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

Enzyme Enzyme-mimics

Function Enzymes are biocatalysts that fasten the rate of specific Enzyme-mimics are chemical/ synthetic substances that imitate the catalytic mechanism of
reactions converting substrate into product. enzyme and alter the rate of reaction without undergoing a change.
Molecular weight High molecular weight globular proteins. Low molecular weight inorganic compounds.
Nature Enzymes are complex proteins having active sites Biomimics are simple inorganic molecules.
Alternate terms Organic catalyst or bio catalyst. Inorganic catalyst/artificial enzyme/biomimics.
Specificity Enzymes are highly specific for substrate Not highly specific
Reaction rates Several times faster Typically slower
Activation Energy Lowers AE of the overall reaction Lowers AE of the overall reaction
Conditions Mild conditions, physiological pH and temperature May require high temp, pressure to initiate the reaction
Stability Not stable/denatures easily Stable under ambient condition

companies like CO2 Solution Technologies, Novozymes, Codexis, and influence the orientation of the active site molecules such as steric
Carbozyme have done impressive work on CA production along with hindrance, nucleophilicity/phobicity and oxidation/reduction potential
CO2 capture [77–79]. Technology validation and demonstration for etc. Other parameters such as electron density, spin density, orbital
enzymatic CO2 capture was carried out by CO2 solution, Canada in level, ligand field, solvent participation are responsible to improve
2015. The demonstration unit was built in Salaberry-de-Valleyfield has catalytic properties [81]. Hydrophobic or hydrophilic micro environ-
a capacity of 10 tonnes/day. The capture was carried out at 30–40 °C ment near the active center can affect the catalytic activity of enzyme
using 1.45 M K2CO3 as base solvent. The plant stripper has an operating mimics. In case of carbonic anhydrase, hydrophobic pockets act as
pressure of 0.3 bar while the absorption was carried out at 1 bar [80]. microenvironment containing amino acids such as Val-121, Val-143,
CO2 capture in industrial processes operates at harsh condition Leu-198, Thr-199-CH3, Val-207, and Trp-209. These moieties help in
compared to that of biological conditions. Thus, researchers are trying stabilizing the transition state, protein folding and substrate binding.
to design robust and cost effective enzyme mimics by imitating the Zinc coordinated histidine (His-94, His-96, and His-119) and amide
active site of CA. The enzyme mimics could withstand in the harsh CO2 nitrogen of Thr-199 plays crucial role in stabilizing Zinc bound hy-
capture condition and subjected to mass production. 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
3. Carbonic anhydrase inspired complexes: the carbonic center, and to control the substrate binding. Fig. 3 represents a sche-
anhydrase mimics matic diagram for the synthesis of an ideal CA-mimic.

