Efficient catalytic conversion of terminal/internal epoxides to cyclic carbonates by porous Co(ii) MOF under ambient conditions: Structure-property correlation and computational studies

Article abstract of DOI:10.1039/c8ta10631b

A mixed ligand three-dimensional neutral porous framework, {[Co(OBA)(L)]xG}_n (CoMOF-1) (H₂OBA = 4,4′-oxybis(benzoic acid); L = (E)-N′-(pyridin-4-ylmethylene)isonicotinohydrazide; G = DMF, EtOH, MeOH, H₂O), was successfully synthesized via a hydrothermal and reflux method. The activated MOF (CoMOF-1′) not only showed good affinity toward CO₂ molecules, but also exhibited a good catalytic performance for CO₂ conversion with a variety of terminal and internal epoxides. Grand Canonical Monte Carlo (GCMC) simulation proved the strong interactions of CO₂ molecules with the amide functional groups of the MOF. The Lewis acidity of the Co(ii) centers endowed by the weakly chelated carboxylate from the OBA ligand and Lewis basicity originating from the acylamide functionality of the pyridyl-based Schiff base ligand L favored the efficient solvent-free cycloaddition reaction of CO₂ with different epoxides. Strikingly, CoMOF-1′ exhibited good catalytic efficiency for CO₂ coupled with various terminal epoxides at ambient temperature and pressure (1 bar, 60 °C, 12 h) and with a variety of internal epoxides at moderate reaction conditions (30 bar, 100 °C, and 8 h) with good yield and recyclability. Further, the binary heterogeneous catalyst showed good chemical stability, easy separation and recyclability (6 cycles) without a noticeable decrease in activity. To the best of our knowledge, this is the first investigation on a neutral porous MOF as a potential heterogeneous solvent-free catalyst toward CO₂ utilization for internal epoxide under moderate reaction conditions. Based on the structural evidence, a plausible mechanism for the cycloaddition reaction was proposed, which is further reinforced by the relative energy of each stage obtained from periodic Density Functional Theory (DFT) calculations.

Full text of DOI:10.1039/c8ta10631b

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Kun Chang, Zhaorong Chang et al.
Bubble-template-assisted synthesis of hollow fullerene-like
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ARTICLE
Efficient Catalytic Conversion of Terminal/ Internal Epoxides to
Cyclic Carbonates by Porous Co(II) MOF at Ambient Conditions:
Structure Property Correlation and Computational Studies
Received 00th January 20xx,
Accepted 00th January 20xx
Bhavesh Parmar,a,b Parth Patel,c,d Renjith S. Pillai,e Rukhsana I. Kureshy,b,c,d Noor-ul H. Khan,b,c,d and
Eringathodi Suresh*a,b
DOI: 10.1039/x0xx00000x
www.rsc.org/
Mixed ligand three-dimensional neutral porous framework {[Co(OBA)(L)]·xG}n (CoMOF-1) (H2OBA = 4,4′-Oxybis(benzoic
acid); L = (E)-N'-(pyridin-4-ylmethylene) isonicotinohydrazide; G = DMF, EtOH, MeOH, H2O) has been successfully synthesized
by hydrothermal and reflux method. Activated MOF (CoMOF-1′) not only showed good affinity toward CO2 molecules, but
also disclosed good catalytic performance for CO2 conversion with variety of terminal and internal epoxides. Grand Canonical
Monte Carlo (GCMC) simulation proved the strong interactions of CO2 molecules with the amide functional groups of MOF.
Lewis acidity of Co(II) centers endowed by weakly chelated carboxylate from OBA ligand and Lewis basicity originated from
the acylamide functionality of the pyridyl based Schiff base ligand L favors efficient solvent free cycloaddition reaction of
CO2 with different epoxides. Strikingly, CoMOF-1′ exhibits good catalytic efficiency for CO2 coupled with various terminal
epoxide at ambient temperature and pressure (1 bar, 60 C, 12 h) and with variety of internal epoxides at moderate reaction
condition (30 bar, 100C, 8 h) with good yield and recyclability. Further, the binary heterogeneous catalyst showed good
chemical stability, easy separation and recyclability (6 cycles) without noticeable decrease in activity. To the best of our
knowledge, the present investigation is the first neutral porous MOF as a potential heterogeneous solvent-free catalyst
toward CO2 utilization for internal epoxide under moderate reaction parameters. Based on the structural evidence, plausible
mechanism for the cycloaddition reaction is proposed and further reinforced by the relative energy of each stages obtained
from periodic Density Functional Theory (DFT) calculations.
low-cost resource of carbon feedstock.4-9 The resulted cyclic
carbonates can be used as valuable chemicals and finds
applications such as intermediates as electrolyte components in
Lithium ion battery, petroleum products, methanol/diol
synthesis and in pharmaceuticals.10-21 By this strategy not only
the emitted CO2 can be recycled for a better and cleaner
environment but also decrease our dependence on
petrochemicals.
Metal-Organic Frameworks (MOFs) are new class of crystalline
materials composed of metal or metal cluster nodes bridged by
organic linkers in a 3-D arrangement possessing good surface
areas and pore volumes. The unique structural features, such as
ultrahigh porosity, tunable pore size and surface area as well as
adaptable surface property support the MOFs for their versatile
applications in adsorption, separation, drug delivery,
biomedical applications, sensing, catalysis, etc.22-35 CO2
mitigation technologies is greatly influenced by the
development of new catalytic materials, where MOF stands as
a potential candidate due to the attributes mentioned above for
CO2 capture and its utilization.36-37 Various types of
homogeneous and heterogeneous catalytic systems have been
developed for the CO2 fixation to cyclic carbonates, which
includes ionic liquids (ILs), metal complexes, porous organic
polymers (POPs), and metal-organic frameworks (MOFs).38-54
Homogeneous catalysts hold excellent catalytic performance
Introduction
Carbon dioxide (CO2) expelled from the power plants has been
referred as one of the leading reason in climate changes
inducing the rise of temperature in the atmosphere, therefore
reduction of CO2 emission is the need of the hour.1-3 An
attractive strategy for addressing the reduction of excess CO2
emission to atmosphere is the chemical conversion of CO2 into
commercially important value-added chemicals such as cyclic as
well as polymeric carbonates by means of catalytic materials in
cycloaddition reaction with epoxides to furnish non-toxic and
a.Analytical and Environmental Science Division and Centralized Instrument Facility,
CSIR-Central Salt and Marine Chemicals Research Institute, G. B. Marg, Bhavnagar-
364 002, India.
