Processes 08 00548

processes
Review
Green Pathway in Utilizing CO2 via Cycloaddition
Reaction with Epoxide—A Mini Review
Kunlanan Kiatkittipong 1 , Muhammad Amirul Amin Mohamad Shukri 2 ,
Worapon Kiatkittipong 3, * , Jun Wei Lim 4 , Pau Loke Show 5 , Man Kee Lam 6
and Suttichai Assabumrungrat 7
1 Department of Chemical Engineering, Faculty of Engineering, King Mongkut’s Institute of Technology
Ladkrabang, Bangkok 10520, Thailand; [email protected]
2 Department of Fundamental and Applied Sciences, Universiti Teknologi PETRONAS,
Seri Iskandar 32610, Perak Darul Ridzuan, Malaysia; [email protected]
3 Department of Chemical Engineering, Faculty of Engineering and Industrial Technology,
Silpakorn University, Nakhon Pathom 73000, Thailand
4 Department of Fundamental and Applied Sciences, HICoE-Centre for Biofuel and Biochemical Research,
Institute of Self-Sustainable Building, Universiti Teknologi PETRONAS,
5 Department of Chemical and Environmental Engineering, University of Nottingham Malaysia, Broga Road,
Semenyih 43500, Malaysia; [email protected]
6 Department of Chemical Engineering, HICoE-Centre for Biofuel and Biochemical Research,
Institute of Self-Sustainable Building, Universiti Teknologi PETRONAS,
7 Center of Excellence in Catalysis and Catalytic Reaction Engineering, Department of Chemical Engineering,
Faculty of Engineering, Chulalongkorn University, Bangkok 10330, Thailand; [email protected]
* Correspondence: [email protected]; Tel.: +66-3421-9368

Received: 5 April 2020; Accepted: 28 April 2020; Published: 8 May 2020
Abstract: Carbon dioxide (CO2 ) has been anticipated as an ideal carbon building block for organic
synthesis due to the noble properties of CO2 , which are abundant renewable carbon feedstock,
non-toxic nature, and contributing to a more sustainable use of resources. Several green and proficient
routes have been established for chemical CO2 fixation. Among the prominent routes, this review
epitomizes the reactions involving cycloaddition of epoxides with CO2 in producing cyclic carbonate.
Cyclic carbonate has been widely used as a polar aprotic solvent, as an electrolyte in Li-ion batteries,
and as precursors for various forms of chemical synthesis such as polycarbonates and polyurethanes.
This review provides an overview in terms of the reaction mechanistic pathway and recent advances
in the development of several classes of catalysts, including homogeneous organocatalysts (e.g.,
organic salt, ionic liquid, deep eutectic solvents), organometallic (e.g., mono-, bi-, and tri-metal salen
complexes and non-salen complexes) and heterogeneous supported catalysts, and metal organic
framework (MOF). Selection of effective catalysts for various epoxide substrates is very important in
determining the cycloaddition operating condition. Under their catalytic systems, all classes of these
catalysts, with regard to recent developments, can exhibit CO2 cycloaddition of terminal epoxide
substrates at ambient temperatures and low CO2 pressure. Although highly desired conversion
can be achieved for internal epoxide substrates, higher temperature and pressure are normally
required. This includes fatty acid-derived terminal epoxides for oleochemical carbonate production.
The production of fully renewable resources by employment of bio-based epoxy with biorefinery
concept and potential enhancement of cycloaddition reactions are pointed out as well.
Keywords: carbon capture and utilization (CCU); CO2 as chemicals feedstock; CO2 coupling with
epoxide; polymeric carbonates; aliphatic-polycarbonates; bio-based epoxy
Processes 2020, 8, 548; doi:10.3390/pr8050548 www.mdpi.com/journal/processes

