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Page 1 of 59 Physical Chemistry Chemical Physics
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DOI: 10.1039/C5CP03364K
A Detailed Study of Cholinium Chloride and Levulinic Acid Deep Eutectic

Solvent System for CO2 Capture via Experimental and Molecular
Physical Chemistry Chemical Physics Accepted Manuscript

Simulation Approaches
Ruh Ullah,a Mert Atilhan,a* Baraa Anaya,a Gregorio García,b Ahmed ElKhattat,a Mohammad
Published on 30 June 2015. Downloaded by Yale University Library on 04/07/2015 12:47:34.
Tariq,a and Santiago Apariciob*
a
Department of Chemical Engineering, Qatar University, P.O. Box 2713, Doha, Qatar
b
Department of Chemistry, University of Burgos, 09001 Burgos, Spain
*
Corresponding authors: [email protected] (M. A.) [email protected] (S. A.)
Abstract.
Choline chloride + levulinic acid deep eutectic solvent is studied as a suitable material for
CO2 capturing purposes. The most relevant physicochemical properties of this solvent are
reported together with the CO2 solubility as a function of temperature. The corrosivity of this
solvent is studied showing better performance than amine-based solvents. A theoretical study
using both Density Functional Theory and Molecular Dynamics approaches is carried out to
analyze the properties of this fluid from the nanoscopic viewpoint and their relationship with
the macroscopic behavior of the system and its ability for CO2 capturing. The behavior of
liquid – gas interface is also studied and its role on the CO2 absorption mechanism is
analyzed. The combined experimental plus theoretical reported approach leads to a complete
picture of the behavior of this new sorbent with regard to CO2, which together with its low
pricing, and the suitable environmental and toxicological properties of this solvent, lead to a
promising candidate for CO2 capturing technological applications.
Keywords: Deep eutectic solvents; carbon capture; thermodynamics; molecular simulations.
1
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Physical Chemistry Chemical Physics
DOI: 10.1039/C5CP03364K
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1. Introduction
Carbon dioxide capture is one of the most relevant technological,1environmental,2 social3 and

economic4 needs nowadays. The effect of anthropogenic CO2 atmospheric emissions on
global warming has been widely proven,5,6 which in all the considered scenarios will lead to
increasing temperatures at a global level,7 with large economic, social and environmental
consequences.8,9 The most important source of anthropogenic CO2 emissions rises from fossil
fuels combustion for transportation, power generation and industrial purposes.10,11,12In

particular, electricity production from fossil fuelled power plants takes account of a large
percentage of total CO2anthropogenic emissions,13,14 and thus, reducing these emissions has a
pivotal role for controlling climate change. In spite of the remarkable advances in renewable
electricity production approaches, the state-of-the-art of these methods is not alternative to
fossil fuels, and thus, all the projections show that power plants based on fossil fuels would
develop a pivotal role for energy production along the next decades.15,16 Therefore, a realistic
approach for reducing CO2 emissions in a reasonable timeframe is to develop suitable
technologies that allow for capturing CO2 from flue gases in fossil fuelled power
plants.17,18,19,20,21,22
The state-of-the-art of CO2 capture technologies does not allow carbon capturing without an
unacceptable increase in the costs of electricity generation,23,24,25 which hinders their
application for the required large scale. The most common approach for carbon capturing is
post-combustion sorption based on alkanolamine liquid sorbents,26,27 which although showing
large affinity for CO2 molecules has serious technological drawbacks, such as facilitates
corrosion, solvent evaporation or degradation, and large capturing costs.23,28,29,30,31.32,33,34,35
Therefore, alternative CO2 sorbents have been studied in the last few years such as metal-
organic frameworks,36 solid sorbents,37 carbon-based materials,38 or membranes.39One
alternative that has attracted great attention are ionic liquids, IL,40, 41,42
because of the
possibility of tuning their properties, and thus their affinity for CO2 molecules, through the
selection of suitable ions. Nevertheless, ILs have also showed some problems with regard to
their application for carbon capture purposes such as their large viscosity or their cost, which
have hindered their application for capturing purposes at industrial scale.43,44,45,46,47,48
Therefore, although these drawbacks should not be considered as a motive for discarding ILs
as possible CO2 capturing candidates,49,50,51,52several alternatives have been proposed to
maintain the design flexibility of ILs while avoiding their well-known problems. Deep
eutectic solvents (DES) are among the most promising options to overcome these IL problems
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while maintaining their positive properties and the ability of tuning their behavior.53,54 DES
are usually a binary mixture of a salt (or IL) with an hydrogen bond donor (HBD), which at a

