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pubs.acs.org/journal/ascecg Letter

Deep Eutectic Solvent Formed by Imidazolium Cyanopyrrolide and

Ethylene Glycol for Reactive CO2 Separations
Yun-Yang Lee, Drace Penley, Aidan Klemm, William Dean, and Burcu Gurkan*
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ABSTRACT: Solvents made from a reactive ionic liquid, with an

imidazolium cation and pyrrolide anion, and ethylene glycol at a wide
compositional range were studied for separations of CO2 at low
partial pressures (≪0.1 bar up to 1 bar). Thermal analysis and
measurements of viscosity and density show compacting of the liquid
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upon mixing with enhanced stability achieved by hydrogen bonding.

A detailed mechanistic study was performed by IR, quantitative NMR,
and ab initio calculations that show significant CO2 absorption
capacity below 5000 ppm of CO2 in N2. Three reversible routes are
found that yield carbonate (major product), carboxylate (moderate),
and carbamate (minor) species. With CO2 at 100% RH, bicarbonate
along with carbonate species form. The CO2-ethlyene glycol reaction
complex, the carbonate anion, is stabilized by the hydrogen bonding
and Coulombic interactions, thus preventing evaporation of the solvent during regeneration. This study demonstrates a promising
approach to designer green solvents for CO2 separations in open systems such as direct air capture.
KEYWORDS: Direct Air Capture, DAC, carbon capture, Negative emissions science, Ionic liquid, Carbon dioxide, Gas separations

■ INTRODUCTION
As CO2 emissions continue to rise due to human activity,1 so
upon repeated absorption−desorption cycles. The capsules
demonstrated superior stability in the presence of water
does the need for novel carbon capture materials.2 Ionic liquids compared to zeolites, although with more sluggish break-
(ILs), particularly CO2-reactive ionic liquids (rILs), have been through curves under dry conditions. Here, we report dilution
a steady target of research as relatively benign solvents for CO2 of the rIL with ethylene glycol (EG) to improve the CO2
capture, owing to their negligible volatility.3,4 ILs also have absorption rate while also changing the reaction mechanism, as
high CO2 solubilities, relatively high thermal stabilities revealed by NMR, IR, and computational studies.
EG is a common hydrogen bond donor (HBD) in deep
compared to volatile organic solvents, and versatile chemical
eutectic solvents (DESs).11 DESs have been investigated for
structures for tailorable physical properties.5 rILs with aprotic
CO2 capture, as they can absorb CO2 through the entropic
heterocyclic anions have shown distinct promise in CO2
voids within the liquid, similar to nonreactive ILs.12,13 A DES
capture due to their favorable reaction energetics (about −45
is a mixture for which the melting point is significantly lower
kJ/mol of CO2 at 25 °C), achieving regeneration easily at
than either of the parent compounds: a hydrogen bond
moderate temperatures (i.e., 60 °C) without a significant
acceptor (HBA), usually a halide salt, and a hydrogen bond
viscosity increase upon absorption.6 Still, initially high
donor (HBD), such as EG. Recent studies showed that DESs
viscosities, even prior to CO2 absorption, and low gravimetric
and DES-like mixtures with superbase additives,14 superbase
capacities due to the large molecular weight of rILs have
HBAs,15 or superbases as the tertiary component16 have CO2
limited their widespread application. It has been reported that
capacities ranging from 3.6 to 17.34 wt % at 1 bar of CO2 with
the gravimetric capacity and viscosity can be further improved
typical absorption temperatures of 45−60 °C. The highest
by the choice of the cation.7,8 We have previously shown that
gravimetric CO2 capacity at 33.7 wt % is reported for a mixture
the challenge of CO2 transport in viscous rILs can be mitigated
by encapsulation, where the gas−liquid surface area is
enhanced dramatically for improved mass transport.9 More Received: September 30, 2020
recently, we have reported CO2 capacities of 1.5 mol CO2 per Revised: December 30, 2020
kg of sorbent for capsules of 1-ethyl-3-methylimidazolium 2- Published: January 14, 2021
cyanopyrrolide, [EMIM][2-CNpyr] (60 wt % of capsule), at
25 °C and low partial pressures of CO2 (<0.1 bar).10
Regeneration was achieved at 40 °C with no loss of capacity

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ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Letter

