion of C­ O2, is among the most
promising fuel alternative for various applications [129,
130]. Formate dehydrogenase (Fdh) is a typical oxidore-
ductase enzyme, which requires NADH as a cofactor for
the fixation of C
­ O2 and its conversion to formate. Since
NADH is having quite a low stability in the oxygen-rich
environment, several attempts have been made to enhance
the efficacy of the process. As an attempt, Lu and cow-
orkers used an immobilization approach to encapsulate
NADH- dependent Fdh in alginate-silica hybrid gels,
which revealed approximately 95% C ­ O2 conversion effi-
ciency and was able to retain approximately 70% of its
activity over 10 batches of recycling [131]. In another
report, Lee and coworkers copolymerized Fdh and NADH
over an electrochemically synthesized polydopamine
(PDA) thin films for formic acid production [132]. The
copolymerized system demonstrated facilitated electron
transport and increased stability over a longer period.
Moreover, to decrease the NADH usage, Yadav and the
group developed a graphene-based photocatalyst-enzyme
system for NADH regeneration and formate production
[133]. The artificial photosynthetic system demonstrated
54% NADH regeneration with 144 mol of formate pro-
duction. Similarly, Amao and coworkers have developed
Biomass Conversion and Biorefinery
an synthetic leaf device, which comprises co-immobili-
zation of chlorin-e6 with an alkane chain and NAD(P)
H-dependent Fdh on a silica gel-based substrate [134].
On application, the artificial leaf exhibited higher for-
mate production, NAD(P)H regeneration, and improved
enzyme stability. Interestingly, Muller and coworkers dis-
covered a bacterial hydrogen-dependent ­CO 2 reductase
from Acetobacterium woodii that eliminates the expense
of NAD(P)H from the formate conversion reaction [135,
136]. Similarly, researchers have also identified NAD(P)
H-independent Fdh with molybdenum or tungsten at the
center of active sites [137–139].
To the best of our knowledge, the tungsten-containing
Fdh from Syntrophobacter fumaroxidans [139] is the most
active enzyme for formate production. Besides, artificial
photosynthetic systems, the approach of enzymatic elec-
trosynthesis, have also been employed for the formate
production. An enzymatic electrosynthesis cell comprises
enzymatic anode and cathode separated by an electrolyte
solution and an external circuit with power supply. Using
this approach, Zhang et  al. studied the enzymatic elec-
trosynthesis of formate from ­NaHCO3 by enzymatic fuel
cell system with FDH immobilized and NADH as a cofac-
tor, and observed a maximum formate production rate of 60
mg ­L−1 ­h−1 [140]. Recently, Choi and colleagues extracted
FDH from Rhodobacter capsulatus and used it with differ-
ent mediators (44 mMof alizarin red S, anthraquinone-2-
sulfonic acid, benzyl viologen, and methyl viologen [MV])
for effective electron transfer to reduce ­CO2, which dem-
onstrated ­CO2 reduction to 6 mM of formate in 5 h [141].
4.3 Conversion of CO2 by carbon monoxide
dehydrogenases
Conversion of C ­ O 2 to carbon monoxide (CO) through
methanol catalyzed by carbon monoxide dehydrogenases
(CODHs) is gaining extensive interest [142, 143]. In nature,
two types of codes are available, i.e., ­O2-sensitive [Fe4S4Ni]
and air-stable [MoSCu] [137], among which oxygen-sensi-
tive CODHs have been observed to exhibit CO oxidation,
while the [MoCu] CODHs do not generate CO [137, 143].
As reported, oxygen-sensitive CODHs possess Ni and Fe
centers bridged by a [3Fe–4S] cluster, which causes proxim-
ity in these metal centers. Inspired by this in vivo system,
the development of in vitro system for C ­ O2 reduction to CO
is always a topic of interest among researchers. Shin and co-
workers firstly observed that [NiFe] CODH (from Moorella
thermoacetica) CODH as an appropriate enzymatic catalyst
for ­CO2 reduction [144]. Later, Parkin and colleagues immo-
bilized [NiFe] CODH on a pyrolytic graphite electrode and
investigated its efficiency in an anaerobic sealed cell and
reported significantly higher standard reduction potential for
the inter-conversion between C ­ O2 and CO as compared to
without catalyst with a much lower required overpotential
and extremely high selectivity [142].
