Journal of CO₂ Utilization 24 (2018) 419–429

Contents lists available at ScienceDirect

Journal of CO2 Utilization

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

Enzyme inspired complexes for industrial CO2 capture: Opportunities and T

challenges
⁎
Prakash C. Sahoo, Manoj Kumar , S.K. Puri, S.S.V. Ramakumar
Research and Development Center, Indian Oil Corporation Limited, Sector-13, Faridabad, Haryana, 121007, India

A R T I C L E I N F O A B S T R A C T

Keywords: In this paper, we have analyzed carbon dioxide (CO2) capture and hydration using enzyme inspired complexes.
Carbon dioxide Particularly, efforts have been made to investigate the carbonic anhydrase (CA) mimic complexes discovered in
Enzyme mimics the last five years. CA, a well known zinc containing enzyme, can hydrate CO2 in unprecedented rate
Carbonic anhydrase (Kcat = 106 s−1). It has been recently used in commercial CO2 capture unit or blended with amines to enhance
Metal complexes
CO2 capture and ease the stripping. However, the uses of the native enzyme face several intrinsic difficulties such
as thermal stability, pH stability and storage issues etc. Therefore, mimicking the active site of CA is of enormous
interest among the scientific communities. These enzyme inspired complexes not only reproduce similar ac-
tivities of CA but also thermally stable over a broad range of temperature and robust at drastic conditions. In this
attempt we have precisely summarized the zinc and non-zinc complexes, de-novo enzymes along with the im-
portance of supramolecular-scaffolds during mimic design. The current use and shortcomings of these enzyme
mimics in industrial prospective are also discussed. Finally, the development of ab initio and classical molecular
simulation methods for modeling enzyme mimics are discussed for the futuristic design of next generation CO2
capture catalyst.

1. Introduction
Due to rising concentrations of CO2, climate change has become the
prime concern of 21th century. Currently, over 80% of our energy
supply is from fossil fuel, while the renewable is only 10% [1,2]. As per
prediction, fossil fuels, which contribute in CO2 emission, will still
continue to be the front runner to compensate our escalating energy
needs in the foreseeable future [3]. Consequently, to maintain a synergy
between energy equivalent and sustainable development, we need to
develop appropriate technology for large scale carbon capture, utili-
zation and storage. At Paris climate summit 2015 (COP21), nations are
agreed to reduce rising temperature by cutting CO2 emission to a large
extent [4].
Mainly two strategies such as carbon capture and storage (CCS) and
carbon capture and utilization (CCU) are being followed to mitigate
CO2 emission into the atmosphere (Fig. 1). In CCS, CO2 is captured and
transferred to a desired site for storage, whereas, in CCU, captured CO2
is converted into valuable products [5–7]. In CCU, CO2 is used as feed
stock for synthesis of fuels, carbonates, polymers and chemicals. CO2
also have its potential application for enhanced oil and gas recovery
(EOR, EGR) and for production of several mineral carbonates. CCU
technology is developing rapidly and entered in to demonstration
phases. However, considering the massive scale of CO2 emission, CCS is
still the dominating method for CO2 capture in industrial sectors [5–7].
Among the different method of CCS, post combustion CO2 capture is
heavily practiced in industrial sector as it can be easily retrofitted to the
existing CO2 sources. Here, the removal of CO2 from the flue gases can
be done, using traditional amine scrubbing technology explored by
Bottoms in 1930 [8]. In this process CO2 is allowed to pass through an
amine column and is captured as carbamates due to the exothermic
reaction between amine and CO2 [9,10]. Amine based CO2 capture is
considered as most promising technology for post combustion CO2
capture [11]. However, the energy intensive amine regeneration makes
CO2 capture expensive [10]. Therefore, many efforts are undergoing to
improve the efficiency of both capture and stripping of CO2.
The use of carbonic anhydrase (CA) to promote CO2 absorption and
desorption has become an interesting field of research in the present
scenario. CA is a metalloenzyme that occur in many organisms and can
accelerate the CO2 hydration and dehydration rate [12–16]. In ideal
condition, a single enzyme could catalyze 106 molecules of CO2 per
second. According to Saeed et al. the catalytic efficiency of CA is almost
4000 times higher than that of conventional amines such as mono-
ethanolamine (MEA) with low energy consumption (7 times less than
MEA) [17–20]. Therefore, CA alone or blended with amines such as

⁎
Corresponding author at: Industrial Biotechnology Department, Research and Development Centre, Indian Oil Corporation Limited, Sector-13, Faridabad, Haryana, 121007, India.
E-mail address: upretim@indianoil.in (M. Kumar).

https://doi.org/10.1016/j.jcou.2018.02.003
Received 4 December 2017; Received in revised form 23 January 2018; Accepted 12 February 2018
2212-9820/ © 2018 Elsevier Ltd. All rights reserved.
P.C. Sahoo et al. Journal of CO₂ Utilization 24 (2018) 419–429

Fig. 1. Different technologies used for CO2 capture.