Processes 2020, 8, 548 2 of 22
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1. Introduction
The significant concern
concern with
with regard
regard to
to the environmental
environmental impactimpact ofof anthropogenic
anthropogenic CO CO22 emission
into the
the atmosphere has directly contributed to global warming, thus demanding themitigating
atmosphere has directly contributed to global warming, thus demanding the need for need for
CO 2 emission
mitigating CO[1]. Avoidance
2 emission [1]. of CO2 emission
Avoidance of COthrough
2 emissionimproved
throughenergy and material
improved energyefficiency and
and material
the use of renewable
efficiency and the use energy and material
of renewable would
energy andbe the most desirable
material would becarbon management
the most desirablestrategy.
carbon
After this, utilization
management strategy.ofAfter
CO2 bythis,extending material
utilization of CO2use, referred tomaterial
by extending as “carbonuse,capture
referredand utilization
to as “carbon
(CCU)”,
capture andfor making repeated
utilization (CCU)”,use of
foremitted
makingCO 2 , woulduse
repeated be beneficial,
of emittedfollowed
CO2, wouldby carbon capture
be beneficial,
and storage
followed by (CCS)
carbonfor long-term
capture geological
and storage (CCS)sequestration
for long-term of geological
inevitable sequestration
residual CO2 of [2].inevitable
CCU is
emphasized as an adjunct, not alternative, to CCS [3]. There are many diverse approaches
residual CO2 [2]. CCU is emphasized as an adjunct, not alternative, to CCS [3]. There are many diverse for CO2
utilization;
approaches however, they generally
for CO2 utilization; can be
however, divided
they into can
generally twobe main approaches:
divided into two(1) direct
main use, and
approaches:
(2) transformation via chemical and biological processes, as depicted in Figure 1.
(1) direct use, and (2) transformation via chemical and biological processes, as depicted in Figure 1.
Figure 1. The approaches to utilize carbon dioxide.
CO direct uses
CO22 direct uses have
have been
been found
found in in oil
oil and
and gas
gas industries,
industries, as as well
well as in food
as in food and beverages such
and beverages such
as carbonated drinks. Presently, the
as carbonated drinks. Presently, the major COmajor CO utilization is based on a direct use
2 2 utilization is based on a direct use of 2COof CO in the
2 in oil
theand
oil
gas
andindustries, which
gas industries, mainly
which reliesrelies
mainly on enhanced
on enhancedoil recovery (EOR)
oil recovery or other
(EOR) related
or other technologies,
related such
technologies,
as
suchenhanced coal-bed
as enhanced methane
coal-bed recovery
methane (ECBM)
recovery and enhanced
(ECBM) shale gas
and enhanced shalerecovery (ESGR).
gas recovery It is worth
(ESGR). It is
nothing that, considering
worth nothing the carbon
that, considering thelife cycle, life
carbon these enhanced
cycle, these production of fossil fuelof
enhanced production technologies
fossil fuel
still produce astill
technologies surplus of COa2 emissions.
produce surplus of Readers are referred
CO2 emissions. to a current
Readers review performed
are referred to a current by review
Zhang
et al. [3] for more insightful information. For the second approach,
performed by Zhang et al. [3] for more insightful information. For the second approach, transformation via chemical and
biological
transformationprocessviaincludes
chemicalmineralization,
and biological fuelprocess
and chemical
includes production,
mineralization,and biological
fuel andutilization.
chemical
Although these CO
production, and biological
2 transformations cannot mitigate the enormous
utilization. Although these CO2 transformations CO 2 emissions, converting
cannot mitigate CO2theto
chemicals has emerged and has drawn much research attention because
enormous CO2 emissions, converting CO2 to chemicals has emerged and has drawn much research it offers extending material
use with higher
attention becausevalue. COextending
it offers 2 has beenmaterial
foreseenuse as with
a carbon building
higher value. block
CO2 has for been
organic syntheses,
foreseen as a
as
carbon2 building block for organic syntheses, as CO2 is renewable, non-toxic, and economical and
CO is renewable, non-toxic, and economical [4]. However, the thermodynamically stable [4].
kinetic
However, inertness of CO2 has hindered
the thermodynamically COand
stable 2 activation and fixation
kinetic inertness [5].2 The
of CO has enhancement
hindered CO2ofactivation
efficient
chemical
and fixationprocesses
[5]. Thefor the chemicalof
enhancement fixation
efficientof chemical
CO2 into processes
high value-added organic chemicals
for the chemical fixation ofshould
CO2 intobe
vigorously developed. Several proficient routes have been established for
high value-added organic chemicals should be vigorously developed. Several proficient2 routes have chemical CO fixation [6].
However, in general,
been established only several
for chemical CO2processes
fixation [6].have been commercialized
However, in general, only because
severalofprocesses
limitation in terms
have been
of precursor and efficiency of the reactions due to the requirement of reactive agents
commercialized because of limitation in terms of precursor and efficiency of the reactions2 due to the for CO activation
(Figure 2) [7–9].
requirement of reactive agents for CO2 activation (Figure 2) [7–9].
The Kolbe–Schmitt reaction (Figure 2; red box number 1) is one of the most essential and
renowned carboxylation reactions, offering an economical pathway to produce salicylic acids by
carboxylation of phenoxides with CO2 [10]. Salicylic acids are crucial chemicals in pharmaceuticals
Processes 2020, 8, 548 3 of 22
and agrochemicals, including vital precursors in organic synthesis [11]. Because of the low cost of
the reaction, the Kolbe–Schmitt reaction is most stable and extensively used in industry, especially
in the synthesis process of aspirin. Consequently, there is no considerable change that can be made
to improve this reaction. In addition, the reaction of propargylic alcohol with CO2 to produce cyclic
carbonate with the presence of base is applicable in industry (Figure 2; red box number 2) [11,12].
However, its industrial applicability on a larger scale is limited because of salt waste formation due to
Processes
the need 2020,
of 8,the
x FOR
acidPEER REVIEW
addition to form free carboxylic acid [13]. 3 of 22
Figure 2. Examples of CO as C1 feedstock in organic synthesis. The synthesis reactions marked with
Figure 2. Examples of CO2 2as C1 feedstock in organic synthesis. The synthesis reactions marked with
red boxes have been industrialized [7–9].
red boxes have been industrialized [7–9].
This review focuses on the most prominent route, which is the cycloaddition of epoxides
The Kolbe–Schmitt reaction (Figure 2; red box number 1) is one of the most essential and
into CO2 , producing cyclic carbonate and polymeric carbonate (Figure 2; red box number 3) [14].
renowned carboxylation reactions, offering an economical pathway to produce salicylic acids by
The five-membered ring cyclic carbonates are extensively utilized as sustainable polar aprotic solvents,
carboxylation of phenoxides with CO2 [10]. Salicylic acids are crucial chemicals in pharmaceuticals
value-added compound for fuel, and electrolytes for lithium-ion batteries, and are the precursor for
and agrochemicals, including vital precursors in organic synthesis [11]. Because of the low cost of the
polymerization reactions and pharmaceuticals [15]. The CO2 coupling with epoxide captivates the
reaction, the Kolbe–Schmitt reaction is most stable and extensively used in industry, especially in the
interest of industries because of readily available precursors and widely used products that are cyclic
synthesis process of aspirin. Consequently, there is no considerable change that can be made to
carbonates [6]. Figure 3 shows typical and some emerging epoxide species, which can be classified as
improve this reaction. In addition, the reaction of propargylic alcohol with CO 2 to produce cyclic
terminal epoxides (Figure 3a–g) and internal epoxides (Figure 3h–i). Their structure and abbreviations
carbonate with the presence of base is applicable in industry (Figure 2; red box number 2) [11,12].
used in this manuscript are provided.
However, its industrial applicability on a larger scale is limited because of salt waste formation due
Ethylene carbonate and propylene carbonate are the most significant cyclic carbonates employed
to the need of the acid addition to form free carboxylic acid [13].
in industry. They are commercially catalyzed by quaternary ammonium or phosphonium salts, which
This review focuses on the most prominent route, which is the cycloaddition of epoxides into
are relatively inefficient, and thus require high temperature and pressure [16]. For the past decades,
CO2, producing cyclic carbonate and polymeric carbonate (Figure 2; red box number 3) [14]. The five-
numerous catalysts, either homogeneous or heterogeneous, therefore have been extensively investigated.
membered ring cyclic carbonates are extensively utilized as sustainable polar aprotic solvents, value-
This paper aims to review recent advances and trends in catalytic CO2 cycloaddition, including
added compound for fuel, and electrolytes for lithium-ion batteries, and are the precursor for
homogeneous organocatalyst (e.g., organic salt, ionic liquid, deep eutectic solvents), organometallic
polymerization reactions and pharmaceuticals [15]. The CO2 coupling with epoxide captivates the
interest of industries because of readily available precursors and widely used products that are cyclic
carbonates [6]. Figure 3 shows typical and some emerging epoxide species, which can be classified as
terminal epoxides (Figure 3a–g) and internal epoxides (Figure 3h–i). Their structure and
abbreviations used in this manuscript are provided.
Processes 2020, 8, 548 4 of 22
This paper aims to review recent advances and trends in catalytic CO2 cycloaddition, including
homogeneous organocatalyst (e.g., organic salt, ionic liquid, deep eutectic solvents), organometallic
(e.g.,(e.g.,
mono-, bi-,bi-,
mono-, and tri-metal
and tri-metalsalen
salen complexes and non-salen
complexes and non-salencomplexes),
complexes), andand heterogeneous
heterogeneous
supported catalyst and metal organic frameworks (MOFs), along with the reaction
supported catalyst and metal organic frameworks (MOFs), along with the reaction mechanistic mechanistic pathway.
Substitution
pathway.with bio-basedwith
Substitution epoxy is a proposed
bio-based epoxy isrepresentation of pathways via
a proposed representation the amorphous
of pathways via thesugar,
lipid,amorphous
and lignocellulosic biomass
sugar, lipid, platform. Last
and lignocellulosic but notplatform.
biomass least, theLast
possibility
but not of enhancing
least, cycloaddition
the possibility of
enhancing
reactions cycloaddition
through emergingreactions through
strategies emerging strategies is discussed.
is discussed.
Terminal epoxides:
(a) (b) (c) (d)
(e) (f) (g)
Internal epoxides:
(h) (i)
Figure
Figure 3. Structure
3. Structure of typical
of typical and some
and some emerging
emerging epoxide
epoxide species:
species: (a) ethylene
(a) ethylene oxideoxide
(EO);(EO); (b)
(b) propylene
propylene oxide (PO); (c) butylene oxide (BO); (d) allyl glycidyl ether (AGE); (e) hexene oxide (HO);
oxide (PO); (c) butylene oxide (BO); (d) allyl glycidyl ether (AGE); (e) hexene oxide (HO); (f) styrene
(f) styrene oxide (SO); (g) epichlorohydrin (ECH); (h) cyclohexene oxide (CHO); (i) spiro-epoxy
oxide (SO); (g) epichlorohydrin (ECH); (h) cyclohexene oxide (CHO); (i) spiro-epoxy oxindole (SEO).
oxindole (SEO).
2. Cycloaddition Reaction Mechanism of Epoxide with CO2
2. Cycloaddition Reaction Mechanism of Epoxide with CO2
The reaction involving cycloaddition of CO2 with epoxides can be instigated via activating of
The reaction involving cycloaddition of CO2 with epoxides can be instigated via activating of
either the CO or epoxide, or both concurrently [17]. Figure 4 illustrates the general mechanistic
either the 2 CO2 or epoxide, or both concurrently [17]. Figure 4 illustrates the general mechanistic
pathway of COof2 cycloaddition
pathway reaction.
CO2 cycloaddition The CO
reaction. The2 activation can take
CO2 activation canplace
take either
place through a nucleophilic
either through a
(Nu) attack byoxygen atom to act as a nucleophile (cycle 1, first step) or an electrophilic attack by
carbon atom to act as an electrophile (cycle 2, second step). The epoxide can be activated readily
by interacting the oxygen atom with Lewis acid (LA), followed by a nucleophilic attack, promoting
epoxide ring opening (cycle 2, first step). Thus, most of the catalytic systems used for CO2 addition
into epoxides contain Lewis acid sites (LA) for the later electrophilic activation of epoxide [18].
nucleophilic (Nu) attack byoxygen atom to act as a nucleophile (cycle 1, first step) or an electrophilic
attack by carbon atom to act as an electrophile (cycle 2, second step). The epoxide can be activated
readily by interacting the oxygen atom with Lewis acid (LA), followed by a nucleophilic attack,
promoting epoxide ring opening (cycle 2, first step). Thus, most of the catalytic systems used for CO2
addition
Processes 2020, 8, into
548 epoxides contain Lewis acid sites (LA) for the later electrophilic activation of epoxide5 of 22
[18].
Intermediate (1)
Intermediate (2)
Intermediate (4)
Intermediate (3)
Figure 4. Reaction
Figure mechanistic
4. Reaction mechanisticpathways
pathways of cycloaddition
cycloadditionofof epoxide
epoxide with
with CO2CO
. 2.
CycleCycle 1 demonstrates
1 demonstrates thethe activationofofCO
activation CO22 through
through nucleophilic
nucleophilic attack
attackto form
to form an intermediate
an intermediate
(1), which later promotes epoxide ring opening (the presence of Lewis
(1), which later promotes epoxide ring opening (the presence of Lewis acid (LA) site acid (LA) site maymay
facilitate
facilitate
the ring opening), leading to the second intermediate (2). Then, cyclization
the ring opening), leading to the second intermediate (2). Then, cyclization occurs to produceoccurs to produce a cyclic
a cyclic
carbonate while the nucleophile is recycled for a new catalytic cycle. Furthermore, cycle 2
carbonate while the nucleophile is recycled for a new catalytic cycle. Furthermore, cycle 2 demonstrates
demonstrates a commonly proposed pathway through activation of epoxide. The Lewis base
a commonly proposed pathway through activation of epoxide. The Lewis base compounds, such as
compounds, such as quaternary ammonium halide salts and phosphonium salts [16], acting as
quaternary ammonium
nucleophiles attack halide salts to
the epoxide and phosphonium
enable ring opening,salts [16], acting
producing as nucleophiles
an intermediate attack may
(3), which the epoxide
be
to enable
assisted by a Lewis acid (LA) species in proximity to metal centers. Subsequently, upon ring opening, (LA)
ring opening, producing an intermediate (3), which may be assisted by a Lewis acid
species
theinCO proximity to occurs
2 insertion metal centers. Subsequently, bond
in the metal–alkoxide upon ofringtheopening, the CO
intermediate, 2 insertion
producing a occurs
new in
the metal–alkoxide
intermediate (4).bond of the intermediate,
The cyclization producing
of the intermediate a new cyclic
produces intermediate
carbonate (4).
as The cyclization
the final product,of the
and nucleophile
intermediate producesiscyclic
recycled for further
carbonate reaction.
as the final product, and nucleophile is recycled for further reaction.
3. Catalysts
3. Catalysts for Cycloaddition
for Cycloaddition ofof Epoxidewith
Epoxide with CO
CO22
Figure Figure 5 displays

