energies

Review
Recent Progress and Novel Applications in Enzymatic
Conversion of Carbon Dioxide
Nguyen Van Duc Long 1,2 , Jintae Lee 2 , Kee-Kahb Koo 3 , Patricia Luis 4, * and Moonyong Lee 2, *
1 Department for Management of Science and Technology Development & Faculty of Applied Sciences,
Ton Duc Thang University, Ho Chi Minh City, Vietnam; nguyenvanduclong@tdt.edu.vn
2 School of Chemical Engineering, Yeungnam University, Gyeongsan 712-749, Korea; mynlee@yu.ac.kr
3 Department of Chemical and Biomolecular Engineering, Sogang University, Seoul 04107, Korea;
koo@sogang.ac.kr
4 Materials & Process Engineering (iMMC-IMAP), Université catholique de Louvain, Place Sainte Barbe 2,
1348 Louvain-la-Neuve, Belgium
* Correspondence: patricia.luis@uclouvain.be (P.L.); mynlee@yu.ac.kr (M.L.);
Tel.: +32-(0)10-472402 (P.L.); +82-53-810-2512 (M.L.)

Academic Editor: Fernando Rubiera González

Received: 4 March 2017; Accepted: 27 March 2017; Published: 3 April 2017

Abstract: Turning carbon dioxide (CO2 ) into fuels and chemicals using chemical, photochemical,
electrochemical, and enzymatic methods could be used to recycle large quantities of carbon.
The enzymatic method, which is inspired by cellular CO2 metabolism, has attracted considerable
attention for efficient CO2 conversion due to improved selectivity and yields under mild reaction
conditions. In this review, the research progress of green and potent enzymatic conversion of CO2 into
useful fuels and chemicals was discussed. Furthermore, applications of the enzymatic conversion of
CO2 to assist in CO2 capture and sequestration were highlighted. A summary including the industrial
applications, barriers, and some perspectives on the research and development of the enzymatic
approach to convert CO2 were introduced.

Keywords: carbon dioxide (CO2 ); enzymatic conversion of CO2 ; CO2 utilization; CO2 capture;
CO2 sequestration

1. Introduction
Global warming and climate change, referring to increased average global temperatures, have
inspired a global effort to reduce the amount of atmospheric carbon dioxide (CO2 ). Many approaches
have been considered and adopted for reducing CO2 emissions, including enhancing energy efficiency
and promoting energy conservation; increasing the usage of low carbon fuels, including natural gas,
hydrogen, or nuclear power; deploying renewable energy sources such as solar, wind, hydropower,
and bioenergy; applying geoengineering approaches such as afforestation and reforestation; CO2
capture and storage (CCS); and converting CO2 into fuels and chemicals [1]. Among these approaches,
turning CO2 into fuels and chemicals offers a win–win strategy to both decrease atmospheric CO2 and
efficiently exploit carbon resources [2].
From fundamental research to industrial applications, the efficient transformation of CO2 has
attracted growing international interest. The concept behind the CO2 conversion to chemicals and
fuels is attractive: the direct energy supply via combustion of carbonaceous energy carriers produces
CO2 , which could be converted back into the energy carrier, thereby resulting to an artificial carbon
cycle that recycles CO2 and balances anthropogenic emissions [3,4]. To catalyze CO2 conversion,
chemical, photochemical, electrochemical, and enzymatic methods have been employed. In the first
three methods, high operating temperature and pressure or additional electric or luminous energy are

Energies 2017, 10, 473; doi:10.3390/en10040473 www.mdpi.com/journal/energies

Energies 2017, 10, 473 2 of 19

required, and some selectivity and yield issues accompany these methods [5]. Meanwhile, occurring
under mild reaction conditions with high yields and selectivity and without any side effect on the
environment, the enzymatic conversion of CO2 has comparative benefits [5–7].
Interestingly, the enzymatic conversion of CO2 can be applied not only for efficient CO2
utilization [7],2017,
Energies but10,also
473 for assisting CO2 capture [8], the process of capturing waste CO22 of from
19 fossil
fuel power plant flue gas using absorption or membrane technologies, and CO2 sequestration [9], the
captureoccurring under mild
and long-term reaction
storage ofconditions
atmosphericwith high
CO2yields and selectivity
. Although and without concepts
these promising any side effect
have been
on the environment, the enzymatic conversion of CO2 has comparative benefits [5–7].
applied in industry, their application is still in the interim period between the research stage and the
Interestingly, the enzymatic conversion of CO2 can be applied not only for efficient CO2
application stage,[7],
utilization in but
addition
also fortoassisting
other barriers.
CO2 capture Thus, in this
[8], the paper,
process we review
of capturing recent
waste developments
CO2 from fossil in
the enzymatic conversion of CO
fuel power plant flue gas using in vitro, which mimics cellular
2 absorption or membrane technologies, CO metabolic processes. Applications
2 and CO2 sequestration [9], the
of the enzymatic
capture and conversion of CO2oftoatmospheric
long-term storage assist CO2 CO capture and sequestration
2. Although these promisingare highlighted.
concepts have beenIndustrial
appliedbarriers,
applications, in industry, their
and application
some is still in the
perspectives on interim period between
the research the research stage
and development and enzymatic
of the the
application stage, in addition to other barriers. Thus, in this paper, we review recent developments
conversion of CO2 are also discussed.
in the enzymatic conversion of CO2 in vitro, which mimics cellular CO2 metabolic processes.
Applications of the enzymatic conversion of CO2 to assist CO2 capture and sequestration are
2. Natural Conversion of CO2 in Cells
highlighted. Industrial applications, barriers, and some perspectives on the research and
Thedevelopment
fixation of of the enzymatic
inorganic conversion
carbon of CO2material
into organic are also discussed.
(chemoautotrophy) is a prerequisite for life
and represents the starting point of biological evolution [10]. Biological fixation, an essential factor
2. Natural Conversion of CO2 in Cells
in controlling atmospheric CO2 concentrations, can occur through six major pathways including the
The fixation of inorganic
Calvin–Benson–Bassham carbon
cycle, the into organic
reductive citricmaterial (chemoautotrophy)
acid cycle, the reductive is aacetyl-CoA
prerequisite for life
pathway, the
and represents the starting point of biological evolution [10]. Biological fixation, an essential factor in
3-hydroxypropionate/malyl-CoA cycle, the 3-hydroxypropionate/4-hydroxybutyrate cycle, and the
controlling atmospheric CO2 concentrations, can occur through six major pathways including the
dicarboxylate/4-hydroxybutyrate
Calvin–Benson–Bassham cycle, the cycle [11]. They
reductive impact
citric acid cycle,substantially to the global
the reductive acetyl-CoA carbon
pathway, the 3-cycle, in
which enzymes play crucial roles in catalyzing the CO fixation [12].
hydroxypropionate/malyl-CoA cycle, the 3-hydroxypropionate/4-hydroxybutyrate
2 Beside, a largecycle, andofthe
number enzymes,
such as dicarboxylate/4-hydroxybutyrate
decarboxylase enzymes in carboxylation
cycle [11]. They reactions derived from
impact substantially to the catabolic pathways,
global carbon cycle, in utilize
CO2 or which − as a reaction
HCO3enzymes play crucial roles in catalyzing
substrate and do notthe CO 2 fixation
belong to [12]. Beside, a large number
chemoautotrophic of enzymes,
pathways [2,12,13].
such as decarboxylase enzymes in carboxylation reactions derived from catabolic pathways, utilize CO2
Generally,− such CO2 transformation processes are coupled with oxidation processes that
or HCO3 as a reaction substrate and do not belong to chemoautotrophic pathways [2,12,13].
generate reducing equivalents, sometimes conjunctive with the hydrolysis of phosphoanhydride
Generally, such CO2 transformation processes are coupled with oxidation processes that
bonds [12,14–16]. Adenosine
generate reducing equivalents,triphosphate
sometimes(ATP) and nicotinamide
conjunctive with the hydrolysisadenine dinucleotide hydride
of phosphoanhydride
(NADH) or their
bonds equivalents
[12,14–16]. Adenosinearetriphosphate
required in(ATP) all known natural CO
and nicotinamide 2 conversion
adenine pathways
dinucleotide hydride [12,15].
Various(NADH)
pathways or their
for equivalents are required
the conversion of COin2 all known natural
associated to the COdependence
2 conversion pathways [12,15].
of chemoautotrophic
Various
organisms on CO pathways
have for
beenthedeveloped
conversion (Figure
of CO2 associated
1) [10,12]. toThese
the dependence
enzymatic ofconversions
chemoautotrophic
of CO2 and
2
organisms on CO2 have been developed (Figure 1) [10,12]. These enzymatic conversions of CO2 and
carboxylation reactions derived from catabolic pathways are considered fundamental to science and
carboxylation reactions derived from catabolic pathways are considered fundamental to science and
have inspired in vitro
have inspired studies
in vitro andand
studies industrial
industrialapplications.
applications.