b.Academy of Scientific and Innovative Research (AcSIR), CSIR-Central Salt and
Marine Chemicals Research Institute, G. B. Marg, Bhavnagar-364 002, Gujarat,
India.
c. Inorganic Materials and Catalysis Division, CSIR-Central Salt and Marine Chemicals
Research Institute, G. B. Marg, Bhavnagar-364 002, Gujarat, India.
d.Charotar University of Science & Technology, Changa-388 421, Anand, Gujarat,
India.
e. Department of Chemistry, SRM Institute of Science and Technology, Kattankulathur
603203, Tamil Nadu, India.
*E-mail: esuresh@csmcri.res.in; sureshe123@rediffmail.com
Electronic Supplementary Information (ESI) available: [details of any supplementary
information available should be included here]. See DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
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under mild conditions. Nevertheless, due to the difficulties in
catalyst separation and lack of catalyst recyclability limits their
industrial applications. On the other hand, product separation
and catalyst reusability are an added advantage for
heterogeneous catalyst and robust as well as chemically stable
MOF with high CO2 adsorption capacity play an important role
in enhancing the possibility of epoxide-CO2 interaction in
cycloaddition reaction. It is worth mentioning here some of the
celebrated MOF materials developed by different research
groups such as Ni-TPCE,55 Gea-MOF-1,56 ZnGlu,57 Hf-Nu-1000,58
MMPF-9,59 PCN-224(Co),60 MMPF-18,61 MMCF-2,62 Cu4MTTP,63
Zn6(TATAB)4(DABCO)3,64 JUC-100065 for the catalytic conversion
of CO2 to cyclic carbonates. Efficient capture of CO2 by well-
designed MOFs with porosity can lower the reaction pressure,
and MOFs with densely distributed Lewis acid or Lewis base
sites can favor for the activation of CO2 in the cycloaddition
reaction.36 For scaling up the sustainable utilization CO2 to
useful chemicals, development of new materials including
MOFs as a heterogeneous catalyst are vital with better product
yield at ambient reaction condition as well as recycling and
product separation.
Results and discussion
Gas Adsorption Experiment and Computational Correlation
View Article Online
DOI: 10.1039/C8TA10631B
Detailed synthetic procedure, characterization and N2/ CO2
adsorption measurements of activated CoMOF-1 has been
provided in supporting data as section S1. The N2 adsorption
isotherm at 77 K reveals that CoMOF-1′ exhibits type I
adsorption isotherms with slight hysteresis which can be
attributed to the dynamic features and flexibility of the
framework.70-71 As depicted in Figure 1a, steep slope at low P/Po
value with a type I character, indicating microporous nature of
the material and the N2 adsorption at 1 atm and 77 K is ~171
cm3g-1. The Brunauer–Emmett–Teller (BET) surface area was
found to be 438.8 m2g-1, and the average pore diameter was 24
Å. Pore size distribution measured at lower P/P0 values revealed
micropore size in the range 6.89 Å (Figure S8). Moreover, the
CO2 adsorption isotherms measured at 273 K and 298 K reached
around of 52 cm3g-1 (2.34 mmol g-1) and 30 cm3g-1 (1.34 mmol
g-1) respectively at 1 atm further establishes capability of the
CoMOF-1′ material towards the CO2 adsorption. It is worth
mentioning here that the CO2 sorption capacity of CoMOF-1′ is
comparable with porous materials like Zeolitic Imidazolate
frameworks,72-73 activated carbon,74 celebrated MOFs such as
ZIF-95 and ZIF-10075 as well as MOFs with pore wall decorated
by acylamide76-77 or amide78-79 functional groups. The
Clausius−Clapeyron equation is used to extract the isosteric
In continuation of our efforts to develop efficient MOF based
catalyst herein,66-69 we report synthesis, characterization and
crystal structure of a Co(II) based 3D porous dual ligand MOF
({[Co(OBA)(
Oxybis(benzoic acid) (H2OBA) and N-donor Schiff base ligand (
(E)-N'-(pyridin-4-ylmethylene) isonicotinohydrazide)
L)]·xG}n (CoMOF-1)) composed of flexible 4,4′-
L
heat (Qst) for CO2 adsorption in CoMOF-1′
from their
=
corresponding experimental isotherm at 273 K and 298 K. The
isosteric heat (Qst) for CO2 reaches to ~32.0 kJ mol-1, which
indicate that the amide functional groups of L in the framework
are involved in strong interactions with the adsorbed CO2
molecules.
containing polar acylamide functional group and its application
as a heterogeneous catalyst for CO2 capture and conversion.
The present investigation relates to an excellent catalytic
system for the efficient synthesis of cyclic carbonates under
mild reaction conditions, significantly improving the
transformation, carbon footprint, sustainability and facilitating
the conversion of a broad range of both internal and terminal
epoxides. Due to the presence of active Lewis acidic metal sites,
exposed acylamide functional group in
nature of the material, the activated CoMOF-1 material
CoMOF-1′) found to exhibit high CO2 uptake capacity and
L as well as porous
(
showed efficient catalytic activity in cycloaddition reaction. The
catalytic system consists of robust and highly efficient porous
Co(II) based MOF which provides a powerful and versatile tool
for the efficient and sustainable production of a wide range of
cyclic carbonates under mild conditions from a broad range of
internal and terminal epoxides. Interestingly, CoMOF-1′ catalyst
found to be robust and stable in solution/solid state including
acidic/basic medium and act as an excellent heterogeneous
catalyst for fixation of CO2 with different pool of internal
epoxide to form cyclic carbonates at ambient reaction condition
to value added chemicals. To the best of our knowledge
CoMOF-1′ is one of the most efficient and robust MOF based
heterogeneous catalyst for cycloaddition of internal epoxides
with CO2 reported so far with good recyclability. Grand
Canonical Monte Carlo (GCMC) molecular simulation studies
revealed preferable adsorption sites for the CO2 with CoMOF-
1′. Plausible reaction mechanism for the catalytic activity and
the computational studies to validate the mechanistic aspects is
also discussed.