MEA shows a great potential towards CO2 adsorption and desorption ubiquitous enzyme and its active site contains a zinc coordination
[16–21]. Currently, a number of critical reviews have been published to sphere that increases reaction rates upto106 times faster than the un-
comprehend on enzyme based CO2 capture [22–41]. The important catalyzed reaction. Human carbonic anhydrase has a tetrahedrally co-
benefits of the employing enzymes include less solvent requirement and ordinated Zn2+ along with coordinated histidine residues such as:
low heat of regeneration. Few studies on enzymatic CO2 capture on His94, His96 and His119 and a water molecule to complete the co-
pilot scale showed reduce operating cost with improved plant effi- ordination sphere [74]. There are two other prominent regions of the
ciencies [42,43]. However, several critical issues such as cost of these active site, such as a hydrophilic portion in the region of His64 (im-
enzymes, mass production, stability with time and their resistance to portant in proton movement) and a hydrophobic (so-called ‘deepwater’)
pollutants such as SOx and NOx are still debated considering their large- site important in the transport of CO2 to the active site. The modern
scale implementation. Native enzymes further have several intrinsic research finding suggests a three step mechanism for this enzyme
limitations like lower catalytic lifetime, pH and thermal stability; which (Fig. 2): (1) deprotonation: the proton releases from the Zn-bound
are considered to be the prime obstacles for their commercial applica- water to form ZneOH−; (2) CO2 addition: the hydroxide bound to the
tion [44–46]. zinc act as a nucleophile and react with CO2 to form bicarbonate, and
To overcome the above issues several researchers proposed the subsequently (3) HCO3− substitution: the zinc-bound carbonate is ex-
synthesis of robust enzyme mimic that can imitate the function of pelled from the metal coordination by the action of another water
natural enzyme [47–70]. Enzyme mimics can have several desired ad- molecule (from the surrounding salvation layer) replacing it in the zinc-
vantages such as tunable molecular structures and catalytic efficiencies, bound complex, finishing the catalytic cycle [74,75].
high tolerance to harsh experimental conditions, lower cost, and purely Due to the unprecedented CO2 hydration abilities, CA acts as an
synthetic method of preparation [47]. To design an ideal enzyme efficient CO2 sequestering agent having fast kinetics and can work
mimic, it is important to have a well understanding about the molecular under ambient condition of temperature and pressure [76]. Several
structure of active site, mechanism of reactions, and the factors af-
fecting the enzyme catalysis [71].
Since several decades it is well understood that the active site of CA
contains a Zn (II) ion counter coordinated with three imidazole groups
and a hydroxy group in a tetrahedral geometry [72]. With careful
metal-ligand combination and scaffold optimization the activity and
selectivity of the CA could be mimicked in synthetic complexes [73].
Several literatures currently published illustrate that zinc and other
transition metal complexes can have catalytic activity similar to CA
[47–71]. CA mimics can have even better catalytic activity in com-
parison to natural enzyme and can be an advantageous option for fu-
turistic large-scale CO2 capture technologies due to their excellent
stability under flue gas condition, low cost and high selectivity.
The objective of this review is to address advances, mechanism and
challenges of CA-mimics obtained in the last five years with their
possible applications in industrial CO2 capture. Here, enzyme models
with zinc, non-zinc, de-novo enzymes, nanozymes, ab initio and clas-
sical molecular simulation methods for modeling enzyme mimics are
discussed in details.

2. Enzyme mediated CO2 capture

In enzymatic CO2 capture, the efficiency of existing solvent system Fig. 2. Schematic representation of active site of carbonic anhydrase and its CO2 hy-
dration mechanism.
can be improved by using the CO2 hydration ability of CA. CA is a