Figure 1. Biocatalytic routes for the conversion of CO2 into compounds with carbon in the reduced
1. Biocatalytic
Figure oxidation routes for the conversion of CO2 into compounds
states indicated at the top. FDH: formate dehydrogenase,
with carbon in the
FaldDH: formaldehyde
reduceddehydrogenase,
oxidation states indicated
ADH: at the top. FDH:
alcohol dehydrogenase, formate
CODH: carbondehydrogenase, FaldDH:RuBisCO:
monoxide dehydrogenase, formaldehyde
dehydrogenase, ADH: alcoholcarboxylase
ribulose-1,5-bisphosphate dehydrogenase, CODH:
oxygenase, carbonanhydrase,
CA: carbonic monoxide dehydrogenase,
R: H, CH3 [12]. RuBisCO:
ribulose-1,5-bisphosphate carboxylase oxygenase, CA: carbonic anhydrase, R: H, CH3 [12].
Energies 2017, 10, 473 3 of 19
Energies 2017, 10, 473 3 of 19

3. Enzymatic
3. Enzymatic Conversion
Conversion of
of CO
CO22 In
In Vitro
Vitro
A tremendous
A tremendous amount
amount ofof effort
efforthas
hasbeen
beendedicated
dedicatedtotoconstructing
constructingCO CO2 conversion systems in
2 conversion systems
vitro inspired by cellular CO 2 metabolic processes. These processes can consist of a single enzyme,
in vitro inspired by cellular CO2 metabolic processes. These processes can consist of a single
using oxidoreductases
enzyme, or lyases,
using oxidoreductases or of or
or lyases, multiple enzymes
of multiple enzymessuch as asmultiple
such multipledehydrogenases
dehydrogenases in
in
methanol production.
methanol production.

3.1. Reduction Reactions

3.1.1. Conversion of CO22 to

to Carbon
Carbon Monoxide
Monoxide
Converting CO CO2 2toto carbon
carbon monoxide
monoxide (CO),(CO), the feedstock
the feedstock for various
for various synthetic synthetic
processes, processes,
through
through the production
the production of hydrocarbons
of hydrocarbons (Fischer-Tropsch
(Fischer-Tropsch process),
process), acetic
acetic acid(Monsanto
acid (Monsantoand and Cativa
processes),
processes), and andmethanol
methanolcatalyzed
catalyzed bybycarbon
carbonmonoxide
monoxide dehydrogenases
dehydrogenases (CODHs)
(CODHs) has received much
has received
attention
much attention[17–19].[17–19].
There are twoare
There types
twooftypes
CODHs including
of CODHs the O2 -sensitive
including enzymesenzymes
the O2-sensitive from obligate
from
anaerobes containing
obligate anaerobes [Fe4 S4 Ni][Fe
containing and air-stable
4S4Ni] enzymes
and air-stable with [MoSCu]
enzymes active sites
with [MoSCu] active[20]. The
sites [NiFe]
[20]. The
CODHs result turnover frequencies for CO oxidation as high as 40,000 s −1 and 45 s− 1 for CO reduction,
[NiFe] CODHs result turnover frequencies for CO oxidation as high as 40,000 s and 45 2s for CO2 −1 −1

while the [MoCu]

reduction, while theCODHs[MoCu]do not catalyze
CODHs dothe reduction
not catalyzeoftheCOreduction
2 to CO [19,20].
of CO The
2 to conversion
CO [19,20]. of COThe2
to CO is accomplished
conversion of CO2 to usingCO is[NiFe] CO dehydrogenases
accomplished using [NiFe] with
COthe proposed mechanism
dehydrogenases with the presented
proposed in
Scheme 1 [20].
mechanism presented in Scheme 1 [20].
Shin et al. (2003)
(2003) [21]
[21] first
first found
found that
that CODH
CODH is a suitable catalyst for electrochemical CO2
reduction, exhibiting almost no overpotential.
reduction, exhibiting almost no overpotential. Woolerton Woolerton et al. et
[17,22] discovered
al. [17,22] an innovative
discovered efficient
an innovative
technique that combines
efficient technique photocatalysis
that combines efficientlyefficiently
photocatalysis and cleanly and incleanly
the enzymatic conversionconversion
in the enzymatic of CO2 to
CO.
of CO Figure
2 to CO. 2 shows
Figurethe hybrid
2 shows thesystem
hybridcomprising metal oxide
system comprising metal nanoparticles functionalized
oxide nanoparticles with the
functionalized
enzyme CODH, and sensitized to visible light using a ruthenium bipyridyl
with the enzyme CODH, and sensitized to visible light using a ruthenium bipyridyl photosensitizer photosensitizer [22]. Of the
semiconductor materials that
[22]. Of the semiconductor they investigated,
materials photocatalysts
that they investigated, prepared with
photocatalysts Evonik Degussa
prepared with Evonik P25
TiO 2 (a
Degussa commercially
P25 TiO 2 (a available
commercially 3:1 mixture
available of anatase/rutile)
3:1 mixture of and ordinary
anatase/rutile) anatase
and TiO
ordinary 2 nanoparticles
anatase TiO 2

were found to be the most effective, in terms of overall turnover

nanoparticles were found to be the most effective, in terms of overall turnover rate. rate.

Scheme 1. Proposed mechanism for the reduction of CO2 to CO by [NiFe] CODH [20].
Scheme 1. Proposed mechanism for the reduction of CO2 to CO by [NiFe] CODH [20].
Energies 2017, 10, 473 4 of 19
Energies 2017, 10, 473 4 of 19

Figure 2. Cartoon representation of CO2 reduction at an enzyme-modified metal oxide nanoparticle,

Figure 2. Cartoon representation of CO2 reduction at an enzyme-modified metal oxide nanoparticle,
sensitized with a ruthenium dye. D represents a sacrificial electron donor, used to regenerate the dye
sensitized with a ruthenium dye. D represents a sacrificial electron donor, used to regenerate the dye
following photoinjection into MOx. Dimensions of each species are approximately to scale for when
following photoinjection into MOx . Dimensions of each species are approximately to scale for when
MOx is a Degussa P25 anatase TiO2 nanoparticle [22].
MOx is a Degussa P25 anatase TiO2 nanoparticle [22].

More recently, Bachmeier et al. [23] demonstrated that semiconducting electrodes can be used
More recently,
to impose Bachmeier
directionality et al. [23] catalysts
on reversible demonstrated that semiconducting
operating in the region ofelectrodes can be
the flatband used to
potential.
impose
Althoughdirectionality on reversible
these enzymes catalysts
are unsuited foroperating in the
long-term, region of the
large-scale flatband
systems, potential.
their resultsAlthough
provide
these enzymes are unsuited for long-term, large-scale systems, their results provide valuable
valuable insight for developing integrated artificial systems (based ultimately on abundant chemical insight
for developing
catalysts) [23]. integrated artificial systems (based ultimately on abundant chemical catalysts) [23].

3.1.2. Conversion of CO2 to Formic Acid/Formate

3.1.2. Conversion of CO2 to Formic Acid/Formate
Formic acid/formate, which can be used for silage preservation, animal feed additives, textile
Formic acid/formate, which can be used for silage preservation, animal feed additives, textile
finishing, and chemical intermediates [24], as one of the most promising candidate fuels for
finishing, and chemical intermediates [24], as one of the most promising candidate fuels for low-
low-temperature fuel cells [25], and in paper and pulp production, is one of main products from
temperature fuel cells [25], and in paper and pulp production, is one of main products from the
the enzymatic conversion of CO2 [26]. The formate oxidation to CO2 occurs with the concomitant NAD++
enzymatic conversion of CO2 [26]. The formate oxidation to CO2 occurs with the concomitant NAD
reduction to NADH catalyzed by formate dehydrogenase (FDH or Fate DH) [27]. Interestingly, the reverse
reduction to NADH catalyzed by formate dehydrogenase (FDH or FateDH) [27]. Interestingly, the
reaction, the reduction of CO2 to formate, can be catalyzed by the same enzyme [28,29]. FDH from
reverse reaction, the reduction of CO2 to formate, can be catalyzed by the same enzyme [28,29]. FDH
Pseudomonas oxalaticus has been used to reduce CO2 into formate using oxidized methyl viologen as an
from Pseudomonas oxalaticus has been used to reduce CO2 into formate using oxidized methyl
electron relay [30]. The tungsten-containing FDH from Syntrophobacter fumaroxidans, known to be the
viologen as an electron relay [30]. The tungsten-containing FDH from Syntrophobacter fumaroxidans,
most active catalyst for the reaction so far, has also been used to reduce CO2 to formate [31].
known to be the most active catalyst for the reaction so far, has also been used to reduce CO2 to
To generate NADH, novel graphene-based visible light active photocatalyst which covalently
formate [31].
bonded the chromophore, such as multianthraquinone substituted porphyrin with the chemically
To generate NADH, novel graphene-based visible light active photocatalyst which covalently
converted graphene as a photocatalyst of the artificial photosynthesis system was reported [32].
bonded the chromophore, such as multianthraquinone substituted porphyrin with the chemically
The rhodium complex shuttles as an electron mediator between the graphene photocatalyst
converted graphene as a photocatalyst of the artificial photosynthesis system was reported [32]. The
and NAD+ , proving to be an efficient factor for regeneration of the NADH cofactor. Recently,
rhodium complex shuttles as an electron mediator between the graphene photocatalyst and NAD+,
a photocatalyst–biocatalyst coupled system developed using graphene-based visible light active
proving to be an efficient factor for regeneration of the NADH cofactor. Recently, a photocatalyst–
photocatalyst in a highly efficient manner, leading to high NADH regeneration (54.02% ± 0.61%),
biocatalyst coupled system developed using graphene-based visible light active photocatalyst in a
followed by its consumption in exclusive formic acid production (144.2 ± 1.8 µmol) from CO2 [33].
highly efficient manner, leading to high NADH regeneration (54.02% ± 0.61%), followed by its
Because the NADH-independent FDH enzymes are highly unstable and inactive in the presence
consumption in exclusive formic acid production (144.2 ± 1.8 µmol) from CO2 [33].
of O2 , Kim et al. [34] focused on the NADH-dependent FDH from Candida boidinii (CbsFDH), which
Because the NADH-independent FDH enzymes are highly unstable and inactive in the presence
was sufficiently stable for commercial use, and found that almost 100% selectivity can be achieved for
of O2, Kim et al. [34] focused on the NADH-dependent FDH from Candida boidinii (CbsFDH), which
was sufficiently stable for commercial use, and found that almost 100% selectivity can be achieved for
formate formation from CO2 in recent study (as shown in Scheme 2). The reaction rate can be increased
Energies 2017, 10, 473 5 of 19