5 displays the classification
the classification of catalyst
of catalyst for cycloaddition
for cycloaddition of epoxide
of epoxide withwith
CO2 .CO 2. The
The contents
contents are outlined following the classification.
are outlined following the classification.
Figure
Figure 5. Classificationof
5. Classification ofcatalysts
catalysts for
for cycloaddition
cycloadditionof of
epoxide with
epoxide CO2CO
with . 2.
3.1. Homogeneous Catalyst

Homogeneous catalysis generally involves the catalyst and reactant presenting together in the
same phase (generally liquid). Homogeneous catalytic systems usually display the most active high
conversion and selectivity. On the contrary, for the heterogeneous catalytic system, the catalyst is
usually in a solid form while the reactant can be in liquid or gas phases. Usually, the heterogeneous
Processes 2020, 8, 548 6 of 22
3.1. Homogeneous Catalyst

Homogeneous catalysis generally involves the catalyst and reactant presenting together in the
same phase (generally liquid). Homogeneous catalytic systems usually display the most active high
conversion and selectivity. On the contrary, for the heterogeneous catalytic system, the catalyst is
usually in a solid form while the reactant can be in liquid or gas phases. Usually, the heterogeneous
catalyst is less active when compared with their homogeneous analogues because the limitation of the
reactant to migrate to the catalytic sites causes low activity of heterogeneous catalysts, originating from
poor diffusion [14]. However, homogeneous catalysts have several practical disadvantages, namely,
lesser robust and lower recyclability as opposed to heterogeneous catalysts. One of the most use
techniques for combining the high activity of a homogeneous catalyst with easily and effectively catalyst
recovery is the “heterogenization” of the active species via such functionalization/immobilization
support materials [19].
Table 1 summarizes different classes and types of homogeneous catalysts on CO2 cycloaddition
reaction performance.
Table 1. Operational conditions and the corresponding outputs from the CO2 cycloaddition reactions
catalyzed by different homogeneous catalysts.
T P Time Yield Conv.

Epoxide Catalyst Class/Type Cocatalyst Ref.
(°C) (bar) (h) (%) (%)
Organocatalysts
TBACl 25 1.01 24 52 ND
ECH Ionic liquid/2,6-pyridinedimethanol TBAB 25 1.01 24 67 ND [14]
TBAI 25 1.01 24 92 ND
DES/ChCl:glycerol - 40 1.01 5 20 ND
DES/ChCl:Ethylene glycol - 40 1.01 5 10 ND
DES/ChCl:benzoic acid - 40 1.01 5 12 ND
- 40 1.01 5 49 ND
SEO [20]
DES/ChCl:Urea(100mg) - 60 1.01 5 85 ND
- 70 1.01 5 89 ND
DES/ChCl:Urea (200mg) - 70 1.01 3 93 ND
DES/ChCl:Urea (300mg) - 70 1.01 2 98 ND
Monometallic salen complexes
TBAB 25 1 3 ≈37 a 37 [21]
Salophen (Figure 6a; R = tert-butyl, a
6 ≈60 60
X = Cl)
24 ≈100 a 100
SO
3 ≈44 a 44
Salophen (Figure 6a; R = MeO, X = Br) TBAB 25 1 6 ≈71 a 71
24 ≈100 a 100
Bimetallic salen complexes
PO Bimetallic Salen-Co TBAB 25 10 48 75.8 ND [22]
PO Bimetallic Salen-Al TBAB 25 10 48 73.2 ND
PO Bimetallic Salen-Zn TBAB 25 10 48 72.1 ND
Monometallic non-salen complexes
HO Zn(II) TPP - 20 1 43 82 ND [23]
PO TBAB 0 1.01 8 43 ND
SO Co-cryptand TBAB 20 1.01 12 32 ND
TBAB 20 1.01 24 48 ND [24]
ECH - 20 1.01 48 6 ND
- TBAB 20 1.01 48 11 ND
Processes 2020, 8, 548 7 of 22
Table 1. Cont.

Epoxide Catalyst Class/Type Cocatalyst Ref.
(°C) (bar) (h) (%) (%)
Bimetallic non-salen complexes
R = (S)-CH(PhMe; TBAB RT 1 24 75.0 b 77
Bi-aluminium X = Et TBAB RT 10 24 b 100 [25]
SO 97.3
scorpionate
R = Ph; X = Me TBAB RT 10 24 58.6 b 60
Trimetallic non-salen complexes
TBAB RT 10 24 97.3 b 100
R = Bu; X = Et
TBAB RT 1 24 75.0 b 77
TBAB RT 10 24 90.2 b 92
R = (S)-CH(Ph)Me;
Trinuclear X = Me TBAB RT 1 24 50.4 b 52
SO aluminium [25]
scorpionate R = (S)-CH(Ph)Me; TBAB RT 10 24 97.3 b 100
X = Et TBAB RT 1 24 75.0 b 77
TBAB RT 10 24 97.3 b 100
R = Ph; X = Me
TBAB RT 1 24 97.3 b 100
TBAB 80 20.68 24 66.3 67
Trimetallic-Co
TBAI 80 20.68 24 38.6 39
CHO TBAB 80 20.68 24 90.0 91 [26]
Trimetallic-Zn
TBAI 80 20.68 24 87.1 88
Trimetallic-Ni TBAB 80 20.68 24 42.6 43
Abbreviations: ChCl, choline chloride; Conv, conversion; ND, not determine; RT, room temperature; TBAB,
tetrabutylammonium bromide; TBACl, tetrabutylammonium chloride; TBAI, tetrabutylammonium iodide.
a Calculated from reported conversion with a selectivity higher than 99%, b Calculated from turnover frequency (TOF).
(b)
(a)
(c)
Figure
Figure6.6.Organometallic
Organometallicsalen-based catalysts:
salen-based (a) homogeneous
catalysts: monometallic
(a) homogeneous salensalen
monometallic complexes; (b)
complexes;
homogeneous bimetallic
(b) homogeneous salen
bimetallic complex;
salen (c) (c)
complex; heterogeneous bimetallic
heterogeneous salen
bimetallic complex
salen complexsupported
supportedby
by
various
varioussupports.
supports.
3.1.1.Organocatalysts
3.1.1. Organocatalysts
The characteristics
The characteristics of
oforganocatalysts
organocatalysts areare
readily available,
readily non-toxic,
available, affordable,
non-toxic, and inert
affordable, andtowards
inert
air. Thus, organocatalysts are easy to handle and have recently attracted considerable
towards air. Thus, organocatalysts are easy to handle and have recently attracted considerable attention and
interest in this field as an alternative to the metal-based catalyst. Several types of organocatalysts
attention and interest in this field as an alternative to the metal-based catalyst. Several types of
including, but not
organocatalysts limited to,
including, butorganic salts to,
not limited andorganic
ionic liquids, amines,
salts and ionic organic
liquids, bases,
amines,and deep eutectic
organic bases,
solvents are of major interest among researchers.
and deep eutectic solvents are of major interest among researchers.
Quarternary ammonium halides, one of the organic salts, were among the first active catalysts
for the cyclic carbonates synthesis [27,28]. Tetrabutylammonium bromide (TBAB) effectively
catalyzed ethylene oxide cycloaddition to ethylene carbonate with 97% yield, but at a harsh condition
of 200 °C and initial CO2 pressure of 34 bar [27]. Other organic salts such as phosphonium salt and
imidazolium salt have been later introduced as effective organocatalysts.
Processes 2020, 8, 548 8 of 22
Quarternary ammonium halides, one of the organic salts, were among the first active catalysts for
the cyclic carbonates synthesis [27,28]. Tetrabutylammonium bromide (TBAB) effectively catalyzed
ethylene oxide cycloaddition to ethylene carbonate with 97% yield, but at a harsh condition of 200 ◦ C
and initial CO2 pressure of 34 bar [27]. Other organic salts such as phosphonium salt and imidazolium
salt have been later introduced as effective organocatalysts.
Ionic liquid as a catalyst such as imidazolium salt-based ionic liquids (ILs), namely,
1-n-butyl-3-methylimidazolium tetrafluoroborate, exhibited 100% propylene oxide conversion with
almost 100% selectivity of propylene carbonate at 110 ◦ C and CO2 initial pressure of 40 bar. Good
recyclability can be obtained with a slight decrease in conversion and selectivity after 5 cycle runs [29].
The ILs are defined as salts that melt at 100 ◦ C or less. Organic salts and ILs can be classified and
differentiated by their cation structures. The mechanism of these organocatalysts is intrinsically based
on the nucleophilic attack of the anion and the stabilization by interacting with the cation [30]. Because
the reaction occurs in the liquid phase, the solubility of the catalyst plays an important role. Many
types of ILs have been used to catalyze the reactions, including ILs based on imidazolium, ammonium,
phosphonium, and pyridinium salts. For example, Wang et al. [14] studied the dual functional catalytic
system by incorporating pyridine alcohol with tetrabutylammonium iodide (TBAI). The results of the
binary catalytic showed increase of yield of the different usage of halides ions in the order of Cl− < Br−
< I− with yield of 52%, 67%, and 92%, respectively (Table 1). This is probably because chloride ion
has stronger hydrogen bond interactions with the alcohol component, when compared to bromide
and iodide ions. This study displays conversion of diverse epoxides with high yield, ranging from
85–97%, for which ECH is the highest yield due to electron withdrawing effect of the substituent,
which favors the nucleophilic attack at the carbon atom of the epoxide ring. The catalytic system of
2,6-pyridinedimethanol/TBAI was sustainable and economical because the activity was almost constant
after recycling at least six times.
Deep eutectic solvents (DESs) have recently emerged as captivating multifunctional media. DESs
possess analogous properties of ILs; however, it has been proposed as a promising alternative to
conventional ILs because of easier preaparation and lower cost. DESs are eutectic mixtures of hydrogen
bond donor (HBD) and hydrogen bond acceptor (HBA) in a certain stoichiometric ratio. Tak et al. [20]
studied the reaction of DES by using choline chloride (ChCl) as HBA and various HBDs, these being
urea, ethylene glycol, glycerol, and benzoic acid, with a constant mole ratio of ChCl to HBD of 1:2,
finding that urea served as the best HBD of SEO conversion among others because of the greater
solubility of CO2 in a ChCl/urea DES mixture (0.301 mol CO2 /mol DES). With regard to the activation
barrier that hindered the formation of bicyclic spiro-cyclic carbonate, the studies investigated the
effect of temperature from 40 to 70 ◦ C, significantly influencing the yield of spiro-cyclic carbonate
with the increment of 49% to 89% in 5 h. The effect of catalyst loading of ChCl/urea (100–300 mg)
was observed, and 300 mg achieved the highest yield (98%) in a shorter reaction period. The effect of
substitutions of benzyl (Bn) attached to nitrogen (Figure 3i) with other substrate (i.e., methyl, allyl,
and methylbenzyl) provided excellent yields (95–98%); in comparison, the substitutions of aromatic
ring-derived substrates (Figure 3i); R = H, F, Cl, benzyl, etc.) required additional duration (6–8 h) in
achieving a comparable yield (67–90%), which was somewhat expected due to the steric hindrance of
the substituted substrate, and the author suggested that providing higher pressure and temperature
may achieve better conversion. The recyclability of ChCl/urea DES displayed consistent yield (≈98%)
in four runs.
3.1.2. Metal Salt