4.4 Conversion of CO2 by nitrogenases
Nitrogenases are another group of enzymes which has shown
potential in capturing ­CO2. The main product formed by
capturing ­CO2 is methane, while reports are also avail-
able for the conversion of ­CO2 into CO and other hydro-
carbons with the action of nitrogenases. It was observed
that the nitrogenase MoFe protein can convert ­CO2 to ­CH4
through a multielectron (six-electron) reduction of N
­ 2 [145].
Besides methane, engineered nitrogenase can also catalyze
the fixation of C
­ O2 with acetylene, producing propylene. It
has been reported that substituting the amino acids present
in the active site of nitrogenase MoFe protein with other
appropriate molecules may alter its catalytic behavior. The
doubly substituted MoFe protein can catalyze the generation
of propylene through the reaction of ­CO2 and acetylene [6].
Recently, Rebelein and coworkers have demonstrated the
role of vanadium nitrogenase in reducing the C ­ O2 molecule
to hydrocarbons [146].
4.5 Conversion of CO2 by ribulose‑1,5‑bisphosphate
carboxylase/oxygenase
The involvement of the RuBisCO is substrates specific, i.e.,
as carboxylase, it catalyzes the carboxylation of ribulose-
1,5-biphosphate glucose, while as an oxygenase, it initiates
C2 photorespiration for the generation of 2-phosphoglycer-
ate, and C
­ O2 [140]. In nature, RuBisCO demonstrates lower
specificity towards C­ O2 over O­ 2, and therefore researchers
are attempting to modify RuBisCO to increase its specific-
ity towards ­CO2 [58]. Liang and coworkers engineered a
Synechocystis PCC 6803 strain to overexpress RuBisCO,
which revealed improved growth and photosynthesis activity
[147]. In another report, a synthetic photosynthetic system
coupled with Calvin cycle enzyme was constructed for con-
verting ­CO2 to sugars, which demonstrated 96% conversion
efficiency [148].
4.6 Conversion of CO2 by decarboxylases
The decarboxylases are used to develop hydrophilicity to
toxic compounds for subsequent reduction in their lipophilic
affinity. The application of decarboxylases can be catego-
rized into four main groups, including (i) epoxides, (ii) aro-
matic compounds, (iii) hetero-aromatic compounds, and (iv)
aliphatic compounds [149]. In contrary to the carboxyla-
tion of epoxides, the aromatics carboxylation involves the
use of phenyl phosphate enzymes from Thauera aromatica
for the carboxylation of phenolics to develop p-hydroxy-
benzoic acid [6]. Trichosporon moniliforme WU-0401
13

was used for the heterologous expression of salicylic acid
decarboxylase (Sdc) for the conversion of t m-aminophenol
into p-aminosalicylic acid with approximately 70% yield
[150]. Recently, Wuensh and coworkers demonstrated the
regioselective carboxylation of para-hydroxystyrene deriv-
atives with decarboxylases to generate the corresponding
(E)-cinnamic acid derivatives with bicarbonate as a source
of carbon dioxide [151]. Moreover, resorcylic acid decar-
boxylases from Rhizobium sp., Agrobacterium tumefaciens,
have also been reported to catalyze 1,3-dihydroxybenzene
to 2,6-dihydroxybenzoic acid [6]. For the carboxylation of
aliphatic compounds, pyruvate decarboxylase from Baker’s
yeast with thiamine pyrophosphate as a cofactor has been
employed. The enzyme has been successfully exploited for
the synthesis of pyruvate by carboxylation of acetaldehyde,
which on optimization of reaction conditions revealed an
81% pyruvate yield at pH 11 with sodium bicarbonate buffer
as ­CO2-source [152].
4.7 Conversion of CO2 by multi‑enzyme system
Production of methanol from ­CO2 is a multi-enzymatic step-
wise process and requires NADH cofactor. Obert and Dave
encapsulated formate dehydrogenase (Fdh), formaldehyde
dehydrogenase, and alcohol dehydrogenase in a porous
silica sol–gel matrix for enzymatic conversion of ­CO2 to
methanol and observed higher methanol yield as compared
to free enzymes [153]. However, the major drawback of
this low water solubility of these enzymes and deteriora-
tion of catalysts is due to ethanol, which is liberated dur-
ing hydrolysis [154]. To overcome these problems, Xu
and coworkers, encapsulated these dehydrogenases in the
alginate-silicate composite, which on application demon-
strated higher enzyme stability [154]. Later, different kinds
of immobilizing carriers were also synthesized to produce
microenvironments for enzymatic reactions. Sun and cow-
orkers co-immobilized these dehydrogenases in ­TiO2 nano-
particles and obtained high methanol yield [155]. In another
report, Wang and group immobilized these dehydrogenases
in the lumen of ultrathin hybrid microcapsules to reduce the
mass transfer resistance and observed a remarkable increase
in the yield and selectivity than free enzymes (35.5% and
47.3%) [156].