Figure 1. (a) N2 adsorption isotherm of CoMOF-1′ at 77 K; (b) CO2 adsorption curve for
CoMOF-1′ measured at 273 K and 298 K; (c) Local views of the snapshots extracted from
the GCMC simulations for CO2 in CoMOF-1′ at 1 bar and 298 K. The interacting distances
are reported in Å (Gray, carbon; blue, nitrogen; white, hydrogen; red, oxygen; green,
cobalt).
2 | J. Name., 2012, 00, 1-3
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,ViLewaAnrtdicleCOon(liInIe)
In an attempt to understand the preferable adsorption sites of inversion involving one molecule each of OBA
CoMOF-1′ to the CO2 gas
the Grand Canonical Monte Carlo cation. The hexa-coordination of each meDtaOlI:in10t.1h0e39d/iCm8eTAri1c06u3n1iBt
,
(GCMC) simulations have been conducted and the details of the is composed of four carboxylate oxygens from three different
simulations studies are provided in the supporting information OBA ligand generating a distorted square base and the axial
(S2). The GCMC simulations predicted the trend of coordination from two different Schiff base ligands through the
experimentally observed single component CO2 adsorption pyridyl nitrogen. Among the three different OBA ligands
isotherms in CoMOF-1′ at two different temperatures, i.e. 273 involved as linkers, one is in a chelating mode and the other two
K and 298 K (Figure 1b and S9). Theoretical and experimental link Co(II) metal of the dimeric unit in bridging mode through
surface area (492.2 m2g-1 vs 438.8 m2g-1) obtained for the the carboxylate oxygens. Thus, the carboxylate oxygens of the
CoMOF-1′ showed some variation (~55 m2g-1) which is reflected OBA ligands are involved in chelated and bridging mode of
in slight overestimation (~1.0 mmol g-1) of the simulated CO2 coordination (µ3-1111) generating {Co2(OBA)4}n corrugated
adsorption capacity 3.38 and 2.53 mmol g-1 when compared to grids along bc-plane (Figure 2b). Co(II)···Co(II) distance across
the experimental value 2.33 and 1.36 mmol g-1 at 273 and 298 the dimeric unit is 4.05 Å; edge lengths between the centers of
K respectively. Both experimental and simulated adsorption Co(II) pairs of the rhombic grid window in {Co2(OBA)4}n 2D net
enthalpy of CO2 by CoMOF-1′ is in the range ~32.0 kJ mol-1, and is 16.35 Å and the respective diagonal distance of the grid is
this high adsorption enthalpy reveals the strong interaction of 26.84 and 18.70 Å. Due to the large opening of the grids in the
CO2 with MOF framework. The origin of the high interaction {Co2(OBA)4}n nets, parallel interpenetration between two such
energy for CO2 towards the CoMOF-1′ framework can be corrugated (4,4) grids is observed (Figure 2c). Interestingly,
explained on the basis of an in-depth analysis of the microscopic similar parallel double interpenetrated of M2(obc)2 layered
mechanism in force. As depicted in Figure 1c, the carbonyl structure is observed in mixed ligand Co(II) and Ni(II) MOFs
group of amide moiety strongly influences the adsorption reported by Vittal et. al and Natrajan et. al respectively.80-81 As
mechanism. The CO2 molecules interacting with carbonyl-group depicted in Figure 2d, the doubly interpenetrated {Co2(OBA)4}n
of the amide functionalized Schiff base ligand
characteristic O(CO2)-OCarbonyl distance of 2.7 Å (Figure S12
favoring the adsorption capacity of the polar CO2 molecule dimensional architecture. The Co–O(OBA) and Co–N(
L
with a mean layers are linked further by the pyridyl nitrogens of the Schiff
base ligands from either end leading to a porous three
) bond
)
L
inside the pores. In addition to CO2-OCarbonyl interaction, etherial lengths ranges from 1.996(3) - 2.303(4) Å and 2.149(3) - 2.155(3)
oxygen of OBA ligand is also involved in Oether– CCO2 contacts and Å respectively which are in the range of reported MOFs with
hence the driving force for the CO2 adsorption can be attributed [Co2(N−N)2(obc)2] SBU units.80, 82-83
to the =CO and -O- moiety present in the linkers of CoMOF-1′
available for various supramolecular interactions.
Crystal and Molecular Structure CoMOF-1
Figure 3. (a) 3D porous assembly observed in CoMOF-1 view down a-axis; (b) Topological
analysis of 3D interpenetrated network depicting 6-connected uninodal rob nets; (c&d)
Close up view of Hydrogen bonding interaction and three-dimensional supramolecular
interaction stabilizing the interpenetrated network in CoMOF-1.
Figure 2. (a) Coordination sphere around the dimeric Co(II) metal cluster; (b)
{Co2(OBA)4}n corrugated grids along bc-plane; (c) parallel interpenetration between two
corrugated (4,4) grids in CoMOF-1; (d) {Co2(OBA)4}n layers are linked by N-donor linker
L from either end leading to a porous 3D architecture.
Packing viewed down a-axis clearly demonstrate, due to the
flexibility of the OBA to adopt the bend conformation creating
corrugation of the 2D {Co2(OBA)4}n layers which is further
pillared by the Schiff base ligand in crisscrossed manner in the
Crystallographic analysis revealed that CoMOF-1 is a three-
dimensional porous Co(II) network composed of flexible
dicarboxylate OBA along with amide functionalized Schiff base
3D porous assembly (Figure 3a). As shown in Figure 3b
,
ligand
L and crystallized in monoclinic system with P2/c space
topological analysis revealed that the resulting 3D
interpenetrated network can be considered as 6-connected
uninodal rob nets with the point symbol {48.66.8} as calculated
group. The coordination sphere around the metal is depicted in
Figure 2a and the asymmetric unit is constituted by half of the
dimer building block [Co2(OBA)2(L)2] possessing center of
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using TOPOSPro software.84 Hydrogen bonding analysis oC, 1 bar PCO2, 1.8 mol% of catalyst and 2.5 mol% co-catalyst
View Article Online
DOI: 10.1039/C8TA10631B
revealed that three-dimensional MOF is involved in various loading) to yield styrene carbonate (SC).