The most commonly used metal salts are those based on alkali metal salts (also called alkali-metal
halides). Alkali metal salts of sodium, potassium, or lithium, which are abundant, low-cost, and
non-toxic can be employed to catalyze the CO2 /epoxide coupling. For instance, many researchers
reported the production of ethylene carbonate under high temperature and pressure. For example,
Dow Chemical and Shell patented KI as a catalyst for the ethylene carbonate production from CO2
Processes 2020, 8, 548 9 of 22
and ethylene oxide under harsh conditions, around T = 190 ◦ C and P = 13 bar [16]. For propylene
carbonate production, 99% of propylene oxide conversion can be achieved at 120 ◦ C and 30 bar within
5 h when the reaction is catalyzed by KI, whereas only 27% and 3% conversion occurs in the cases of
KBr and KCl catalysts, respectively [31]. However, the activity of alkali metal salts is relatively low,
and therefore a co-catalyst is commonly necessary [32,33].
3.1.3. Metallic Salen Complex
Monometallic Salen Complex

Homogeneous metal–salen and affine complexes (salphen, salophen, salalen, etc.) have been
well developed over the last two decades as salen ligands that can coordinate with many transition
metals, and have been widely studied for cycloaddition reaction [5]. Salen complexes are readily
available, and can be finely tuned and prepared in enantiomerically pure form, thus enabling the
creation of an asymmetric environment around the active metal site [21]. These metal complex catalysts
have been used in many organic reactions, targeting cycloaddition reaction of CO2 . Castro-Osma
et al. [21] found an interesting finding of Cr(III) salen complexes with the use of the salophen ligand
and tetrabutylammonium bromide (TBAB) that could catalyze CO2 coupling under ambient condition
(Figure 6). Regarding the monometallic salen complex (Figure 6a; R = tert-butyl, X = Cl) with TBAB as
a co-catalyst, the cycloaddition of CO2 with styrene oxide gave 100% conversion with selectivity higher
than 99% under ambient condition for 24 h. Modifying the salen complex (Figure 6a; R = tert-butyl,
X = Cl) by replacing the tert-butyl substituents with methoxy groups (Figure 6a; R = MeO, X = Br),
results in higher rate of reaction, verifying the fact that replacing substituent with electron-donating
groups (MeO) could produce more active catalysts.
Bimetallic Salen Complexes

The development of bimetallic salen complex with TBAB as co-catalyst was the earliest catalytic
system capable of catalyzing the insertion of CO2 into terminal epoxides at ambient pressure and
temperature [34]. On the basis of Wang et al. [22], the calculation using density functional theory (DFT)
proved bimetallic (salen-Co) complexes were one of the most efficient catalysts, with an activation
energy of merely 9.94 kcal/mol, indicating that the reaction could occur under ambient conditions. The
experimentally produced yield of 75.8% with salen-Co catalyst was the highest yield attained when
compared with salen-Al and salen-Zn at ambient conditions (Figure 6b) [17].
3.1.4. Metallic Non-Salen-Based Complexes
Monometallic Non-Salen-Based Complexes

Due to a unique framework of porphyrin, coordination with metal referred to as “metalloporphyrin”
is highly versatile and allows tunable electronic properties of the metal center, which can enhance
catalytic activity and exhibit good thermal stability [23]. It is one of the most studied organometallic
complexes besides salen-based complexes. For example, Maeda et al. [23] studied functionalized Zn(II)
TPP (tetraphenylporphyrin) with eight quaternary ammonium bromides at the ortho, meta, or para
positions of the meso-phenyl groups (Figure 7a; R = O(CH2 )6 N+ Bu3 Br− ). The meta-substituted Zn(II)
complexes showed very high activity. At 20 ◦ C, they reported a cyclic carbonate yield of 82% with
a TON (turnover number) of 1640 in 48 h under atmospheric pressure of CO2 . A very high TON of
240,000 can be achieved by increasing reaction temperature to 120 ◦ C and initial CO2 pressure to 17 bar.
In a mechanistic approach, DFT (density functional theory) calculation was employed to reveal the
origin of merit of the meta-substituted catalyst.
De et al. [24] reported the synthesis of nonsymmetric aza-oxa cryptand derivatized with L-proline.
The trinuclear Co(II) complex {[Co3 (L)2 (NCS)6 ]·(15CH3 CN) (5acetone)(6H2 O)} can be formed by
reacting the cryptand and Co(II) perchlorate in the presence of KSCN. With TBAB as a co-catalyst,
studied organometallic complexes besides salen-based complexes. For example, Maeda et al. [23]
studied functionalized Zn(II) TPP (tetraphenylporphyrin) with eight quaternary ammonium
bromides at the ortho, meta, or para positions of the meso-phenyl groups (Figure 7a;
R=O(CH2)6N+Bu3Br−). The meta-substituted Zn(II) complexes showed very high activity. At 20 °C,
they reported
Processes a cyclic carbonate yield of 82% with a TON (turnover number) of 1640 in 48 h under
2020, 8, 548 10 of 22
atmospheric pressure of CO2. A very high TON of 240,000 can be achieved by increasing reaction
temperature to 120 °C and initial CO2 pressure to 17 bar. In a mechanistic approach, DFT (density
all differenttheory)
functional epoxides could bewas
calculation converted to cyclic
employed carbonates
to reveal withof100%
the origin meritselectivity at 20 ◦ C under
of the meta-substituted
atmospheric pressure, however, with low to moderate yields of 32–49% within 12–24 h of reaction time.
catalyst.
(a) (b) (c)