Figure 1. (a) DSC curves of [EMIM][2-CNpyr]:EG under a heating rate of 2 °C/min. Ratios in parentheses are the molar ratios of rIL to EG. (b)
Melting points of rIL:EG with respect to the mole fraction of rIL (lower x-axis) and molar ratio (upper x-axis). Samples 1:2, 1:3, and 1:5 did not
present a phase transformation within the accessible temperature range of the DSC. The gray dashed line is the hypothetical trend of the melting
temperature, while the solid lines are connecting the data points to guide the eye. (c) Excess molar volume as a function of the mole fraction of rIL
(lower x-axis) and molar ratio (upper x-axis). Excess molar volumes were calculated from the measured densities reported in Table S1. The dashed
line is the Redlich−Kister fit.31 (d) Temperature-dependent viscosity of rIL:EG (1:2) in comparison to the neat rIL10 (1:0) and EG30 (0:1). The
dashed line is the expected viscosity from the Grunberg−Nissan ideal mixture. Solid lines are Vogel−Tamman−Fulcher fits to the viscosity data;
fitting parameters are in Table S2.

of monoethanolammonium chloride, [MEA.Cl], and ethlyene-
diamine at 1 bar of CO2 and 30 °C.17 It should be noted that
these high gravimetric capacities were at the expense of very
slow rates as the viscosity of the DESs made of alkanolamines
reached about 4000 cP and required sorbent regeneration at
100 °C.17 Cui, Lv, and Yang studied mixtures of ammonium/
phosphonium azolide ILs with EG and reported capacities of
0.118 g CO2 per gram of solvent (10.5 wt %) at 25 °C and 1
atm of CO2 with regeneration at 70 °C under N2.18 While
these reports are promising in terms of the development of
combination with ATR-FTIR show the imidazolium cation,
pyrrolide anion, and EG, all bind with CO2, resulting in three
different reaction routes that yield carboxylate, carbamate, and
carbonate species, respectively. Calculations of the transition
states suggest that the formation of carbonate from EG has the
smallest energy barrier, in agreement with the experimentally
determined majority product. All of the reactions are reversible
and solvent regeneration was achieved at as low as 40 °C. This
study demonstrates a route to achieving CO2 reactive sorbents
that are water-lean, thermally stable, minimally volatile, and
regenerable, which is promising for open systems such as DAC.

alternative solvents for CO2 capture, DESs have not been
explored for direct air capture (DAC) or indoor air where the
partial pressure of CO2 is extremely low (410−5000 ppm).
In this study, we report a new reactive DES formed between
the rIL, [EMIM][2-CNpyr], and EG. Various rIL:EG
compositions are studied by differential scanning calorimetry
(DSC) with the following molar ratios: 1:0.5, 1:1, 1:2, 1:3, 1:4,
1:5, and 1:10. The rIL:EG (1:2) forms a thermally stable and
low viscosity DES with an absorption capacity of 10.3 and 11.4
wt % at 0.005 bar (0.5% CO2 in N2) and 1 bar of CO2 (100%
CO2), respectively. Quantitative analysis of 13C NMR in
■
EXPERIMENTAL SECTION
Preparation of rIL:EG Mixtures and Characterization. Details
to the materials, synthesis of [EMIM][2-CNpyr] and [EMMIM][2-
CNpyr] (methyl substitution at α carbon of imidazolium), and
characterization techniques are described in the Supporting
Information (see Figures S1 and S2 for confirmation of synthesis by
NMR). Mixtures of [EMIM][2-CNpyr] with EG at molar ratios of
1:0.5, 1:1. 1:2, 1:3, 1:4, 1:5, and 1:10 were prepared using a vortex
mixer in an argon-purged glovebox (VTI, H2O < 0.1 ppm, O2 < 0.1
ppm). The water contents of samples were measured by a Karl

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Figure 2. (a) CO2 absorption capacities measured by TGA using 2.5 mg of rIL:EG sorbent under 1 bar of CO2. (b) Gravimetric CO2 capacities at
25 °C. Red circles are for neat [EMIM][2-CNpyr] (1:0) measured gravimetrically from a mixed CO2/N2 feed at 1 bar. Blue triangles and green
diamonds are for rIL:EG mixtures with a molar ratio of 1:1 and 1:2, respectively. CO2 capacity from TGA data in panel a (hexagons) and capacities
measured under 100% RH (stars) are also shown. The partial pressure of CO2 was adjusted for each set point by the mass flow controllers. The
capacity previously reported for [EMIM][2-CNpyr] under pure CO2 is included for comparison (gray squares).10 Uncertainties of the gravimetric
capacities are estimated to be 10%. (c) CO2 capacities in panel b replotted for the low pressure region (left; 0−6 mbar) and the higher pressure
region (right; 900−1100 mbar). (d) Three consecutive absorption (1 bar CO2, 25 °C) and desorption (1 bar N2, 40 °C) cycles of rIL:EG (1:2).