supramolecular interaction in stabilizing the interpenetrated
network. Thus, the carboxylate oxygen O4 of the OBA acts as an
acceptor and involved in a bifurcated N-H···O and C-H···O
Table 1. Cycloaddition of Styrene oxide (SO) and CO2 for styrene carbonate (SC)
formation*
interactions with the acyl hydrogen H3C and pyridyl hydrogen
H26 of the Schiff base ligand . Details of these hydrogen
bonding interactions and symmetry code is provided in Figure
3c&d and Table S6
Catalyst/
Co-catalyst
None
CoMOF-1′
TBAB
CoMOF-1′/TBAB
CoMOF-1′/TBAB
CoMOF-1′/TBAB
CoMOF-1′/TBAB
CoMOF-1′/TBAB
None
CoMOF-1′
TBAB
CoMOF-1′/TBAI
CoMOF-1′/KI
CoMOF-1′/TBAB
PCO2
(bar)
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
10
Temp.
(oC)
RT
RT
RT
RT
40
60
60
60
60
60
60
60
60
60
Time
(h)
24
24
24
24
24
24
6
12
12
12
12
12
12
6
SO Con.
(%)#
02
06
12
42
83
99
71
99
04
08
18
86
90
99
Entry
L
1
2
3
4
5
6
7
8
9
10
11
12
13
14
.
Parameter Optimization and Substrate Screening Using
CoMOF-1′ Catalyst for Cycloaddition of CO2 with Terminal and
Internal Epoxides
Scheme 1. Reaction scheme of cycloaddition of CO2 with terminal/internal epoxides
using CoMOF-1′.
*Reaction conditions: SO = 8.7 mmol (1.0 mL at 25 oC), 600 rpm. Catalyst mol%:
CoMOF-1′ = 1.8 mol%; tetrabutyl ammonium bromide (TBAB)/TBAI/KI = 2.5 mol%.
#SO Selectivity = 99%.
Considering the attributes professed by crystal structure and
analytical methods such as porosity, amide functional group as
basic sites, densely populated Lewis acidic sites with weakly
coordinated carboxylate, high CO2 adsorption capacity,
excellent stability and robust nature of CoMOF-1′, we have
decided to investigate the catalytic performance for the
cycloaddition reaction of CO2 and epoxides to form cyclic
carbonates under solvent-free conditions (scheme 1). Detailed
procedure for catalytic reaction for both internal and terminal
epoxide is summarized in supporting data (S1). The cyclic
carbonate products were extracted and analyzed by using GC,
1H and 13C NMR spectroscopy (Figure S17-S36). To optimise the
reaction conditions, experiments in catalytic reaction with
different parameters, such as the amount of catalyst/co-
catalyst, temperature, gas pressure and reaction duration, were
conducted using styrene oxide (SO) and cyclohexene oxide
(CHO) as model substrate for terminal and internal epoxides
respectively using CoMOF-1′ as the catalyst under solvent free
condition. Experimental details and results of optimization
reaction parameters for terminal and internal epoxide model
Excellent SO conversion with 99% SC selectivity was achieved
for CoMOF-1′/TBAB as catalyst/co-catalyst system with set
reaction parameters in 12 h reaction time (Table 1, entry 7).
Retaining the same reaction parameters, CoMOF-1′/KI and
CoMOF-1′/TBAI could attain only 86% and 90% SO conversion
with 99% SC selectivity within 12 h (Table 1, entry 9 and 10).
Using 2.5 mol% of respective co-catalyst the product yield was
in the order TBAB > KI > TBAI under the same reaction condition.
Co-catalyst TBAI and KI was less effective compared with TBAB
and can be attributed to the bigger size of the iodide can hinder
the diffusion in the reaction process and better activity of
bromide over iodide.85-86 Keeping CO2 pressure 1 bar, variation
of time and temperature was also monitored for CoMOF-
1′/TBAB system. Thus, SO conversion was only 42% at RT with
24 h reaction time but upon increasing the temperature to 40
oC and 60 oC, 83% and a maximum of 99% SO conversion has
been achieved (Table 1, entry 3-5). Retaining the pressure 1 bar
and temperature 60 oC the SO conversion at 6 and 12 h time
duration was 71% and 99%, respectively (Table 1, entry 6-7).
Upon increasing the pressure 10 bar at 60 oC the SO conversion
reached to 99% within 6 h (Table 1, entry 11). Preliminary
screening based on various parameters and SO conversion using
CoMOF-1′/TBAB combination disclosed the experimental
conditions for the best catalytic performance for further studies
has been fixed with catalyst/ co-catalyst and SO concentration
1.8 mol%/ 2.5 mol% and 8.7 mmol respectively. We next probed
systematically the effects of other reaction parameters such as
temperature, reaction time and catalyst loading in styrene
carbonate formation using CoMOF-1′/TBAB.
substrates are shown in Table 1&3. Blank reaction and reaction
with only MOF between model substrates and CO2 under 1 bar
CO2 pressure/ RT/ 24 h for SO and 10 bar CO2 pressure/ RT/ 12
h for CHO were conducted to gauge their individual catalytic
cycloaddition ability. As it can be seen, no significant amount of
product was obtained in the absence of any catalyst and only
with MOF independently (Table 1
presence of only TBAB co-catalyst with reaction condition 1 bar
CO2 pressure/ 60 / 24 h for SO and 30 bar CO2 pressure/ 100
/ 12 h for CHO yielded only 18% and 22% conversion
&3, entry 1-2). However, in
℃
℃
respectively (Table 1, entry 8; Table 3, entry 11). For selection
of suitable co-catalyst in the case of terminal epoxide, CO2
cycloaddition was performed with SO in the presence of
different co-catalysts (tetrabutylammonium bromide (TBAB),
tetrabutylammonium iodide (TBAI) and potassium iodide (KI))
by setting up the following reaction condition (solvent-free, 60
As revealed in Figure S14a, upon gradual increase in the
temperature up to 40 oC, 83% SO conversion was observed and
almost 99% conversion is achieved at 60 oC. Time-dependent
catalytic activity in the range of 0 to 14 h revealed that fast SO
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conversion up to 82% is observed within the range of 0 to 8 h. leading to cyclic carbonates is often ignored in substrate scope
View Article Online
As depicted in Figure S14b, under the optimized reaction may be this reaction requires a suitable enDeOrgI:y1-0e.1ff0i3c9ie/Cn8tTcAa1t0a6l3y1sBt
conditions 99% conversion of SO within 12 h proved to be and typically high reaction temperatures /CO2 pressures with
excellent and alleviated the separation procedures of SO–SC long reaction time favors the product yield. Details of the
mixture. Catalytic loading studies in the range 0-2.0 mol% catalytic reaction and experimental parameters are provided in
revealed a steady increment of the SO conversion from 0 to 1.5 Table 3 in which CHO substrate = 20 mmol; CoMOF-1′ = 2.8
mol%, followed by reaching a saturation point of 99% at 1.8 mol%; TBAB/TBAI/KI = 5 mol% has been optimized and set for
mol% of CoMOF-1′
(Figure S14c).