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P.C. Sahoo et al.
Table 1
Generalized comparison chart between enzyme and enzyme mimics.
Enzyme
Function Enzymes are biocatalysts that fasten the rate of specific
reactions converting substrate into product.
Molecular weight High molecular weight globular proteins.
Nature Enzymes are complex proteins having active sites
Alternate terms Organic catalyst or bio catalyst.
Specificity Enzymes are highly specific for substrate
Reaction rates Several times faster
Activation Energy Lowers AE of the overall reaction
Conditions Mild conditions, physiological pH and temperature
Stability Not stable/denatures easily
companies like CO2 Solution Technologies, Novozymes, Codexis, and
Carbozyme have done impressive work on CA production along with
CO2 capture [77–79]. Technology validation and demonstration for
enzymatic CO2 capture was carried out by CO2 solution, Canada in
2015. The demonstration unit was built in Salaberry-de-Valleyfield has
a capacity of 10 tonnes/day. The capture was carried out at 30–40 °C
using 1.45 M K2CO3 as base solvent. The plant stripper has an operating
pressure of 0.3 bar while the absorption was carried out at 1 bar [80].
CO2 capture in industrial processes operates at harsh condition
compared to that of biological conditions. Thus, researchers are trying
to design robust and cost effective enzyme mimics by imitating the
active site of CA. The enzyme mimics could withstand in the harsh CO2
capture condition and subjected to mass production.
3. Carbonic anhydrase inspired complexes: the carbonic
anhydrase mimics
Enzyme mimics are synthetic catalysts that can catalyze specific
chemical reactions with high selectivity and can be considered as viable
alternatives to natural enzymes. A typical difference between enzyme
and enzyme mimics are provided in Table 1. Recent progresses in the
fields of biological science, synthetic chemistry, computational chem-
istry and polymeric science have provided a unique and co-operative
solution for the synthesis of enzymes mimics [81,82]. For an ideal en-
zyme mimic design, suitable selection of central metal and scaffold
design is very important.
Central metal plays a key role for tuning the catalytic activity of
enzyme and enzyme mimics. In several zinc containing enzymes Zn (II)
is usually coordinated by amino acid residues. According to the hard-
soft acid-base (HSAB) principle Zn(II) is considered as a borderline
metal therefore can coordinate with both hard (N and O) and soft (S)
ligands effectively [83–86]. Zinc has a filled d orbital; therefore, the
redox reactions are prevented and it acts as a Lewis catalyst [83]. The
ligand field stabilization energy for Zn (II) is zero due to its d10 elec-
tronic configuration; therefore, it can coordinate with ligands with
flexible geometry with variable coordination number. Due to rapid li-
gand exchange, Zn (II) complexes enhance efficient product release
during catalytic mechanism.
Furthermore, the protein environments or scaffold have an im-
portant role in providing appropriate environment for lower co-
ordination number and assist structural, catalytic, and co-catalytic
function of the overall process [83–86]. Every enzyme is characterized
by its amino acid sequence appeared in the protein. Amino acid se-
quence plays key role in enzymatic catalysis as it regulates both sub-
strate binding and selectivity. According to Tablbhi, the overall enzyme
activity can be mimicked using a simple general strategy; [81]
Mimicking enzymatic function = Equivalent microenvironment + Iso-
functional substitution
Here, isofunctional substitutions are the molecules, which are
properly oriented towards the active center. Several parameters may
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Journal of CO₂ Utilization 24 (2018) 419–429
Enzyme-mimics
Enzyme-mimics are chemical/ synthetic substances that imitate the catalytic mechanism of
enzyme and alter the rate of reaction without undergoing a change.
Low molecular weight inorganic compounds.
Biomimics are simple inorganic molecules.
Inorganic catalyst/artificial enzyme/biomimics.
Not highly specific
Typically slower
Lowers AE of the overall reaction
May require high temp, pressure to initiate the reaction
Stable under ambient condition
influence the orientation of the active site molecules such as steric
hindrance, nucleophilicity/phobicity and oxidation/reduction potential
etc. Other parameters such as electron density, spin density, orbital
level, ligand field, solvent participation are responsible to improve
catalytic properties [81]. Hydrophobic or hydrophilic micro environ-
ment near the active center can affect the catalytic activity of enzyme
mimics. In case of carbonic anhydrase, hydrophobic pockets act as
microenvironment containing amino acids such as Val-121, Val-143,
Leu-198, Thr-199-CH3, Val-207, and Trp-209. These moieties help in
stabilizing the transition state, protein folding and substrate binding.
Zinc coordinated histidine (His-94, His-96, and His-119) and amide
nitrogen of Thr-199 plays crucial role in stabilizing Zinc bound hy-
droxide ion and represents the Isofunctional groups.
A suitable scaffold around the active center is essential to control
hydrophobic or hydrophilic micro environment near the catalytic
center, and to control the substrate binding. Fig. 3 represents a sche-
matic diagram for the synthesis of an ideal CA-mimic.
3.1. Selection of metal center
Metal centers in enzyme mimic act as an electron donors or ac-
ceptors, Lewis acids/base or structure regulators. The metal centers
directly involves in the catalytic process and display anomalous phy-
sicochemical characteristics that controls the activation energy. For CA
mimic design, Zn is usually considered as the suitable central metal.
However, other non zinc transitional metals, lanthanides and inorganic
nanoparticles can also be used.
3.1.1. Carbonic anhydrase mimics with zinc as metal center
During construction of a CA-mimetics it is quite necessary to have a
tetrahedral geometry around the central metal. The Zn coordinated
hydroxide plays a vital role as it initiates the catalytic cycle by nu-
cleophilic attack on CO2 [87]. However, a reversible Zn hydroxide
coordination is not easy to synthesize and for it a very careful selection
zinc salt is necessary. It is because the other anions that compete with
the hydroxide ion may bind with Zn, which result in catalytic poi-
soning. Several studies reported that the activity of natural CA can be
distorted by external Zn-binding anions. Kim et al. [87] has made a
systematic study to find out the effect of counter ions on the activity of
CA-mimics. They synthesized CA mimics by the self-assembly of histidyl
bolaamphiphile using different of zinc salts (ZnCl2, Zn(NO3)2, Zn
(CH3CO2)2, and Zn (OH)2). On comparing dissociation enthalpies of the
Zn salts and activation energies of the different CA-mimetic catalysts,
they suggested that the catalytic activity of a CA-mimic could be altered
by anions of zinc salt. Low catalytic activity may arise due to anions
having strong affinity for zinc ions (high dissociation energy) [87,64].