Fischer titrator (Metrohm Coulometric KF 889D) and were in the
range of 700−900 ppm. Viscosity and density were measured
following procedures reported previously.19 Thermal analysis of the
samples was performed by DSC (Mettler Toledo DSC3). In DSC, the
samples were initially chilled from 25 to −84 °C, held isothermally for
10 min, and then heated back to 25 °C with a rate of 2 °C/min under
N2 atmosphere. A three-step heating−cooling−heating cycle was
performed, and it was confirmed for [EMIM][2-CNpyr] that there
are no significant differences between the heating cycles. Therefore,
only the first heating scan is reported for all of the solvents.
CO2 Absorption and Desorption Experiments. The CO2
capacity of the rIL:EG was measured gravimetrically by weighing
the sample before and after CO2 absorption using an analytical
balance (accuracy of ±0.001 g). In brief, 0.25 g of liquid was placed in
a 9 mL glass scintillator vial with a stir bar, and a CO2/N2 gas mixture
was introduced at a flow rate of 200 mL/min and 1 bar at 25 °C until
the weight of the sample reached equilibrium as established by the
maintenance of constant weight for 1 h. All CO2 absorption
experiments were done under anhydrous feed, unless noted otherwise.
The partial pressure of CO2 in the feed was varied by mass flow
controllers on N2 and CO2 lines (Brooks 5850I) using LabVIEW. The
CO2 concentration was monitored by a CO2 analyzer (SBA-5,
PPSystems Inc.). This gravimetric method is confirmed to yield
capacities within 10% of the CO2 isotherm reported previously for
[EMIM][2-CNpyr].9 This comparison also verifies that the CO2
capacity of the rIL is virtually unaffected by the presence of N2 during
absorption within our uncertainties. The CO2 isotherm of neat
[EMMIM][2-CNpyr] was measured barometrically at 25 °C using a
Micrometrics TriStar II sorption analyzer, following our previous
method.9
CO2 desorption and solvent regeneration following an absorption
at 25 °C was studied by the gravimetric method described above.
Briefly, the feeding gas was switched from N2 to CO2 for absorption at
25 °C for 40 min and then switched back to N2 during desorption at
40 °C for 30 min. The sample gas flow rate was 200 mL/min at 1 bar.
Identification of Reaction Routes and Distribution of
Products. The chemical composition of the samples before and
after an absorption experiment was characterized by ATR-FTIR using
a Nicolet iS50 FTIR (Thermo Scientific) with 32 scans, at a
resolution of 4 cm−1, on a diamond crystal and quantitatively by 13C
NMR (125.75 MHz, Bruker Ascend HD NMR). The relaxation time
of the C nucleus was drastically reduced by a paramagnetic
compound, chromium acetylacetonate in deuterated dimethyl
sulfoxide (0.1 M Cr(ACAC)3 in DMSO). The T1 relaxation times
of the different CO2 complexes were measured by the inversion
recovery method (see Figure S3 and SI for details). The energetics
and the transition states associated with the reactions were computed
at the level of density functional theory (DFT) using the
Turbomole20 software. The calculations were performed with the
def2-SVP21 basis set using the Karlsruhe split valence polarization,
Tao−Perdew−Staroverov−Scuseria (TPSS)22 functional with D3
dispersion corrections,23 Becke and Johnson (BJ) damping,24 and
resolution of identity (RI) approximation.25 All calculations were run
at a m4 grid size. For simplicity, the transition state search for each
reaction route is performed separately. A bond was created between
the CO2 and the investigated reaction site according to the scheme

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Table 1. Measured CO2 Capacities in This Study in Comparison to Previously Reported DESs with Specified Absorption and
Desorption Conditionsa
Solvent Absorption conditions Regeneration under N2 CO2 capacity (mol CO2/kg DES) ref
[Ch][Cl]+MEA+Piperazine (1:7:1) 1.57 bar CO2, 25 °C N/A 0.96 32