In another report, Marques Netto and group immobi-
lized the above-mentioned four enzymes on functionalized
nanoparticles and demonstrated 64-times conversion than
free multi-enzyme complex [157]. In another report, Yadav
and coworkers developed a hybrid system by combining a
photocatalyst with enzymes (FDH, formaldehyde dehydro-
genase, and ADH) for highly selective methanol produc-
tion [158]. Similarly, Ji and colleagues reported an artifi-
cial photosynthesis system, where enzyme cascade coupled
with a cofactor regeneration system was immobilized into a
13
Biomass Conversion and Biorefinery
polyelectrolyte-doped polyurethane lumen [159]. The artifi-
cial photosynthetic system revealed a 35.6–90.65% increase
in the methanol production than the solution-based system.
Recently, Schlager and coworkers for the first time dem-
onstrated electrochemistry assisted direct methanol conver-
sion from ­CO2by immobilizing the requisite enzymes in an
alginate-silicate hybrid gel matrix [160].
5 Product portfolio of ­CO2 conversion
There is a wide array of potential C
­ O2 use and applications,
which includes (a) direct use or non-conversion where
­CO2 is not chemically altered and (b) use of ­CO2 by trans-
formation via multiple technological routes to fuels, chemi-
cals, and other high-value compounds (Fig. 3) [161]. This
section presents the range of possible compounds that can
be produced from ­CO2.
5.1 Syngas production
Syngas is gaining worldwide attention because of its versa-
tility to generate many chemicals and fuels. It is a mixture
of CO and ­H2 gases, which is toxic, odorless, and colorless
[162]. For the production of syngas, any carbon source can
be used; however, steam reforming of methane is the most
commonly used production process for syngas [163]. Con-
sidering the high emissions, carbon dioxide is gaining exten-
sive interest to be used as a primary feedstock in the syngas
production. The new technologies involve various routes
with ­CO2 reforming processes using hydrocarbons. Other
ways can be catalytic reverse water gas shift (RWGS), ther-
mocatalytic route, plasma process, electro- or photocatalysis,
and other bioprocesses such as enzyme coupled nanoparticle
systems, using a biomass char, bio-electrochemical reduc-
tion, and catalysts [163, 164].
Generation of value-added commodities by combining
­CO2 and methane has always been attractive as these are
cheap molecules. The process, “dry reforming,” is an endo-
thermic reaction, and the gas evolved can be exploited to
produce various important hydrocarbon compounds [165].
CO2 + CH42CO + 2H2;ΔH298K = 247.3kJ∕mol (1)
Here, ­CH4 and ­CO2 adsorb on different active sites: meth-
ane on noble metal (e.g., Pt) and ­CO2 adsorbs on support
(e.g., ­ZrO2). The carbonate is formed by chemisorption of
­CO2 at the metal or support, and the interface is reduced to
formate by methane dissociation on the noble metal [164,
166]. Syngas is produced via methane reforming and subse-
quently converted in situ via Fischer–Tropsch synthesis or
methanol synthesis. ­CH4 decomposition or CO dispropor-
tionation is one of the major problems in the dry reforming
Biomass Conversion and Biorefinery
Fig. 3  Classification of pathways for C
­ O2 assimilation
process. Supported nickel is the most studied among the
catalysts among a few other supported noble metals like Rh,
Ru, and Pt [163, 164, 166].
In the ­CO2 reforming of ­CH4 or dry reforming process,
steam is replaced by the ­CO2 in the conventional reforming
process [164, 166]. Highly pure synthesis gas with lower ­H2/
CO ratio of unity is produced that is suitable for a variety of
products including Fischer–Tropsch fuels without further
post-reformer reactions [164, 167]. Two types of greenhouse
gases ­(CO2 and C ­ H4) are also utilized here with the flex-
ibility of using installed infrastructure to the manufacture
of important chemical commodities [163, 164]. However,
the biggest limitation of this process is the unavailability
of a well-developed catalyst to work at high temperatures
for high conversions, contributing to carbon deposition by
both ­CO2 and ­CH4 [164, 167]. However, the progress in
this direction for the development of suitable catalysts with
high activity and stability have been reported by numerous
authors [168–175],Zheng et al. 2013). Also, a variation of
dry reforming has been used industrially [166]:
a. Calcor process: It involves dry reforming of methane,
optimized to reduce the hydrogen content of the product
gas [176, 177], Teuner et al. 2001), and the hydrogen is
further separated by membrane permeators.
b. Sparg process: Here, the active catalytic sites are blocked
by poisoning the feed gas with hydrogen sulfide ­(H2S)
to produce high CO content [178],O’Connor and Ross
1998; [179].