Enzyme mimics are synthetic catalysts that can catalyze specific


chemical reactions with high selectivity and can be considered as viable 3.1. Selection of metal center
alternatives to natural enzymes. A typical difference between enzyme
and enzyme mimics are provided in Table 1. Recent progresses in the Metal centers in enzyme mimic act as an electron donors or ac-
fields of biological science, synthetic chemistry, computational chem- ceptors, Lewis acids/base or structure regulators. The metal centers
istry and polymeric science have provided a unique and co-operative directly involves in the catalytic process and display anomalous phy-
solution for the synthesis of enzymes mimics [81,82]. For an ideal en- sicochemical characteristics that controls the activation energy. For CA
zyme mimic design, suitable selection of central metal and scaffold mimic design, Zn is usually considered as the suitable central metal.
design is very important. However, other non zinc transitional metals, lanthanides and inorganic
Central metal plays a key role for tuning the catalytic activity of nanoparticles can also be used.
enzyme and enzyme mimics. In several zinc containing enzymes Zn (II)
is usually coordinated by amino acid residues. According to the hard- 3.1.1. Carbonic anhydrase mimics with zinc as metal center
soft acid-base (HSAB) principle Zn(II) is considered as a borderline During construction of a CA-mimetics it is quite necessary to have a
metal therefore can coordinate with both hard (N and O) and soft (S) tetrahedral geometry around the central metal. The Zn coordinated
ligands effectively [83–86]. Zinc has a filled d orbital; therefore, the hydroxide plays a vital role as it initiates the catalytic cycle by nu-
redox reactions are prevented and it acts as a Lewis catalyst [83]. The cleophilic attack on CO2 [87]. However, a reversible Zn hydroxide
ligand field stabilization energy for Zn (II) is zero due to its d10 elec- coordination is not easy to synthesize and for it a very careful selection
tronic configuration; therefore, it can coordinate with ligands with zinc salt is necessary. It is because the other anions that compete with
flexible geometry with variable coordination number. Due to rapid li- the hydroxide ion may bind with Zn, which result in catalytic poi-
gand exchange, Zn (II) complexes enhance efficient product release soning. Several studies reported that the activity of natural CA can be
during catalytic mechanism. distorted by external Zn-binding anions. Kim et al. [87] has made a
Furthermore, the protein environments or scaffold have an im- systematic study to find out the effect of counter ions on the activity of
portant role in providing appropriate environment for lower co- CA-mimics. They synthesized CA mimics by the self-assembly of histidyl
ordination number and assist structural, catalytic, and co-catalytic bolaamphiphile using different of zinc salts (ZnCl2, Zn(NO3)2, Zn
function of the overall process [83–86]. Every enzyme is characterized (CH3CO2)2, and Zn (OH)2). On comparing dissociation enthalpies of the
by its amino acid sequence appeared in the protein. Amino acid se- Zn salts and activation energies of the different CA-mimetic catalysts,
quence plays key role in enzymatic catalysis as it regulates both sub- they suggested that the catalytic activity of a CA-mimic could be altered
strate binding and selectivity. According to Tablbhi, the overall enzyme by anions of zinc salt. Low catalytic activity may arise due to anions
activity can be mimicked using a simple general strategy; [81] having strong affinity for zinc ions (high dissociation energy) [87,64].
As per their finding, Zn(OH)2 showed optimal reactivity in CO2 hy-
Mimicking enzymatic function = Equivalent microenvironment + Iso-
dration. Therefore, a suitable Zn source that can minimize the anion
functional substitution
disturbance will be beneficial for the preparation of efficient CA-mi-
Here, isofunctional substitutions are the molecules, which are metic.
properly oriented towards the active center. Several parameters may Along with metal, ligand selection also plays a key role during CA-

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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- complexes of tris (3-t-butyl-5-methylpyrazolyl) hydroborato and tris(2-
nuclear zinc complex having μ3-oxoanions for CO2 conversion (Fig. 4a). pyridylthio) methyl were synthesized by Sattler et al. (Fig. 4c) [90].
From X-ray crystallographic study it has been found that the Zn(II) ion These complexes provide important information regarding the me-
is tri-coordinated in distorted trigonal-bipyramidal geometry. The chanism of enzymatic CO2 hydration. Ibrahim et al. [91] studied the
group suggested that the activity of the μ3-carbonate unit can be zinc complexes of tripod ligand tris(2-benzimidazolylmethyl) amine
sterically controlled, which makes the carbon dioxide fixation cycle (L1) and its methylated derivative tris(N-methyl-2-benzimidazo-
feasible. They successfully used these CA-mimics to catalyze the con- lylmethyl)amine (L2) (Fig. 4d). On reaction with AgPF6 followed by
version of CO2 to carbonates under mild conditions. KOH treatment, they from the hydroxide complexes [L1Zn–OH)](PF6)
A similar C3-symmetrical tripodal amine ligand, N1,N3,N5-tris (2- and [L2Zn–OH)](PF6). Interestingly, these complexes could able to
aminoethyl) benzene-1,3,5-tricarboxamide (L) was designed by Bera produce bicarbonate ion on reaction with CO2. These results demon-
et al. (Fig.4b) [89]. Two different complexes such as [ZnL (H2O)] 2+ strate that tripodal ligand due to their unique geometry can help in
and [ZnL (OH)] + were synthesized using the tripodal ligand. Here, no construction of efficient CA-mimic.
dimmer formation observed and the pKa of the zinc-bound water mo- Not only tripodal ligands, macrocyclic ligands are also proved to
lecule was found to be 7.84. The coordination behavior of the ligand have an efficient CA-mimicking activity. Koziol et al. [92] has synthe-
and suitable pKa make the complex a viable CA-mimic. Di-merization of sized different zinc-chelated aza-macrocycle ligands as CA mimics and
complexes is sometimes problematic as it can permanently block the studied their catalytic behavior towards CO2 using quantum-mechan-
active site by bridging them resulting in activity loss. However, in this ical methods and stopped-flow experiments (Fig. 4e–i). They found that
case the steric repulsion of the ligand was probably the main attractive bicarbonate release is the rate limiting step in CO2 hydration by aza-
feature that prevented the dimerization. In a similar attempt, Zn macrocyclic zinc complexes. From the study it was established that