certain molar ratio leads to a system with a melting point close to ambient temperature and
lower than those for the pure compounds generating the DES.53,54, Although several salts have
been proposed for developing DES, most of the available literature is based on cholinium
chloride ([CH][Cl]) (Figure 1).54 [CH][Cl] is a non-toxic and biodegradable compound; and it
can be obtained at very low cost.55,56 [CH][Cl] may lead to DES when mixed with different
types of HBDs such as urea, polyols (glycerol or ethylene glycol), sugars or carboxylic acids.
To maintain the suitable characteristics of [CH][Cl] when developing DES, this salt has to be
combined with suitable HBDs, and thus, an approach is using HBDs.57,58 In recent works
Maugeri et al.59 and Florindo et al.60 proposed the use of HBDs combined with [CH][Cl].
Levulinic acid ([LEV]) is a compound fully biodegradable, non-toxic, that may be obtained
from biomass at low costs,61,62,63 and thus [CH][Cl] + [LEV] DES (Figure 1. ) may be
considered as a renewable materials. [CH][Cl] + [LEV] lead to DES when mixed ([CH][Cl] :
[LEV] at 1:2 molar ratio, CHCl_LEV_1_2).59,60 The available studies on CO2 capture using
[CH][Cl] based DES are mostly limited to systems containing HBDs such as urea, glycerol,
ethyleneglycol or carboxylic acids such as malonic or lactic,64,65,66,67,68,69,70,71,72 but no studies
for DES involving [LEV] are reported. Therefore, a study on the suitability of
CHCl_LEV_1_2 DES for CO2 capturing purposes is reported in this work. Considering that a
full characterization of this material is required for analyzing their weaknesses and strengths
for carbon capture purposes, a physicochemical characterization of CHCl_LEV_1_2 was
carried out, in which the most remarkable properties were selected both because they are
required for process design purposes and/or because they provide information about the
structure and behavior of the fluid. CO2 absorption was studied at isothermal conditions
pressures up to 30 bar. Likewise, in order to understand the mechanism of CO2 absorption at a
nanoscopic level, a theoretical study using both molecular dynamics, MD, and quantum
chemistry (in the Density Functional Theory, DFT, framework) approaches was reported. The
fluid’s structure was studied for pure CHCl_LEV_1_2 and for this fluid after CO2 absorption
as a function of temperature, pressure and amount of absorbed CO2 via MD simulations.
Short-range interactions in the fluid were analyzed in detail from DFT calculations. Likewise,
considering the relevance of liquid – gas interfacial behavior for CO2 capturing purposes, MD
simulations were also carried out for analyzing the behavior of CO2 molecules at the DES
surface. The reported study shows for the first time a combined full experimental and
computational characterization of DES as sorbents for CO2 capturing purposes.
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2. Methods
2.1 Materials

Levulinic acid (CAS:123762, Aldrich) and choline chloride (CAS: 67481, Iolitec) were used
as received. A mixture of 1:2 molar ratio of [CH][Cl]:[LEV] acid (CH_Cl_LEV_1_2 DES)
was prepared by mixing 46.54 g of chlorine chloride and 77.41 g of [LEV]. The resulting
mixture was stirred for 2 hours using a magnetic stirrer. The formation of eutectic solution
was examined and confirmed using both NMR (Varian Unity Inova 400 MHz) and FTIR
spectrometer (Spectrum 400, PerkinElmer, USA). CH_Cl_LEV_1_2 DES sample is prepared
by mixing the ionic liquid and acid at room temperature in a glove box compartment. Water
content (1.69 wt %) was measured using Karl Fischer coulometric titration (Metrohm 831 KF
coulometer) to 0.3% accuracy in water mass content.
2.2 Experimental details

NMR measurements were done using a Varian Unity Inova 400 MHz equipment at 298.15 K
(± 0.1 K) for the 1H and 13C nuclei. CHCl_LEV_1_2 samples were prepared on 5 mm NMR
tubes, with 0.005 g of CHCl_LEV_1_2 mixed with 1 mL of D2O.
The formation of DES was examined and confirmed using the FTIR spectrometer, Spectrum
400, PerkinElmer, USA. Other than the FTIR studies for characterization of the DES system,
in-situ FT-IR measurements were carried out by using Bruker® Vertex 80 Fourier transform
infrared spectrometer, which is coupled with temperature controlled high pressure liquid cell
(HPL-TC) that can go up to 30 bars and supplied by HarrickTM Scientific. HPL-TC was
equipped with high-resolution Si windows, teflon spacers of 2280 micron path-length and
Viton® o-rings. The path-length was intentionally kept long to provide more volume, and
therefore increase the contact opportunity between CO2. In order to adjust CO2 pressure a gas
feeding manifold system was designed and the schematics are shown in Figure S1.
Density and viscosity were both measured through an Anton Paar DMA 4500M and Lovis
200 M/ME units respectively. The density meter uses the oscillating U-tube sensor principle
and it has a volume requirement of 1 mL of sample. The density meter has the accuracy of
density measurement reported as 0.00005 g/m3 in density and ± 0.05 K in temperature. Anton
Paar Lovis 200 rolling ball viscometer measures the rolling time of a ball through transparent
and opaque liquids according to Hoeppler's falling ball principle with ± 3 % viscosity
uncertainty and ± 0.02 K accuracy in temperature measurements.
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The pH and conductivity measurements were performed at 293.15 K by pH/conductivity

meter (3200M Multi-parameter Analyzer, Agilent Technologies, USA). The conductivity and