DBN+EU (2:1) 1 bar CO2, 45 °C 90 °C 5.23 15

1 bar CO2, 45 °C 90 °C 4.54 (14% CO2 in N2) 15

[N2222][Im]+EG (1:2) 1 bar CO2, 25 °C 70 °C 2.68 18

[N2222][Triz]+EG (1:2) 1 bar CO2, 25 °C 70 °C 2.68 18

[P2222][Im]+EG (1:2) 1 bar CO2, 25 °C 70 °C 2.84 18

[P2222][Triz]+EG (1:2) 1 bar CO2, 25 °C 70 °C 2.93 18

DBN (9 v%) in [Ch][Cl]+EG (1:2) 1 bar CO2, 25 °C 100 °Cb 0.86 14

DBU (9 v%) in [Ch][Cl]+EG (1:2) 1 bar CO2, 25 °C 100 °Cb 0.83 14

DBN (9 v%) in [Ch][Cl]+MEA (1:4) 1 bar CO2, 25 °C 100 °Cb 5.11 14

[MEA.Cl]+EDA (1:3) 1 bar CO2, 30 °C 100 °C 7.16 17

[Ch][Cl]+Glycerol+DBN (1:3:10) 1 bar CO2, 25 °C 60 °Cc 2.36 16

[TETA.Cl]+EG (1:3) 1 bar CO2, 40 °C 100 °C 3.98 33

[HDBU][Im]+EG (7:3) 1 bar CO2, 40 °C 70 °Cc 3.20 27

[HDBU][Ind]+EG (7:3) 1 bar CO2, 40 °C 70 °Cc 2.66 27

[HDBU][Triz]+EG (7:3) 1 bar CO2, 40 °C 70 °Cc 2.45 27

[EMIM][2-CNpyr]+EG(1:2) 1 bar (CO2:N2), 25°C 40 °C 2.59 (100% CO2) This study

1 bar (CO2:N2), 25°C 40 °C 2.35 (0.5% CO2) This study
1 bar (CO2:N2), 25°C 40 °C 2.08 (2000 ppm of CO2) This study
1 bar (CO2:N2), 25°C 40 °C 0.95 (410 ppm of CO2) This study
a
Compositions in parentheses are molar ratios. All of the reported CO2 capacities are converted to units of mol CO2 per kg of sorbent for
comparison purposes. For this study: 2.59 mol CO2 per kg DES corresponds to 11.4 wt % (g CO2 per g DES). b35% regeneration. cSignificant mass
loss; EU = ethylene urea; MEA = monoethanolamine; [MEA.Cl] = monoethanolamine and HCl mixture; DBN and DBU are superbases; [Im] =
imidazolide; [Triz] = triazolide; [TETA.Cl] = triethylenetetramine and HCl mixture; [Ch][Cl] = choline chloride; [HDBU] = protonated DBU;
[Ind]=indolide.

suggested by experimental spectroscopic analysis. These bonds were
scanned via a potential energy surface scan to obtain a bonding
distance that resulted in the highest optimized energy that
corresponds to the transition state. The obtained transition states
were confirmed via frequency analysis where a transition state yields
one imaginary frequency corresponding to the CO2 bonding with the
molecule of interest.26−28
heating step of the 1:10 mixture, indicating that an exothermic
structural reordering process occurred before melting. Figure
1b shows the dependence of the melting temperature with
respect to the mole fraction of the rIL (lower axis) and also in
terms of the molar ratio of rIL:EG (upper axis). While it is not
certain how deep the melting point depression is between 1:2