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P.C. Sahoo et al. Journal of CO₂ Utilization 24 (2018) 419–429

Lewis acidity of the CA-mimic and charge-donating character of the alteration of binding energy. The exact role of gold surface is not clearly
ligand plays key role in controlling pKa of the coordinated water, which explained; however it may assist in modulating electronic property of
tunes the transition state and catalytic efficiency. Thus a deep under- the active center. Moreover, the Zn-AM showed enhanced catalytic
standing of the transition state will be useful in designing ester hy- activity on CO2 hydration and p-NPA hydrolysis. The authors estimated
drolysis catalysts. the kinetic parameters: Km and kcat, to be 27.2 mM and 506.5 s−1, re-
Satcher et al. [93] performed a study to compare the activities of spectively.
two different cyclic amine (cyclen and cyclam) complexes. Both the In a new approach Sahoo et al. [98] studied the catalytic activity of
mimics showed enhanced catalysis at elevated pH depending on the a Zn (II)-model complex (Zn-His) immobilized on a magnetic Chitosan/
availability of the Zn-OH- nucleophile. Yet, cyclen-Zn2+ displayed ∼8 SiO2/Fe2O3 composite (Fig. 5b). They established that the core mag-
times faster catalytic activity than cyclam-Zn2+ at pH 7.5. The pKa of netic material (Fe2O3) helps for an easy recovery of the catalyst by
Zn bound water was found to be responsible for such catalytic behavior. using magnetic fields. The catalytic performance of the CA-mimic was
Therefore, for an industrial application, cyclen-Zn2+ can catalyze CO2 evaluated using ester hydrolysis and CO2 hydration. Interestingly after
hydration at the mild pH conditions [93]. immobilization, the thermal and storage stability was enhanced for Zn-
NMR is found to be an important tool to characterize biomimetic His complex. Moreover, the immobilized CA can retain activity and can
complex with high precision. Using liquid-state NMR spectroscopy be used for 10 cycles. Yao et al. synthesized poly (N-vinylimidazo-
Lesnichin et al. [94] have calculated the proton-donating ability of Zn- le)–zinc complex (PVI–Zn (II)) that mimics the activity of carbonic
bound water molecule in active site of a organometallic CA-mimic; anhydrase [99]. Further the PVI–Zn (II) was used to prepare mem-
which is quite important to understand reaction mechanism. Using 1H branes for selective separation of CO2/N2. They confirmed that the
and 15N NMR for solutions of a CA-mimic named [TpPh, MeZnOH] biomimetic membrane shows excellent separation CO2 from its mixture.
(TpPh, Me = tris (2-methyl-4- henylpyrazolyl) hydroborate) they found
that there exist an interaction between nitrogen base of the ligand and 3.1.2. Carbonic anhydrase mimics with non zinc metal centers
zinc bound aqua molecule. Furthermore, Sattler et al. [95] by using low Not only Zn, other metal ions are also efficient enough to mimic
temperature 1H and 13C NMR spectroscopic studies of the tris(3-t-butyl- models carbonic anhydrase activity. There are several advantages as-
5-methylpyrazolyl) hydroborato zinc hydroxide complex [TpBut;Me] sociated with this (1) due to the poor spectral quality of Zn (II), its
ZnOH in the presence of CO2 confirmed the identification of the bi- complexes and intermediates are difficult to characterize, so spectro-
carbonate moiety. scopic ally active complexes of Co (II) and Cd (II) can helpful in ob-
Immobilization technique is considered to be a specialized tech- taining in detail structural information (2) The role of metal ions and its
nique to maximize the stability, and reusability of catalyst/biocatalyst coordination environment can be obtained on various metal-substitu-
and is helpful for the overall economics of the process [96]. Considering tion [100].
this point, an immobilized carbonic anhydrase mimic was synthesized Keum et al. [101] substituted Zn cofactor with various transition
by immobilizing Fc-histidine conjugate on gold surfaces followed by metal ions such as Co2+, Cd2+, and Ni2+ in a CA–mimetic obtained by
chelating Zn2+ ions (Zn-AM) (Fig. 5a). Cheng et al. [97] used both coordination of histidyl bolaamphiphiles. From ester hydrolysis and
electrochemical and spectroscopic methods to evaluate the activity of activation energy calculation, the catalytic order of CA-mimics with
this CA-mimic towards CO2. They used XPS to evaluate the binding different metal ion substitution is found to follow order: Zn > Co >
energy of ligand and confirmed the Zinc (II) coordination from the 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-
Fig. 5. Immobilized CA-mimic on different support. The N atoms (in red) are directly nificant activity towards CO2. Bag et al. [105] prepared several
coordinated to central Zn atom.
mononuclear lanthanide (III) complexes [Ln(LH2)(H2O)3Cl] (ClO4)2