further experiments. As mentioned earlier, no noticeable
Based on catalyst optimization studies, CoMOF-1′ has been conversion of CHO was observed at room temperature in blank
chosen as a potential catalyst for different terminal epoxide reaction and in presence of only catalyst with the substrate at
substrate in cycloaddition with CO2. Following aliphatic and 10 bar CO2 pressure and 12 h reaction time (Table 3, entry 1-2)
.
aromatic substrates (epichlorohydrin, 1,2-epoxyoctane, styrene However, the binary catalyst CoMOF-1′/TBAB under the
oxide, 1,2-epoxy-3-phenoxypropane and 2,4-dibromophenyl mentioned reaction parameters revealed promising 28% CHO
glycidyl ether) has been chosen as terminal epoxides, setting up conversion with 99% CHC selectivity (Table 3, entry 3). In further
the optimized parameters for catalyst/co-catalyst, temperature optimization experiments with CoMOF-1′/TBAB combination
o
and pressure as 1.8 mol%/2.5 mol%, 60 C, 12 h and 1.0 bar retaining other parameters constant, upon increasing the
o
respectively in cycloaddition reactions. As shown in Table 2, the temperature to 60, 80 and 100 C CHO conversion was 51, 63
catalytic system could convert all terminal epoxides studied to and 65% with 99% CHC selectivity (Table 3, entry 4-6). Hence,
o
the corresponding cyclic carbonates effectively under the set the temperature was set to 100 C and increment in CO2
optimised mild reaction condition. Overall, aliphatic epoxides pressure to 20 and 30 bar yielded the CHO conversion 81 and
exhibited good product yield ranging from 71 - 96% while in the 99% respectively with high CHC selectivity in 12 h reaction time
case of aromatic epoxide the cyclic carbonate yield was in the
range 68 - 99% (Table 2). Increase in chain length for aliphatic
epoxide revealed a decreasing trend in the corresponding cyclic
carbonate formation (Table 2, entry 2 and 4). For aromatic
epoxide, substitution of bulky Br on the aromatic ring has a
considerable decrease in the corresponding cyclic carbonate
yield which can be attributed to the low diffusion and steric
factor retarding the approach of the substrate towards the
catalytic sites.
(Table 3, entry 7-8).
Table 3. Cycloaddition of cyclohexene oxide (CHO) and CO2 for cyclohexene carbonate
(CHC) formation*
Catalyst/
Co-catalyst
PCO2
(bar)
10
10
10
10
10
10
10
20
30
30
30
30
30
30
30
30
Temp.
(oC)
RT
RT
RT
RT
60
80
100
100
100
100
100
100
100
100
100
100
Time CHO Con.
Entry
(h)
12
12
12
12
12
12
12
12
12
6
(%)#
04
06
11
28
51
63
65
81
99
92
99
06
09
22
89
90
1
2
None
CoMOF-1′
3
TBAB
4
5
6
7
8
9
10
11
12
13
14
15
16
CoMOF-1′/TBAB
CoMOF-1′/TBAB
CoMOF-1′/TBAB
CoMOF-1′/TBAB
CoMOF-1′/TBAB
CoMOF-1′/TBAB
CoMOF-1′/TBAB
CoMOF-1′/TBAB
None
CoMOF-1′
TBAB
CoMOF-1′/TBAI
CoMOF-1′/KI
Table 2. Substrate screening using CoMOF-1′ as catalyst in the cycloaddition of terminal
epoxide with CO2*
Entry
Epoxide
Yield (%)
1
2
99
96
8
8
8
8
3
84
12
12
4
5
71
68
*Reaction conditions: CHO = 20 mmol (2.0 mL at 25 oC), 600 rpm. Catalyst mol%:
CoMOF-1′ = 2.8 mol%; tetrabutyl ammonium bromide (TBAB)/TBAI/KI = 5 mol%.
#CHO selectivity = 99%.
*Reaction conditions: Epoxide = 8.7 mmol, Catalyst mol%: CoMOF-1′ = 1.8
mol%; tetrabutyl ammonium bromide (TBAB) = 2.5 mol%; PCO2 = 1.0 bar, 12
h, and 60 oC, 600 rpm.
In order to fine-tune the reaction parameters, reaction
temperature and CO2 pressure was fixed (at 100 oC and 30 bar)
and catalysis experiment was conducted with 6 and 8 h reaction
time. CHO conversion 92 and 99% was achieved in respective
reaction time with 99% CHC selectivity (Table 3, entry 9-10).
Setting up these optimized experimental conditions, CoMOF-
1′/TBAI and CoMOF-1′/KI borne comparatively lower CHO
conversion (Table 3, entry 12-13) and CoMOF-1′/TBAB has been
chosen as the ideal catalyst/co-catalyst pair for further
cycloaddition reaction of more challenging internal epoxide
substrates with CO2 experiments.