As per their finding, Zn(OH)2 showed optimal reactivity in CO2 hy-
dration. Therefore, a suitable Zn source that can minimize the anion
disturbance will be beneficial for the preparation of efficient CA-mi-
metic.
Along with metal, ligand selection also plays a key role during CA-
P.C. Sahoo et al.
Fig. 3. Schematic diagram for the synthesis of an ideal carbonic anhydrase mimic.
Fig. 4. Tripodal and macrocyclic ligands used for CA-mimic synthesis. The N atoms (in red) are directly coordinated to central Zn atom.
mimic design. For instance, Liu et al. [88] successfully designed a tri-
nuclear zinc complex having μ3-oxoanions for CO2 conversion (Fig. 4a).
From X-ray crystallographic study it has been found that the Zn(II) ion
is tri-coordinated in distorted trigonal-bipyramidal geometry. The
group suggested that the activity of the μ3-carbonate unit can be
sterically controlled, which makes the carbon dioxide fixation cycle
feasible. They successfully used these CA-mimics to catalyze the con-
version of CO2 to carbonates under mild conditions.
A similar C3-symmetrical tripodal amine ligand, N1,N3,N5-tris (2-
aminoethyl) benzene-1,3,5-tricarboxamide (L) was designed by Bera
et al. (Fig.4b) [89]. Two different complexes such as [ZnL (H2O)] 2+
and [ZnL (OH)] + were synthesized using the tripodal ligand. Here, no
dimmer formation observed and the pKa of the zinc-bound water mo-
lecule was found to be 7.84. The coordination behavior of the ligand
and suitable pKa make the complex a viable CA-mimic. Di-merization of
complexes is sometimes problematic as it can permanently block the
active site by bridging them resulting in activity loss. However, in this
case the steric repulsion of the ligand was probably the main attractive
feature that prevented the dimerization. In a similar attempt, Zn
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Journal of CO₂ Utilization 24 (2018) 419–429
complexes of tris (3-t-butyl-5-methylpyrazolyl) hydroborato and tris(2-
pyridylthio) methyl were synthesized by Sattler et al. (Fig. 4c) [90].
These complexes provide important information regarding the me-
chanism of enzymatic CO2 hydration. Ibrahim et al. [91] studied the
zinc complexes of tripod ligand tris(2-benzimidazolylmethyl) amine
(L1) and its methylated derivative tris(N-methyl-2-benzimidazo-
lylmethyl)amine (L2) (Fig. 4d). On reaction with AgPF6 followed by
KOH treatment, they from the hydroxide complexes [L1Zn–OH)](PF6)
and [L2Zn–OH)](PF6). Interestingly, these complexes could able to
produce bicarbonate ion on reaction with CO2. These results demon-
strate that tripodal ligand due to their unique geometry can help in
construction of efficient CA-mimic.
Not only tripodal ligands, macrocyclic ligands are also proved to
have an efficient CA-mimicking activity. Koziol et al. [92] has synthe-
sized different zinc-chelated aza-macrocycle ligands as CA mimics and
studied their catalytic behavior towards CO2 using quantum-mechan-
ical methods and stopped-flow experiments (Fig. 4e–i). They found that
bicarbonate release is the rate limiting step in CO2 hydration by aza-
macrocyclic zinc complexes. From the study it was established that
P.C. Sahoo et al.
Lewis acidity of the CA-mimic and charge-donating character of the
ligand plays key role in controlling pKa of the coordinated water, which
tunes the transition state and catalytic efficiency. Thus a deep under-
standing of the transition state will be useful in designing ester hy-
drolysis catalysts.
Satcher et al. [93] performed a study to compare the activities of
two different cyclic amine (cyclen and cyclam) complexes. Both the
mimics showed enhanced catalysis at elevated pH depending on the
availability of the Zn-OH- nucleophile. Yet, cyclen-Zn2+ displayed ∼8
times faster catalytic activity than cyclam-Zn2+ at pH 7.5. The pKa of
Zn bound water was found to be responsible for such catalytic behavior.
Therefore, for an industrial application, cyclen-Zn2+ can catalyze CO2
hydration at the mild pH conditions [93].
NMR is found to be an important tool to characterize biomimetic
complex with high precision. Using liquid-state NMR spectroscopy
Lesnichin et al. [94] have calculated the proton-donating ability of Zn-
bound water molecule in active site of a organometallic CA-mimic;
which is quite important to understand reaction mechanism. Using 1H
and 15N NMR for solutions of a CA-mimic named [TpPh, MeZnOH]
(TpPh, Me = tris (2-methyl-4- henylpyrazolyl) hydroborate) they found
that there exist an interaction between nitrogen base of the ligand and
zinc bound aqua molecule. Furthermore, Sattler et al. [95] by using low
temperature 1H and 13C NMR spectroscopic studies of the tris(3-t-butyl-
5-methylpyrazolyl) hydroborato zinc hydroxide complex [TpBut;Me]
ZnOH in the presence of CO2 confirmed the identification of the bi-
carbonate moiety.
Immobilization technique is considered to be a specialized tech-
nique to maximize the stability, and reusability of catalyst/biocatalyst
and is helpful for the overall economics of the process [96]. Considering
this point, an immobilized carbonic anhydrase mimic was synthesized
by immobilizing Fc-histidine conjugate on gold surfaces followed by
chelating Zn2+ ions (Zn-AM) (Fig. 5a). Cheng et al. [97] used both
electrochemical and spectroscopic methods to evaluate the activity of
this CA-mimic towards CO2. They used XPS to evaluate the binding
energy of ligand and confirmed the Zinc (II) coordination from the
Fig. 5. Immobilized CA-mimic on different support. The N atoms (in red) are directly
coordinated to central Zn atom.
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Journal of CO₂ Utilization 24 (2018) 419–429
alteration of binding energy. The exact role of gold surface is not clearly
explained; however it may assist in modulating electronic property of
the active center. Moreover, the Zn-AM showed enhanced catalytic
activity on CO2 hydration and p-NPA hydrolysis. The authors estimated
the kinetic parameters: Km and kcat, to be 27.2 mM and 506.5 s−1, re-
spectively.
In a new approach Sahoo et al. [98] studied the catalytic activity of
a Zn (II)-model complex (Zn-His) immobilized on a magnetic Chitosan/
SiO2/Fe2O3 composite (Fig. 5b). They established that the core mag-
netic material (Fe2O3) helps for an easy recovery of the catalyst by
using magnetic fields. The catalytic performance of the CA-mimic was
evaluated using ester hydrolysis and CO2 hydration. Interestingly after
immobilization, the thermal and storage stability was enhanced for Zn-
His complex. Moreover, the immobilized CA can retain activity and can
be used for 10 cycles. Yao et al. synthesized poly (N-vinylimidazo-
le)–zinc complex (PVI–Zn (II)) that mimics the activity of carbonic
anhydrase [99]. Further the PVI–Zn (II) was used to prepare mem-
branes for selective separation of CO2/N2. They confirmed that the
biomimetic membrane shows excellent separation CO2 from its mixture.
3.1.2. Carbonic anhydrase mimics with non zinc metal centers
Not only Zn, other metal ions are also efficient enough to mimic
models carbonic anhydrase activity. There are several advantages as-
sociated with this (1) due to the poor spectral quality of Zn (II), its