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Fig. 6. Schematic representation of non zinc CA-mimics.

(Ln = La, Nd, Sm, Eu, Gd, Tb, Lu) of the tetraiminodiphenolate mac- Kim et al. [113] used a molecular self-assembly approach to re-
rocyclic ligand (Fig. 6c). In a methanol-water mixture, the rare earth plicate the active site of CA. According to their observation the self-
complexes can fix CO2 through a carbonato-bridged trinuclear complex. assembly of a bolaamphiphilic molecule having histidine motifs is
Like CA, here Ln-OH has been considered as the key intermediate in the helpful for synthesis of CA mimics. The Zn coordinated self-assemblies
catalytic cycle. From the kinetic analysis it was found that with heavy hydrated CO2 in an efficient manner similar to CA. The kinetic para-
lanthanides the CO2 capture occurs in a faster rate. CO2 hydration to meter suggested that the CA-mimic activity was enhanced with increase
HCO3– by borate has been proposed by Guo et al. [106]. They found in Zn concentration. However an excess Zn concentration can distort
that tetrahydroxyborate ion, B(OH)4− is the active species that was the self assembly resulting in decreased activity. The activity of the self
responsible for CO2 hydration. assembly can be optimized depending on the pH value and tempera-
ture. Interestingly, the self assembly can sequestrate CO2 as CaCO3 in
3.1.3. Inorganic nanoparticles as carbonic anhydrase mimics presence of Ca2+ ion.
Due to tremendous development in nanotechnology enzyme mimics Similarly, to mimic an enzyme like environment a cobalt complex of
based on nanomaterials are gaining huge attention. Several nanoma- BBP was synthesized and encapsulated in the cage of a metal organic
terials including fullerene, Au-nanoparticles, nanoparticles of rare framework [114]. To evaluate the importance of MOF, the authors
earth, iron nanoparticles and quantum dots reported to show enzyme studied the esterase activity both before and after the Co-BBP en-
like catalytic activity [107]. How these nano materials behave like capsulation. An activity enhancement of nearly 14.39% was obtained
enzyme is still illusive as there is a strict difference between enzyme due to encapsulation in Tb-MOF. They concluded that the MOF helps to
and nano-materials. Enzymes are proteins and act like soft materials prevent the dimerization of the CA-mimics, and assist in the enhance-
while nanoparticles are crystalline in nature. However, several prop- ment of activity. In a parallel approach the same group synthesized
erties such as particle size, shape, surface charge, polarity enable na- biomimetic complexes of Co and Zn inside the nano cages of meso-
noparticles/quantum dots to mimic enzyme like activity [107]. porous silica (MS) [115]. The synthesized biomimetic complexes
In a report by Bhaduri et al. [108] nickel nanoparticles (NiNPs) Co–Im@MS and Zn–Im@MS imitate the active site of carbonic anhy-
showed a reversible CO2 hydration at ambient condition. pH of the drase and perform CO2 hydration. The catalytic activities of both the
medium is found to affect catalytic activity of the NiNPs. Being mag- caged complex were improved by imposing a hydrophobic environ-
netically active and insoluble, it can be easily separated and used in ment. This result indicated that the hydrophobic environment tailors
next run. The reaction mechanism was established by X-ray photo- the nucleophilicity of the active site by removing excess water mole-
emission spectroscopy (XPS) and found to be similar that of CA. In cules.
another work, Park’s group found out that nanoparticle organic hybrid Based on the above examples is confirmed that the role of scaffold is
material (NOHMs) has excellent properties to capture CO2 [109]. quite important during CA-mimic design. Scaffold like self-assembled
NOHMs consist of polymeric canopy anchored to the surface-modified supramolecule, metal organic frameworks or hydrobic nanocages can
nanoparticles through ionic or covalent bonds. They established that act as positive modulator for CO2 hydration in CA-mimics. Table 2
both enthalpy and entropy influence the CO2 capture in NOHMs [110]. summarizes CO2 capture by CA-mimics under appropriate condition.