■
RESULTS AND DISCUSSION
The [EMIM][2-CNpyr]:EG mixtures at compositions ranging
from 1:0.5 to 1:10 were observed to be liquids at room
temperature, and their DSC curves are shown in Figure 1a.
While the 1:10 mixture has a melting point of −22.6 °C,
between that of EG (−11.5 °C) and rIL (−60.8 °C), it is seen
that 1:0.5 and 1:1 mixtures form eutectics. The other
compositions, 1:2, 1:3, and 1:5 did not present a phase
transition within the temperature range studied possibly due to
the melting occurring below the temperature limit of the
instrument, −80 °C. A cold crystallization is observed in the
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and 1:5 mixtures compared to the rIL and EG parent
compounds, excess molar volumes calculated from measured
densities are negative, indicating that there is compacting of
the liquid, as shown in Figure 1c. The negative deviation may
stem from a hydrogen bond network formation, a characteristic
trait of DESs, further supporting the DES formation between
[EMIM][2-CNpyr] and EG. The measured viscosities of
rIL:EG (1:2) also show a closer interaction between rIL and
EG than would be expected from an ideal mixture: see
comparisons of viscosities in Figure 1d with rIL, EG, and the
estimated viscosity from the classic Grunberg−Nissan29 mixing
rule (dashed line).30 These results suggest tight hydrogen
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Figure 3. (a) Proposed reaction network with NMR labeling of the reactants (1, a, b, c, ...) and CO2 bound products (α, 2, 3, 4, m, l, a′, b′, ...). (b)
Quantitative 13C NMR of [EMIM][2-CNpyr]:EG (1:2) prior to (black) and after CO2 absorption at 2000 ppm (red) and 5000 ppm (blue) of CO2
in N2 (1 bar, 25 °C). For comparison, measurements with dry (0% RH, green) and moist (100% RH, purple) CO2 at 1 bar are included. The
integration of peaks was done by setting the d or d′ position carbon of the anion to 1. The carbamate peak (l) is difficult to see due to the strong H-
bonds between rIL and EG; Figure S8 is the magnified NMR where it is better seen.