complexes and intermediates are difficult to characterize, so spectro-
scopic ally active complexes of Co (II) and Cd (II) can helpful in ob-
taining in detail structural information (2) The role of metal ions and its
coordination environment can be obtained on various metal-substitu-
tion [100].
Keum et al. [101] substituted Zn cofactor with various transition
metal ions such as Co2+, Cd2+, and Ni2+ in a CA–mimetic obtained by
coordination of histidyl bolaamphiphiles. From ester hydrolysis and
activation energy calculation, the catalytic order of CA-mimics with
different metal ion substitution is found to follow order: Zn > Co >
Cd≈Ni. Interestingly, due to inhibition factor imposed by the counter
anion, the CA mimics with cobalt showed enhanced catalytic activity
than Zn.
Some nickel complexes showed extremely high affinity towards
carbon dioxide capture. Huanga et al. [102] reported a planar nickel
complex [NiII(NNN)OH]1− containing a tridentate 2, 6-pyridine di-
carboxamidate pincer ligand, where the metal-bound hydroxide effi-
ciently react with CO2 to produce bicarbonate or carbonate (Fig. 6a).
The report suggested that the catalytic activity of the complex is in the
range of carbonic anhydrase. From DFT calculation, it was established
that the complex [NiII(NNN)OH]1− catalyze in a similar mechanism as
that of CA where CO2 is inserted into Ni-OH bond. The same group
showed the influence of steric effect on the catalytic activity of nickel
complexes [103]. According to their study a planar complexes
[NiII(pyN2R2)(OH)]− having terminal hydroxo group helps in CO2
conversion to bicarbonate via a second order kinetics. Interestingly, the
rate of the reaction changes with change in alkyl group (R). The order is
as follows: Me > macro > Et > Pri > Bui > Ph (macro = macro-
cylic pincer ligand) indicate that the increasing steric hindrance at the
reactive site prefers catalytic activity.
It is very rare to find a faster CA-mimic with copper as active center.
Comba et al. developed dicopper (II) complexes of six pseudo-octa-
peptides (Fig. 6b) [104]. The complexes show excellent reactivity to-
wards CO2 with a Kcat up to 7.3 × 103 s−1 with a turnover number
(TON) of 1700. They found that the rate of CO2 activation is strongly
dependent on the ligand structure. Ligand with R*, S*, R*, S* geometry
shows enhanced catalysis compared to S*, S*, S*, S* isomers. Further-
more, the results provide experimental evidence that the nucleophilic
attack of Cu2+-OH on CO2 is the rate determining step.
Not only have transition elements, rare earth metals also had sig-
nificant activity towards CO2. Bag et al. [105] prepared several
mononuclear lanthanide (III) complexes [Ln(LH2)(H2O)3Cl] (ClO4)2
P.C. Sahoo et al.
Fig. 6. Schematic representation of non zinc CA-mimics.
(Ln = La, Nd, Sm, Eu, Gd, Tb, Lu) of the tetraiminodiphenolate mac-
rocyclic ligand (Fig. 6c). In a methanol-water mixture, the rare earth
complexes can fix CO2 through a carbonato-bridged trinuclear complex.
Like CA, here Ln-OH has been considered as the key intermediate in the
catalytic cycle. From the kinetic analysis it was found that with heavy
lanthanides the CO2 capture occurs in a faster rate. CO2 hydration to
HCO3– by borate has been proposed by Guo et al. [106]. They found
that tetrahydroxyborate ion, B(OH)4− is the active species that was
responsible for CO2 hydration.
3.1.3. Inorganic nanoparticles as carbonic anhydrase mimics
Due to tremendous development in nanotechnology enzyme mimics
based on nanomaterials are gaining huge attention. Several nanoma-
terials including fullerene, Au-nanoparticles, nanoparticles of rare
earth, iron nanoparticles and quantum dots reported to show enzyme
like catalytic activity [107]. How these nano materials behave like
enzyme is still illusive as there is a strict difference between enzyme
and nano-materials. Enzymes are proteins and act like soft materials
while nanoparticles are crystalline in nature. However, several prop-
erties such as particle size, shape, surface charge, polarity enable na-
noparticles/quantum dots to mimic enzyme like activity [107].
In a report by Bhaduri et al. [108] nickel nanoparticles (NiNPs)
showed a reversible CO2 hydration at ambient condition. pH of the
medium is found to affect catalytic activity of the NiNPs. Being mag-
netically active and insoluble, it can be easily separated and used in
next run. The reaction mechanism was established by X-ray photo-
emission spectroscopy (XPS) and found to be similar that of CA. In
another work, Park’s group found out that nanoparticle organic hybrid
material (NOHMs) has excellent properties to capture CO2 [109].
NOHMs consist of polymeric canopy anchored to the surface-modified
nanoparticles through ionic or covalent bonds. They established that
both enthalpy and entropy influence the CO2 capture in NOHMs [110].
3.2. Supramolecular scaffolds in carbonic anhydrase mimic design
Enzymes are delicate supramolecular structures consists of peptides
folded to form self assembly and can confront catalysis under biological
condition with unprecedented efficiency. Such catalytic activities arise
due to versatile functional groups and their proper orientation near the
active sites of the enzymes. However, it is immense challenging to
mimic catalytic mechanism of enzyme due to unsuitable design of
scaffolds [111]. These supramolecular scaffolds help in substrate re-
cognition and catalysis. Several molecules such as macrocycles, metal
organic frameworks, calixarenes, cyclodextrins, cyclophanes, crown
ethers, cavitands, capsules, molecular cages, micelles, vesicles, nano-
particles, nanotubes and nanogels with hierarchical functionality have
attracted considerable attention in the scientific community [111,112].
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Journal of CO₂ Utilization 24 (2018) 419–429
Kim et al. [113] used a molecular self-assembly approach to re-
plicate the active site of CA. According to their observation the self-
assembly of a bolaamphiphilic molecule having histidine motifs is
helpful for synthesis of CA mimics. The Zn coordinated self-assemblies
hydrated CO2 in an efficient manner similar to CA. The kinetic para-
meter suggested that the CA-mimic activity was enhanced with increase
in Zn concentration. However an excess Zn concentration can distort
the self assembly resulting in decreased activity. The activity of the self
assembly can be optimized depending on the pH value and tempera-
ture. Interestingly, the self assembly can sequestrate CO2 as CaCO3 in
presence of Ca2+ ion.
Similarly, to mimic an enzyme like environment a cobalt complex of
BBP was synthesized and encapsulated in the cage of a metal organic
framework [114]. To evaluate the importance of MOF, the authors
studied the esterase activity both before and after the Co-BBP en-
capsulation. An activity enhancement of nearly 14.39% was obtained
due to encapsulation in Tb-MOF. They concluded that the MOF helps to
prevent the dimerization of the CA-mimics, and assist in the enhance-
ment of activity. In a parallel approach the same group synthesized
biomimetic complexes of Co and Zn inside the nano cages of meso-