3.2. Supramolecular scaffolds in carbonic anhydrase mimic design 4. Photo sensitive biomimetic complexes for CO2 conversion

Enzymes are delicate supramolecular structures consists of peptides Solar assisted CO2 conversion to valuable product is one of the
folded to form self assembly and can confront catalysis under biological challenges in the field of catalysis. To develop an efficient catalyst for
condition with unprecedented efficiency. Such catalytic activities arise CO2 reduction, we must consider several critical properties such as
due to versatile functional groups and their proper orientation near the visible-light harvesting ability, selectivity and cost of catalyst. The
active sites of the enzymes. However, it is immense challenging to crucial entities of any photo-catalyst consist of a semiconductor (as
mimic catalytic mechanism of enzyme due to unsuitable design of light harvester) and cocatalysts (to promote redox reaction) [116–118].
scaffolds [111]. These supramolecular scaffolds help in substrate re- It has been known that some efficient and low cost photo sensitive
cognition and catalysis. Several molecules such as macrocycles, metal biomimetic complexes can acts as cocatalysts. These cocatalysts will
organic frameworks, calixarenes, cyclodextrins, cyclophanes, crown assist in the charge separation and catalyze the CO2 reduction reaction.
ethers, cavitands, capsules, molecular cages, micelles, vesicles, nano- Several researchers focused on the development of efficient and low
particles, nanotubes and nanogels with hierarchical functionality have cost photo sensitive biomimetic complexes that are efficient for CO2
attracted considerable attention in the scientific community [111,112]. reduction. For instance, Sekizawa et al. synthesized a Ru(II) dinuclear

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Table 2
P.C. Sahoo et al.

Various CA-mimics and their mediated CO2 capture process.

CA-mimic complexes Activity analysis CO2 Capture technique Remark Ref.

−3
Zn-Histidyl bolaamphiphile - Hydrolysis of p-NPA (kcat = 8.69*10 ) - Precipitation as CaCO3 - Use of Zn(OH)2 salt showed the highest catalytic [87]
- pH variation in CO2-saturated water activity at 25 °C and pH 7
[Zn3L(ClO4)6] - CO2 to carbonate by 13C NMR spectroscopy - Precipitation as CaCO3 - CO2 to carbonates under mild conditions with ∼100 [88]
L = tris(xylyl) amine scaffold turnovers
[TpBut,Me]ZnOCO2H, Tp = tris(3-t-butyl-5- - X-ray diffraction to characterize bicarbonate in complexes - CO2 capture in the presence of water as - High reactivity and forms carbonate complex upon [90]
methylpyrazolyl) hydroborato bridging carbonate exposure to air
[L1Zn–Cl](PF6), L1 = tris(2-benzimidazolylmethyl) - 1H NMR titration of the ligands with Zn(II) ions and FTIR - Reacted with CO2 in triethylamine to give - Microwave assisted easy synthesis of ligand. [91]
amine bicarbonate complex - Coordination of ligand to zinc induces Lewis acidity
resulting higher activity
Zinc-chelated aza-macrocycle ligands - CO2 hydration reaction studied using stopped-flow - CO2 conversion to HCO3– in presence of - Bonding between CO2 and Zn plays an important [92]
spectrophotometry water role in stabilization of the transition state and hence
enhance activity
Zinc Fc-histidine conjugate on gold - p-NPA assay with kcat obtained as 506.5 s−1 - CO2 conversion to HCO3−/CO32- in 1 M - pH of the medium influence the activity [97]
NaClO4 solution monitored by Cyclic - Can be recycled
voltammeter (CV)
Zn-His on Chitosan/SiO2/-Fe2O3 - p-NPA assay with overall activity (Kcat/Km) 52.32 M−1 s−1 - CO2 was captured from a CO2 + N2 mixed - Easy synthesis method [98]
gas stream using a sensitive pH meter - Can be reused up to 10 conjugative cycles
poly(N-vinylimidazole)–zinc complex - Measuring partial pressure difference between the upstream - CO2 separation from with CO2/N2 using - Permeance of CO2 can be higher than 1000 GPU [99]
and downstream side of the membrane. membrane technology - The CO2/N2 selectivity can be as high as 83
II 1−
[Ni (NNN)OH] , containing tridentate 2,6- - Activity were studied in dimethylformamide solutions by - Fixation of CO2 as the bicarbonate complex - The local geometry changes associated with [102]
pyridinedicarboxamidate pincer ligand stopped-flow spectrophotometry at 218–243 substrate insertion influence the repaid CO2