the pH of the final product was 752.85 ± 5.2 µs/cm and 2.7 ± 0.2 at temperature of 293.15 K.
Indeed, conductivity is an important indicating property, where IL can play the role of both
solvents and electrolytes in electrochemical reactions. Ionic liquids exhibit a broad range of
conductivities from 0.1 to 20 mS cm-1 as conductivity is affected by many factors such as
density, viscosity, anionic charge, ion size, delocalization, aggregations and ionic motions.73
Recently, some DES liquid systems based on choline chloride,74 with properties similar to
those of ionic liquids, have been prepared by mechanically mixing two different components,
where choline can be used as alternative cation in combination with suitable anion to generate
ionic liquids.
Refractive Index with regard to the sodium D-line were measured (±1×10−5) using an
automated Leica AR600 refractometer, with the sample temperature being controlled using a
Julabo F25 external circulator and measured with a built-in thermometer (±0.01 K). A
standard supplied by the manufacturer was used for refractometer calibration.
Corrosion experiments were conducted using circular specimens of carbon steel 1018 (0.186
wt% C, 0.214 wt% Si,0.418 wt% Mn, 0.029 wt% P, 0.019 wt% S, balance Fe) with 1.93 cm2
surface area of specimen exposed to the medium. Carbon steel 1018 is selected for corrosion
experiments since it is a common material that is used in process equipment in chemical
industries. The specimens were prepared according to ASTM G1-03 standard by wet grinding
and polishing using 320,600 and 1200 grit SiC papers. The specimen was then degreased by
high purity acetone, rinsed with deionized water and dried with hot dry air.75 Electrochemical
experiments were conducted in 100 cm3 jacketed micro cell supplied by Autolab (Figure 2).
The microcell was equipped with a potentiostat (Autolab PGSTAT101) and data acquisition
system (NOVEA 1.7). The corrosion cell consisted of Ag/AgCl reference electrode filled with
3M KCl solution, two 316 stainless steel counter electrodes and the working electrode.
Heated water circulator was connected to the outer cell jacket throughout experiments for
temperature control. Water-cooled condenser was utilized to minimize vaporization losses of
the test solution. Gas supply streams and CO2 gas flow meter was connected to the cell.
Throughout all experiments, a gas stream was maintained in the gas phase of the cell. Open
circuit potential OCP measurement of the specimen against the reference electrode was
recorded until it is stable (defined as ± 0.01 mV between successive readings). The
polarization curve was generated directly by the data acquisition system in the range of ±250
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mV vs OCP and a scan rate of 0.001 V/sec. Tafel extrapolation method was used to determine
corrosion current (Icorr) which was converted to corrosion rate by the following equation:

ଷ.ଶ଻×ଵ଴షయ ×ூ೎೚ೝೝ ×ாௐ
‫= ܴܥ‬
ఘ
(1)
2
where CR is corrosion rate in (mm/yr) , Icorr is corrosion current in (µA/cm ) , EW is the
equivalent weight of the carbon steel specimen (g/equivalent) and ρ is the density of the
specimen (g/cm3). The numerical value that appears in equation 1 is a constant that defines
the units for the corrosion rate and it is calculated from the calibration of the apparatus.
Thermal stability analysis of materials was performed with Perkin Elmer Pyris 6 TGA
instrument, where, samples were heated in N2 environment from 303 K to 873 K at the rate of
5/min.
For carbon dioxide adsorption measurements, a high-pressure magnetic suspension sorption
apparatus (MSA) made by Rubotherm Präzisionsmesstechnik GmbH were used. Schematic of
the apparatus is given in Figure S2. MSA apparatus is rated up to 350 bars at 373 K. MSA has
two different operation positions. First, the measurement cell is filled with CO2 gas, and MSA
records the weight change of the sample that is placed in the sample container as the high-
pressure gas is absorbed by the sample. The second measurement position is used to measure
the in-situ density of the high-pressure gas, which is required to calculate the amount of the
adsorbed gas onto the sample in the high-pressure cell. In this work, pressures up to 30 bars is
used as the maximum pressure and at the end of each isotherm, hysteresis check is conducted
at each isotherm by collecting desorption data as the system is depressurized. Physical
adsorption nature is later is cross-checked by comparing before and after FTIR measurements
of the DES sorbent. CO2 adsorption-desorption isotherms were selected as 298.15 K and
323.15 K. Detailed operating principles and data correlation of the magnetic suspension force
transmission is also discussed previously elsewhere.76,77
For buoyancy calculations used in sorption measurements, in-situ density of the pressurized
gas in the high-pressure cell is measured. Archimedes’ principle is used for density
measurements by utilizing a calibrated silicon sinker placed just above the sample basket in
the pressure cell. The silicon sinker used in this apparatus had a volume of 4.4474 cm3
measured at 20 0C with a 0.0015 cm3 uncertainty and a density of 4508 kg/m3 measured at
293.15 K with a 4 kg/m3 uncertainty. On the other hand, the uncertainty for pressure
measurements is ±0.05% in full scale of the 350 bar rated pressure transducer and ±0.1 K for
the temperature measurements.
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2.3 Simulations
Optimizations from those systems composed by one isolated molecule (i.e. ions, levulinic