Figure
Figure 7.
7. Non-salen-based
Non-salen-based complexes:
complexes: (a)
(a) metalloporphyrin-based
metalloporphyrin-based complex;
complex; (b)
(b) binuclear
binuclear aluminum
aluminum
scorpionate; (c) trinuclear aluminum scorpionate.
Bimetallic
De et Non-Salen Complexes
al. [24] reported the synthesis of nonsymmetric aza-oxa cryptand derivatized with L-
proline.
Castro-Osma et al. [25] complex
The trinuclear Co(II) studied {[Co 3(L)2(NCS)6]·(15CH3CN) (5acetone)(6H2O)} can be formed
bimetallic alluminium scorpionate as non-salen complexes
by reacting the cryptand and Co(II) perchlorate
(Figure 7b) and other organometallic complexes. in theBimetallic
presence ofaluminium
KSCN. With TBAB as a co-catalyst,
scorpionate (Figure 7b;
all different epoxides could be converted to cyclic carbonates with 100% selectivity
R = CH(Ph)Me and X = Et) shows the added benefit of using a bimetallic complex that at 20 °Cisunder
very
atmospheric pressure, however, with low to moderate yields of 32%–49% within 12–24
high active over monometallic complex catalysts. However changing this from a large alkyl h of reaction
group
time.
(R = CH(Ph)Me; X = Et) to a simple aryl group (R = Ph; X = Me) resulted in a significant decrease in
catalytic activity, which is also lower than the activity of the monometallic complex. This is critically
Bimetallic Non-Salen Complexes
due to the nature of the subtituted group attached to the enamine nitrogen atom.
Castro-Osma et al. [25] studied bimetallic alluminium scorpionate as non-salen complexes
Trimetallic
(Figure 7b)Non-Salen
and otherComplexes
organometallic complexes. Bimetallic aluminium scorpionate (Figure 7b;
R=CH(Ph)Me andstudy,
In the same X=Et) Castro-Osma
shows the added benefit
et al. of using
[25] also a bimetallic
synthesized complexaluminium
trimetallic that is veryscorpionate
high active
over
(Figuremonometallic
7c) by addingcomplex catalysts. to
trialkylaluminium However
the oxygenchanging
atom ofthis
the from a large
previous alkylcomplex.
bimetallic group
(R=CH(Ph)Me; X=Et) to a simple aryl group (R=Ph; X=Me) resulted in a significant decrease
On the basis of Table 1, all trimetallics provide complete conversion of SO with 97.3% yield of styrene in
catalytic
carbonate,activity, R = (S)-CH(Ph)Me;
exceptwhich X =the
is also lower than Meactivity
given 92%of the monometallic
conversion complex.
and 90.2% yieldThis
at is
10critically
bar and
due
roomtotemperature
the nature of forthe
24subtituted
h. Among group attached
trimetallic to thecomplexes,
non-salen only R =atom.
enamine nitrogen Ph; X = Me can maintain
the highest catalytic activity of 97.3% yield of styrene carbonate when the CO2 opearting pressure
decreases to 1 bar.
Another example is trimetallic amine-bis(benzotriazole phenolate) complexes with Ni(II), Co(II),
and Zn (II) metal centers [26]. Trimetallic-nickel, trimetallic-cobalt, and trimetallic-zinc achieved
conversion of 43%, 67%, and 91%. All the catalysts displayed the same trend of catalytic systems, for
which TBAB gave better conversion as a co-catalyst than TBAI. A reasonable explanation for TBAB as
a better co-catalyst for the cycloaddition of CO2 with CHO might be attributed to the balance between
nucleophilicity and leaving ability of the bromide anion.
3.2. Heterogeneous Catalyst

Various heterogeneous catalysts have been developed for the past few decades. The high demand
for heterogeneous catalysts is due to the simple separation process [30]. In addition, the advantages
of heterogeneous catalyst employment is their high recyclability and recovery of the product and
catalyst [5]. However, due to their relatively low catalytic activity, most heterogeneous catalytic systems
Processes 2020, 8, 548 11 of 22
must be applied under the conditions of high temperature and high pressure or in the presence of
a solvent and/or co-catalyst.
3.2.1. Supported Catalyst

A wide range of heterogeneous catalysts have been created, with the active sites being immobilized
on various types of support, for example, ionic liquid grafted on polymer matrix [35,36], imidazolium
derivatives functionalized on MCM-41 (Mobil Composition of Matter No. 41) silica-based materials [37],
or triazolium-based ionic liquids on SBA-15 (Santa Barbara Amorphous-15) [38]. Normally, the
covelent immobilization/functionalization is robust and can prevent the leaching of active species from
the support.
Supported Ionic Liquid

Han et al. [39] synthesized highly cross-linked poly(N-vinylimidazole-co-divinylbenzene) (PVIm)
beads with grafted ILs. By varying molar ratio of divinylbenzene to N-vinylimidazole, various pore
sizes could be obtained and the highest IL immobilization of 0.92 mmol/g could be achieved. This
study used several alkyl halides that covalently anchored on the PVIm surfaces to obtain variation of
ILs-grafted porous polymer beads (PVIm2-RX). However, the author extensively studied PVIm grafted
with N-butyl bromide (BuBr) by varied reaction parameters. The effect of temperature (90, 100, and
110 ◦ C) on conversion of allyl glycidyl ether (AGE) showed increasing conversion of 49%, 60%, and
65%, respectively (Table 2). For the effect of pressures on catalytic activity at pressures of 8.6, 13.4, 16.2,
and 18.2 bar, AGE conversion increased to 65%, 855, 94%, and 98%, respectively. PVIm-BuBr exhibited
a good reusability with almost constant yield for five consecutive runs.
Table 2. Supported catalysts for cycloaddition of CO2 to epoxides.

Epoxide Catalyst Cocatalyst Reusability Ref.
(◦ C) (bar) (h) (%) (%)
- 90 8.6 6 48.02 49
- 100 8.6 6 58.8 60
- 110 8.6 6 64.35 65 5 times, drop
AGE PVIm2-BuBr slightly after [39]
- 110 13.4 6 84.15 85 fourth run
- 110 16.2 6 93.06 94
- 110 18.2 6 97.02 98
Bimetallic salen-merrifield
100%, 94%,
resin - 26 1 20 100 -
74%, 70%
(single TBAB)
[40]
Bimetallic salen-merrifield
79%, 71%, 67%,
resin - 26 1 20 79 -
64%
SO (four TBAB)
Bimetallic salen-silica
- 26 1 24 86 -
supported(R = t-butyl)
Bimetallic - [41]
salen-aluminium pillared - 26 1 24 21 -
clay (R = t-butyl)
TBAB 25 5 48 92.83 96.3 -
TBAB 50 1 7 74.28 75.8 -
MgFeAl-LDH
ECH TBAB 50 5 7 96.04 98.0 - [42]
- 50 5 7 7.39 7.6 -
- - 50 5 7 16.6 17.0 -
Supported Bimetal–Organic Salen Complexes

Although homogeneous catalysts such as Co(III) and Al(III) salen complexes show an effective
catalytic system, it displays poor separation and low recyclability [17]. Thus, North et al. [40] attempted
Processes 2020, 8, 548 12 of 22
to immobilize bimetallic salen catalysts that can undergo reaction under mild conditions, deeming
them as potential catalysts that can be utilized for continuous flow system as packed-bed reactor.
This advancement of heterogeneous of bimetal–organic complexes catalysts enables the recovery of
catalysts as an essential approach due their relatively high molecular weight and high production
costs. This work utilized the salen complexes that are able to operate under ambient conditions by
immobilization on Merrifield resin support via a pendant ammonium moiety (tetraalkylammonium
bromide). The recyclability of the catalytic system of bimetallic salen (R1 = t-butyl, R2 = C2 H8,
X = + NEt2 ) (Figure 6c), which consists of a single pendant ammonium moiety showing conversion
SO in yields of 100%, 94%, and 70% upon two runs. The bimetallic salen (R1 = t-butyl, R2 = C2 H8 ,
X = + NEt2 Bn − Br) (Figure 6c) with four quaternary ammonium moieties provided conversion of styrene
oxide in four successive runs with yields of 79%, 73%, 66%, and 60%. In the continuation of their
study, North et al. [41] attempted to change the Merrifield resin with a few types of supports, such
as amorphous silica (Figure 6c), due to the excellent results gained using Merrifield resin-supported
complexes. However, the silica-supported and aluminium-pillared clay only provided 86% and 21%
yields of cyclic carbonate, respectively. In this study, the continuous flow reactor also operated as
a silica-supported thermally stable reactor. The catalyst bimetallic salen (R1 = t-butyl, R2 = C2 H8 ,
X = + NEt2 ) supported on silica (Figure 6c) at 100 ◦ C showed slow deactivation over the first 8 days,
for which it retained 50% conversion, but the restoration by treatment with benzyl bromide provided
original activity of the catalyst.
Trimetallic Layered Double Hydroxide (LDH)

Zhang et al. [42] synthesized trimetallic MgFeAl-LDH from industrial solid wastes of red mud
and ferronickel slag. The acid-extracted solutions of solid waste and exfoliation of the LDH by washing
with acetone resulted in high surface area of MgFeAl-LDH (319 m2 /g) and high CO2 uptake of 70.2 mg/g
at room temperature and atmospheric pressure. The MgFeAL-LDH with TBAB as co-catalyst was
tested for solvent-free CO2 cycloaddition under different pressures. ECH conversion increased from
75.8% to 98% with high selectivity (≈98%) by increasing pressure from 1 to 5 bar. The paper also
studied the effect of conversion toward various epoxides (i.e., ECH, PO, SO, CHO, and AGE) at 50
◦ C and 5 bar after 7 h. The results showed significant conversion and selectivity for all epoxides, for
which epichlorohydrin attained the highest conversion of 98.0% and 98.2% selectivity. To verify the
synergistic effect between Lewis acid sites of MgFeAl-LDH and the bromine nucleophile of TBAB,
MgFeAl-LDH and TBAB were tested separately, giving the ECH conversions of 7.6% and 17.0%,
respectively. The MgFeAl-LDH showed high recyclability, which provided stable ECH conversion no
less than 96% and selectivity around 97% in five consecutive runs.
3.2.2. Metal–Organic Framework