formateEnergies
formation from
2017, 10, 473 CO2 in recent study (as shown in Scheme 2). The reaction rate can be 5 of increased
19

only within the optimized reaction conditions of electrochemical NADH regeneration. Therefore,
only within the optimized reaction conditions of electrochemical NADH regeneration. Therefore, a
a robustEnergies
new 2017,
FDH 10, that
473 operates in high NADH and enzyme concentrations should be identified 5 of 19 or
robust new FDH that operates in high NADH and enzyme concentrations should be identified or
developed for an electroenzymatic method to convert CO into formate on a preparative
2 formate on a preparative scale.
developed for an electroenzymatic method to convert CO2 into scale.
only within the optimized reaction conditions of electrochemical NADH regeneration. Therefore, a
robust new FDH that operates in high NADH and enzyme concentrations should be identified or
developed for an electroenzymatic method to convert CO2 into formate on a preparative scale.

Scheme 2. Schematic diagram of electroenzymatic CO2 reduction using CbsFDH [34].

Scheme 2. Schematic diagram of electroenzymatic CO2 reduction using CbsFDH [34].
3.1.3. Conversion of CO2 to Methanol
3.1.3. Conversion Scheme
of CO22.to
Schematic diagram of electroenzymatic CO2 reduction using CbsFDH [34].
Methanol
Methanol, a fuel and key starting material for many important industrial applications, can be
produced
3.1.3.
Methanol, afrom
fuelCO
Conversion reduction.
of2CO
and Obertmaterial
2 to Methanol
key starting and Davefor
[7]many
reported an enzymatically
important coupled
industrial sequential can be
applications,
reduction of carbon dioxide to methanol using three different dehydrogenases including FDH,
produced from CO2 areduction.
Methanol, fuel and keyObert and
starting Davefor
material [7]many
reported an enzymatically
important coupled
industrial applications, cansequential
be
formaldehyde dehydrogenase (FaldDH), and alcohol dehydrogenase (ADH). The overall reaction
produced
reduction of from CO
carbon 2 reduction.
dioxide to Obert and using
methanol Dave [7] reported
three an enzymatically
different coupled sequential
dehydrogenases including FDH,
process, in which terminal electron donor in each dehydrogenase-catalyzed reduction is reduced
reduction
formaldehyde of carbon dioxide to methanol using three different dehydrogenases including FDH,
NADH, isdehydrogenase
shown in Figure 3(F ald DH), and alcohol dehydrogenase (ADH). The overall reaction
[35].
formaldehyde dehydrogenase (FaldDH), and alcohol dehydrogenase (ADH). The overall reaction
process, in which terminal electron donor in each dehydrogenase-catalyzed reduction is reduced
process, in which terminal electron donor in each dehydrogenase-catalyzed reduction is reduced
NADH,NADH,
is shown in Figure
is shown 3 [35].
in Figure 3 [35].

Figure 3. CO2 reduction to methanol in water promoted by FateDH, FaldDH, and ADH where three
consecutive 2e− steps are involved [35].

Figure 3. CO2 reduction to methanol in water promoted by FateDH, FaldDH, and ADH where three
However,
Figure 3. this process
CO2 reduction still has several
to methanol problems
in water promoted suchbyasFcosolvents and catalysts are in the sol-
ate DH, Fald DH, and ADH where three
consecutive 2e− steps are involved [35].
gel process due
− to low water solubility
consecutive 2e steps are involved [35]. and reactivity of the silica precursor, and the alcohol liberated
from hydrolysis, cosolvents, and catalysts are deleterious to bioactivity [36]. To overcome these
However, this process still has several problems such as cosolvents and catalysts are in the sol-
problems, several modifications to the sol-gel technique were proposed to improve the stability of
gel process
However, due
this to low water
process solubility
still has severaland reactivitysuch
problems of theas
silica precursor,and
cosolvents andcatalysts
the alcoholare
liberated
in the sol-gel
the biological activity [36–40]. The dehydrogenases encapsulated in the alginate-silicate composite
from hydrolysis, cosolvents, and catalysts are deleterious to bioactivity [36]. To overcome these
process showed
due to highlow initial
waterenzyme
solubility andretention,
activity reactivity andof the silica improved
significantly precursor, and the
stability alcohol
during liberated
storage
problems, several modifications to the sol-gel technique were proposed to improve the stability of
and reuse [36].
from hydrolysis, These enzymes can be are also deleterious
immobilized to in bioactivity
flat-sheet polymeric membranes
the biological activity [36–40]. The dehydrogenases encapsulated in the alginate-silicate composite these
cosolvents, and catalysts [36]. To overcome
simultaneously
problems, several or separatelytobythe simple pressure-driven filtration (i.e., bytodirecting membrane
showed highmodifications
initial enzyme activity sol-gel
retention, technique were
and significantly proposed
improved stability improve
duringthe stability of
storage
fouling formation), without any addition of organic solvent [41]. As a result, enzyme activity was
the biological
and reuse activity
[36]. [36–40].
These enzymesThe dehydrogenases
can be also immobilizedencapsulated in the polymeric
in flat-sheet alginate-silicate
membranescomposite
fully retained byorthis non-covalent immobilization strategy.
showedsimultaneously
highThree
initial enzyme separately
activity byretention,
simple pressure-driven
and filtration
significantly (i.e., bystability
improved directing
moles of NADH is required to produce one mole of CH3OH from CO2 (Figure 3), therefore,
membrane
during storage and
fouling
reuse [36]. These formation), without
enzymes iscan any addition
be also[35]. of
immobilized organic solvent [41]. As a result, enzyme activity was
NADH regeneration necessary To provide in theflat-sheet
possibilitypolymeric
for practical membranes
application, simultaneously
a hybrid
fully retained by this non-covalent immobilization strategy.
or separately by simple pressure-driven
enzymatic/photocatalytic filtration
approach for efficient (i.e., by
converting CO directing membrane
2 into methanol fouling
was recently formation),
proposed
Three moles of NADH is required to produce one mole of CH3OH from CO2 (Figure 3), therefore,
[35].
anyThe
withoutNADH proposed
addition of approachsolvent
organic includes twoAs
[41]. processes:
a result, the enzymatic
enzyme transformation
activity was fully of CO2 to by this
retained
regeneration is necessary [35]. To provide the possibility for practical application, a hybrid
non-covalent immobilization approach
enzymatic/photocatalytic strategy.for efficient converting CO2 into methanol was recently proposed
Three
[35]. moles of NADH
The proposed is required
approach includes to twoproduce
processes:one
the mole
enzymatic of CH 3 OH from of
transformation COCO2 2(Figure
to 3),
therefore, NADH regeneration is necessary [35]. To provide the possibility for practical application,
a hybrid enzymatic/photocatalytic approach for efficient converting CO2 into methanol was recently
Energies 2017, 10, 473 6 of 19

proposed [35]. The proposed approach includes two processes: the enzymatic transformation of CO2
Energies 2017, 10, 473 6 of 19
to methanol promoted by NADH, and the in situ photocatalytic reduction of NAD+ to generate NADH
Energies 2017, 10, 473 6 of 19
using semiconductors
methanol promoted with
by the expected
NADH, and themechanism shown in
in situ photocatalytic Scheme
reduction of 3.
NADAs+ atoresult,
generate100 to 1000 mol
NADH
of CH3 OH
using can be produced
semiconductors from
with the 1 mol
expected NADH,
mechanism creating
shown inthe possibility
Scheme 3. As a
methanol promoted by NADH, and the in situ photocatalytic reduction of NAD to generate NADH for
result,
+ practical
100 to 1000application.
mol
of CH
More recently, OHa can be produced from
photocatalyst/biocatalyst 1 mol NADH, creating
integrated the
system possibility
for for
highly practical
selective
using semiconductors with the expected mechanism shown in Scheme 3. As a result, 100 to 1000 mol
3 application.
methanol More
production
recently,
directlyof CH3OH
from CO acan
photocatalyst/biocatalyst
be produced from 1 mol integrated
NADH, system
creating
wasthe forpossibility
highly by
selective methanol
forcombining
practical production
application. More
2 was reported [42]. The system obtained a newly developed
directly
recently, from
a CO2 was reported [42]. integrated
photocatalyst/biocatalyst The systemsystem
was obtained
for by selective
highly combining a newly production
methanol developed
graphene-based photocatalyst with sequentially coupled enzymes (FDH, Fald DH, and ADH) as
graphene-based
directly from COphotocatalyst
2 was reportedwith
[42].sequentially
The system coupled enzymes
was obtained (FDH, FaldDH,
by combining anddeveloped
a newly ADH) as
depicted in Scheme
depicted 4. 4.
in Scheme
graphene-based photocatalyst with sequentially coupled enzymes (FDH, FaldDH, and ADH) as
depicted in Scheme 4.