bonding alongside Coulombic interactions, similar to the case
of ionic DESs.
Figure 2a shows the TGA curves of rIL:EG mixtures with
1:0, 1:0.5, 1:1, and 1:2 as they absorb CO2 under atmospheric
pressure at 25 °C (initial masses were tared). Despite having
about the same initial mass of liquid (2.5 mg), the time to
reach equilibrium varies slightly between samples because of
their different viscosities. For the neat rIL, equilibrium is still
not reached after 40 min due to its relatively high viscosity,
while it takes 10 min for the rIL:EG (1:2) to reach equilibrium.
The viscosities before and after CO2 for rIL and rIL:EG (1:2)
are given in Table S3. The mixtures with less EG (1:0.5, 1:1,
and 1:2) show a stable equilibrium with no mass loss, whereas
rIL:EG (1:3), as shown in Figure 2a, loses mass following an
initial mass gain after 10 min due to evaporation of EG.
CO2 capacities measured by the gravimetric method using
the stirred absorption cell for rIL:EG (1:1 and 1:2) are shown
in Figure 2b. The CO2 capacity obtained under a CO2/N2
mixture for the neat rIL (red circles) compares similarly to the
isotherm of neat rIL (gray squares) from our previous report
based on a barometric measurement.10 The equilibrium
capacities obtained by TGA in Figure 2a are very similar and
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shown in Figure 2b with hexagonal symbols. When the feeding
gas was saturated with water by bubbling through a water
reservoir (100% RH), the resulting CO2 capacities (star
symbols in Figure 2b) measured for 1:0 and 1:2 mixtures show
no significant difference from the dry feed experiments. At
CO2 concentrations of 2000 and 5000 ppm, the capacity of
rIL:EG (1:1 and 1:2) exceeds that of the neat rIL which is
better seen in Figure 2c. This suggests EG is participating in
the reaction network as discussed later. The CO2 cyclability of
rIL:EG (1:2) was studied by performing three consecutive
absorption−desorption cycles. As shown in Figure 2d, the
absorbed CO2 at 25 °C can easily be released under N2 at 40
°C. While the CO2 capacity stays about the same in the second
and third cycles, small mass loss is observed during
regeneration following the third cycle when the regeneration
is prolonged from 30 to 50 min. This is possibly due to the
evaporation of EG. However, the CO2 capacity is maintained
from the first cycle to the third, suggesting no evaporation until
CO2 is stripped. Therefore, we believe the CO2 complexation
stabilizes the sorbent, preventing EG evaporation. Spectro-
scopic evidence suggests the stabilization of EG as discussed
later. Table 1 summarizes the measured CO2 capacities for the
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rIL+EG system in comparison to similar DESs investigated.
The main advantage of the studied solvent in this work is the
improved CO2 absorption rates, milder regeneration temper-
atures, and the high CO2 capacity at extremely low partial
pressures of CO2 that have not been reported for these types of
sorbents.
IR analysis of the reaction products between dry CO2 and
rIL:EG (1:2) indicates multiple species for bound CO2, as
shown in Figure S4a. The reaction scheme in Figure 3a is
proposed to take place. Route 1 is the complexation of CO2
with the pyrrolide anion that forms carbamate (−N−COO).
Route 2 is the deprotonation of the imidazolium cation by the
anion that forms a carbene zwitterion, which then binds with
CO2 to form carboxylate (−C−COO). Route 3 is the
protonation of the anion by EG, resulting in deprotonated
EG that subsequently reacts with CO2 to form carbonate
(−O−COO). In the presence of water, bicarbonate (HO−
COO) also forms via Route 4. The carbamate and carboxylate
formations are consistent with CO2 absorption products by the
neat rIL (Figure S4b), similar to prior literature.7 Yan et al. also
reported the observation of both carbonate and carbamate
routes in a superbase and EG mixture upon CO2 absorption.27
To further probe the CO2 absorption mechanism, Route 2 is
eliminated by blocking the α carbon (k) on the imidazolium
with a methyl group, synthesizing [EMMIM][2-CNpyr]. The
resulting CO2 capacity of [EMMIM][2-CNpyr] at 25 °C is
measured to be significantly smaller than [EMIM][2-CNpyr]
(isotherms compared in Figure S5). At 0.002 bar (2000 ppm,
1.5 Torr), the capacity of [EMMIM][2-CNpyr] is 0.16 mol
CO2 per mol IL, compared to 0.35 for [EMIM][2-CNpyr].
Even under these very low pressures, [EMIM][2-CNpyr] has
significantly higher capacity due to the strong CO2 affinity of
the α carbon (k) on the imidazolium (Route 2). In the absence
of a carbene formation, there is still measurable CO2 capacity,
suggesting that the carbamate formation in Route 1 takes place
with [EMMIM][2-CNpyr]. However, the IL solidifies at 0.013
bar CO2 (10 Torr). In the presence of EG and carbene, Route
1 is suppressed for [EMIM][2-CNpyr] at low partial pressures
(≪1 bar).
A more quantitative analysis of the extent of each reaction
route was performed by 13C NMR as shown in Figure 3b. The
relaxation times obtained for each reaction product are shown
in Figure S4 and summarized in Table S4. Comparing the
NMR of rIL:EG (1:2) before and after exposure to CO2 in
Figure 3b, it is shown that the cation peaks split into two sets,
similar to what is observed for the neat IL (Figure S7a). One
set (a, b, c, g, i, and k, Figure 3a) at the original peak locations
is for the unreacted cation. The other set is the downfield shift