porous silica (MS) [115]. The synthesized biomimetic complexes
Co–Im@MS and Zn–Im@MS imitate the active site of carbonic anhy-
drase and perform CO2 hydration. The catalytic activities of both the
caged complex were improved by imposing a hydrophobic environ-
ment. This result indicated that the hydrophobic environment tailors
the nucleophilicity of the active site by removing excess water mole-
cules.
Based on the above examples is confirmed that the role of scaffold is
quite important during CA-mimic design. Scaffold like self-assembled
supramolecule, metal organic frameworks or hydrobic nanocages can
act as positive modulator for CO2 hydration in CA-mimics. Table 2
summarizes CO2 capture by CA-mimics under appropriate condition.
4. Photo sensitive biomimetic complexes for CO2 conversion
Solar assisted CO2 conversion to valuable product is one of the
challenges in the field of catalysis. To develop an efficient catalyst for
CO2 reduction, we must consider several critical properties such as
visible-light harvesting ability, selectivity and cost of catalyst. The
crucial entities of any photo-catalyst consist of a semiconductor (as
light harvester) and cocatalysts (to promote redox reaction) [116–118].
It has been known that some efficient and low cost photo sensitive
biomimetic complexes can acts as cocatalysts. These cocatalysts will
assist in the charge separation and catalyze the CO2 reduction reaction.
Several researchers focused on the development of efficient and low
cost photo sensitive biomimetic complexes that are efficient for CO2
reduction. For instance, Sekizawa et al. synthesized a Ru(II) dinuclear
 Table 2
Various CA-mimics and their mediated CO2 capture process.
CA-mimic complexes
Zn-Histidyl bolaamphiphile
[Zn3L(ClO4)6]
L = tris(xylyl) amine scaffold
[TpBut,Me]ZnOCO2H, Tp = tris(3-t-butyl-5-
methylpyrazolyl) hydroborato
[L1Zn–Cl](PF6), L1 = tris(2-benzimidazolylmethyl)
amine
Zinc-chelated aza-macrocycle ligands
Zinc Fc-histidine conjugate on gold
Zn-His on Chitosan/SiO2/-Fe2O3
poly(N-vinylimidazole)–zinc complex
II 1−
[Ni (NNN)OH] , containing tridentate 2,6-
pyridinedicarboxamidate pincer ligand
425
Dicopper(II) complexes of six pseudo-octapeptides
[Ln(LH2)(H2O)3Cl](ClO4)2 with
tetraiminodiphenolate macrocyclic ligand
B(OH)4−
Nickel nanoparticles
Zn-histidyl
Co-BBP, BBP = 2, 6-bis(2-benzimidazolyl)
Co–Im@MS and Zn–Im@MS
[Hg(II)]S[Zn(II)(H2O/OH2)]N(CSL9PenL23H)3
Zinc(II) cyclen in K2CO3
Zinc(II) cyclen encapsulated in silicone
microcapsules
Zinc PDC complex, PDC = 2,6-pyridinedicarbonyl
dichloride in
Zinc-bis(hydroxyphenyl)phenanthroline in
monoethanolamine
Activity analysis CO2 Capture technique
−3
- Hydrolysis of p-NPA (kcat = 8.69*10 ) - Precipitation as CaCO3
- pH variation in CO2-saturated water
- CO2 to carbonate by 13C NMR spectroscopy - Precipitation as CaCO3
- X-ray diffraction to characterize bicarbonate in complexes - CO2 capture in the presence of water as
bridging carbonate
- 1H NMR titration of the ligands with Zn(II) ions and FTIR - Reacted with CO2 in triethylamine to give
bicarbonate complex
- CO2 hydration reaction studied using stopped-flow - CO2 conversion to HCO3– in presence of
spectrophotometry water
- p-NPA assay with kcat obtained as 506.5 s−1 - CO2 conversion to HCO3−/CO32- in 1 M
NaClO4 solution monitored by Cyclic
voltammeter (CV)
- p-NPA assay with overall activity (Kcat/Km) 52.32 M−1 s−1 - CO2 was captured from a CO2 + N2 mixed
gas stream using a sensitive pH meter
- Measuring partial pressure difference between the upstream - CO2 separation from with CO2/N2 using
and downstream side of the membrane. membrane technology
- Activity were studied in dimethylformamide solutions by - Fixation of CO2 as the bicarbonate complex
stopped-flow spectrophotometry at 218–243
K.cat∕KM = 9.5 × 105 M−1 s−1)
- Stopped-flow kinetics, using the color change of a pH - CO2 conversion to HCO3–
indicator (kcat ∼ 7.3 × 103 s−1)
- IR and 1H NMR spectra used in the study of reaction rate - In methanol-water solution fix CO2 in few
hours to produce the carbonato bridged
trinuclear complexes
- Stopped-flow pH indicator technique was adopted to study - CO2 is sequestrated as in aqueous
HCO3−
CO2 hydration medium
- -CO2 hydration was measured via pH and conductivity - CO2 is sequestrated as HCO3− in aqueous
medium
- p-NPA assay with kcat obtained as 0.075 s−1 - CO2 was sequestered in CaCO3
- Hydrolysis of p-NPA - CO2 was sequestered in CaCO3 via in-vitro
crystallization
- Hydrolysis of p-NPA - CO2 was sequestered in CaCO3 via in-vitro
crystallization
- Hydrolysis of p-NPA (Activity only ∼100-fold less than that - CO2 sequestrated as HCO3− in aqueous
of human CA) medium (pH 9.5 and 25 °C)
- CO2 hydration reaction were determined using stopped-flow - CO2 sequestrated as HCO3− in aqueous
spectrophotometry medium and as measured by pressure drop
- The CO2 released activity was analyzed using pyrolysis-gas - CO2 capture was measured using pressure
chromatography/mass spectrometry (GC/MS) drop apparatus
- Using 13C NMR spectra - CO2 capture was measured using pressure
drop apparatus
- pH drop in presence and absence of complex - The CO2 concentration was analyzed using a
CO2 analyzer
P.C. Sahoo et al.
Remark Ref.
- Use of Zn(OH)2 salt showed the highest catalytic [87]
activity at 25 °C and pH 7
- CO2 to carbonates under mild conditions with ∼100 [88]
turnovers
- High reactivity and forms carbonate complex upon [90]
exposure to air
- Microwave assisted easy synthesis of ligand. [91]
- Coordination of ligand to zinc induces Lewis acidity
resulting higher activity
- Bonding between CO2 and Zn plays an important [92]
role in stabilization of the transition state and hence
enhance activity
- pH of the medium influence the activity [97]
- Can be recycled
- Easy synthesis method [98]
- Can be reused up to 10 conjugative cycles
- Permeance of CO2 can be higher than 1000 GPU [99]
- The CO2/N2 selectivity can be as high as 83
- The local geometry changes associated with [102]
substrate insertion influence the repaid CO2
capVture activity
- Configuration of the isopropyl side chains can alter [104]
the CO2 hydration rate.
- CO2 fixation occurs faster with the heavier [105]
lanthanides (III).
- The pK value of the Ln–H2O bond determines the
activity
- The concentration of Boron and pH of the medium [106]
are the determining factor for enhanced activity
- Being insoluble and magnetic, they can be [108]
magnetically separated for reuse.
- The self-assembly of a [113]
- Encapsulation of complex in MOF enhances the [114]
activity
- Hydrophobic environment imposed by hexadecanol [115]
enhances the activity
- Zn(II) ion induces catalytic activity and a Hg(II) ion, [126]
provides structural stability.
- Zinc cyclen is a robust catalyst for industrial [45]
application due to high thermal and pH stability.
- The micro capsules are highly permeable, [138]
mechanically robust, chemically stable and
environmentally benign.
- The complex found to be thermally stable and have [139]
maximum regeneration efficiency with MDEA
- The complex is robust in concentrated primary [134]
amine solutions
Journal of CO₂ Utilization 24 (2018) 419–429
P.C. Sahoo et al. Journal of CO₂ Utilization 24 (2018) 419–429