acid or CO2) up to systems composed by DES and CO2 (CHCl_LEV_1_2···CO2) were
optimized. Optimized minima were checked trough their vibrational frequencies. For those
simulations wherein two or more molecules are present, different starting points were
employed in order to study different relative dispositions, focusing our attention on the
disposition of minimal energy. All these calculations were carried out using B3LYP78,79
coupled with dispersion corrections according to Grimme’s scheme80 (B3LYP-D2), with 6-
31+G** basis set. B3LYP has been selected since it has showed a remarkable performance
over a wide range of systems,81 while dispersion corrections are adequate since we are
considering systems with dispersive interactions such as hydrogen bonds.80 Besides,
calculated energies after dispersion corrections are comparable with more reliable values,
such as those obtained at MP2 level.82
From those systems composed by two or more molecules, computed energies were corrected
(to avoid basis set superposition error) according to counterpoise procedure.83Interaction
energies (ΔE) for different process related with CO2 capture and formation of DES were
computed. Thus, ∆E for CHCl_LEV_1_2···CO2 (i.e. CO2 capture using DES) was calculated
as: ΔEDES·CO2 = EDES·CO2 – (EDES + ECO2), being EDES-CO2, EDES and ECO2 the (counterpoise
corrected) energies for CHCl_LEV_1_2···CO2, CHCl_LEV_1_2 and CO2, respectively.
Intermolecular interactions were analyzed by means of Atoms in Molecules (AIM) theory.84
Topological analyses according AIM theory were carried out using MultiWFN package.85
According to Bader’s theory,84 there are four kinds of critical points, but giving the
characteristics of the studied systems and to improve and clarify data analysis we have mainly
focused over bond critical points (BCP), which raises the criteria for considering the presence
of intermolecular interactions. Finally, atomic charges were computed to fit the electrostatic
potential according to the ChelpG scheme.86 All calculations were carried out with Gaussian
09 (Revision D.01) package.87
MD simulations were carried both for pure CHCl_LEV_1_2 and for CHCl_LEV_1_2 + CO2
systems. In the case of pure DES, 250 [CH][Cl] ion pairs plus 500 [LEV] molecules were
considered for all the simulations in the 298 to 348 K temperature range at 0.1 MPa of
pressure. Mixed CHCl_LEV_1_2 + CO2 were prepared according to the experimental
solubility data obtained in this work, and thus, four different mixed systems were prepared for
simulations at 298 K, all of them containing the same number of ion pairs an [LEV]
molecules as for pure DES simulations and with different number of CO2 molecules to mimic
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experimental adsorption isotherm up to 1 MPa (samples CHCl_LEV_1_2_CO2_I,

CHCl_LEV_1_2_CO2_II, CHCl_LEV_1_2_CO2_III, and CHCl_LEV_1_2_CO2_IV; Table

S2, ESI). All these simulations were carried out in the NPT ensemble, with initial low density
boxes (~ 0.2 g×cm-3) built using the Packmol program.88 Simulations were carried out starting
from these initial boxes being equilibrated during 5 ns with additional 10 ns runs collected for
production purposes.
In the case of MD simulation for the analysis of interfacial behavior, a box of

CHCl_LEV_1_2 with the same characteristics of those used for the simulation of pure DES,
and previously equilibrated, was put in contact along the z-direction with i) a vacuum layer
(with the vacuum layer dimension in the z-coordinate three-times larger than the DES layer)
for describing the DES – vacuum interface, and ii) with a CO2 gas phase (with gas layer also
being three-times larger in the z-dimension than the DES liquid layer) for considering DES –
CO2 gas interface. The density of the CO2 gas layer correspond to that at 298.15 K and 10 bar
obtained from CO2 reference equations of state.89 These interfacial simulations were carried
out in the NVT ensemble at 298.15 K.
All the MD simulations were carried out using the MDynaMix v.5.2 molecular modeling
package.90 Pressure and temperature were controlled using the Nose–Hoover thermostat.
Coulombic interactions were handled with the Ewald summation method,91 with cut-off
radius of 15 Å. Tuckerman–Berne double time step algorithm,92 with long and short time
steps of 1 and 0.1 fs, was considered for solving the equations of motion. Lorentz-Berthelot
mixing rules were used for Lennard-Jones terms.
The forcefield parameterization used along MD simulations is reported in Table S1
(Electronic Supplementary Information, ESI). This parameterization was developed using
DFT calculations for clusters formed by 1 [CH][Cl] + 2 [LEV] molecules which were
optimized as reported in previous section, and thus, ChelpG86 charges were calculated for this
cluster. The optimized structures for this model cluster show that LEV molecules may interact
in two different positions (see Results and Discussion Section), with [LEV] molecules having
different charges depending on the interacting site. Therefore, the used parameterization
considers two types of levulinic acid molecules (LEV_I and LEV_II) with different charge
parameters (Table S1, ESI). The proposed parametrization leads to charges of +0.8254 for
[CH]+, -0.6849 for Cl-, -0.0663 for LEV_I, and -0.0743 for LEV_II. This parameterization
was developed to obtain a more realistic physical picture of the charge distribution in the
studied DES instead of applying the simplified option of +/- 1 total charge for the
cation/anion and null charges for any LEV molecule.
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3. Results and discussion