By choosing the r ight propor tions of
­CH4:water:CO2 (3/2/1 usually), the combination
13
 Biomass Conversion and Biorefinery

of steam and dry reforming of methane can gen- produced from ­CO2 and ethylene oxide followed by produc-
erate syngas with a H
­ 2/CO ratio of ideal 2 [180, tion of DMC and ethylene glycol by reaction with excess
181]. methanol [189].
c. Bi-reforming: Dry reforming with partial oxidation is
5.4 Cyclic carbonate from CO2 and epoxide
adaptable for reforming varied natural gas and C ­ O2
sources and, thus, allowing to alter the H­ 2/CO ratio by
Cyclic carbonates can be used as an electrolyte in the sec-
controlling the extent of reaction [166, 182].
ondary batteries, a precursor for polycarbonates, and some
d. Autothermal reaction (ATR): Combination of exother-
other polymeric materials. It can also be useful as intermedi-
mal and endothermal reaction requires the addition of
ates in some fine chemicals production (e.g., pyrimidines,
­CO2 or ­CO2-rich gas to adjust the syngas composition
dialkyl carbonates, glycols, carbamates). Cyclo-addition of
for desired ­H2/CO ratio [183].
­CO2 to an epoxide for the production of cyclic carbonate is
e. Tri-reforming: It uses natural and flue gases with the
an effective route for C
­ O2 conversion with a market of more
waste heat in power plants and in situ heat generated
than 20 million tons per year. However, the stability, activity,
from oxidation with the oxygen that is present in flue gas
and recovery of the catalysts are not satisfactory, although
[184, 185]. The process results in the production of syn-
the process has now reached an industrial scale [190].
gas with desired ­H2/CO ratios (1.5–2.0) and eliminates
carbon formation in the ­CO2 reforming of ­CH4 [184].
5.5 Production of polymers

Incorporation of ­CO2 into polymers is a promising ­CO2

5.2 Methanol production
assimilation approach with a potential of worldwide annual
production exceeding 200 million tons per year [190, 191].
Methanol due to its application as carbon source for various
Urea–formaldehyde and melamine–formaldehyde resins
chemicals (acetic acid, Di-methyl-ether, formaldehyde, ole-
use ­CO2 as primary carbon source. Polyalkylene carbon-
fins, and methyl tert-butyl ether production) and as a blend-
ates can also be generated by the reaction of ­CO2 with
stock for motor fuels is considered among the most valuable
epoxides or by transesterification of C ­ O2 with dimethyl
chemical [186]. Industrially, it is produced from compounds
carbonate, which subsequently can be used in the manufac-
containing ­H2, CO, and ­CO2 such as natural gas, syngas, or
ture of thermoplastic polyurethanes, elastomers, varnishes,
coal in the presence of a catalyst. Direct ­CO2 hydrogena-
foams, adhesives, sealants, or impact-resistant modifiers
tion, electro- or photo-processes, and enzymatic processes
[192, 193]. Moreover, polyoxymethylene that could chal-
have also been reported as nonconventional routes. Methanol
lenge polyolefins and might replace polyethylene and poly-
production from C ­ O2 comprises syngas production as an
propylene partially can be developed from reaction of ­CO2
intermediate step [163]. Efforts are being made to produce
with formic acid and 1,3,5-trioxane. Moreover, ­CO2 can
methanol in a single step (via C ­ O2 hydrogenation or CO
also be captured in polymethylmethacrylate and bisphenol
from reacting with hydrogen) without syngas formation. The
A for long-term use [194, 195].
conventional process using homogeneous or heterogeneous
catalysts (Cu/ZnO/Al2O3) occurs at a pressure of 5–10 MPa
5.6 Production of fine chemicals
and a temperature of 210–350 °C [164].