complex for CO2 reduction [119]. Using the hybrid Ag-loaded TaON as
semiconducting material and Ru(II) dinuclear complex as cocatalyst,
they found formic acid as the primary product in photocatalytic CO2
reduction. In another observation, semiconductor (C3N4) coupled Ru
(II) binuclear complex selectively catalyses the formation of HCOOH
(87–99%) [120]. In comparison to Ru complex iridium complexes are
found to be advantageous due to their high activity and selectivity. For
instance, Sato et al establish that a mononuclear Iridium complex can
selectively reduced CO2 to CO under visible irradiation [121]. Earth
abundant Ni complexes are found to be highly selective for CO2 to CO
formation. Thoi et al. developed an efficient Ni photo redox complex
that catalyses the conversion of CO2 to CO with a turnover numbers of
98,000 [122].

5. Computational approach for carbonic anhydrase mimic design

Computational approach for design of enzyme has become an im-

portant tool for construction of new active sites that catalyze specific
reactions [123]. Several new approaches such as De-novo protein de-
sign, ab initio and molecular simulation have been used for successful
design of CA-mimic.

5.1. De-novo design of potential carbonic anhydrase mimics

De novo design of bio-mimetic complex is a new trend in chemistry.

The objective of this method is to understand the three dimensional
(3D) structure of a desired enzyme to design ligands with similar
functionality [124,125]. Proteins with three dimensional structures
have been used to study ligand design by several researchers resulting
feasible and new structure of molecules. Basically, during de novo de-
sign, the protein structure was analyzed by computational approach,
and based on the knowledge models were generated via force field
geometry optimizations.
Zastrow et al. [126] studied the importance of metal ions in the de
novo design of CA mimic. The group synthesized a metallo hydrolase
having Zn(II) ion as catalytic site and Hg(II) ion for controlling struc-
ture. The structure was confirmed by X-ray crystallography and the CA-
mimic displayed catalytic activity similar to that of natural CA enzyme.
The synthesized CA-mimic showed an esterase activity that was 550
times faster than any synthetic complexes [126]. In a parallel approach,
Cangelosi et al. [127] prepared a novel Zn(II) metalloenzyme using de
novo design. The group successfully constructed α3DH3 folds that
strongly bind with Zn (II) via the His3O coordination. Surprisingly, this
de novo CA-mimic shows a CO2 hydration efficiency of 1400-fold
higher than any small molecule model.
In summary, de novo ligand design shows a great potential and
opportunity towards enzyme mimic design. With substantial progress in
computational tool we can design much more efficient biocatalysts for
medical and environmental application. A workflow diagram for de
novo design of enzyme has been presented in Fig. 7.
5.2. ab initio and molecular simulation approach for modeling carbonic
anhydrase mimics
Molecular modeling has become one of the essential tools for many
areas of chemistry including biocatalysis. The structure of new complex
molecules can be ab-initio determined and compare with experimental
data. Experimentally undetermined and important intermediates such
as metastable intermediate/transition states or possible mechanism can
be accurately determined by the use of computational chemistry.
Several methods have been used during computational simulation:
molecular mechanics (MM) and quantum mechanics (QM). One of the
QM approach called density functional theory (DFT) has wider appli-
cations. DFT allows the use of Hartree-Fock calculations that is highly
applicable for organometalics and allow the insertion of fine electronic
effects for a relatively low additional cost over the typical [128].
Fig. 7. de novo design of enzymes mimic.
Piazzetta et al. studied a rhodium-substituted human carbonic an-
hydrase for CO2 conversion [129]. From computational analysis they
concluded that the catalysis at the active center was controlled by σ-
bond metathesis mechanism. The water molecules play a key role and
affect the shape and stiffness of the enzyme pocket. Consequently, there
was a lowering in the activation energy from 21.0 kcal mol−1 to
11.7 kcal mol−1 for CO2 catalysis.
Deshpande performed the DFT calculation of a copper cluster (Cu7)
that imitates the mechanism of α-carbonic anhydrase [130]. The cluster
efficiently catalyses the CO2 conversion to bicarbonate and possesses
equivalent energy in solvated as well as vacuum condition. In another
study, Verma et al. evaluated the CO2 hydration activity of different
borate species using DFT calculation [131]. They found that the hy-
droxy center of borate species was the key factor for its catalysis and an
endergonic and bent CO2 complex was formed during the transition
state. Lee et al. [132] studied the catalytic hydrolysis reaction in metal
porphyrin carbon nanotube using DFT calculations. They found that the
catalytic process can be tailored by controlling the oxidation of por-
phyrin as well as by changing the central metal of the porphyrin. The
study provided two important conclusions desirable for CA-mimics: (1)
in the initial hydration reaction step, oxidation state and the metal
substitution, both have strong influence on reactivity; (2) the product-
release step was influenced either by oxidation state or metal sub-
stitution, but not by both the factors simultaneously.
Similarly, based on molecular dynamics simulations and quantum
mechanical calculations Koziol et al. explored a supramolecular tris
(imidazolyl)calix [6] arene Zn2+ aqua complex, as CA-mimic. Based on
MD and DFT calculations, the researchers provided clarification re-
garding the free-energy of the encapsulated water molecule and found
that the interaction between CO2 and water inside the cavity of CA-
mimic determines the stability of transition state [133]. Kelsey et al.
was able to identify some important reaction parameters to predict the
mechanism by using DFT [134]. In summary, by understanding the
chemical processes computationally in model compounds, we can de-
sign or improve our CA-mimics in a controlled manner.