3.1 Density, refraction index and viscosity

These properties were collected, Table S3 (ESI) and presented in Figure 3. Similar DES
systems have been studied and their density and viscosity profiles have been reported for
CHCl and levulinic acid,60 glyceric acid,60 phenol,93 urea,94 and glycerol95 containing DES
systems elsewhere. Density and viscosity values are important for these exotic mixtures for
development of suitable equations of state, which has a crucial role in calculation of further
thermodynamic properties for developing industrial processes including gas separation
operations that runs with novel solvents substitutes of amines. Most of the studied DES
system densities are in the range of 1 – 1.35 gcm-3 at 25 °C. DES systems that contain
metallic salts show tendency to have higher densities at room temperature in the range of 1.3
– 1.6 g/cm3. [CH][Cl] and urea DES systems (with 1:2 ratio) have been reported to have 1.25
g cm-3 density at 293.15 K.96 For the experimented CHCl_LEV_1_2 DES system, density
values falls in the range of 1.14 – 1.10 g cm-3 between temperature range of 293.15 K to
363.15 K. This shows a similarity of the values of a similar DES system formed with
[CH][Cl] and a different acid based HBD. Refractive index follow a linear trend in the 298.15
K to 238.15 K range with values in the 1.466 to 1.455 range. These refractive index values are
in the lower range for the DES studied in the literature, nevertheless they show that
CHCl_LEV_1_2 DES is a highly polarizable solvent.96
On the other hand, viscosity has also been extensively measured for the available DES, due to
its importance for industrial purposes. Viscosity data are required for DES applications not
only in gas solubility and separation processes but also in fields such as lubrication or any
other potential high-pressure operation have been considered as well.97 Moreover, viscosity
data is essential to realize the possible mass transfer coefficient limitations as well as fluid
pumping issues for advanced process system and equipment design purposes. [CH][Cl]
couple with various HBD DES systems have recently been investigated and their viscosities
have been reported and quite high viscosity values have been observed. For [CH][Cl] and
urea 1 to 2 DES system viscosity of 750 mPa×s at 298.15 K has been reported.94 Moreover,
again for [CH][Cl] and glycerol,95 ethylene glycol,94 glycolic acid,60 and phenol93 DES
systems, viscosity values of 246.8, 35, 394.8 and 35.1 mPa×s at 303.15 K have been observed
respectively. For the experimented CHCl_LEV_1_2 DES system, viscosity at of 171.3 mPa×s
at 298.15 K has been observed in this work. Florindo et al.60 also reported a viscosity value of
a same system for temperatures between 298.15 K and 350 K (e.g. 226.8 mPa×s at 298.15 K).
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The difference between viscosity data reported in this work and those by Florindo et al.60 rises
from i) the different methodology for sample preparation (grinding, Florindo et al.,60 or

mixing, this work, DES components), and ii) the different water content. The most
remarkable feature should be the water content, which develops a pivotal role for viscosity
measurements. The sample used in this work has a water content of 1.6 wt % which is higher
than the 0.23 wt % of the sample used by Florindo et al.,60 which would justify the lower
viscosity data reported in this work, Figure 3b. This is confirmed by the viscosity data
reported by Florindo et al.60 for CHCl_LEV_1_2 DES saturated with water (9.88 wt %),
which shows less viscous behavior than the sample used in this work.
3.2 NMR and FTIR

1
H and 13C NMR features are summarized in Table S4 (ESI), the data are in good agreement
with those by Florindo et al.60 and it discards the presence of relevant impurities at least at the
NMR detection levels. FTIR characterization of the DES structure provides information about
interactions and complexation between constituents. FTIR spectra of pure [LEV] and choline
chloride are given in Figure S1 (ESI). Regarding pure [LEV], vibrational bands at 1720-1695
cm-1, 1435-1400 cm-1, 1380-1345 cm-1 and 1225-1100 cm-1 refers to the presence of aliphatic
ketone, while the vibrational bands 1720-1701 cm-1 refers to a carbonyl compound. The FTIR
spectrum of the [LEV] confirms its classification as a keto-acid. For pure choline chloride,
vibrational bands at 3540-3200 cm-1 and 1205-885 cm-1 refers to the presence of hydroxyl or
amino group, while those bands at 2990-2855 cm-1 and 1485-1415 cm-1 refers to the presence
of an alkyl group cm-1. On the other hand, the formation of formation of DES was confirmed
from by the FTIR spectrum of CHCl_LEV_1_2 DES 1:2 molar ratio as shown in Figure 4,
where, the vibrational bands at 2990-2855 cm-1 and 1485-1415 cm-1 indicate the presence of
alkyl group, 1720-1695 cm-1 bands, 1435-1400 cm-1, 1380-1345 cm-1 and 1225-1100 cm-1
bands represent the aliphatic ketone group, 1720-1701 cm-1 bands refer to a carbonyl
compound, and 1745-1710 and 1300-1000 cm-1 bands refer to an ester or ketone compound.
3.3 In-situ FTIR