Metal–organic framework (MOF), a combination between metal ions or clusters and interconnected
organic ligands, is expected to be a good candidate of heterogeneous catalysts [43]. The distinctive
features of adjustable structures, large surface area, and coordinated pore surface portray a vital role
in yielding high CO2 sequestration and its effective conversion to valuable products [44,45]. Table 3
summarizes operational conditions for the synthesis of cyclic carbonates using MOFs.
Liu et al. [1] synthesized In2(OH)(btc)(Hbtc)0.4 (L)0.6 ·3H2 O (Figure 8a) with TBAB as cocatalyst.
The catalyst retained excellent recyclability with no significant change within five cycles of reaction.
The catalyst also showed high selectivity toward size and shape of the substrate. PO showed the highest
(77.9%) reactivity among substrates, which was likely caused by sterically hindrance for diffusion onto
the pore of MOF.
There are several researchers who have demonstrated that incorporation of accessible nitrogen
donor sites, such as amine, imidazole, pyridine, tetrazole, or triazole into MOFs can drastically influence
the CO2 sorption capacity and selectivity on account of dipole–quadrupole interactions between the
CO2 molecule and the accessible nitrogen site [46–50].
Processes 2020, 8, 548 13 of 22
Table 3. Metal organic framework (MOF) catalysts for cycloaddition of CO2 to epoxides.
MOF Active Site T (◦ C) P (bar) Time (h) Epoxide Yield (%) Conv. (%) TOF Reusability Ref.
PO 77.9 - 7.1
5 times
In2 (OH)(btc)(Hbtc)0.4 (L)0.6 ·3H2 O Metal RT 1.01 48 BO 60.1 - 5.4 [1]
(almost constant)
SO 31.6 - 2.9
Metal and RT 1.01 48 84.15 85 - 5 times

{[Co(BDC)(L)]·2H2 O·xG}n SEO [44]
pyridine 40 1.01 24 98.01 99 - (almost constant)
PO 96 - -
Metal and BO 85 - - (96%, 96%, 95%,
{Cu2 [(C20 H12 N2 O2 )(COO)5 ]}n RT 1.01 48 [43]
acylamide ECH 88 - - 95%, 95%)
Octene oxide 10 - -
PO 96 - 200
Metal and (96%, 96%, 96%,
{Cu4 [(C57 H32 N12 )(COO)8 ]}n RT 1.01 48 BO 83 - 172.9 [45]
triazole 95%, 95%)
ECH 85 - 177
Parmar et al. [44] synthesized [Co(BDC)(L)·2H2O]·xG}n or CoMOF-2 (Figure 8b) with nitrogen-
rich pyridine as basic site. They demonstrated an excellent catalytic activity of CoMOF-2 and KI as
binary catalyst in epoxide−CO2 cycloaddition. SEO conversion of 85% was obtained at room
temperature for 48 h. In addition, 99% conversions were achieved within 24 h, with increasing
temperature
Processes to 40 °C. The recyclability remained constant with 99% conversion and yield through
2020, 8, 548 14 of 22
five successive cycles.
(a) (b) (c) (d)