Scheme 3. Expected mechanism of NADH regeneration and further dioxide reduction to methanol [35].
Scheme 3. Expected mechanism of NADH regeneration and further dioxide reduction to methanol [35].
Scheme 3. Expected mechanism of NADH regeneration and further dioxide reduction to methanol [35].

Scheme 4. Schematic illustration of the photocatalyst/biocatalyst integrated system for producing

methanol
Scheme 4.from CO2 [42].
Schematic illustration of the photocatalyst/biocatalyst integrated system for producing
4. Schematic
Schememethanol from COillustration
2 [42].
of the photocatalyst/biocatalyst integrated system for producing
Very
methanol recently,
from direct injection of electrons into immobilized dehydrogenases without any
CO2 [42].
sacrificial
Very co-enzyme delivered
recently, direct for theofelectrochemical
injection electrons into CO 2 reduction dehydrogenases
immobilized to methanol around 0.15 ppm
without any
was reported [43]. Faradaic efficiencies of around 10% were obtained. These results
sacrificial co-enzyme delivered for the electrochemical CO2 reduction to methanol around 0.15 show for theppm
first
Very recently,
time direct
that all three injection of electrons intobe immobilized withdehydrogenases without any sacrificial
was reported [43].dehydrogenases can directly
Faradaic efficiencies of around addressed electrochemistry
10% were obtained. These resultswithout
show forrequiring
the first
co-enzymeany delivered
timesacrificial
that all three for
mediator the electrochemical
or electron
dehydrogenases donor
can suchbe
directly CO 2 reduction
as addressed
NADH. to methanol around
with electrochemistry 0.15 ppm was
without requiring
reportedany[43]. Faradaic
Nevertheless,
sacrificial efficiencies
the or
mediator reported of reaction
electron around
donor such 10%
ratesas were
and
NADH. obtained. These
equilibrium yields results show for
are generally lowtheand,first time
therefore,
that all three are not suited
dehydrogenases
Nevertheless, forcan
large-scale
the reported directly CO
reactionbe2 utilization
and [44].
addressed
rates withFor electrochemistry
kinetic
equilibrium considerations,
yields therelow
without
are generally isrequiring
a need
and, any
to intensify
therefore, arebiocatalysts
not suited for large-scale
for faster and more
CO efficient CO
utilization 2 conversion.
[44]. For kinetic This requires the
considerations, discovery
there is a needof
sacrificial mediator or electron donor such as NADH. 2
new enzymes
to intensify and the engineering
biocatalysts of reaction
for faster and systemsCO
more efficient for2 conversion.
improved catalytic efficiency.
This requires the discovery of
Nevertheless, the reported reaction rates and equilibrium yields are generally low and, therefore,
new enzymes and the engineering of reaction systems for improved catalytic efficiency.
are not suited for large-scale
3.1.4. Conversion of CO2CO 2 utilization [44]. For kinetic considerations, there is a need to intensify
to Methane
biocatalysts
3.1.4.Itfor faster and
Conversion
was found of
more
CO
that
efficient CO2 conversion.
2 to Methane
the nitrogenase MoFe
This requires the discovery of new enzymes
protein is able to catalyze the CO2 reduction to methane
and the(CH
engineering
) [45].
4It was found
of reaction
In total, 21the
that nmol systems
nitrogenase
for
of CH4 can
MoFe
improved
be protein
formed is catalytic
using
able 1tonmol
efficiency.
of this
catalyze enzyme
the CO undertooptimized
2 reduction methane
conditions
(CH4) [45]. within 2021
In total, min. Theofdoubly
nmol substituted
CH4 can be formedMoFe protein
using 1 nmolalso
ofhas
thisthe capacity
enzyme to catalyze
under the
optimized
3.1.4. Conversion of CO
unprecedented
conditions within 2 to
20
Methane
formation of doubly
min. The propylene throughMoFe
substituted the reductive coupling
protein also has the of CO2 and
capacity acetylene.
to catalyze the
unprecedented
It was found thatformation of propylene
the nitrogenase MoFethrough
proteinthe reductive
is able coupling
to catalyze theofCO
CO2reduction
and acetylene.
to methane
2
(CH4 ) [45]. In total, 21 nmol of CH4 can be formed using 1 nmol of this enzyme under optimized
conditions within 20 min. The doubly substituted MoFe protein also has the capacity to catalyze the
Energies 2017, 10, 473 7 of 19

unprecedented formation of propylene through the reductive coupling of CO2 and acetylene. Recently,
Rebelein et al. [46] observed that vanadium nitrogenase can reduce CO2 to C2 hydrocarbons involving
C–C coupling.
Energies 2017, 10, 473 7 of 19
3.1.5. Conversion of CO2 to Glucose
Recently, Rebelein et al. [46] observed that vanadium nitrogenase can reduce CO2 to C2 hydrocarbons
A varietyC–C
involving of energy-storing
coupling. carbon compounds can be formed via the photosynthetic carbon
reduction cycle using ATP resulting from the light-dependent reactions in conjunction with the
3.1.5. Conversion
carbon-fixing enzymeofribulose-1,5-bisphosphate
CO2 to Glucose carboxylase/oxygenase (RuBisCO) [47]. Inspired by
this, an inAvitro artificial
variety photosynthesis
of energy-storing system
carbon coupling
compounds theberequisite
can enzymes
formed via of the Calvincarbon
the photosynthetic cycle with
a nanoscale
reductionphotophosphorylation system
cycle using ATP resulting wasthe
from constructed for converting
light-dependent COconjunction
reactions in 2 to sugars with
[48]. the
In total,
carbon-fixing
116 nmol enzyme ribulose-1,5-bisphosphate
of glucose/(mL/h) can be produced with carboxylase/oxygenase
a chemical conversion (RuBisCO) [47].
efficiency Inspired by 96%
approaching
usingthis,
thisan in vitro artificial
photosynthetic photosynthesis system coupling the requisite enzymes of the Calvin cycle
foam.
with a nanoscale photophosphorylation system was constructed for converting CO2 to sugars [48]. In
total, 116 nmol
3.2. Conversion of2glucose/(mL/h)
of CO to Bicarbonatecan be produced with a chemical conversion efficiency approaching
96% using this photosynthetic foam.
As another strategy of CO2 conversion, an enzyme called carbonic anhydrase (CA) can directly
convert
3.2.CO 2 to bicarbonate
Conversion (HCO3 − ) via catalysis at a high turnover rate, up to 106 per second [49,50]:
of CO2 to Bicarbonate
As another strategy of CO2 conversion, an enzyme called
− carbonic anhydrase (CA) can directly
convert CO2 to bicarbonate (HCO3−) via
H2 O →atHCO
CO2 +catalysis + H+ ,
a high3 turnover rate, up to 106 per second [49,50]:
(1)

CA has one of the fastest reaction CO 2 + H

rates 2O → HCO
among 3− + H+,
all enzymes [51]. The CA-mediated catalytic (1)
conversion of CO
CA has one has attracted much research interest and used to assist
2 of the fastest reaction rates among all enzymes [51]. The CA-mediated catalytic three techniques
including absorption,
conversion of CO2 hasmembrane, and mineralization
attracted much research interestinandCO 2 capture,
used to assistsequestration,
three techniquesand utilization.
including
absorption, membrane,
CO2 absorption is slower inand mineralization
solvents, in CO2 capture,
but absorption sequestration,
can be accelerated andCA
with utilization. CO2
[52]. In addition,
absorption is slower in solvents, but absorption can be accelerated with CA
CA has been also shown to allow a lower heat of desorption, thus a far lower energy requirement [52]. In addition, CA has is
been also shown to allow a lower
feasible for CO2 capture and sequestration [53].heat of desorption, thus a far lower energy requirement is feasible
for CO2 capture and sequestration [53].
However, under the rough conditions of these processes such as from 50 to over 125 ◦ C in
However, under the rough conditions of these processes such as from 50 to over 125 °C in
operating temperature; high organic amine concentrations; and the presence of sulfur, nitrogen oxides
operating temperature; high organic amine concentrations; and the presence of sulfur, nitrogen
and trace
oxidescontaminants such as heavy
and trace contaminants such asmetals,
heavy the stability
metals, and activity
the stability of naturally
and activity derived
of naturally derivedCA are
poor, CA
which
are poor, which have restricted their use [53]. To overcome these limitations, several approach been
have restricted their use [53]. To overcome these limitations, several approach have
proposed
have including
been proposed sourcing CAssourcing
including from thermophilic organisms,organisms,
CAs from thermophilic using protein
using engineering techniques
protein engineering
to create thermotolerant
techniques enzymes, immobilizing
to create thermotolerant the enzyme
enzymes, immobilizing the(for both(for
enzyme stabilization and restriction
both stabilization and
restriction to cooler process zones), or process modifications such as cooling
to cooler process zones), or process modifications such as cooling the flue gas [54,55]. Recently, the flue gas [54,55].
Recently, potassium
an innovative an innovative potassium carbonate-based
carbonate-based absorption
absorption process, inprocess,
which thein which the CA is
CA enzyme enzyme is
immobilized
immobilized onto a new group of nonporous nanoparticles to improve thermal
onto a new group of nonporous nanoparticles to improve thermal stability and chemical resistance, stability and chemical
resistance, has been proposed to improve energy efficiency when capturing CO2 from coal
has been proposed to improve energy efficiency when capturing CO2 from coal combustion flue gas
combustion flue gas (shown in Figure 4) [56]. After ◦60-day test period at 50 °C, the immobilized
(shown in Figure 4) [56]. After 60-day test period at 50 C, the immobilized enzymes remained 56–88%
enzymes remained 56–88% of their original activity as compared to a 30% activity retention when
of their original
using free CAactivity
enzyme. as compared to a 30% activity retention when using free CA enzyme.