For in-situ FT-IR measurements temperature controlled high-pressure liquid cell (HPL-TC)
manufactured by Harrick Scientific was used. HPL-TC was equipped with specific internal
parts: high-resolution Si windows, TeflonTM spacers of 2280-micron path-length and Viton O-
rings. The path-length was intentionally kept thick to provide more volume, and therefore
increase the contact opportunity between CO2 and the solvent molecules as well as to provide
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a more stable sealed system. In order to manipulate CO2 injection at the desired pressures
under isothermal condition, a particular system was designed and attached to the

spectrometer. In-situ FTIR experiment was performed under 50 ºC over a range of low CO2
pressures. To ensure thermal stability, the thermo-regulator was kept operating for at least one
hour prior to the experiment. A background spectrum of the HPL-TC system under vacuum is
collected before and after each DES in-situ FTIR measurement and this background is
subtracted from the DES+CO2 spectrum data. To this end, the sample spectrum was collected
upon exposure to CO2. This sample spectrum is believed to be influenced by the contribution
of both CO2 in the absorbed phase (dissolved in DES) and gaseous CO2 in the bulk especially
that the path-length is thick. Hence, in order to eliminate the gaseous CO2 contribution, pure
CO2 spectra were collected separately at same conditions of the sample spectrum, and then
each was subtracted from the sample spectrum that corresponds to same operating conditions.
In-situ FTIR experimental findings of CHCL_LEV_1_2 DES with the presence of pressurized
CO2 at different pressures are shown in Figure S3 (ESI). Near CO2 fundamental bending
mode (600-700 cm-1), interesting gradual bands appear around 619 cm-1 analogous to the red-
shifted bending mode band observed in the computational results which was overlapping with
other CO2-free DES and CO2-loaded DES bands. The subtraction of gaseous CO2 and DES
spectra resulted in a loss of CO2 related bands that are overlapped and appear as negative split
bands. Nevertheless, the effect of the increasing pressure was observed and recognized by the
increase in intensity that is corresponding to the increase in the concentration of absorbed CO2
in liquid DES phase.
3.4 TGA
Thermal gravimetric analysis (TGA) of the DES system has been checked to see the
temperature limitation of the absorbent. Figure 5 shows the TGA profile of the experimented
DES system. Single step degradation behavior was observed and the analysis shows that the
DES system is stable up to 453 to 473 °C, which makes the experimented DES system
suitable for high temperature post combustion CO2 capture process conditions as well.
3.5 Corrosion Measurements

Needless to say that corrosivity is one of the most important concerns in process operation
point of view to forecast the equipment depreciation with time and make plans for not only
during material selection for equipment design but also during the operation by selection the
appropriate corrosion inhibitors to prevent the potential corrosion within the pipe and
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absorption column vessel. For this purpose, corrosion experiments have been conducted for
the DES system and monoethanolamine (MEA) system, as it is the most widely used CO2

capture agent in chemical plants. Figure 6 shows the current density vs potential plot for the
two studied DES and MEA systems. The details on how to interpret the polarization curve are
given in section 2.2 of this work. Two identical carbon steel samples are used for the
corrosion experiments and they were prepared for the measurements as per ASTM G1-03
standards as mentioned in above section. The surface area of the specimens was calculated as
1.93 cm2. The analysis on the polarization curves for the CO2 loaded DES system showed that
the corrosion potential is -0.43 V and the corresponding corrosion rate behavior is 0.027
mm/year. On the other hand, the corrosion behavior of the identical carbon steel specimen in
CO2 loaded MEA solution was conducted. Corrosion potential was recorded as -0.75 V and
the corresponding corrosion rate was calculated as 0.54 mm/year. The results shows that from
corrosion point of view the DES system exhibits much more corrosion resistant behavior
when compared with MEA system and this considerable order of magnitude difference is a
great advantage in reducing the both operating and fixed cost of the absorber column and its
ancillary equipment in a CO2 capture plant.
3.6 CO2 Solubility

CO2 solubility studies were conducted by using state of the art magnetic suspension based
MSA and the details of the apparatus mentioned above. Pressure transducers (Paroscientific,
US) were used in a range from vacuum up to 35 MPa with an accuracy of 0.01% in full scale.
The temperature was kept constant with an accuracy of ± 0.5 K for each measurement (Minco
PRT, US). In situ density values for CO2 are measured during sorption measurements as it is
necessary to calculate the absorbed CO2 amount, and density values are cross-checked with
REFPROP 9.098 for consistency purposes. Absorption measurements were carried out using 2
to 3 mL DES samples. First the system is taken under vacuum for 8 hours at 293 K, 298 K,
308 K, 318 K and 323 K. CO2 is then pressurized through Teledyne Isco 260D fully
automated compressor and fed into the high-pressure measurement cell in which the CO2
absorption process begins. Once the solubility equilibrium is reached measurements are taken
for a period of 10 minutes; each data point is collected at every 30 seconds. At the end of each
measured pressure point, gas-dosing system triggers the compressor to the next pressure
measurement point, which increases the measurement cell pressure in a step-wise manner. In
this work, pressure up to 3 MPa (30 bars) is used for maximum pressure and 293 K, 298 K,
308 K, 318 K and 323 K isotherms were investigated for CO2 absorption in DES system.
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Solubility hysteresis check was conducted at each isotherm by collecting desorption data as
the system is depressurized. Details of the solubility experiment is based on the amount of

absorbed carbon dioxide on the sample is calculated by using below equation:
W + Wbuoy,sample + Wbuoy,sink = mabs + msample + msink (2)
where;
W = signal read by the instrument
Wbuoy,sample = Vsample× dgas = buoyancy correction due to sample