Figure8.8.The
Figure The3D 3Dstructure
structureofofMOFs:MOFs:(a)(a)InIn 2(OH)(btc)(Hbtc)0.4(L)0.6·3H2O (reprinted with permission
2 (OH)(btc)(Hbtc)0.4 (L)0.6 ·3H2 O (reprinted with permission
fromLiu,
from Liu,L.;
L.;Wang,
Wang,S.M.; S.M.;Han,
Han,Z.B.;Z.B.;Ding,
Ding,M.;M.;Yuan,
Yuan,D.Q.;
D.Q.;Jiang,
Jiang,H.L.
H.L.Exceptionally
ExceptionallyRobust RobustIn-Based
In-Based
Metal-Organic Framework for Highly Efficient Carbon Dioxide Capture
Metal-Organic Framework for Highly Efficient Carbon Dioxide Capture and Conversion. Inorg. Chem. and Conversion. Inorg. Chem.
2016, 55, 3558–3565. Copyright (2016) American Chemical Society.);
2016, 55, 3558–3565. Copyright (2016) American Chemical Society.); (b) {[Co(BDC)(L)]·2H2 O·xG} (b) {[Co(BDC)(L)]· 2H 2 O·xG}nn
(CoMOF-2) (reprinted
(CoMOF-2) (reprinted with with permission
permissionfrom fromParmar,
Parmar,B.;B.;Patel,
Patel,P.;P.;
Pillai, R.S.;
Pillai, Tak,Tak,
R.S.; R.K.;R.K.;
Kureshy,
Kureshy,R.I.;
Khan,
R.I.; N.H.;
Khan, Suresh,
N.H.; E. Cycloaddition
Suresh, E. Cycloaddition of COof 2 with
CO2 an Epoxide-Bearing
with an Epoxide-Bearing Oxindole Scaffold
Oxindole by a Metal–
Scaffold by a
Organic Framework-Based
Metal–Organic Framework-Based Heterogeneous
HeterogeneousCatalystCatalyst
under Ambient Conditions.
under Ambient Inorg. Chem.
Conditions. Inorg. 2019, 58,
Chem.
2019, 58, 10084–10096. Copyright (2019) American Chemical Society.); (c) {Cu2 [(C20 H12 N2 O2 )(COO)4 ]}]}nn
10084–10096. Copyright (2019) American Chemical Society.); (c) {Cu 2 [(C 20 H12 N2 O 2 )(COO) 4
(reprinted with
(reprinted with permission
permission from from Li, Li, P.Z.;
P.Z.; Wang,
Wang,X.J.;
X.J.; Liu,
Liu, J.;
J.; Phang,
Phang, H.S.;
H.S.; Li,
Li, Y.;
Y.; Zhao,
Zhao, Y. Y. Highly
Highly
EffectiveCarbon
Effective CarbonFixation
Fixationviavia Catalytic
Catalytic Conversion
Conversion of COof CO
2 by an by an Acylamide-Containing
2 Acylamide-Containing Metal-OrganicMetal-
Organic Framework.
Framework. Chem. Mater.Chem. Mater.
2017,2017, 29, 9256–9261.
29, 9256–9261. Copyright
Copyright (2017)American
(2017) AmericanChemical
Chemical Society.);
Society.);
(d){Cu
(d) {Cu44[(C
[(C57 32N
57H32 N1212)(COO)
)(COO)8]}8 ]}
nn (reprinted
(reprintedwithwithpermission
permissionfrom fromLi, Li,P.Z.;
P.Z.; Wang,
Wang, X.J.; Liu, J.; Lim, Lim, J.S.;
J.S.;
Zou,R.;
Zou, R.;Zhao,
Zhao,Y. AY.Triazole-Containing
A Triazole-Containing Metal-Organic
Metal-Organic FrameworkFramework as aEffective
as a Highly Highly andEffective and
Substrate
Substrate Size-Dependent
Size-Dependent Catalyst for CO Catalyst for CO2J.Conversion.
2 Conversion. Am. Chem. Soc. J. Am.
2016,Chem. Soc. 2016,Copyright
138, 2142–2145. 138, 2142–2145.
(2016)
CopyrightChemical
American (2016) American
Society.).Chemical Society.).
Parmar
Li et al. et al. [44]synthesized
[43] synthesized [Co(BDC)(L)·2H O]·xG}n4]or(Figure
Cu2[(C20H12N2O22)(COO) CoMOF-2 (Figure
8c), which8b)incorporated
with nitrogen-richboth
pyridine as basic site. They demonstrated an excellent catalytic activity
accessible nitrogen-rich acylamide groups and exposed Cu metal sites expressing a high CO2 of CoMOF-2 and KI as binary
catalyst
adsorption in epoxide−CO
capability. The 2 cycloaddition.
results showed SEO96%
conversion of 85%oxide,
for propylene was obtained
85% for at room temperature
butylene oxide, 88% for for
48 h. In addition, 99% conversions ◦ C.
epichlorohydrin, and 10% 1-octenewere
oxide achieved within 24 h,
(1,2-epoxyoctane) onwith increasing at
cycloaddition temperature
1.01 bar of to CO402 and
The
room recyclability
temperature, remained
which constant with 99%
demonstrated highconversion
selectivityand yield size
toward throughand five
shape successive cycles.The
of substrate.
catalystLi et displayed
al. [43] synthesized Cu2 [(C20of
slight decrease H12 N2 O2 )(COO)
conversion ] (Figure 8c),oxide
of 4propylene whichafter
incorporated
second run bothwithin
accessible
five
nitrogen-rich
cycles. acylamide groups and exposed Cu metal sites expressing a high CO 2 adsorption capability.
The results
Li et al.showed 96% for
[45] utilized a propylene
highly porous oxide, 85% for butylene
triazole-based MOF,oxide,
Cu4[(C88% for
57H32 N12epichlorohydrin,
)(COO)8] (Figure and 8d),
10%
which 1-octene
showed oxidehigh(1,2-epoxyoctane)
activity towardsonsize- cycloaddition at 1.01 bar of
and shape-selective CO2 andofroom
synthesis temperature,
carbonates. MOF
which demonstrated
incorporating high selectivity
both unsaturated metaltoward sizeaccessible
sites and and shapenitrogen-rich
of substrate. triazole
The catalyst
unitsdisplayed
exhibited aslight
high
decrease of conversion
affinity towards CO2. Theof propylene oxide after
MOF exhibited high second
catalytic run within five
selectivity cycles.epoxide substrate—96%
to small
Li et al. [45]
for propylene utilized
oxide, 83%afor highly porous
butylene triazole-based
oxide, and 85% for MOF, Cu4 [(C57 H32 N
epichlorohydrin, 12 )(COO)
with a very8 ]low
(Figure
yield8d),
for
which showed high activity towards size- and shape-selective synthesis of carbonates.
large epoxide substrate. The catalyst displayed slight (≈1%) decrease of conversion after the third run MOF incorporating
both
within unsaturated
five cycles. metal
On thesitesbasis
and of
accessible nitrogen-rich
this observation, MOF triazole units exhibited
is an effective catalystaforhighCO affinity towards
2 cycloaddition
CO .
reaction,
2 The MOF exhibited high catalytic selectivity to
specifically in terms of recyclability and selectivity.small epoxide substrate—96% for propylene oxide,
83% for butylene oxide, and 85% for epichlorohydrin, with a very low yield for large epoxide substrate.
4. Sustainable
The Epoxide
catalyst displayed Sources
slight (≈1%)for Cycloaddition
decrease Reaction
of conversion after the third run within five cycles. On the
basis of this observation, MOF is an effective catalyst for CO2 cycloaddition reaction, specifically in terms
Ethylene oxide and propylene oxide are the most employed epoxides at the industrial scale for
of recyclability and selectivity.
CO2/epoxide coupling synthesis. Epoxides are still mainly derived from petrochemical feedstock
4.such as ethylene
Sustainable and propylene,
Epoxide Sources forandCycloaddition
increasing interest has focused on developing bio-based routes
Reaction
Ethylene oxide and propylene oxide are the most employed epoxides at the industrial scale for
CO2 /epoxide coupling synthesis. Epoxides are still mainly derived from petrochemical feedstock
such as ethylene and propylene, and increasing interest has focused on developing bio-based routes
to produce these two compounds. On the basis of three platforms of biomass feedstock, including
Processes 2020, 8, 548 15 of 22
(1) amorphous sugar (e.g., molasse, starch), (2) lipids (e.g., vegetable oils), and (3) lignocellulosic
biomass (the non-edible portion of biomass, e.g., bagasse, rice husk) and their current technologies,
a green pathway for the generation of sustainable ethylene, propylene, and butylene have been
proposed, as illustrated in Figure 9. Bio-based ethylene can be produced via the dehydration of
ethanol [51] or via the cracking of renewable naphtha [52]. The bio-ethylene production from
bioethanol, which is derived from fermentation of amorphous sugar, is an established method in
polymer manufacturing and has been extensively used for polyethylene glycol production. Several
industrial plants producing bio-ethylene through the dehydration of bioethanol have been established
in China, India, and Brazil [53].
Ethanol or higher alcohols such as butanol can also be produced from lignocellulosic biomass via
two main pathways. For the first pathway, pretreatment to breakdown the lignocellulosic structure and
hydrolysis for converting to sugar are necessary before fermentation. Another pathway is gasification
to produce syngas (as called ‘bio-based syngas’), and then further fermentation of the syngas to ethanol
or a higher alcohol. Moreover, the bio-based syngas can be utilized to produce methanol which be
converted to ethylene, propylene, and/or butylene via methanol-to-olefins (MTO) technology. Butylene
can be produced from dehydration of butanol. Optionally, butylene can be subsequently reacted to
with ethylene to produce propylene via meta-thesis.
For the lipid platform, transesterification of vegetable oil or animal fat for biodiesel production
produces glycerol as a by-product, which can be converted to propylene by hydrodeoxygenation [54].
Moreover, the bio-hydrotreated diesel production yields propane as a by-product, which can produce
propylene via dehydrogenation of propane. The direct catalytic cracking of lipids (plant-based oil)
may also produce propylene [55].
In addition, aside from ethylene oxide and propylene oxide, other types of epoxide can be
produced from bio-waste, such as limonene oxide and limonene dioxide, which can be synthesized
via the promising epoxidation of biomass waste limonene, such as citrus peels, oak, and pine tree,
under solvent-free conditions with hydrogen peroxide and a tungsten-based catalyst [56]. Moreover,
triglycerides and fatty acids from vegetable oils and their derivative esters contain a double bond
(Figure 10) that can undergo epoxidation with H2 O2 . The epoxide product can be subsequently
used as the precursor for cycloaddition reaction with CO2 [57,58]. Figure 10 shows an example of
reactions between hydrogen peroxide and methyl oleate (Figure 10; R = CH3 ) or oleic acid (Figure 10;
R = H) to produce epoxidized methyl oleate or epoxidized oleic acid. However, it is worth noting that
epoxidation is a highly exothermic reaction (as ∆H = −55 kcal/mol for each double bond), thus H2 O2 is
slowly added or added by a stepwise manner in semi-batch operations, and requires a long reaction
time. In order to avoid heat and mass transfer limitation, process intensification using a microreactor
has been proposed by applying a novel TiO2 coated-wall microcapillary reactor [59]. The microreactor
could decrease the reaction time from several hours to a few minutes with higher product selectivity.
Processes 2020, 8, 548 16 of 22
Figure 9. Possible pathways for generation of sustainable ethylene, propylene, and butylene as epoxide precursors.
Figure 9. Possible pathways for generation of sustainable ethylene, propylene, and butylene as epoxide precursors.
produce epoxidized methyl oleate or epoxidized oleic acid. However, it is worth noting that
epoxidation is a highly exothermic reaction (as H = −55 kcal/mol for each double bond), thus H2O2
is slowly added or added by a stepwise manner in semi-batch operations, and requires a long reaction
time. In order to avoid heat and mass transfer limitation, process intensification using a microreactor
has been proposed by applying a novel TiO2 coated-wall microcapillary reactor [59]. The microreactor
Processes 2020, 8, 548 17 of 22
could decrease the reaction time from several hours to a few minutes with higher product selectivity.
Figure10.
Figure 10.Synthesis
Synthesisofofepoxidized
epoxidizedmethyl
methyloleate = CH33)) and
oleate(R(R=CH and epoxidized
epoxidized oleic
oleic acid (R = H).
acid (R=H).
The two-step
The two-stepprocess process synthesis
synthesisof epichlorohydrin
of epichlorohydrin from from
bio-based glycerolglycerol
bio-based (Dow’s GTE (Dow’s(glycerol
GTE
(glycerol to epichlorohydrin) process) has been industrialized, producing 100 kilotons per year, anda
to epichlorohydrin) process) has been industrialized, producing 100 kilotons per year, and has
notably
has more more
a notably sustainable impact
sustainable in its in
impact technology whenwhen
its technology compared with with
compared the fossil-based routeroute
the fossil-based [60].
Epichlorohydrin is used as the precursor in CO cycloaddition reaction
[60]. Epichlorohydrin is used as the precursor in CO2 cycloaddition reaction and also to prepare
2 and also to prepare glycidyl
ether-type
glycidyl epoxides, epoxides,
ether-type which are frequently
which are used as monomers
frequently used asformonomers
polymerization reaction [61]. As
for polymerization shown
reaction
in Figure
[61]. 11, theinreaction
As shown Figure 11, consists of chlorination
the reaction consists ofof liquid glycerol
chlorination of with
liquid HCl gas, inwith
glycerol the existence
HCl gas, in of
a catalyst, typically an organic carboxylic acid [62]. Next, the reaction induces
the existence of a catalyst, typically an organic carboxylic acid [62]. Next, the reaction induces ring ring closure, which
produceswhich
closure, the epoxide,
produceswhere theanepoxide,
inorganicwherebase such as sodiumbase
an inorganic hydroxide
such or as potassium hydroxideor
sodium hydroxide is
added andhydroxide
Processes
potassium 2020, chloride salt
8, x FOR PEER is obtained
REVIEW
is added as a co-product
and chloride [63]. However,
salt is obtained the use[63].
as a co-product of hydrochloric
However, theacid 18 ofas
use of22
chloride source causes the process to be not fully sustainable [62]. Vitiello et al.
hydrochloric acid as chloride source causes the process to be not fully sustainable [62]. Vitiello et al. [64] used acyl chloride
as awell
as as thefor
catalyst fact
thethat
GTEit process,
also can finding
be used aashigher
a reactant to substitute
activity HCl. The
than carboxylic acid,reaction
asthan of
asglycerol
wellcarboxylic and
the factacid,
that
[64] used acyl chloride as a catalyst for the GTE process, finding a higher activity
acyl chloride provide in situ HCl, for which hydrochlorination can occur,
it also can be used as a reactant to substitute HCl. The reaction of glycerol and acyl chloride provide being stoichiometrically
sufficient.
in situ HCl,
Processes
In x; addition,
2020, 8,for which
doi:
carboxylic acid is formed
FOR hydrochlorination
PEER REVIEW can occur,as abeing
reaction by-product,
stoichiometrically which can beInseparated,
sufficient. addition,
www.mdpi.com/journal/processes
purified, and sent back to the acyl chloride supplier to again synthesize
carboxylic acid is formed as a reaction by-product, which can be separated, purified, and sent back the corresponding acyl
to
chloride. Although bio-based resources were considered as decent alternatives,
the acyl chloride supplier to again synthesize the corresponding acyl chloride. Although bio-based the biggest challenge
of this alternative
resources were consideredwas signified
as decent byalternatives,
the cost and theavailability, whichofshould
biggest challenge fulfil thewas
this alternative anticipated
signified
demand of the cyclic or polymeric carbonate products.
by the cost and availability, which should fulfil the anticipated demand of the cyclic or polymeric
carbonate products.
Figure 11. The reaction of glycerol to epichlorohydrin (GTE process).