Figure 4. Schematic representation of the CA-catalytic CO2 conversion process and potassium
Figure 4. Schematic representation of the CA-catalytic CO2 conversion process and potassium
carbonate-based absorption process [56].
carbonate-based absorption process [56].
The catalytic conversion of CO2 by CA has been applied to improve the performance of
membranes including enhanced efficiency, speed, and increased specificity [57]. This invention is a
Energies 2017, 10, 473 8 of 19

Energies 2017, 10, 473 8 of 19

The catalytic conversion of CO2 by CA has been applied to improve the performance of
membranes including
process for gas enhanced
separation wherein efficiency, speed,in
carbon dioxide and increased
a mixed specificity
gas stream [57]. This
is converted to invention
bicarbonate is
ainprocess for gas separation
the temperature range ofwherein
40–85 °C.carbon dioxide in a mixed
The consequence is that gas
many stream is converted
outlet gas streams to such
bicarbonate
as flue
in the temperature range of 40–85 ◦ C. The consequence is that many outlet gas streams such as
gases can be used directly without the need for heat exchangers or other costly equipment or
flue gases The
processes. can selective
be used directly without
separation of CO2the fromneed for gas
mixed heatstreams
exchangers or other
has been costlyusing
developed equipment or
a hollow
processes. The selective
fiber membrane reactorseparation
supportedof byCO 2 from mixed
immobilized CAgas streams
(shown inhas been5)developed
Figure [58]. This using a hollow
enzyme-based
fiber membrane reactor supported by immobilized CA (shown in Figure 5)
membrane reactor allows CO2 at low concentrations to be separated from mixed gas streams. [58]. This enzyme-based
membrane
However, areactor
varietyallows CO2problems
of major at low concentrations
including shortto be separated
lifetime, fromand
fouling mixed gas streams.
biofouling, However,
separation of
athe
variety of major problems including short lifetime, fouling and biofouling, separation
enzyme from the immobilization surface, have limited the application of these enzymes in of the enzyme
from the immobilization
industrial settings [57]. surface, have limited the application of these enzymes in industrial settings [57].

Figure 5.
Figure 5. Schematic
Schematicillustration
illustrationof
ofaa hollow-fiber
hollow-fiber containing
containing immobilized-enzyme
immobilized-enzyme membrane
membrane reactor
reactor [58].
[58].

Current carbon storage research has primarily focused on sequestering CO2 in underground
Current carbon storage research has primarily focused on sequestering CO2 in underground
geologic formations such as saline aquifers, depleted oil and gas fields, and unmineable coal seams
geologic formations such as saline aquifers, depleted oil and gas fields, and unmineable coal seams [59].
[59]. Although these methods have the advantage of being relatively low-cost, sequestration in
Although these methods have the advantage of being relatively low-cost, sequestration in geologic
geologic formations still has several potential issues including permanence, long-term monitoring,
formations still has several potential issues including permanence, long-term monitoring, and
and verification, with many unknown effects and potential risks still to be determined [60]. Thus,
verification, with many unknown effects and potential risks still to be determined [60]. Thus, carbon
carbon mineralization, where CO2 is reacted with metal cations such as calcium to form calcium
mineralization, where CO2 is reacted with metal cations such as calcium to form calcium carbonate
carbonate (CaCO3), is considered an effective alternative to conventional geologic sequestration [61].
(CaCO3 ), is considered an effective alternative to conventional geologic sequestration [61]. Note that
Note that bivalve shell composed of CaCO3 is abundant and stable biomaterials in ocean [62]. This
bivalve shell composed of CaCO3 is abundant and stable biomaterials in ocean [62]. This process can
process can be seen in Equations (2)–(6) below:
be seen in Equations (2)–(6) below:
CO2 (gaseous) → CO2 (aqueous), (2)
CO2 (gaseous) → CO2 (aqueous), (2)
CO2 (aqueous) + H2O → H2CO3, (3)
CO2 (aqueous) + H2 O → H2 CO3 , (3)
H2CO3 → HCO−3− + H++, (4)
H2 CO3 → HCO3 + H , (4)
HCO− 3− → CO23−
2− + H+
+ H ,, (5)
+
HCO 3 → CO3 (5)
2+ 2−
CaCa + +CO
2+ 3 32− →
CO → CaCO
CaCO33,, (6)
(6)
Because these
theseemerging
emergingmineralization
mineralization methods
methods areare rapid,
rapid, environmentally
environmentally friendly,
friendly, and
and cost-
cost-effective while offering permanent carbon dioxide disposal, they have rapidly grabbed
effective while offering permanent carbon dioxide disposal, they have rapidly grabbed a great a great deal
of interest [61]. However, in the whole
whole process,
process, HH22CO33 formation
formation isis the rate-limiting step [63]. Thus,
Thus,
CA has recently been utilized to enhance
has recently been utilized to enhanceCO 2 sequestration through the conversion and mineralization
CO2 sequestration through the conversion and
mineralization of CO2 into CaCO3 [62]. The converting CO2 into carbonate compounds by using CA
as a catalyst in a biomimetic approach is thermodynamically advantageous compared to other CO2
storage methods and technologies. Furthermore, the biomimetic CO2 storage approach does not need
Energies 2017, 10, 473 9 of 19

of CO2 into CaCO3 [62]. The converting CO2 into carbonate compounds by using CA as a catalyst in a
biomimetic approach is thermodynamically advantageous compared to other CO2 storage methods
and technologies. Furthermore, the biomimetic CO2 storage approach does not need a monitoring
system for potential leaks as CCS strategies do, and carbonate compounds can be used for building or
industrial materials [62,64]. Recently, a new carbonic anhydrase isolated and characterized from the
thermophilic bacterium Sulfurihydrogenibium sp. YO3AOP1 was reported [65].
Although CA can efficiently accelerate mineralization for CO2 sequestration, CA recycling can be
a barrier. Several efforts have attempted to address this challenge. A recent study reported the strategy
of CA-assisted formation of biomineralized calcium carbonate crystalline composites (CCCCs) [66].
The CCCCs produced in this study preserved their catalytic activity even after ten repeated usages,
and were stable for more than 50 days at room temperature.
The success of enzymatic CO2 conversion requires the successful immobilization and stabilization
of CA, which enables enzyme recycling and improves the economics of enzymatic conversion and the
eventual CO2 utilization. Various methods for immobilizing CA have been reported. CA immobilization
on SBA-15 was explored [67]. Recently, CA has been immobilized on chitosan stabilized iron nanoparticles
for the biomimetic carbonation reaction [68]. CA binding to carboxylic acid group-functionalized
mesoporous silica (HOOC-FMS) was also investigated [51]. This resulted in a partial conformational
change compared to the free enzyme in solution, but can allow increased protein loading density,
resulting in higher enzymatic activity and immobilization efficiency. In addition, the use of bioinspired
silica supporting CA for carbon capture has been presented [69]. The immobilization route was
favorable compared to traditional methods due to its simplicity, mild conditions, low cost, one-step
procedure, and short preparation time. More recently, a process for one-pot CO2 utilization based on
the simple conversion of CO2 to bicarbonate at ambient temperature with no energy input, using the
crosslinking-based composites of carboxylated polyaniline nanofibers and CA was developed [49].
The cell concentration with magnetically separable enzyme precipitate coatings was maintained as
high as the first cycle after two repeated uses.
Keeping in mind the large-scale application of CA-driven CO2 sequestration into mineral
carbonates, the development of an adequate and economical means of pH control is presently a
major research need since CaCO3 is pH sensitive [70]. With the available research on CA-driven
processes for CO2 sequestration, smart efforts are needed with respect to choosing the right material
and right CA immobilization technique so that enzyme leakage can be conquered and reusability
can be enhanced, which eventually contributes to improved economic feasibility. Furthermore, more
efforts are needed to build the fundamentals of mass transfer in CA mediated CO2 sequestration [71].

3.3. Carboxylation Reactions

Carboxylation is a chemical reaction in which a carboxylic acid group is introduced in a substrate.
Several decarboxylase enzymes, which catalyze the decarboxylation processes, exist in cells and also
have potential for biocatalytic applications of carboxylation processes, including: (i) carboxylation
of epoxides; (ii) carboxylation of aromatics; (iii) carboxylation of hetero-aromatic systems; and
(iv) carboxylation of aliphatic substrates [72]. The main target of carboxylation reactions by decarboxylases
is to make toxic raw compounds more hydrophilic. Overall, little (or no) energy is required by these
reactions [72]. Recently, these decarboxylase enzymes have been utilized in CO2 utilization as follows.