Vsample = volume of the sample
dgas = density of the gas
Wbuoy,sink = Vsinker× dgas = buoyancy correction due to sinker
Vsinker = volume of the sinker
mads = absorption amount
msample = mass of the sample
msink = mass of the sinker (sinker is a float that is used for in-situ gas density measurements)
Figure 7 shows the findings of the solubility measurements at 5 different isotherms up to 30
bars. It was observed that the maximum amount of CO2 solubility was decreased with the
increase in temperature. The DES system absorbed 2.316, 2.220, 2.100, 2.027 and 1.934
mmol of CO2 per gram of DES sample at 293 K, 298 K, 308 K, 318 K and 323 K respectively
at maximum operating pressure of 30 bar. Direct weight measurement technique allows in situ
observation of the behavior of the measured sample. In other words, potential swelling effect
can be observed during the measurements. In case of swelling of the sample, the increased
sample volume would cause loss in the buoyancy on the measurement cell, which in turn
would be obvious to see decrease in the amount of captured CO2. However, as it can be seen
from Figure 7 that the CO2 absorption trend has been reported as a curve with a positive
curvature. During the solubility measurements, sorption hysteresis was also checked by
conducting absorption/desorption cycle analysis and none of measurements at each isotherm
did not show a sign of chemisorption and weight measurements were obtained during the
desorption along with the same absorption path. Moreover, in order to check whether there is
a degradation of the sorption activity with the experimented DES system, each isotherm
measurements were repeated three times and there was no significant absorption activity loss
observed.
On the other hand, the kinetics of the absorption on DES system has been investigated. Figure
8 shows the amount of absorbed CO2 in DES system with time at both low and high
pressures. At 1 bar pressures average of 7 minutes were required reaching the equilibrium for
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a fully saturated DES solution. Whereas at 30 bars, 12 minutes passed to reach the
equilibrium conditions.

3.7 Nanoscopic behavior from Molecular Dynamics
Forcefield parameterization used in this work was validated through the comparison of
predicted physical properties with experimental values. Deviation between experimental and
simulated density, ρ, data in the 298 to 348 K range are reported in Figure 9 Density data
from MD are slightly lower than experimental data, but being closer to those by Florindo et
al.60 Nevertheless, deviations are lower than 0.9 % in the whole temperature range, which
show the suitable performance of the used parameterization for describing macroscopic
properties of the studied system. The temperature evolution of density, both for experimental
and molecular dynamics predicted data, allows obtaining isobaric thermal expansion
coefficient, αp, from its thermodynamic definition, leading to 0.583×10-3, 0.576×10-3 and
0.593×10-3K-1 at 298 K, for the experimental data obtained in this work, from Florindo et al.,60
and from molecular dynamics simulations, respectively, which show excellent agreement for
the simulated data with experimental values.
Self-diffusion coefficients were also calculated, using Einstein’s equation from mean
square displacements (msd), for all the involved molecules leading to values of 0.42×10-11
([CH]+), 0.68×10-11 ([Cl]-), and 0.63×10-11 ([LEV]) m2×s-1, at 298 K. The absence of
experimental data hinders the comparison of simulated self-diffusion coefficients data;
nevertheless, [CH]+ cation moves slower than [Cl]- and [LEV], which show similar mobilities
at 298 K. Perkins et al.99 reported self-diffusion data from molecular dynamics simulations of
reline DES (composed of [CH][Cl]+urea in 1:2 molar ratio), their values are lower than those
obtained in this work for CHCL_LEV_1_2 (roughly the half) in agreement with the larger
viscosity of reline in comparison with CHCL_LEV_1_2. Likewise, self-diffusion for [CH]+ in
reline are lower than for Cl- and the corresponding HBD (urea), which is also in agreement
with values for CHCL_LEV_1_2, but HBD in reline has larger molecular mobilities than that
of [Cl]-, whereas they have similar mobility in HCL_LEV_1_2. Perkins et al.99 justified the
self-diffusion data of [Cl]- and HBD in reline indicating that in spite of the strong hydrogen
bonding between both compounds their movements are not tied. On the contrary in the case of
CHCL_LEV_1_2 mobility of [Cl]- and HBD (LEV) seems to be strongly correlated.
A key point in the determination of self-diffusion coefficients from molecular dynamics
simulations is if the condition of fully diffusive regime is reached in the timeframe used,
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which is commonly measured through the so-called βparameter, defined as the slope of log-
log plots of msd vs. simulation time.