of the original set of peaks, indicated by (′), corresponding to
the cation-CO2 complex (carboxylate). As the CO2 concen-
tration increases, the downshifted peaks of the cation increase
in intensity. The split of peaks in the cation is ascribed to the
change in aromatic ring current after CO2 complexation.34
Such a split is not seen for the anion, and instead, a downfield
shift is observed for the set of anion peaks (d′, e′, f′, h′, and j′,
Figure 3a) possibly due to participation in hydrogen bonding
(see Figure S8 for zoomed in spectra). The HMBC spectra
confirm the correlation between cation and anion, and the
observed couplings (Figure S9a) indicate interaction through
H-bonding upon complexation via Routes 1 and 2. HMBC
spectra in Figure S9b also confirm the assignments of
carbamate at 146 ppm (l), carboxylate at 154 ppm (m), and
carbonate at 158 ppm (4). Using the integral values obtained
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in the quantitative 13C NMR (Table S5), the CO2 capacity can
be broken down into the contributions from each reaction
route, yielding the final product distributions represented in
Figure 4. Under dry CO2, the complexation between CO2 and
Figure 4. Breakdown of CO2 capacities determined from the NMR
integrals (Table S5) with respect to the three reaction routes: from
anion (carbamate, peak l at 146 ppm), cation (carboxylate, peak m at
154 ppm), and EG (carbonate, peak 4 at 158 ppm) as a function of
CO2 percentage in the feed.
EG is the dominating route, as opposed to the case of CO2
absorption in [EMIM][2-CNpyr] (Figure S7b), where the
CO2-cation pathway dominates. Under moist CO2 (100%
RH), the formation of carbonate (Route 3) is superseded by
bicarbonate (Route 4). The mixture absorbs as much as 30 wt
% water under 100% RH feed. New hydrogen bonds occur
under water-rich conditions, as indicated by the downshift of
the bicarbonate peak from 158 ppm (α) to 160 ppm, as well as
the downshift of EG (1). However, the total CO2 capacity is
not compromised by the presence of water. We hypothesize
that the deprotonated EG is stabilized by the H-bonding
network and the presence of the [2-CNpyr]/2-CNpyrH
adduct (conjugate base and acid). Stabilization of the EG-
CO2 reaction complex through H-bonds and Coulombic
interactions (since the product is an anion) supports our
interpretation for the consistent CO2 capacities obtained in
Figure 2d.
In order to understand the reaction mechanism and
energetics, calculations at the DFT level were performed.
The calculated relative energies of the transition states and
final products are shown in Figure 5 for the proposed reaction
network (see Table S6 for tabulated energies). DFT analysis
suggests the carbonate formation via Route 3 has the smallest
activation energy barrier at 2.6 kJ/mol (TS3 in Figure 5), in
comparison to 6.2 for carbamate (TS1 for Route 1), 5.9 for
carbene intermediate (TS2*), and 10.7 (TS2**) kJ/mol for
carboxylate via carbene (Route 2). These relatively low
activation energies are consistent with the literature for gas
phase simulations of CO2 absorption by azolide28 and
superbase27 ILs as well as imidazolium acetate.26 Route 2 is
absent in the previously investigated phosphonium ILs with
the [2-CNpyr] anion where the reaction energy for Route 1
was reported as −64 kJ/mol.6 We calculated a similar reaction
energy of −70.7 kJ/mol for CO2 binding directly to the
individual anion alone, with the difference attributed to the
different basis sets used (see Table S7 for species energies). In
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Figure 5. Calculated relative energies (left) of the reaction systems shown for Routes 1−3 (right). Calculated transition states correspond to the
CO2 binding to the anion (TS1 in Route 1), CO2 binding to the cation via carbene (TS2* and TS2** Route 2), and CO2 binding to EG (TS3 in
Route 3). TS2* is the hydrogen transfer step from the [EMIM] cation to the [2-CNpyr] anion, in the presence of CO2, whereas TS2** is the
carboxylate formation from carbene. Color code: carbon (green), oxygen (red), nitrogen (blue), and hydrogen (gray). Dotted lines are H-bonds.
the presence of [EMIM] and the associated H-bonding that is
observed in the calculated TS1 product in Figure 5, a much
smaller reaction energy at −18.63 kJ/mol was obtained for
Route 1. Similarly, for TS3 product, the presence of H-bonds
yields a reaction energy of −16 kJ/mol. This is much smaller
than the calculated −56.9 kJ/mol for CO2 binding directly to
EG without any interaction between the anion and EG. The
impact of H-bonding in ILs has been discussed in the literature
to result in lower estimated reaction energies.35 In a study by
Low et al.,36 it is discussed that the H-bonds in ILs is usually
predicted to be shorter when calculated in the gas phase
compared to the implicit solvent. This results in lower
estimated total energies due to the underestimated electro-
statics. According to our calculations of the rIL pair, the H-
bond lengths between the anion and cation are in the orders of
1.9 and 2.2 Å which indicate moderate H-bond formation with
induced electrostatics. The H-bond length between EG and
the anion that is calculated in Route 3 is 1.5 Å in reactants, 1.3
in TS3 (consistent with covalent bonding), and 1.6 in
carbonate, all of which are shorter than that of the ion pair
of rIL. This can explain the reduced nucleophilicity of the
anion toward CO2 and Route 1 products being the minority.