3.3.1. Carboxylation of Epoxides

A novel enzymatic reaction involving the metabolism of aliphatic epoxides by Xanthobacter strain
Py2 has been investigated [73]. Cell extracts catalyzed the CO2 -dependent carboxylation of propylene
oxide (epoxypropane) to form acetoacetate and beta-hydroxybutyrate, while propylene oxide and
1,2-epoxybutane were isomerized to form acetone and methyl ethyl ketone, respectively, as this process
consumes CO2 . However, the potential for in vitro application and practical applicability of this
process is low because the responsible enzymes could not be purified [72].
Energies 2017, 10, 473 10 of 19

3.3.2. Carboxylation of Aromatics

There are several applications available for the enzymatic carboxylation of aromatics using
Energies 2017, 10, 473 10 of 19
decarboxylases. These processes can overcome the disadvantages of the Kolbe–Schmitt reaction
because ofThere
occurring under applications
are several conditions of high temperature
available and pressure,
for the enzymatic but cannot
carboxylation achieve completely
of aromatics using
mastered selectivity, which requires high energy in purification and
decarboxylases. These processes can overcome the disadvantages of the Kolbe–Schmitt produces waste [74,75]. The 4-OH
reaction
benzoic
because of occurring under conditions of high2 temperature and pressure, but cannot achieve completely of
acid synthesis from phenol and CO at room temperature and sub-atmospheric pressure
CO2 with 100%
mastered selectivity
selectivity, whichis the first high
requires application
energy inofpurification
a phenol carboxylase
and produces enzyme [6]. The
waste [74,75]. use of the
The 4-OH
entirebenzoic
cell wasacid synthesisbecause
excluded from phenoltheand CO2product
target at room temperature and sub-atmospheric
is further used by the bacteria pressure of COsource.
as a carbon 2

Thus,with 100%
cells were selectivity
lysed to is obtain
the first the
application of a phenol
crude extract, carboxylase
which was then enzyme [6]. The
purified use of
using the entire to
a membrane
cell was
eliminate mostexcluded
proteins because the target
and other cell product
componentsis further
thatused by the
are not bacteriain
involved asthe
a carbon source. Thus,
carboxylation reaction.
cells were lysed to obtain the crude extract, which was then purified using a membrane to eliminate
A turnover number of approximately 16,000 can be obtained in this clean process [75].
most proteins and other cell components that are not involved in the carboxylation reaction. A turnover
Recently, a new method was explored for the selective and ecological salicylic acid production
number of approximately 16,000 can be obtained in this clean process [75].
by the enzymatic
Recently, aKolbe–Schmitt
new method was reaction
explored(as forshown in Figure
the selective 6) [76]. In
and ecological particular,
salicylic salicylic acid
acid production
decarboxylase (Sdc) is used for producing salicylic acid from phenol. The yeast
by the enzymatic Kolbe–Schmitt reaction (as shown in Figure 6) [76]. In particular, salicylic Trichosporon moniliforme
acid
WU-0401 was enzymatically
decarboxylase (Sdc) is used characterized
for producingwith salicylic
the Sdc gene
acid heterologously
from phenol. The expressed. More recently,
yeast Trichosporon
Sdc enzyme has WU-0401
moniliforme also beenwas applied to convertcharacterized
enzymatically m-aminophenol to p-aminosalicylic
with the acid with
Sdc gene heterologously a conversion
expressed.
yieldMore
of 70%recently,
(mol/mol)Sdc enzyme
[77]. has also been applied to convert m-aminophenol to p-aminosalicylic acid
with a conversion
Similarly, yield of 70% (mol/mol)
1,2-dihydroxybenzene [77]. can be carboxylated to 3,4-dihydroxybenzoic acid
(catechol)
Similarly, 1,2-dihydroxybenzene (catechol)
using 3,4-dihydroxybenzoate decarboxylase in Enterobacter can be carboxylated
cloacae P241 to with
3,4-dihydroxybenzoic
a conversion of 28% acid after
using◦3,4-dihydroxybenzoate decarboxylase in Enterobacter cloacae P241 with a conversion of 28%
14 h at 30 C [78]. Although the enzyme was completely regioselective for its “natural” substrate, it
after 14 h at 30 °C [78]. Although the enzyme was completely regioselective for its “natural” substrate,
was also able to convert phenol, 1,2-dihydroxybenzene, and m-aminophenol at very low rates, while
it was also able to convert phenol, 1,2-dihydroxybenzene, and m-aminophenol at very low rates,
consuming considerable
while consuming amount amount
considerable of CO2 of [74,79,80].
CO2 [74,79,80].

Figure 6. Reversible enzymatic conversion of salicylic acid and phenol [76].

Figure 6. Reversible enzymatic conversion of salicylic acid and phenol [76].
Recently, phenolic acid decarboxylases from bacterial sources catalyzed the β-carboxylation of
Recently, phenolic acid
para-hydroxystyrene decarboxylases
derivatives from bacterial
with excellent regio- andsources catalyzed the β-carboxylation
(E/Z)-stereoselectivity by exclusively of
acting at the bcarbon atom of the C=C side chain to furnish the corresponding
para-hydroxystyrene derivatives with excellent regio- and (E/Z)-stereoselectivity by exclusively(E)-cinnamic acidacting
at thederivatives
bcarbon atom in upoftothe
40%
C=Cconversion
side chainat the expensethe
to furnish of bicarbonate
corresponding as carbon dioxide acid
(E)-cinnamic source [81].
derivatives
in up to 40% conversion at the expense of bicarbonate as carbon dioxide source [81]. Enzyme the
Enzyme kinetics together with the reaction thermodynamics in line with the verification of kinetics
catalytic mechanism of 2,6-dihydroxybenzoic acid decarboxylase from Rhizobium sp. with catechol as
together with the reaction thermodynamics in line with the verification of the catalytic mechanism of
the phenolic substrate was investigated [82]. This study provides insights into the catalytic behavior
2,6-dihydroxybenzoic acid decarboxylase from Rhizobium sp. with catechol as the phenolic substrate
of a nonoxidative aromatic decarboxylase and reveals key limitations (e.g., substrate oxidation, CO2
was investigated
pressure, enzyme [82].deactivation,
This studyand provides insights
low turnover into the in
frequency) catalytic
view ofbehavior of a nonoxidative
the employment of this
aromatic decarboxylase and reveals key limitations (e.g.,
system as a “green” alternative to the Kolbe–Schmitt processes. substrate oxidation, CO 2 pressure, enzyme
deactivation, and low turnover frequency) in view of the employment of this system as a “green”
3.3.3. Carboxylation
alternative of Hetero-Aromatics
to the Kolbe–Schmitt processes.
Pyrrole-2-carboxylate, a potential herbicide employed in the synthesis of various pharmaceuticals,
3.3.3. Carboxylation of Hetero-Aromatics
can be synthesized from pyrrole and CO2 using pyrrole-2-carboxylate decarboxylase, which was
obtained from Bacillus megaterium
Pyrrole-2-carboxylate, a potential PYR2910
herbicide(as shown in Scheme
employed in the 5) [83–85]. The
synthesis bioconversion
of various yield
pharmaceuticals,
was limited to 77–81% by the reaction equilibrium [84].
can be synthesized from pyrrole and CO2 using pyrrole-2-carboxylate decarboxylase, which was
Energies 2017, 10, 473 11 of 19

obtained from Bacillus megaterium PYR2910 (as shown in Scheme 5) [83–85]. The bioconversion yield
was limited to 77–81% by the reaction equilibrium [84].
Energies 2017, 10, 473 11 of 19

Energies 2017, 10, 473 11 of 19

Energies 2017, 10, 473 11 of 19

Scheme 5. Possible carboxylation mechanism [85].