426
P.C. Sahoo et al.
Fig. 8. A schematic representation of a commercial amine based CO2 capture unit.
6. Opportunities and challenges of enzyme inspired complexes in
industrial CO2 capture
Post combustion CO2 capture from industrial flue gases has a wide
potential for reduction of green house gas emissions as it can be easily
retrofitted in existing plants [135]. Generally, in this technology, low
concentrated CO2 is captured at ∼1 bar containing impurities such as
SOx and NOx [136]. To date amine scrubber has been used to capture
CO2 followed by stripping at high temperature to regenerate the ab-
sorbent [135,136]. The efficient absorption of CO2 in a liquid stream
usually involves the reversible reaction between acidic gas and the
absorbent. Chemically absorbed CO2 is then stripped from liquid stream
to reverse the reaction and regenerate the absorbent (Fig. 8). Amine
absorption has been used by the natural gas industry for removing CO2.
Most common amines used as absorbent includes monoethanol amine
(MEA), diethanolamine (DEA), and methyl diethanolamine (MDEA).
However, the regeneration of amine after CO2 capture is energy in-
tensive and expensive. In order to address these issues, research com-
munity is trying to find novel adsorbents or additive with high ab-
sorption capacity and low heat of regeneration.
Increase in the rate of CO2 hydration in amine solvents help to in-
crease the mass transfer coefficients of a CO2 capture system, hence can
lower the costs for carbon-capture process [134]. Using carbonic an-
hydrase, a swift hydration of CO2 can be obtained at ambient condition.
Therefore, a CA blended amine can be used for enhanced CO2 capture.
However, due to some intrinsic limitation such as thermal and pH in-
stability, the application of CA was unsuitable in aqueous amine-based
solvents in power plants. Therefore, robust CA-mimic catalysts are
gaining importance in enhancing industrial carbon capture processes
[17,18,137].
Floyd et al. [45] studied Zinc (II) cyclen as CA-mimic in an in-
dustrial carbon capture process using rigorous conditions. They found
that the use of zinc cyclen accelerate the CO2 capture in high tem-
perature and pH. The activity however decreases at low pH and high
bicarbonate concentrations due the interference of bicarbonate with the
active site of the complex. Here, the CO2 absorption in K2CO3 solvent
was promoted by Zn-cyclen complex in a membrane reactor [45].
427
Journal of CO₂ Utilization 24 (2018) 419–429
Interestingly the CO2 absorption kinetics in the K2CO3 solvent was
enhanced by ∼10 fold by CA-mimic compared to the experiment
without mimic enzyme. Moreover, the CA-mimic shows a higher sta-
bility, lifetime in the solvent system indicating its potential for in-
dustrial CO2 capture. In order to have low-cost and energy-efficient CO2
capture, Vericella et al. [138] synthesized microfluidic assembly
polymer microcapsules composed of liquid carbonate cores and highly
permeable silicone shells. It was found that microcapsules containing
carbonate sorbents exhibit higher CO2 absorption rate compared to
equivalent neat sorbents. Moreover, insertion of zinc cyclen as CA-
mimic to the microcapsules along with carbonate significantly increases
the CO2 absorption rates and the mimic remain stable at higher tem-
perature.
Choi et al. [139] studied a new CA-mimicking catalyst based process
to overcome the huge energy requirement of conventional amines based
process. The group synthesized a PDC-based ligand with Zn ion. They
studied the effect of addition of CA-mimic with primary (MEA), sec-
ondary (DEA) and tertiary (MDEA) alkanolamine absorbents on the
regeneration of carbon dioxide. The results suggested that the re-
generation time decreases as well as absorption rate increases on ad-
dition of CA-mimics to MEDA. Further, the CA-mimics show good
thermal stability and do not corrode the quality of amine solvent after
prolonged reaction. The same group also improved CO2 sequestration
by using model complexes via continuous stirred-tank reactor (CSTR)
system. Using stopped-flow spectrophotometer, they studied the effect
of substituent on CA-mimic and found that hydrophilic group showed
the highest absorption or hydration of CO2 in MEDA solution [140].
The study suggested that CA-mimic in amine can efficiently absorbs and
desorbs CO2 and hence can be used in post-combustion processing.
Kelsey et al. [134] studied two new CA-mimics using zinc complex of
salen like ligand bis(hydroxyphenyl) phenanthroline. The catalytic ac-
tivity under post-combustion carbon capture was estimated using
acetonitrile solution of the CA-mimics in 24% monoethanolamine
(MEA). Nearly, 15% enhanced CO2 absorption rate was seen compared
to the amine solvent without catalyst. Moreover, > 95% of the catalyst
remained intact after exposure to CO2, which indicated the robustness
of the complex.
P.C. Sahoo et al.
From the examples, it can be realized that CA-mimics have a great
potential towards industrial carbon capture [141]. Addition of small
[18]
amount of those complexes can tailor the CO2 adsorption and deso-
rption parameter to great extents. Cyclane and Salene type ligands of
Zinc ion are the mostly used CA-mimics for industrial carbon capture
[19]
due to their robustness at high pH and thermal stability. Moreover, the
introduction of hydrophobic and hydrophilic functional groups on the
ligand can enhance the CO2 absorption and desorption in tertiary amine
solution. [20]
7. Summary and outlook
[21]
In this review we have highlighted some of the recent accomplish- [22]
ments in the field of enzyme inspired complexes for CO2 capture. CA- [23]
mimics with Zinc & non zinc cofactor, nanozymes, de-novo enzyme
mimics based in the catalytic mechanism of carbonic anhydrase have a
great potential in industrial gas capture [142]. Moreover, a tuning of [24]
electronic, steric, isomeric and hydrophobic/hydrophilic properties of [25]
metal and ligand is quite necessary for efficient design of CA-mimics. In [26]
parallel with experimental studies, computational chemistry based on
ab initio and molecular simulation approach is essential to understand [27]
the complexity of enzyme models and their mechanism of action to [28]
design smart enzyme models with superior activity. [29]
It’s the time to take amine-based solvents to the next stage of de-
[30]
velopment in terms of CO2 capture. The critical challenges associated [31]
with amines need to be addressed by the use of novel additives such as
CA-mimics to lower regeneration energy and improve other para- [32]
[33]
meters. Till now the potential of few complexes such as Zn-Cyclen and
some Salene complexes are studied in rigorous industrial condition. In [34]
spite of their highest CO2 hydration, the use of de-novo enzymes is still
unexplored. Moreover, how impurities like NOx and SOx in the flue gas [35]
affect the CO2 capture process is yet to be explored. [36]
Using Metal-organic frameworks (MOFs) as synthetic systems to [37]
design CA-mimic is still new area to be explored. MOFs are interesting
[38]
due to their unique characteristics such as permanent porosity, high
surface area, and uniform open cavities [143]. Moreover, multi fictio- [39]
nalization can be attended on the same cluster. Therefore, on integra-
[40]
tion of a high density of catalytic centers and ultra-large open channels,
MOFs can be catalytically more proficient than that of metal complexes. [41]
In conclusion, we believe that successful development of robust CA-
[42]
mimic can improve CO2 capture and lower the stripping energy re-
[43]
quirement in harsh industrial condition. However, the overall eco-
nomical analysis and suitable reactor engineering is necessary for its [44]
[45]
successful commercial application.
[46]
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