Although the carboxylate formation in Route 2 seems to be
thermodynamically most favorable, with an overall reaction
energy of −69.2 kJ/mol, it involves the carbene intermediate
by the cation deprotonation which requires a higher activation
energy (TS2**). The determination of the transition state
from [EMIM] to [EMIM]+-CO2− in a single step was not
possible due to the complexity of simultaneous CO2 binding
and hydrogen transfer, as also discussed previously for CO2
binding to [EMIM][acetate] by Mao et al.26 In the absence of
solvation effects, we treated the [EMIM]-CO2 complex to
occur by a two-step reaction. This approach does not account
for the stabilization of the carboxylated imidazolium by
another imidazolium via H-bond as reported by Mao et al.26
After a certain CO2 loading, there would be no free
imidazoliums to stabilize the carboxylated imidazolium;
therefore, Route 2 would be terminated. This may explain
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pubs.acs.org/journal/ascecg Letter
why we do not experimentally find Route 2 products as the
majority. Future ab initio molecular dynamics simulations
investigating the solvation environment would be helpful in
determining the possible complexes for a transition state search
in Route 2 and better compare with experimental results.
■ CONCLUSIONS
In summary, we present a new sorbent for reactive CO2
separations based on [EMIM][2-CNpyr] and EG. The 1:2
molar mixture of rIL:EG forms a DES via hydrogen bonding. A
detailed mechanistic investigation of the CO2 absorption by
rIL:EG shows that carbonate formation by the deprotonated
EG, in the presence of the pyrrolide anion, is the most
significant reaction. Even at extremely low partial pressures of
CO2, carbonate formation is accompanied by the carboxylate
formation via the carbene intermediate. Unlike previous
studies on reactive ILs with aprotic heterocyclic anions,
carbamate formation in the rIL:EG sorbent is minimal. The
specific advantages of the rIL:EG solvent are the high capacity
at low CO2 concentration, improved absorption rates, and mild
solvent regeneration temperature compared to amines and
rILs. The stability of the sorbent under absorption and
desorption conditions studied are a result of the extended
hydrogen bonded network among all species. While the
presence of a significant amount of water (30 wt %) favored
bicarbonate over carboxylate and carbamate products, the CO2
capacity was maintained. Further studies on solvent regener-
ation in the presence of water and thermal stability are needed
to assess the suitability of these new sorbents for direct air
capture of CO2.
■
ASSOCIATED CONTENT
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acssuschemeng.0c07217.
Materials; synthesis; tabulated densities, viscosities, and
water contents; details of NMR and IR analysis;
https://dx.doi.org/10.1021/acssuschemeng.0c07217
ACS Sustainable Chem. Eng. 2021, 9, 1090−1098
ACS Sustainable Chemistry & Engineering
calculated energies for reaction species; inverse recovery
method; and HMBC spectra (PDF)
■ AUTHOR INFORMATION
Corresponding Author
Burcu Gurkan − Department of Chemical and Biomolecular
Engineering, Case Western Reserve University, Cleveland,
Ohio 44106, United States; orcid.org/0000-0003-4886-
3350; Email: beg23@case.edu
Authors
Yun-Yang Lee − Department of Chemical and Biomolecular
Engineering, Case Western Reserve University, Cleveland,
Ohio 44106, United States; orcid.org/0000-0002-4165-
0857
Drace Penley − Department of Chemical and Biomolecular
Engineering, Case Western Reserve University, Cleveland,
Ohio 44106, United States
Aidan Klemm − Department of Chemical and Biomolecular
Engineering, Case Western Reserve University, Cleveland,
Ohio 44106, United States
William Dean − Department of Chemical and Biomolecular
Engineering, Case Western Reserve University, Cleveland,
Ohio 44106, United States
Complete contact information is available at:
https://pubs.acs.org/10.1021/acssuschemeng.0c07217
Author Contributions
Y-Y.L. synthesized the solvent, performed CO2 absorption/
desorption measurements, and analysis of NMR and IR
spectroscopy. D.P. performed DFT calculations. A.K. meas-
ured densities and viscosities and performed excess molar
volume analysis. W.D. measured DSC. B.G. oversaw the
experiments, computations, and analysis. All authors con-
tributed to the writing of the manuscript.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors thank Dr. Nalinda P. Wickramasinghe at the
Instrumentation Facility of the Department of Chemistry at
CWRU for feedback on the inverse recovery measurements by
NMR and Prof. Shane Parker for discussions on transition state
calculations. The authors acknowledge the Northeast Ohio
High Field NMR Facility and the Soft Material Character-
ization Laboratories for the access to TGA. The ionic liquid
synthesis and CO2 measurements were supported by an Early
Career Faculty grant from NASA’s Space Technology Research
Grants Program under Award No. 80NSSC18K1505. The
analysis of the absorption mechanism was in part supported by
the American Chemical Society Petroleum Research Fund
59520-DNI4. The phase behavior and the physical property
characterization of the solvents were supported by the
Breakthrough Electrolytes for Energy Storage (BEES), an
Energy Frontier Research Center funded by the U.S.
Department of Energy, Office of Science, Basic Energy
Sciences under Award No. DE-SC0019409.
■
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