CO2 assimilation for generation of fine chemicals. viz.,
5.3 Dimethyl carbonate (DMC) production
esters, carbonic acids, heterocyclics, and lactones particu-
larly, holds immense potential because of their application in
DMC, a biodegradable and non-toxic linear carbonate, is
a wide variety of commodities such as plasticizers, solvents,
used widely in industrial applications, for instance, as sol-
detergents, sun-protection agents, antioxidants, and deform-
vents, reagents for alkylation or acylation reactions, and
ing agents. Acetyl-salicylic acid from ­CO2 and phenols can
octane booster component in gasoline and diesel. Currently,
be synthesized from the carboxylation reaction. Other fea-
the main route for its production is by oxidative carbonyla-
sible reactions are conversion of ­CH4 and ­CO2 to acetic
tion of methanol [187]. Tin is the most commonly used
acid, ­CO2 and benzene to benzoic acid, C ­ O2 and ethylene to
catalyst in direct methylation reaction, which is employed
acrylic acid, and aromatics carboxylation by C ­ O2 using Si/
as an organometallic complex or oxide compound [188].
Al-based catalyst [196–198]. However, the contribution to
However, this process presents low yields (10%) due to the
­CO2 utilization is very limited in this area [190].
chemical inertness of ­CO2 and catalyst deactivation due to
formation of ­H2O [187]. Large-scale production of DMC
took place in a two-step process,first ethylene carbonate, is

13
Biomass Conversion and Biorefinery
5.7 Inorganics production
Calcite ­(CaCO3) is obtained from ­CO2 and Ca(OH)2 as a
product in well-defined grain sizes and purity grades and
used as a filling material in the pharmaceutical industries
and buildings [199, 200]. Hydrotalcite is used widely as
an antacid for gastric acid and produced from magnesium
oxide, sodium aluminate, and C ­ O2 [201]. It also serves as
a catalyst in the aldol reactions and polyesters transesteri-
fication. Along with these, ­CO2 can also be exploited for
metal oxides precipitation [202]. However, due to the slow
kinetics of natural mineral carbonation, these processes are
energy-intensive.
6 Industrial scenario of ­CO2 bioconversion
There are various technological routes such as electrochemi-
cal, catalytic, biological, mineralization, and copolymeriza-
tion to utilize C­ O2 and convert into commercial products
(fuels and chemicals). This section reviews the companies
that concentrate on CO/CO2 bioconversion for the genera-
tion of valued commodity chemicals (Table 3).
LanzaTech (USA) has developed a biological gas-fer-
mentation process that transforms the hydrogen-free-CO-
rich waste gases and residues from industrial processes into
chemicals and fuels and chemicals with high yields in a con-
tinuous process [61, 203]. It started the 56.8 ­m3/year capac-
ity pilot-scale ethanol facility using C
­ O2 from a mill off-gas
exhaust in 2008 followed by the commencement of first
commercial facility with a capacity of 60,567 ­m3 ethanol
production per year in May 2018 (China). Moreover, several
other commercial plants are under planning/construction
stage in Belgium and China (90,850 m ­ 3 per year) [61, 203].
Joule Unlimited Technologies Inc. (USA) works on genet-
ically engineered microbes (e.g., cyanobacteria) to harness
solar energy (patented Solar Converter system) and convert
­CO2 into ethanol and/or hydrocarbon. It has already com-
pleted the pilot testing of ethanol (trademarked as Sunflow-
E) and diesel (trademarked as Sunflow-D) production pro-
cesses [61].
INEOS Bio (UK) is licensing and commercializing its
novel biochemical and thermochemical technology for the
generation of renewable energy from a various low-cost
feedstocks [204]. Their breakthrough gasification and fer-
mentation technology is the first commercial-scale produc-
tion (in 2013) for the transformation of plant waste into
ethanol production and renewable energy [205]. The waste
biomass is superheated with controlled amounts of oxygen
forming synthesis gas (CO + ­H2; heat from the produced
gas is recovered and used to generate renewable power.
Synthesis gas is cleaned, cooled, and then fed through the
fermentation process using naturally occurring anaero-
bic bacteria converting the syngas to bioethanol solution.
Exhaust gases from the fermenter are further used for heat
and power generation [205].
Fitoplancton Marino (Spain) is a company that deals
with microalgae production and conservation systems, nutri-
tion, and products that are rich in vitamins, omega-3 (with
lower content of saturated fatty acids), minerals, antioxi-
dants, and many other functional compounds focusing on
health improvement and well-being [206]. They use propri-
etary algal bio-filters and innovative technologies to cap-
ture ­CO2 and other harmful atmospheric pollutants in urban
centers. Fermentalg and the Suez group have collaborated in
2015 and exploited the exceptional capacity of microalgae
to capture C­ O2 and reduced the smoke from industrial sites
[206].