The excellent activity of the CoMOF-1′/TBAB based binary
catalyst system towards terminal epoxides with mild reaction
condition encouraged us to investigate cycloaddition reaction
of more challenging internal epoxide with CO2. The catalytic
activity of CoMOF-1′ was tested towards the model
cycloaddition of CO2 with bench-mark internal epoxide
cyclohexene oxide (CHO) for cyclohexene carbonate (CHC)
formation (Table 3). The reaction of internal epoxide with CO2
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Journal Name
o
To explore the optimal reaction conditions, systematic pressure as 2.8 mol%/ 5 mol%, 100 C, 8 h and using 20 mmol
View Article Online
reactions were designed upon incremental variation in CO2 of substrate for the catalytic reaction. AsDcOaIn: 10b.e10s3e9e/Cn8TinA1T0a6b31lBe
pressure, temperature, reaction time and catalyst amounts to
4, CoMOF-1′ is an effective bifunctional catalyst for conversion
obtain the best possible combination with the other set of the chosen internal epoxide under the set reaction condition
parameters. Effect of variation of pressure in product yield is except for cyclooctene oxide. Very efficient product yield in the
depicted in Figure S15a. Steep conversion of CHO up to 58% range 95 to 99% was achieved for comparatively small size
within 5 bar CO2 pressure followed by steady increase with a three, five and six membered internal epoxides (Table 4, entry1-
maximum conversion of 99% at 30 bar has been observed and 4). However, in the case of phenyl substituted three membered
the improved CHO conversion can be attributed to the high and eight membered internal epoxides the product yield was 75
solubility of CO2 concentration in the liquid phase under the and 12%, respectively (Table 4, entry 5-6). This poor efficiency
applied pressure. The efficiency of substrate conversion steadily implied can be attributed to the intrinsic lower reactivity, and in
improved with increase in temperature and the maximum 99% fact, due to its bulkiness imparting steric hindrance by these
o
CHO conversion is achieved at 100 C of catalytic reaction substrates in approaching the catalytically active sites, in
(Figure S15b). Time dependent catalytic activity in the range of particular only 12% yield resulted for cyclooctene oxide (Table
0 to 10 h revealed that conversion rate increased with reaction , entry 6). As far as we know this is the first comprehensive
4
time and 99% conversion is achieved within 8h of catalytic report for the choice cyclic carbonate products by an efficient
reaction (Figure S15c). Incremental addition of the catalyst MOF catalytic system for the conversion of internal epoxides
loading revealed that maximum conversion of 99% CHO is displayed in Table 4 with moderate reaction condition. We have
achieved at 2.8 mol% of catalyst loading as shown in Figure also tabulated the recent reports on cycloaddition of CO2 with
S15d. Hence, keeping all other parameters set with optimized cyclohexene oxide as a model internal epoxide substrate with
loading of 2.8 mol% catalyst is engaged in further experiments. different types of catalysts (Table S4).
The systematic study clearly demonstrates that to obtain good It is appropriate to recall here, Kleij et al pioneered on
product yield for internal epoxide, improved reaction interesting yield and selectivity for cycloaddition of CO2 with
parameters such as a reaction temperature of 100 °C and CO2 internal epoxide using metal-Schiff base complexes.8,39,87-90
pressure 30 bar with 8 h reaction time was required.
Major work in cycloaddition of CO2 with internal epoxide has
Internal epoxides are widely considered as difficult substrates been reported using metal complex based (Al, Fe, Ti, V)
in cycloaddition reaction with few achieved successful homogenous catalyst/ organo-catalyst8,39,87-95 and the reaction
conversions and to obtain reasonable product yield higher essentially provide good yield and selectivity only at elevated
temperature, pressure and prolonged reaction time is required. temperature, longer duration of reaction with pressure ranging
The activity of the CoMOF-1′/TBAB system on the synthesis of from 1 to 5 MPa (Table S4). Since most of the mentioned
cyclic carbonates using various internal epoxides was studied by compounds work as a homogenous catalysts separation of the
employing the above optimized reaction conditions (30 bar, 100 catalyst from the reaction system and recyclability are major
°C in 8 h) and the results are summarized in Table 4
.
concerns. The comparison of catalytic performance CoMOF-1′
clearly demonstrate the excellent potential of this material as a
promising catalyst for cyclic carbonates conversion with good
product yield not only for terminal epoxides at mild reaction
condition but also for different pool of internal epoxides which
are scantly explored with MOF catalyst. After demonstrating
the application of CoMOF-1′ in the cycloaddition of carbon
dioxide with both terminal and internal epoxide, it was
imperative to establish the recyclability of the catalyst
considering the application as a prospective catalytic material.
After completion of the representative reaction of terminal and
internal epoxides the product was isolated by extraction and
the catalyst was separated using a centrifuge. The catalyst was
washed with water / acetone, dried and reused, the activity of
the catalyst remains almost intact even after the 6 cycles (Figure
S37). The FTIR, PXRD and XPS data of the catalyst before and
after the 6th catalytic cycle virtually looks identical retaining all
major peaks which substantiates the chemical stability of the
Table 4. Substrate screening using CoMOF-1′ as catalyst in the cycloaddition of
internal epoxide with CO2
*
Entry
Epoxide
Yield (%)
1
2
99
99
3
4
96
95
5
6
75
12
*Reaction conditions: Epoxide = 20 mmol, Catalyst mol%: CoMOF-1′ = 2.8 mol%;
tetrabutyl ammonium bromide (TBAB) = 5 mol%; PCO2 = 30 bar, 8 h, and 100 oC,
600 rpm.
recycled catalyst and its reusability (Figure S2&S37-S38). To
spell out the nature of the reaction hot filtration test was
performed in which the experiment removing the catalyst after
half reaction time revealed that the formation of the cyclic
carbonate is almost arrested after continuing the experiment,
implying that the catalyst has a significant impact on the
transformation rate of substrates (Figure S39).