Figure 11. The reaction of glycerol to epichlorohydrin (GTE process).
5. Potential Enhancement of Cycloaddition Reaction
5. Potential Enhancement of Cycloaddition Reaction
In spite of the increments of bio-based epoxide usage in synthetizing CO2 -based cyclic and
In spite
polymeric of the increments
carbonates, of bio-based
the poisonous epoxide
characteristics of usage in synthetizing
epoxides CO2[65].
is still a concern -basedThiscyclic and
one-pot
polymeric would
approach carbonates, the poisonous
be profitable bothcharacteristics
from the viewpointof epoxides is still a concern
of supportability [65].
and of This one-pot
mechanical
approach would be profitable both from the viewpoint of supportability
appropriateness, as dodging the filtration and dealing with epoxides would result in a low risk and of mechanical
appropriateness,
and expenditure.asThisdodging the needs
strategy filtration and dealingcatalytic
a bifunctional with epoxides would
framework resultainone-component
(either a low risk and
expenditure.
framework Thisisolated
or two strategy needs a bifunctional
non-interfering catalytic
catalysts) capable frameworkboth
of advancing (either a one-component
the oxidation of double
framework or two isolated non-interfering catalysts) capable of advancing both
bond to epoxides and the consequent cycloaddition reaction with CO2 to produce cyclic carbonates, forthe oxidation of
double bond
instance, to epoxides
synthetizing and carbonates
the cyclic the consequent
from thecycloaddition
alkene, which reaction withpathway
is a general CO 2 to produce cyclic
of synthetizing
carbonates,Atfor
epoxides. theinstance, synthetizing
present time, there havethe been
cyclicfewcarbonates from the alkene,
studies conducted which
on the basis of is
thea one-pot
general
pathway[66,67].
strategy of synthetizing
A recentepoxides. At theetpresent
study of Engle al. [66]time,
statedthere
thathave beenchallenge
the main few studiesof conducted on the
one-pot pathway
basis of the one-pot strategy [66,67]. A recent study of Engle et al. [66] stated that the main challenge
of one-pot pathway to synthesize cyclic carbonate is in integrating the epoxidation and cycloaddition
reaction of CO2, because a common catalyst used for a cycloaddition reaction such as TBAB
deactivates a catalyst used for epoxidation reaction.
The advancement of this cycloaddition reaction provides insight into utilizing CO2 directly from
Processes 2020, 8, 548 18 of 22
to synthesize cyclic carbonate is in integrating the epoxidation and cycloaddition reaction of CO2 ,
because a common catalyst used for a cycloaddition reaction such as TBAB deactivates a catalyst used
for epoxidation reaction.
The advancement of this cycloaddition reaction provides insight into utilizing CO2 directly from
waste source CO2 such as flue gas [18]. The perspective of utilizing a waste source of carbon dioxide
used for the reaction with epoxides has received more attention recently in the industrial production of
cyclic and polymeric carbonate. In reality, the objective of this novel reaction is to utilize industrial
sources of CO2 , which comprises impurities such as hydrogen sulfide, carbon monoxide, sulfur oxide,
nitrogen oxide, and water [65]. These compounds theoretically would impact the catalyst activity
due to catalyst poisoning. In the perspective of the industrial use for novel catalytic application
in CO2 /epoxide coupling to produce either cyclic or polymeric carbonates, there should be more
upcoming research investigating the effect of carbon dioxide purity on catalyst performance. This
endorses the viability of this reaction as pathway by employing waste CO2 as precursor.
6. Conclusions
The cycloaddition of CO2 with epoxides is a sustainable pathway for the fixation of CO2
into valuable products, considering the industrial applications of cyclic and polymeric carbonates.
The development of homogeneous and heterogeneous catalysts, including homogeneous organocatalyst
(e.g., organic salt, ionic liquid, deep eutectic solvents), metal salts, organometallic (e.g., mono-, bi-,
and tri-metal salen complexes and non-salen complexes) and heterogeneous supported catalysts,
and metal organic framework for this reaction will enable the reaction of CO2 with many types of
epoxides. Under their catalytic systems, all classes of these catalysts from recent development can
exhibit CO2 cycloaddition to cyclic carbonates at CO2 pressures of 1 bar and reaction temperatures less
than around 50 ◦ C. However, these conditions usually satisfy only terminal epoxide substrates while
are still challenging for internal epoxide substrates. This includes renewable terminal epoxides such as
unsaturated fatty acid esters termed as oleochemical carbonates. The utilization of bio-based epoxides
derived from renewable sources also improves reaction sustainability. There are only a few industrial
bio-based epoxides that have been widely produced, for instance, reaction of glycerol to epichlorohydrin
by Dow and Solvay. The proposed green pathway for the generation of sustainable epoxide precursors
from biomass feedstock could fulfil the implementation of the biorefinery concept. Although bio-based
resources are considered as the decent alternative, the major challenge lies in the cost and availability
that should fulfil the desired market size for the demand for cyclic or polymeric carbonate products.
Apart from what was mentioned above, the one-pot strategy combining epoxidation and cycloaddition
may offer several advantages, especially for the process and cost sustainability of the pathway.
The direct conversion enables a safer way in the handling of epoxides, which are extremely flammable,
toxic, and corrosive, while increasing the efficiency of the process. However, the reaction needs a robust
multi-functional catalyst to promote epoxidation and cycloaddition with CO2 . In order to minimize
the energy penalty for CO2 capture and storage, utilization of CO2 directly from a waste source such
as flue gas is of interest; however, the limitations of CO2 concentration and the presence of reactive
impurities are a challenge. Lastly, CCU cannot mitigate the enormous amount of CO2 emissions,
however, CO2 cycloaddition can be seen as a reasonably competent alternative to CO2 transformation,
offsetting the high value-added nature by extending material use defer CO2 back to the atmosphere
when compared to commodities and fuels such as urea, methanol, and methane.
Author Contributions: Conceptualization, K.K., M.A.A.M.S., and W.K.; writing—original draft preparation,
M.A.A.M.S.; writing—review and editing, K.K., W.K., J.W.L., P.L.S., and S.A.; supervision, W.K.; project
administration, M.K.L.; funding acquisition, K.K. All authors have read and agreed to the published version of
the manuscript.
Funding: This research was funded by the Thailand Research Fund (TRF) and Office of the Higher Education
Commission (grant no. MRG6180262), and King Mongkut’s Institute of Technology Ladkrabang (KMITL) (grant
no. KREF046209).
Processes 2020, 8, 548 19 of 22
Acknowledgments: Financial support provided by the Thailand Research Fund (TRF) and Office of the Higher
Education Commission (grant no. MRG6180262), and King Mongkut’s Institute of Technology Ladkrabang,
KMITL (grant no. KREF046209) is gratefully acknowledged. W. Kiatkittipong and S. Assabumrungrat would also
like to acknowledge the support from the “Research Chair Grant” National Science and Technology Development
Agency (NSTDA). The authors thank Peerawat Wongsurakul for his assistance.
Conflicts of Interest: The authors declare no conflict of interest.
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Figure 1. The approaches to utilize carbon dioxide.

(a) (b) (c) (d)

(e) (f) (g)

Figure Figure 5 displays

3.1. Homogeneous Catalyst

3.1. Homogeneous Catalyst

T P Time Yield Conv.

T P Time Yield Conv.

3.1.2. Metal Salt

3.1.3. Metallic Salen Complex

Monometallic Salen Complex

Bimetallic Salen Complexes

3.1.4. Metallic Non-Salen-Based Complexes

Monometallic Non-Salen-Based Complexes

(a) (b) (c)

3.2. Heterogeneous Catalyst

3.2.1. Supported Catalyst

Supported Ionic Liquid

Table 2. Supported catalysts for cycloaddition of CO2 to epoxides.

T P Time Yield Conv.

Supported Bimetal–Organic Salen Complexes

Trimetallic Layered Double Hydroxide (LDH)

3.2.2. Metal–Organic Framework

Metal and RT 1.01 48 84.15 85 - 5 times

(a) (b) (c) (d)

Figure 11. The reaction of glycerol to epichlorohydrin (GTE process).

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