Scheme 5. Possible carboxylation mechanism [85].
3.3.4. Carboxylation of Aliphatic
SchemeSubstrates
5. Possible carboxylation mechanism [85].
3.3.4. Carboxylation of Aliphatic Substrates
The enzymatic synthesis of pyruvic acid from acetaldehyde and CO2 using the reverse reaction
3.3.4. Carboxylation of Aliphatic
SchemeSubstrates
5. Possible carboxylation mechanism [85].
of Brewer’s
The enzymatic yeast pyruvate
synthesis decarboxylase
of pyruvic was acetaldehyde
acid from explored as presented
and CO2 in Scheme
using 6 [5,86].reaction
the reverse The of
Brewer’s The
maximum enzymatic
yield of synthesis
81% was of pyruvic
achieved inacid
500 from
mM acetaldehyde
NaHCO -Na and
CO CO 2 using
buffer andthe
pH reverse
11. reaction
Especially,
3.3.4.yeast pyruvateofdecarboxylase
Carboxylation was explored as presented in Scheme 6 [5,86]. The maximum
Aliphatic Substrates 3 2 3

of
of Brewer’s
yieldenzymatic
81% was yeast
reaction pyruvate
by lactate
achieved decarboxylase
in 500dehydrogenase
mM NaHCO was
can explored
employedasforpresented in Schemeof 6pyruvic
the hydrogenation [5,86]. acid
The
3 -Na2 CO3 buffer and pH 11. Especially, enzymatic
into The enzymatic
maximum
lactic yield
acid [86]. synthesis
of 81%
Thus,was of pyruvic
achieved
design inacid
500from
a completely mM acetaldehyde
NaHCO3-Nasafe
environmentally 2and CO 2 using
CO3two-step
buffer andthe
pHreverse reaction
11. process
enzymatic Especially,
for
reaction by lactate dehydrogenase can employed for the hydrogenation of pyruvic acid into lactic
of Brewer’s
enzymatic
CO yeast pyruvate
reaction
2 immobilization by lactatedecarboxylase
is possible.dehydrogenasewas can explored
employedasforpresented in Schemeof6pyruvic
the hydrogenation [5,86]. acid
The
acid maximum
[86]. Thus, design
yield of 81% a completely environmentally safe two-step enzymatic process for CO2
into lactic acid [86]. Thus,was achieved
design in 500 mM
a completely NaHCO 3-Na2safe
environmentally CO3two-step
buffer and pH 11.
enzymatic Especially,
process for
immobilization
enzymatic is possible.
reaction by
CO2 immobilization lactate dehydrogenase can employed for the hydrogenation of pyruvic acid
is possible.
into lactic acid [86]. Thus, design a completely environmentally safe two-step enzymatic process for
CO2 immobilization is possible.

Scheme 6. Enzymatic reaction route for synthesis of pyruvic acid from CO2 and acetaldehyde [86].

Recently,
Scheme 6.aEnzymatic
new multienzyme reaction
reaction route system
for synthesis was investigated
of pyruvic acid from CO for L-lactic
2 and acid production,
acetaldehyde [86].
Scheme 6. Enzymatic reaction route for synthesis of pyruvic acid from CO2 and acetaldehyde [86].
which is used in food, cosmetic, pharmaceutical, and chemical industries, from carbon dioxide and
ethanolRecently,
Scheme
(shown 6.aEnzymatic
new
in multienzyme
Scheme reaction reaction
7) [87].route
The for
unique system
synthesis was investigated
of pyruvic
internal acid from
cofactor COfor L-lactic
2 and
regeneration cycle acid
acetaldehydeproduction,
in this [86].
synthetic
Recently,
whichcan
route aeliminate
is usednewin multienzyme
food, need forreaction
thecosmetic, system
pharmaceutical,
additional was investigated
andorchemical
reagents energy for for L-lactic
industries,
cofactor from acid
carbonproduction,
regeneration. dioxide
Up to 41% andwhich
in
is used inRecently,
ethanol
terms (shown
food, a in
of ethanol new
cosmetic, multienzyme
Scheme 7) [87].
conversion
pharmaceutical, reaction
can The
be andsystem
unique
achieved wascofactor
internal
in a batch
chemical investigated
reaction,
industries, for aL-lactic
regeneration
while
from cycleacid
turnover
carbon production,
innumber
this
dioxide synthetic
and of ethanol
2.2
which
(shownroute
day is used
can
−1 was
in Scheme in
reached7)food,
eliminate the
for
[87]. cosmetic,
needunique
cofactor
The for pharmaceutical,
additional
regeneration
internalwith andor
reagents chemical
energy
continuous
cofactor industries,
for
ethanol
regeneration cofactor
feeding
cycle from carbon
regeneration.
[87].
in this dioxide and can
Up toroute
synthetic 41%
ethanol
in terms (shown in Scheme 7) [87]. The unique internal cofactor regeneration cycle in this synthetic
eliminate the of ethanol
need conversion reagents
for additional can be achieved in a for
or energy batch reaction,
cofactor while a turnover
regeneration. Up tonumber
41% inofterms
2.2 of
route can eliminate
day−1 was reached for thecofactor
need for additional reagents
regeneration or energy
with continuous for cofactor
ethanol feedingregeneration.
[87]. Up to 41%
ethanol conversion can be achieved in a batch reaction, while a turnover number of 2.2 day−1 was
in terms of ethanol conversion can be achieved in a batch reaction, while a turnover number of 2.2
reached
day−1 forwascofactor
reachedregeneration with continuous
for cofactor regeneration ethanol feeding
with continuous ethanol[87].
feeding [87].

Scheme 7. Enzymatic reaction route for synthesis of L-lactic acid from CO2 and ethanol [87].

For Scheme
more detailed information
7. Enzymatic regarding
reaction route carboxylation
for synthesis reactions,
of L-lactic acid from CO2as
andwell as [87].
ethanol the enzyme
purification methods applied for those reactions, please refer to Table S1 in the Supplementary
For Scheme
more
Information detailed information
7. Enzymatic
Section reaction
of Reference regarding
route
[72]. carboxylation
for synthesis reactions,
of L-lactic acid from CO2as
andwell as [87].
ethanol the enzyme
Scheme 7. Enzymatic reaction route for synthesis of L-lactic acid from CO and ethanol [87].
purification methods applied for those reactions, please refer to Table S1 2in the Supplementary
For more
Information detailed
Section information
of Reference [72]. regarding carboxylation reactions, as well as the enzyme
purification methods applied for those reactions, please refer to Table S1 in the Supplementary
Information Section of Reference [72].
Energies 2017, 10, 473 12 of 19

For more detailed information regarding carboxylation reactions, as well as the enzyme
purification methods applied for those reactions, please refer to Table S1 in the Supplementary
Information Section
Energies 2017, 10, 473 of Reference [72]. 12 of 19

4. Industrial Applications
4. Industrial Applications
Only
Only aa limited
limited number
number of of examples
examples of of industrial
industrial chemical
chemical processes
processes using
using CO as feedstock
CO22 as feedstock such
such
as
as the Bosch–Meiser process [88] are recognized [12] because it requires large energy input due to
the Bosch–Meiser process [88] are recognized [12] because it requires large energy input due to
strong
strong bonds.
bonds.ThisThishas
hasmotivated
motivatednot notonly fundamental
only fundamental studies butbut
studies alsoalso
industrial applications
industrial of COof2
applications
enzymatic
CO2 enzymaticconversion in recent
conversion years.years.
in recent
A
A successful industrial application of
successful industrial application of enzymatic
enzymatic CO conversion is
CO22 conversion is using
using CACA for
for accelerating
accelerating
CO
CO22 capture [89]. The use of chemical amine solvents has been primarily employed in conventional
capture [89]. The use of chemical amine solvents has been primarily employed in conventional
technology
technology forfor capturing
capturing pure
pure CO
CO22.. However,
However, these
these solvents
solvents require
require significant
significant amounts
amounts of of valuable,
valuable,
high-grade process heat for solvent regeneration, resulting in an inefficient process
high-grade process heat for solvent regeneration, resulting in an inefficient process with high with high operating
costs that suffers
operating costs from
that significant
suffers from operational andoperational
significant environmental andissues including degradation,
environmental toxic
issues including
aerosol emissions,
degradation, toxicsensitivity to flue gassensitivity
aerosol emissions, contaminants, and
to flue corrosivity
gas [89]. To
contaminants, solve
and these challenges,
corrosivity [89]. To
CO 2 these challenges, CO2 Solutions’ technology employs the most powerful known (as
solve Solutions’ technology employs the most powerful known catalyst, the enzyme CA shownthe
catalyst, in
Figure
enzyme7),CA resulting in both
(as shown fast CO7),
in Figure 2 absorption kinetics
resulting in and CO
both fast significantly
2 absorptionreduced energy
kinetics and consumption
significantly
for carbon management.
reduced energy consumption for carbon management.

Figure 7. Schematic representation of CA-catalyzed CO2 conversion and chemical absorption [89].
Figure 7. Schematic representation of CA-catalyzed CO2 conversion and chemical absorption [89].