A series of internal epoxide (cyclohexene oxide, 1,2-epoxy-2-
methylpropane, 2,3-epoxybutane, cyclopentene oxide, stilbene
oxide and cyclooctene oxide) has been chosen setting up the
optimized parameters for catalyst/co-catalyst, temperature and
6 | J. Name., 2012, 00, 1-3
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ARTICLE
Plausible Mechanism of cycloaddition reaction and cyclohexene oxide. Upon the introduction of BVri-ewioAnrticlienOntlhinee
Correlation with DFT Calculation
vicinity of the CHO (IC) resulted a decreasDeOinI: r1e0.l1a0t3iv9e/Ce8nTAe1r0g6y3t1oB
11.4 kcal/mol. Here, the distance between O atom of CHO and
the Cobalt metal of the MOF is 2.72 Å and the Br- ion and the
beta carbon (βC(CHO)) of the CHO is 3.06 Å. In the ring opening
step, bromide ion makes a nucleophilic attack towards the β-
carbon (βC(CHO)) atom of CHO to form an alkoxide species, which
designated as the first transition state (TS-1). The ring opening
of βC(CHO) pave way for stronger Co-O(C6) interaction with an
inter atomic distance of 2.32 Å and the newly formed βC(CHO)-Br
bond with a distance of 2.56 Å. As depicted in the Figure 4, the
energy barrier of TS-1 for the ring opening of CHO is 37.4
kcal/mol and a relative energy between the TS-1 and IC is of
25.9 kcal/mol. According to previous DFT energy profile, the
higher energy barrier ring opening step is the rate determining
step in the CO2 fixation with CHO. In the subsequent step, the
bromide substituted alkoxide species (TS-1) falls into an
intermediate state (Int-2) with a total energy value of 23.8
kcal/mol. It can be seen in Int-2 that a molecule of CO2
approaches the cyclohexene oxide with the distance of 3.35 Å.
Physico-chemical analysis revealed the robustness, thermal /
chemical stability and CO2 adsorption capacity of the catalytic
material. SXRD data of CoMOF-1 disclosed the porous nature,
weakly coordinated chelated carboxylate of the OBA moiety
with the Lewis acid metal centre and -NH moiety of the acyl
decorated ligand
L which can act as a Lewis basic site in the
catalytic reaction. It is worth mentioning here the work
reported by Ma et.al related to the activation of epoxide by the
influence of Lewis basic catalytic site (–NH– functional group)
present in the ligand moiety for cycloaddition reaction with
enhancement of the product yield which is also supplemented
by computational studies.62 Reports are also there for amino/
acylamide functionalized ligand moiety acting as a Lewis basic
site in MOF based catalytic cycloaddition reactions.96-98 Good
Porosity and surface area of the activated catalyst with the
carbonyl hydrazone moiety of L can favor the encapsulation of
the reaction precursors (substrates and CO2) via supramolecular
interaction and increase the catalytic efficiency. This is well
supported by the experimental CO2 adsorption data and the
interaction of CO2 with the ligand moiety documented in our
periodic-DFT studies. Based on these preliminary experimental
results the following mechanism is proposed for the
cycloaddition reaction as depicted in Figure 5, which is further
augmented by periodic-DFT calculation. We performed
periodic-DFT calculation (see S2) to gain deeper insight into the
mechanism of CoMOF-1′ catalyzed CHO-CO2 cycloaddition
reaction with bromide ion (Br-) nucleophile from TBAB co-
catalyst. For the calculation, the total energy of the CoMOF-1′
with Br- nucleophile (catalyst + Br-), CO2 + CHO (isolated
reactants) was considered to zero energy and the relative
energies of the optimized structures of intermediates involving
substrates with catalyst/ Br- are depicted in scheme 2
.
Figure 4. Local views of the mechanistic pathways of the intermediates and transitions
states in the cycloaddition of cyclohexene oxide and CO2 using periodic model structure
of CoMOF-1′ catalyst with Br- ion.
Scheme 2. Energy profile diagram of the intermediates and transitions states calculated
using Periodic DFT calculation in the cycloaddition of cyclohexene oxide and CO2 to form
cyclohexene carbonate, using the CoMOF-1′ catalyst.
In the latter step, the CO2 attacks the negatively charged oxygen
atom of CHO leading to the formation of second transition state
(TS-2). In TS-2, the physical binding of CO2 takes place between
the Co and alkoxide group with a total energy value of 35.8
kcal/mol. The TS-2 involves the formation of new bonds, Co-
It is observed that an intermediate (Int-1) is formed by the
interaction of the oxygen atom of the CHO with the Cobalt
metal center with an energy of 28.0 kcal/mol. In Int-1, the Br-
ion was at a distance of 3.34 Å from the beta carbon (βC(CHO)) of
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O(CO2) and O(CO2)-βC(CHO) with respective corresponding bond have been attracted and activated by Lewis basic siVtieews uArnticdleeOrntlhinee
DOI: 10.1039/C8TA10631B
distances 2.52 Å and 2.16 Å. After TS-2, the ring closure step was applied pressure in the reaction for terminal and internal
determined via the formation of new intermediate Int-3 with an epoxide in particular for efficient product yield. It is worth
energy of 4.9 kcal/mol. In Int-3, the positively charged carbon mentioning here that existence of basic functional sites such as
atom of CO2 attacks the oxygen atom of CHO leading to the -NH2 and -NH in the ligand moiety of the MOF can increase the
formation of cyclohexene carbonate (CHC) through new O(CHO)
-
CO2 capture as per the previous reports64-65,76,99-102 and our
C(CO2) bond. Interestingly, the bond distance of O(CO2)- βC(CHO) is investigation including modelling studies also support this
shortened to 1.48 Å from 2.16 Å while the Co-O(CO2) and C-Br concept, which in turn can favour chemical fixation of CO2.
bond distance is elongated to 2.59 Å from 2.52 Å and 3.51 Å Overall, it can be inferred that the cycloaddition of CO2 with
from 3.06 Å, respectively. Finally, the detachment of epoxide process is significantly supported by the presence of
cyclohexene carbonate is located with an energy of –2.6 thickly populated Lewis acidic metal sites and weak basic
kcal/mol followed by the regeneration of CoMOF-1′ and Br- ion functional group (-NH) within the MOF as active sites to
(FC).
promote the catalytic reaction favouring to achieve decent
product yield. The good catalytic activity of CoMOF-1′ for the
catalytic cycloaddition reactions of both terminal and internal
epoxide with CO2 can be mainly credited to synergic effect of
well oriented high density of active metal sites/ amide
functional moieties of the ligand exposed for interactions with
the substrates within the porous 3D network which is reinforced
by the structural and theoretical studies.