425
K.cat∕KM = 9.5 × 105 M−1 s−1) capVture activity
Dicopper(II) complexes of six pseudo-octapeptides - Stopped-flow kinetics, using the color change of a pH - CO2 conversion to HCO3– - Configuration of the isopropyl side chains can alter [104]
indicator (kcat ∼ 7.3 × 103 s−1) the CO2 hydration rate.
[Ln(LH2)(H2O)3Cl](ClO4)2 with - IR and 1H NMR spectra used in the study of reaction rate - In methanol-water solution fix CO2 in few - CO2 fixation occurs faster with the heavier [105]
tetraiminodiphenolate macrocyclic ligand hours to produce the carbonato bridged lanthanides (III).
trinuclear complexes - The pK value of the Ln–H2O bond determines the
activity
B(OH)4− - Stopped-flow pH indicator technique was adopted to study - CO2 is sequestrated as in aqueous
HCO3− - The concentration of Boron and pH of the medium [106]
CO2 hydration medium are the determining factor for enhanced activity
Nickel nanoparticles - -CO2 hydration was measured via pH and conductivity - CO2 is sequestrated as HCO3− in aqueous - Being insoluble and magnetic, they can be [108]
medium magnetically separated for reuse.
Zn-histidyl - p-NPA assay with kcat obtained as 0.075 s−1 - CO2 was sequestered in CaCO3 - The self-assembly of a [113]
Co-BBP, BBP = 2, 6-bis(2-benzimidazolyl) - Hydrolysis of p-NPA - CO2 was sequestered in CaCO3 via in-vitro - Encapsulation of complex in MOF enhances the [114]
crystallization activity
Co–Im@MS and Zn–Im@MS - Hydrolysis of p-NPA - CO2 was sequestered in CaCO3 via in-vitro - Hydrophobic environment imposed by hexadecanol [115]
crystallization enhances the activity
[Hg(II)]S[Zn(II)(H2O/OH2)]N(CSL9PenL23H)3 - Hydrolysis of p-NPA (Activity only ∼100-fold less than that - CO2 sequestrated as HCO3− in aqueous - Zn(II) ion induces catalytic activity and a Hg(II) ion, [126]
of human CA) medium (pH 9.5 and 25 °C) provides structural stability.
Zinc(II) cyclen in K2CO3 - CO2 hydration reaction were determined using stopped-flow - CO2 sequestrated as HCO3− in aqueous - Zinc cyclen is a robust catalyst for industrial [45]
spectrophotometry medium and as measured by pressure drop application due to high thermal and pH stability.
Zinc(II) cyclen encapsulated in silicone - The CO2 released activity was analyzed using pyrolysis-gas - CO2 capture was measured using pressure - The micro capsules are highly permeable, [138]
microcapsules chromatography/mass spectrometry (GC/MS) drop apparatus mechanically robust, chemically stable and
environmentally benign.
Zinc PDC complex, PDC = 2,6-pyridinedicarbonyl - Using 13C NMR spectra - CO2 capture was measured using pressure - The complex found to be thermally stable and have [139]
dichloride in drop apparatus maximum regeneration efficiency with MDEA
Zinc-bis(hydroxyphenyl)phenanthroline in - pH drop in presence and absence of complex - The CO2 concentration was analyzed using a - The complex is robust in concentrated primary [134]
monoethanolamine CO2 analyzer 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
Fig. 7. de novo design of enzymes mimic.
(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 Piazzetta et al. studied a rhodium-substituted human carbonic an-
feasible and new structure of molecules. Basically, during de novo de- hydrase for CO2 conversion [129]. From computational analysis they
sign, the protein structure was analyzed by computational approach, concluded that the catalysis at the active center was controlled by σ-
and based on the knowledge models were generated via force field bond metathesis mechanism. The water molecules play a key role and
geometry optimizations. affect the shape and stiffness of the enzyme pocket. Consequently, there
Zastrow et al. [126] studied the importance of metal ions in the de was a lowering in the activation energy from 21.0 kcal mol−1 to