Similarly, Algenol Biotech LLC (Florida, USA) is also
commercializing its algal-based technology for the develop-
ment of ethanol, diesel, gasoline, and jet fuels (http://​www.​
algen​ol.​com/ direct-to-ethanol/the-technology); [204]). The
total production level is aimed at around 8 × ­103 gallons fuel/
year/acre, but it has not been achieved successfully to date.
The technology would produce fuels with reduced carbon
footprint (~ 60%) and cost savings to customers (~ 75 cents
per gallon). Their high yield patented technology “Direct
to ethanol®” uses cyanobacteria to convert C ­ O2 dioxide
from industrial sources and seawater into sugars and fur-
ther into ethanol and biomass using patented photobioreac-
tors and provide fresh water also (http://​www.​algen​ol.​com/
direct-to-ethanol/the-technology).
In another report, Cellana, Inc., USA (founded as HR
BioPetroleum, Inc. in 2004), has patented ALDUO™ pro-
cess to cultivate algae in photobioreactors and open raceway
ponds using seawater and C ­ O2, harvest them, and extract oil
from algae for conversion into biodiesel and utilize the resid-
ual high protein biomass for several co-products (2020a).
The company has produced over 20 metric ton dry weight
of algal biomass (branded ReNew Algae™) from a variety
of non-GMO strains. The three-product biorefinery business
model (ReNew™ Fuel, ReNew™ Omega-3, and ReNew™
Feed) involves establishing off-take agreements for biofuels,
Omega-3 nutritional oils, and animal feed to develop the
commercial algae facilities throughout the world (2020a).
Interestingly, Dyecoo Textile systems BV (Netherland)
are harvesting supercritical fluid extraction-CO 2 dyeing
technology. The dyeing machines of the company run at
two textile producers: Tong Siang (Thailand) and Far East-
ern New Century Corp. (Taiwan) for 100% polyester (poly-
ethylene terephthalate) dyeing at a temperature of 120 °C
and 250 bar pressure. DyeOx has a capacity of 4 tons/day
with 20–200 kg of goods/batch in three different chambers
(maximum daily capacity: 4000 kg) (2020b). Nike (branded
13

Table 3  An overview of ­CO2 assimilation companies and their products through various technological routes
CO2 conversion pathway
13
Electrochemical conversion of CO2 1. Sunfire GmbH-pilot (Germany)
2. Etogas (Germany)
3. Haldor Topsøe (Denmark)
4. DNV GL (Norway)
Catalytic conversion of CO2
Mineral carbonation
Bioconversion of CO2
Copolymerization of CO2
Company Main product Process description
1. Syngas and other fuels, 1. Co-electrolysis of steam and C ­ O2 using solid
such as gasoline, diesel, and methane oxide electrolysis cells + Fischer–Tropsch pro-
2. Methanol cess; pilot-scale in operation
3. Methane, CO 2. Alkaline pressurized electrolysis; pilot in Japan
4. Formic acid and formate salts 3. Methanation process called TREMP™ + eCOs™
to produce CO; need more R&D
4. ECFORM process; R&D
1. Carbon Recycling International (CRI), Iceland 1. Methanol 1. Vulcanol™ process; commercial scale
2. Carbon Engineering (Canada) 2. Liquid hydrocarbon fuels 2. Direct Fuel Production™; pilot scale
3. BSE Engineering (Germany) 3. Methanol 3. Demonstration project completed
1. CarbonCure 1. Concrete products 1. ­CO2 concrete™ curing process; commercial
Technologies (Canada) 2. Cement- and concrete-making technology scale
2. Solidia Technologies (USA) 3. Carbon-negative aggregate 2. Concrete™ curing process; commercial scale
3. Carbon8 Systems (UK) 4. Near ­CO2-neutral building material, called 3. Accelerated Carbonisation Technology (ACT);
4. UCLA (University of California, Los ­CO2NCRETE commercial scale
Angeles, USA) 5. Cement-free concrete 4. Carbon Upcycling’s process; R&D
5. Carbstone Innovation NV of Belgium and 6. Inorganic chemicals 5. Carbstone process/carbonation activation pro-
Canadian cess; commercial scale
company CarbiCrete 6. ­CO2-mineralization processes/SkyMine process
6. Carbonfree Chemicals
(formerly Skyonic) (USA)
1. LanzaTech (USA) 1. Ethanol and other fuels 1. Acetogens gas fermentation; commercial-scale
2. Joule Unlimited Technologies Inc. (USA) 2. Ethanol, diesel, or other hydrocarbon fuels production
3. INEOS (UK) 3. Ethanol 2. Genetically engineered cyanobacteria harness the
4. Algenol (USA) 4. Ethanol, diesel, gasoline, and jet fuel sunlight to convert C
­ O2