Conclusions
In summary, a highly stable porous CoMOF-1 with bulk phase
purity has been synthesised by direct reflux of the precursors as
well as crystallized by hydrothermal method and employed as a
recyclable heterogeneous catalyst with routine activation.
Crystal structure of CoMOF-1 revealed three-dimensional
porous network possessing good thermal and chemical stability,
strong CO2 interaction with the pore of CoMOF-1 which is
Figure 5. Proposed catalytic mechanism for cycloaddition of CO2 in to terminal/ internal further substantiated with molecular simulation results, and
epoxides using CoMOF-1′ as heterogeneous catalyst.
represents an efficient reusable heterogeneous MOF catalyst of
high utility for conversion of both terminal and internal
Conversion of CO2 with epoxide in presence of catalyst
producing cyclic carbonates is well recognized and the general
mechanism involves three main elementary steps: epoxide ring
opening, CO2 insertion, and ring closure to form the five-
membered cyclic carbonate. Plausible mechanism for the
epoxides under mild reaction condition and minimum energy
consumption. In all the catalytic reactions, the product analysis
was performed by both GC and NMR spectroscopy. Weakly
coordinated carboxylate oxygen pave way for a vacant
coordination site in Lewis acidic Co(II) sites and the weak basic
efficient catalytic ability of CoMOF-1′ is depicted in Figure 5
.
-NH functional group of L can act as active sites for initiating the
Synergistic involvement of the Lewis Co(II) metal site accessible
upon opening up the weakly coordinated carboxylate oxygen
catalytic reaction. To establish and support the proposed
catalytic mechanism for cyclic carbonate formation from
representative terminal and internal epoxide periodic DFT
calculation is also performed. In addition to porosity of the
and presence of the basic -NH site of the acyl hydrazone from
L
interact with lone pair of oxygen from the epoxides to facilitate
the ring opening. Thus, the reaction commences with activation
of the epoxide ring enabled by coordination of the oxygen from
epoxide ring by opening up the weakly coordinated carboxylate
oxygen (O5) creating a vacant coordination site on Co(II) Lewis
site and forming hydrogen bonds with -NH group of the amide
MOF, accessibility to the functional group -NH of L can assist as
CO2 adsorption sites and enhances the reactivity and yield of
the present catalytic system. The work presented here
illustrates the utility of Co(II) based MOF as potential
heterogeneous catalyst under solvent free condition for CO2
sequestration by cycloaddition reaction of both terminal and
internal epoxides to value added chemicals at ambient
condition with good yield and recyclability. The findings also
provide further insight for the design and bulk synthesis of
robust MOFs with chemical stability and better catalytic
properties by tailor made functionalized ligand moiety towards
cycloaddition reaction of internal epoxides which are seldom
explored.
group on L
. Simultaneously, Br- from TBAB proceed with a
nucleophilic attack on the less-hindered carbon atoms of both
the coordinated and hydrogen-bonded epoxides. Rapidly,
surrounding polar CO2 interacts with the oxygen anion of the
opened epoxy ring to form an alkyl carbonate anion, and
subsequent ring closure step results in the corresponding cyclic
carbonate and regeneration of the catalyst.
Porous nature of the framework enhances the concentration of
CO2 molecules in surrounding catalytic environment, which
8 | J. Name., 2012, 00, 1-3
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Page 9 of 11
Journal of Materials Chemistry A
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ARTICLE
22 H. -C. Zhou and S. Kitagawa, Chem. Soc. Rev., 2014, 43, 5415-
Conflicts of interest
There are no conflicts to declare.
View Article Online
5418.
DOI: 10.1039/C8TA10631B
23 H. Furukawa, K. E. Cordova, M. O’Keeffe and O. M. Yaghi,
Science, 2013, 341, 1230444.
24 H. -C. Zhou, J. R. Long and O. M. Yaghi, Chem. Rev., 2012, 112
,
673-674.
Acknowledgements
25 M. P. Suh, H. J. Park, T. K. Prasad and D. -W. Lim, Chem. Rev.,
2012, 112, 782-835.
26 E. Barea, C. Montoro and J. A. R. Navarro, Chem. Soc. Rev.,
2014, 43, 5419-5430.
27 J. -R. Li, J. Sculley and H. -C. Zhou, Chem. Rev., 2012, 112, 869-
932.
28 S. Qiu, M. Xue and G. Zhu, Chem. Soc. Rev., 2014, 43, 6116-
6140.
29 M. ‐X. Wu, Y. ‐W. Yan, Adv. Mater., 2017, 29, 1606134.
30 P. Horcajada, R. Gref, T. Baati, P. K. Allan, G. Maurin, P.
Couvreur, G. Férey, R. E. Morris and C. Serre, Chem. Rev.,
2012, 112, 1232-1268.
31 S. Keskin and S. Kızılel, Ind. Eng. Chem. Res., 2011, 50, 1799-
1812.
The registration number of this publication is CSIR-CSMCRI –
176/2018. Financial support from CSIR-SRF (BP), DST Project
HCP0009 (PP) and analytical support by AESD&CIF of CSIR-
CSMCRI is gratefully acknowledged. We thank Ms. Pooja
Goswami for PXRD, Dr. Vinod Boricha for NMR data, Mr. Jayesh
Chaudhari for FE-SEM analysis, Mr. Vinod Kumar Agrawal for
FTIR data, Mr. Satyaveer Gothwal for TGA data, Mr. Viral Vakani
for CHN analysis and Mr. Harpalsinh Rathod for N2/CO2-
adsorption desorption analysis. RSP thank SRM Supercomputer
Center, SRM IST for providing the computational facility.
32 L. E. Kreno, K. Leong, O. K. Farha, M. Allendorf, R. P. Van Duyne
and J. T. Hupp, Chem. Rev., 2012, 112, 1105-1125.
33 W. P. Lustig, S. Mukherjee, N. D. Rudd, A. V. Desai, J. Li and S.
K. Ghosh, Chem. Soc. Rev., 2017, 46, 3242-3285.
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Table of Content
DOI: 10.1039/C8TA10631B
Synthesis and Characterization of Robust-Porous CoII Metal-Organic framework for CO2
capture and efficient solvent-free heterogeneous catalysis for conversion of internal/terminal
epoxide to value added chemicals at ambient reaction conditions has been reported.