novo design of CA mimic. The group synthesized a metallo hydrolase 11.7 kcal mol−1 for CO2 catalysis.
having Zn(II) ion as catalytic site and Hg(II) ion for controlling struc- Deshpande performed the DFT calculation of a copper cluster (Cu7)
ture. The structure was confirmed by X-ray crystallography and the CA- that imitates the mechanism of α-carbonic anhydrase [130]. The cluster
mimic displayed catalytic activity similar to that of natural CA enzyme. efficiently catalyses the CO2 conversion to bicarbonate and possesses
The synthesized CA-mimic showed an esterase activity that was 550 equivalent energy in solvated as well as vacuum condition. In another
times faster than any synthetic complexes [126]. In a parallel approach, study, Verma et al. evaluated the CO2 hydration activity of different
Cangelosi et al. [127] prepared a novel Zn(II) metalloenzyme using de borate species using DFT calculation [131]. They found that the hy-
novo design. The group successfully constructed α3DH3 folds that droxy center of borate species was the key factor for its catalysis and an
strongly bind with Zn (II) via the His3O coordination. Surprisingly, this endergonic and bent CO2 complex was formed during the transition
de novo CA-mimic shows a CO2 hydration efficiency of 1400-fold state. Lee et al. [132] studied the catalytic hydrolysis reaction in metal
higher than any small molecule model. porphyrin carbon nanotube using DFT calculations. They found that the
In summary, de novo ligand design shows a great potential and catalytic process can be tailored by controlling the oxidation of por-
opportunity towards enzyme mimic design. With substantial progress in phyrin as well as by changing the central metal of the porphyrin. The
computational tool we can design much more efficient biocatalysts for study provided two important conclusions desirable for CA-mimics: (1)
medical and environmental application. A workflow diagram for de in the initial hydration reaction step, oxidation state and the metal
novo design of enzyme has been presented in Fig. 7. substitution, both have strong influence on reactivity; (2) the product-
release step was influenced either by oxidation state or metal sub-
5.2. ab initio and molecular simulation approach for modeling carbonic stitution, but not by both the factors simultaneously.
anhydrase mimics Similarly, based on molecular dynamics simulations and quantum
mechanical calculations Koziol et al. explored a supramolecular tris
Molecular modeling has become one of the essential tools for many (imidazolyl)calix [6] arene Zn2+ aqua complex, as CA-mimic. Based on
areas of chemistry including biocatalysis. The structure of new complex MD and DFT calculations, the researchers provided clarification re-
molecules can be ab-initio determined and compare with experimental garding the free-energy of the encapsulated water molecule and found
data. Experimentally undetermined and important intermediates such that the interaction between CO2 and water inside the cavity of CA-
as metastable intermediate/transition states or possible mechanism can mimic determines the stability of transition state [133]. Kelsey et al.
be accurately determined by the use of computational chemistry. was able to identify some important reaction parameters to predict the
Several methods have been used during computational simulation: mechanism by using DFT [134]. In summary, by understanding the
molecular mechanics (MM) and quantum mechanics (QM). One of the chemical processes computationally in model compounds, we can de-
QM approach called density functional theory (DFT) has wider appli- sign or improve our CA-mimics in a controlled manner.
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].