Recently, the Quebec City-based company CO2 Solutions verified the results of a carbon capture
Recently, the
demonstration Quebec
project at City-based company CO2 Solutions
Salaberry-de-Valleyfield verifiedreporting
near Montreal, the resultsthat
of a CO
carbon capture
2 Solutions’
demonstration project at Salaberry-de-Valleyfield near Montreal,
proprietary enzyme performed in a stable manner with negligible solvent consumption andreporting that CO 2 Solutions’
without
proprietary enzyme performed in a stable manner with negligible solvent consumption
producing any toxic waste products (shown in Figure 8) [89,90]. Furthermore, a pilot-scale CO2 and without
producing any toxic
capture process waste products
was constructed at the(shown
National in Carbon
Figure 8) [89,90].
Capture Furthermore,
Center a pilot-scale
in Wilsonville, AL, USA CO by2
capture process was constructed at the National Carbon Capture Center
Codexis Inc., in which the rate of CO2 absorption was enhanced 25-fold compared with the non- in Wilsonville, AL, USA
by Codexis
catalyzed Inc., in[91].
reaction which the rate of CO2 absorption was enhanced 25-fold compared with the
non-catalyzed reaction
A process and a plant [91].were invented for the recovery and recycling of the CO2 emissions from
A process and a plant
the cement clinker production were invented
by Lalande for the
andrecovery
Tremblay andofrecycling of the CO
CO2 Solution 2 emissions
[92]. from thea
In this process,
cement clinker
gas/liquid CO2production
packed column by Lalande and Tremblay
absorption of COby
catalyzed 2 Solution [92]. In
CA is used thissubsequent
and process, a gas/liquid
with the
CO 2 packed
production of limestone (CaCO3). The sequence is accomplished when the CaCO3 isthe
column absorption catalyzed by CA is used and subsequent with production
used of
as first class
limestone
raw material(CaCO 3 ). The
for the sequence
fabrication ofisPortland
accomplished
cement. when the CaCO3 is used as first class raw material
for the fabrication of Portland cement.
Climostat Ltd. (Cheshire, UK) has filed a patent application for an enzymatic process that
Climostat
converts CO2 and Ltd. (Cheshire,
methane UK) acid,
to formic has filed a patent
a valuable application
commodity for an[93].
chemical enzymatic process
One fifth of a tonthat
of
converts
methane CO 2 and
(about £50 methane to formic
worth) would acid, a valuable
be potentially commodity
converted chemical
into £720 worth of[93]. One acid.
formic fifth of a ton
Even of
after
methane
conversion (about
costs£50
areworth) would
taken into be potentially
account, converted
the process into £720
is expected to be worth of formic
of significant acid. Evenvalue
commercial after
and especially so when any carbon levy is taken into account. Further value could be added by using
the resulting formic acid as a feedstock for higher-value materials. In addition, Sweetwater Energy
Inc. (New York, NY, USA) and Naturally Scientific Technologies Ltd. (Buckinghamshire, UK)
announced a joint venture to produce sugar from carbon dioxide waste from facilities such as ethanol
plants or natural-gas powered power plants [94].
Energies 2017, 10, 473 13 of 19

conversion costs are taken into account, the process is expected to be of significant commercial value
and especially so when any carbon levy is taken into account. Further value could be added by using
the resulting formic acid as a feedstock for higher-value materials. In addition, Sweetwater Energy Inc.
(New York, NY, USA) and Naturally Scientific Technologies Ltd. (Buckinghamshire, UK) announced
a joint venture to produce sugar from carbon dioxide waste from facilities such as ethanol plants or
natural-gas powered power plants [94].
Recently, within the “Biotechnology 2020+” strategy process, the funding measure “Basic
technologies for a next generation of biotechnological processes” supports three selected projects with
regards to enzymatic conversion of CO2 with a total budget of 4.3 million Euros [95,96]. In addition,
the US Department of Energy (DOE), through the National Energy Technology Labs (NETL) and
academic partners, is funding a spectrum of research projects investigating closed-cycle catalysts to
convert CO2 to commodity products that are ideally energy and carbon neutral [97]. Even though
these projects are still focused primarily on basic research, biotechnological approaches will play an
important role in CO2 utilization in the future [95]. With the current global dependency on fossil fuels
for energy production, these approaches are expected provide a means to reduce human induced
climate change [98].
Energies 2017, 10, 473 13 of 19

Figure 8. Industrial application of CA-catalyzed CO2 conversion and chemical absorption [89].
Figure 8. Industrial application of CA-catalyzed CO2 conversion and chemical absorption [89].
Recently, within the “Biotechnology 2020+” strategy process, the funding measure “Basic
5. Barrierstechnologies
and Future forPerspectives
a next generation of biotechnological processes” supports three selected projects
with regards to enzymatic conversion of CO2 with a total budget of 4.3 million Euros [95,96]. In
Enzymes are generally
addition, expensive
the US Department with poor
of Energy (DOE),stability,
through activity, andEnergy
the National reusability, which
Technology restrict their
Labs
industrial(NETL) and academic
applications. partners,
Several is fundingtechnologies
enzymatic a spectrum of research
such asprojects investigating
enzyme closed-cycle
modification and enzyme
catalysts to convert CO2 to commodity products that are ideally energy and carbon neutral [97]. Even
immobilization need further development for reducing cost, improving the activity/stability of the
though these projects are still focused primarily on basic research, biotechnological approaches will
enzymes, play
andan enhancing
important rolereusability, whichineventually
in CO2 utilization improves
the future [95]. economic
With the current globalfeasibility.
dependency Besides,
on low
reaction rate is one of main barriers for the application of enzymatic CO2 conversion in industry.
fossil fuels for energy production, these approaches are expected provide a means to reduce human
For kineticinduced climatebiocatalysts
concerns, change [98]. are needed for faster and more efficient CO conversion. Thus,
2
the discovery of novel enzymes as
5. Barriers and Future Perspectiveswell as the reaction systems engineering are required to improve
catalytic efficiency.
Enzymes are generally expensive with poor stability, activity, and reusability, which restrict
Especially, cofactor-dependent
their industrial reactions
applications. Several widely
enzymatic occur such
technologies in the enzymatic
as enzyme conversion
modification and of CO2 .
However, enzyme
some cofactors are expensive
immobilization need furtherand have limited
development availability,
for reducing whichthe
cost, improving severely limits large-scale
activity/stability
of theThus,
applications. enzymes, and enhancing research
considerable reusability,effort
which eventually
should be improves
applied economic
towardfeasibility. Besides,
the discovery of new
low reaction rate is one of main barriers for the application of enzymatic CO2 conversion in industry.
low-cost and low-energy approaches for cofactor regeneration and reuse [2].
For kinetic concerns, biocatalysts are needed for faster and more efficient CO2 conversion. Thus, the
In addition,
discovery only a few
of novel multienzyme
enzymes as well as theroutes
reactionhave
systemsbeen constructed
engineering in vitro
are required due to reaction
to improve
complexity. Therefore,
catalytic designing and/or constructing of number of novel multienzyme routes are
efficiency.
imperative to Especially,
sustainably cofactor-dependent
produce fuels reactions widely occur
and chemicals frominCO the [2].
2
enzymatic conversion of CO2.
However, some cofactors are expensive and have limited availability, which severely limits large-
scale applications. Thus, considerable research effort should be applied toward the discovery of new
low-cost and low-energy approaches for cofactor regeneration and reuse [2].
In addition, only a few multienzyme routes have been constructed in vitro due to reaction
complexity. Therefore, designing and/or constructing of number of novel multienzyme routes are
imperative to sustainably produce fuels and chemicals from CO2 [2].
Furthermore, it is important to consider that the technologies for CO2 conversion based on
Energies 2017, 10, 473 14 of 19

Furthermore, it is important to consider that the technologies for CO2 conversion based on
chemical, photochemical, and electrochemical methods also show great application potential [99].
Thus, combining these methodologies with enzymatic conversion is expected to be beneficial in terms
of selectivity and productivity. These combination strategies should be further studied and evaluated.
For an industrial exploitation, the design of a suitable bioreactor is a key issue [40]. Furthermore,
the unit operations for the separation of mixture including biological molecules differ from their
counterparts in the chemical industry. Much effort in separation in downstream needs to investigate
and evaluate. Especially, the use of enzymes within reactive separation to enhance both reaction and
separation has increased its research interest. Because enzymes are sensitive to higher temperatures,
many works are needed to develop. In addition, the development of thermodynamic data and models
for description of systems containing enzyme as well as development of synthesis/design tools are
crucial to support the quick implementation of those systems [100].
Although a considerable number of studies have been carried out, substantial scientific and
technical advances are still needed for a link between fundamental research and industrial application
of enzymatic CO2 conversion.

6. Conclusions
Enzymatic CO2 conversion represents a viable and promising new technology for both greenhouse
gas recycling and efficient production of fuels and chemicals. In this review, we attempted to elucidate
the major challenges for transitioning enzymatic conversion from promise to reality. Although
there is much excitement about the potential of enzymatic CO2 conversion as well as several real
industrial applications, much work is still required in the field to discover facile and low-energy
CO2 conversion routes; improve catalytic efficiency; integrate with chemical, photochemical, and
electrochemical technologies for higher efficiency; and assess downstream processes for large-scale
utilization. There are several real industrial application examples that are working, thus, we are not so
far from the extension of the technology in the industry.

Acknowledgments: This research was supported by C1 Gas Refinery Program through the National
Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT & Future Planning
(NRF-2016M3D3A1A01913262). This study was also supported by Priority Research Centers Program through the
National Research Foundation of Korea (NRF) funded by the Ministry of Education (2014R1A6A1031189).
Author Contributions: Nguyen Van Duc Long designed the paper, conducted the literature review, and wrote
the paper. Jintae Lee advised enzymatic conversion. Kee-Kahb Koo advised novel applications. Patricia Luis and
Moonyong Lee equally conceived the core concepts for the research and provided academic advice. All authors
collaborated in the preparation, revisions, and general editing of this manuscript.
Conflicts of Interest: The authors declare no conflict of interest.

Abbreviations
The following abbreviations are used in this manuscript:

ADH Alcohol dehydrogenase

CO Carbon monoxide
CO2 Carbon dioxide
CCS CO2 capture and storage
CODH Carbon monoxide dehydrogenases
CA Carbonic anhydrase
FDH Formate dehydrogenase
CCCCs Calcium carbonate crystalline composites
Fald DH Formaldehyde dehydrogenase
CH4 Methane
HCO3 − Bicarbonate
HOOC-FMS Carboxylic acid group-functionalized mesoporous silica
RuBisCO Ribulose-1,5-bisphosphate carboxylase/oxygenase
Energies 2017, 10, 473 15 of 19

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