5. Cellana (USA) 5. Biofuels, Omega-3 nutritional oils, and animal and ­H2O directly into fuel; pilot testing completed
feed 3. Gas fermentation; commercial scale
4. Microalgae-based technology; pilot scale
5. ALDUO™ process; commercial scale
1. Asahi Kasei Corporation (Japan) 1. Polycarbonate and monoethylene glycol pro- 1. Uses ethylene oxide,
2. Covestro (Germany) duction its by-product C
­ O2 and bisphenol; commercial-
and its partners 2. Polyether-polycarbonate scale production
3. Novomer Inc. (USA) polyols 2. Cardyon™ polyols; commercial-scale production
4. Low Carbon Technology 3. Polypropylene carbonate polyols 3. Converge® polyols; commercial-scale produc-
Company (China) 4. Catalyst system for the tion
5. Jinlong Green Chemical copolymerization of propylene oxide and C ­ O2 to 4. Commercial-scale production
Company (China) produce biodegradable polypropylene carbonate 5. Polymer-supported bimetallic compound as a
6. Inner Mongolia Mengxi High-Tech Group 5. Aliphatic polycarbonate polyols catalyst and biodegradable polyurethane foam
Company (China) 6. Aliphatic polycarbonate 6. Commercial-scale production
7. Newlight Technologies (USA) 7. Plastics branded as “AirCarbon” (40% oxygen from 7. AirCarbon production process: capture, extrac-
8. Econic Technologies (UK) air and 60% carbon and hydrogen from captured tion and polymerization; commercial-scale
carbon emissions)—a carbon negative product production
8. Homogeneous 8. Demonstration plant opened
catalyst systems to produce polycarbonate polyols
Biomass Conversion and Biorefinery
Biomass Conversion and Biorefinery
as Colour Dry) and Adidas (Dry Dye) are major products of
its polyester technology.
CO2 Solutions Inc. Technology (Canada) is working
on a new 1T1 enzyme that has the catalytic properties of
accelerating ­CO2 capture without using a non-toxic salt
solution. The longevity and performance of 1T1 enzymes
are unmatched with reduced manufacturing costs (2020c).
The  first commercialization project is completed which
involves the capture of C­ O2 up to 30 tons/day, its reuse, and
the conversion of carbonic gas using C ­ O2 Solutions’ enzyme
technology at the Resolute kraft pulp mill (Saint-Félicien,
Québec) (2019, 2020c).
Ethanol fermentation derived ­CO2 has a major share in
global ­CO2 production. In the USA alone, around 50 MT
­CO2 is produced from corn ethanol plants. Brazil is the sec-
ond largest ethanol producing country in the world from
sugarcane this contributing a major chunk in C­ O2 production
from fermentation sector. If this C­ O2 is converted into etha-
nol by CCU technologies, higher amount of ethanol could
be produced within the ethanol producing facility without
additional corn grain inputs. Recently, Lee et al. [207] esti-
mated that 50% more ethanol could be produced using on-
site ­CO2 conversion. Fermentation ­CO2 is nearly pure and
thus presents a great potential in its use in development of
fuels/chemicals, fertilizer, beverages, and food processing,
among others.
6.1 Key indicators in carbon footprints reduction
by CO2 bioconversion
It is well known that the carbon footprints in form of carbon
dioxide and methane are increasingly being released into
the environment by several anthropogenic activities primar-
ily the burning of fossil fuels for the generation of energy
[208]. Other activities such as deforestation for urbaniza-
tion, production of food grains, goods, materials, wood, and
roads for transportation are also responsible for the esca-
lation levels of carbon footprints [209]. Due to complex
interactions between several GHG contributing processes
and natural processes, the total carbon footprint cannot be
quantified exactly [210]. Carbon footprint can be minimized
using alternative sources of energy for instance, solar, and/
or wind energy [211]. The restoration of wild plantation
can further offset the carbon footprints, by countering C­ O2
emissions with their equivalent reduction [212]. Moreo-
ver, to decrease these emissions, the dependence on fossil
fuels, coal mines, and landfills must be lowered. Alterna-
tively, ­CO2 bioconversion based alternative energy sources is
clean for the environment. Livestock operations that con-
tribute to GHG contribution considerably should be more
energy-saving to minimize carbon footprints [61].