426
P.C. Sahoo et al. Journal of CO₂ Utilization 24 (2018) 419–429

Fig. 8. A schematic representation of a commercial amine based CO2 capture unit.

6. Opportunities and challenges of enzyme inspired complexes in Interestingly the CO2 absorption kinetics in the K2CO3 solvent was
industrial CO2 capture enhanced by ∼10 fold by CA-mimic compared to the experiment
without mimic enzyme. Moreover, the CA-mimic shows a higher sta-
Post combustion CO2 capture from industrial flue gases has a wide bility, lifetime in the solvent system indicating its potential for in-
potential for reduction of green house gas emissions as it can be easily dustrial CO2 capture. In order to have low-cost and energy-efficient CO2
retrofitted in existing plants [135]. Generally, in this technology, low capture, Vericella et al. [138] synthesized microfluidic assembly
concentrated CO2 is captured at ∼1 bar containing impurities such as polymer microcapsules composed of liquid carbonate cores and highly
SOx and NOx [136]. To date amine scrubber has been used to capture permeable silicone shells. It was found that microcapsules containing
CO2 followed by stripping at high temperature to regenerate the ab- carbonate sorbents exhibit higher CO2 absorption rate compared to
sorbent [135,136]. The efficient absorption of CO2 in a liquid stream equivalent neat sorbents. Moreover, insertion of zinc cyclen as CA-
usually involves the reversible reaction between acidic gas and the mimic to the microcapsules along with carbonate significantly increases
absorbent. Chemically absorbed CO2 is then stripped from liquid stream the CO2 absorption rates and the mimic remain stable at higher tem-
to reverse the reaction and regenerate the absorbent (Fig. 8). Amine perature.
absorption has been used by the natural gas industry for removing CO2. Choi et al. [139] studied a new CA-mimicking catalyst based process
Most common amines used as absorbent includes monoethanol amine to overcome the huge energy requirement of conventional amines based
(MEA), diethanolamine (DEA), and methyl diethanolamine (MDEA). process. The group synthesized a PDC-based ligand with Zn ion. They
However, the regeneration of amine after CO2 capture is energy in- studied the effect of addition of CA-mimic with primary (MEA), sec-
tensive and expensive. In order to address these issues, research com- ondary (DEA) and tertiary (MDEA) alkanolamine absorbents on the
munity is trying to find novel adsorbents or additive with high ab- regeneration of carbon dioxide. The results suggested that the re-
sorption capacity and low heat of regeneration. generation time decreases as well as absorption rate increases on ad-
Increase in the rate of CO2 hydration in amine solvents help to in- dition of CA-mimics to MEDA. Further, the CA-mimics show good
crease the mass transfer coefficients of a CO2 capture system, hence can thermal stability and do not corrode the quality of amine solvent after
lower the costs for carbon-capture process [134]. Using carbonic an- prolonged reaction. The same group also improved CO2 sequestration
hydrase, a swift hydration of CO2 can be obtained at ambient condition. by using model complexes via continuous stirred-tank reactor (CSTR)
Therefore, a CA blended amine can be used for enhanced CO2 capture. system. Using stopped-flow spectrophotometer, they studied the effect
However, due to some intrinsic limitation such as thermal and pH in- of substituent on CA-mimic and found that hydrophilic group showed
stability, the application of CA was unsuitable in aqueous amine-based the highest absorption or hydration of CO2 in MEDA solution [140].
solvents in power plants. Therefore, robust CA-mimic catalysts are The study suggested that CA-mimic in amine can efficiently absorbs and
gaining importance in enhancing industrial carbon capture processes desorbs CO2 and hence can be used in post-combustion processing.
[17,18,137]. Kelsey et al. [134] studied two new CA-mimics using zinc complex of
Floyd et al. [45] studied Zinc (II) cyclen as CA-mimic in an in- salen like ligand bis(hydroxyphenyl) phenanthroline. The catalytic ac-
dustrial carbon capture process using rigorous conditions. They found tivity under post-combustion carbon capture was estimated using
that the use of zinc cyclen accelerate the CO2 capture in high tem- acetonitrile solution of the CA-mimics in 24% monoethanolamine
perature and pH. The activity however decreases at low pH and high (MEA). Nearly, 15% enhanced CO2 absorption rate was seen compared
bicarbonate concentrations due the interference of bicarbonate with the to the amine solvent without catalyst. Moreover, > 95% of the catalyst
active site of the complex. Here, the CO2 absorption in K2CO3 solvent remained intact after exposure to CO2, which indicated the robustness
was promoted by Zn-cyclen complex in a membrane reactor [45]. of the complex.

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P.C. Sahoo et al. Journal of CO₂ Utilization 24 (2018) 419–429

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