However, as discussed, concerns regarding fossil fuel
depletion and climate changes due to greenhouse gas
emissions have demanded exploration of renewable alter-
natives [213]. Hence, the utilization of microbes to cap-
ture ­CO2 and convert into biofuels and biochemical seems
the best alternative strategy. Moreover, to make renewable
energy sources competitive with fossil fuels, it needs to
identify the efficient ­CO 2 fixing organisms. Six differ-
ent types of ­CO2 fixing pathways have been identified in
several species of photoautotrophic, chemoautotrophic,
and autotrophic electro-synthetic microorganisms [214].
Molecular biology interventions could be revolutionary
to minimize carbon footprints. A wide variety of biofu-
els and biochemical products have been commercially
produced from photoautotrophic microorganisms, such
as cyanobacteria and algae, which could assimilate ­CO2
from marine or terrestrial aquatic water sources in both
fresh and wastewater [215]. Chemoautotrophic microor-
ganisms such as Clostridium species have been widely used
for commercial production of butanol, 2-oxobutyrate, and
3-butanediol. Autotrophic electrosynthesis used by ace-
togenic microbes can be employed for the development of
ethanol, butanol, acetate, and butyric acid. Interestingly,
E. coli strains have been reported for efficient reduction of
­CO2 [111]. Moreover, the engineered ­CO2 fixing E. coli
strain could be exploited for the production of high-value
recombinant products. Hence, ­CO2 bioconversion pathways
can be exploited for a wide range of commercial products,
including bioethanol or biofuels, omega-3-fatty acids, and
organic acids.
The economics of the microalgae-based ­CO2 bioconver-
sion process can be improved using photosynthesis efficien-
cies and economic evaluation of C ­ O2 conversion and its
demand [216]. The raw material processing and refinery
cost usually lead to approximately 50% of biofuels and
biochemical production cost. Hence, it is among the key
concerns governing the economic analysis of ­CO2 biocon-
version, and it is a challenging task to compete with con-
ventional processes [217]. Also, the cost economics of bio-
fuels/biochemicals production mainly depends on the ­CO2
conversion capacity of the organism, biomass harvesting,
and transportation of biomass, water, and nutrients supplied
[218]. Therefore, the technological challenges and eco-
nomic barriers significantly contribute to the adaptation of
renewable energy sources for the commercial production
of biofuels/biochemicals. Life cycle assessment of ­CO2
bioconversion accounts the environmental impacts of the
product derived from it. Müller et al. [219] developed a
detailed protocol for LCA of carbon capture and utilization
(CCU) technologies involving the capture of C ­ O2 from the
origin sources or environment followed by its conversion
into products of commercial significance. While several
LCA studies have been made recently in the CCU tech-
nologies by chemical methods, ­CO2 bioconversion need to
be studied more.
13

7 Conclusion
The earth’s atmosphere contains around 800 giga tons of
­CO2. While the biotransformation of C ­ O2 has been inten-
sively studied over the past three decades, the maturity of
the process on an industrial scale remains a big concern.
Recent technological developments in metabolic engineer-
ing, process engineering, and electrochemistry have led to
the capture and utilization of carbon dioxide and its subse-
quent biotransformation into large quantities of biochemi-
cals and fuels. In addition to various ­CO2 metabolic path-
ways, such as the Calvin-Benson-Bassham (CBB) cycle, the
reductive tricarboxylic acid (rTCA) cycle, and the reductive
acetyl-CoA (Wood-Ljungdahl) pathway, many other enzy-
matic methods for the conversion of CO2 (i.e., carbonic
anhydrases, formate dehydrogenases, monoxide dehydro-
genases, and multi-enzyme systems) have been introduced.
Towards the commercialization, Biotech companies such as
LanzaTech, Joule Unlimited, INEOS, and Algenol Biotech
LLC have successfully developed value-added products by
using ­CO2 as a renewable source.
Acknowledgements  AKC gratefully acknowledges the financial sup-
port from FAPESP (Project number: 2020/12559-6) and CNPq for sci-
entific productivity program (Process number: 309214/2021-1).
Author contributions  AKC and RG had the idea for the article, AM
and YT performed literature search and data analysis, RG and AM
drafted the article, and AKC and YT critically revised the work.
Declarations  org/​10.​1021/​acs.​nanol​ett.​8b002​41
Conflict of interest  The authors declare no competing interests.
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