Fully diffusive regime is reached when β=1 whereas subdiffusive regimes are characterized
by β<1. Perkins et al.99 showed that in the case of reline at 298 K fully diffusive regime is
reached at 30 ns, whereas it is reached at 10 ns for CHCL_LEV_1_2 in this work. This may
be justified considering that reline viscosity94 is twice that for CHCl_LEV_1_2, which leads
to larger molecular mobilities (as showed by the larger self-diffusion coefficients) and thus to
diffusive regimes reached at shorter simulation times. Dynamic viscosity was calculated using
Green-Kubo method leading to 265 mPa×s at 298 K, which is in fair agreement with 226.8
mPa×s obtained by Florindo et al.60
Vaporization enthalpy may be obtained from molecular dynamics simulations as the internal
energy difference between liquid and gas phases (plus and R×T term), which can be
assimilated to the difference between potential energies.100,101 The gas phase was modeled
considering a low density cage (0.006 g×cm-3) composed by a [CH]+ - [Cl]- ion pair and two
LEV molecules not interacting with [CH][Cl]. In the course of gas phase simulations (10 ns
long), LEV molecules aggregated with [CH][Cl] ion pair. The main contributions to
CHCL_LEV_1_2 vaporization enthalpy at 298 K are summarized in Table 1 showing that the
main contribution to the potential energy differences between liquid and gas phases is non-
bonded term rising from intermolecular interactions, whereas bonded and intra-molecular
non-bonded terms are almost negligible. Likewise, the vaporization enthalpy
CHCL_LEV_1_2 is lower than those values reported in the literature for ionic liquids,100
which is in agreement with the strong effect of strong coulombic effects rising in ionic liquids
whereas the strength of LEV – ions intermolecular interactions in the studied DES are
weaker. This effect should be confirmed experimentally in future works.
The structure of CHCL_LEV_1_2 is strongly dominated by the strength and nature of
intermolecular interactions, Einter, and thus, intermolecular interaction energies were
quantified and reported in Figure 10. Anion – cation are the stronger intermolecular
interactions as it may be expected considering their ionic nature. Regarding the ion-[LEV]
interactions, it should be remarked the positive Einter values for [Cl]- - [LEV], rising from the
positive coulombic contribution because both molecules are negatively charged (see Methods
section), in contrast with the larger and negative Einter values (85 % coulombic contribution)
for [CH]+ – [LEV], both moderately decreasing temperature. Nevertheless, the large total
Einter shows the development of very effective intermolecular interactions in the studied DES,
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which remains with minor changes in the studied temperature range. These results are in
contrast with those obtained for reline by Sun et al.102 which showed that [Cl]- - HBD

interactions are roughly three times larger than [CH]+ – HBD in the case of urea.
The main structural features for CHCL_LEV_1_2 may be obtained from the radial
distribution functions, g(r), reported in Figure 11. Results in Figure 11a show ion-ion
interaction in CHCL_LEV_1_2. The anion-cation strong interaction developing the ion pair is
well defined by the strong and narrow peak at short distance in Figure 11a, whereas very
minor features appear for this interaction at larger distances. Anion-anion interaction is
characterized by a broad peak followed by a shoulder in the 5 to 10 Å range, which is in
contrast with the cation-cation interactions, which are characterized by a strong
intermolecular hydrogen bonding inferred from the narrow first peak in Figure 11a followed
by three weaker and wider peaks, which show that [CH]+ develop well-defined hydrogen
bonding through the cation hydroxyl group. For the analysis of ion-[LEV] interactions, it
should be remarked that LEV has three sites that may act as donors and / or acceptors for
developing hydrogen bonding: i) the oxygen atom in -C=O for –COO group, Ol1, ii) the –OH
in –COO group, Ol2 and Hl, and iii) the oxygen atom in –CO terminal group, Ol3, Figure 11.
Radial distribution functions for these three groups are reported in Figure 11b with regard to
ion-LEV interactions. Results in Figure 11b show the development of hydrogen bonding with
LEV both for the anion and cation, the [Cl]- - LEV interaction (developed through the Hl site)
lead to stronger peaks than [CH]+ - [LEV] but the [Cl]- - [LEV] peak appear at 0.3 Å larger
distance, and thus this interaction should be weaker than [CH]+ - LEV. The [CH]+ - LEV
interactions are characterized by the development of hydrogen bonding between the [CH]+
hydroxyl hydrogen, Hc, and two possible acceptor sites in [LEV] (Ol1, and Ol3), which are
characterized by well defined narrow peaks appearing at roughly 1.8 Å but being larger for
the interaction through Ol1 site. The interaction through Ol2 has shown poor interactions
according to wide peak in Figure 11b. Likewise, results in Figure 11b show the development
of [CH]+ - [LEV] hydrogen bonding in which [LEV] acts as a hydrogen bond donor, Hl, and
[CH]+ as acceptor, Oc, although being weaker than those in which [LEV] act as hydrogen
bond acceptor.
Therefore, the [CH]+ - [LEV] interaction is mainly developed through the Ol1 site with
weaker interactions through Ol3 site and through Hl-Oc interaction. [LEV]-[LEV] interaction
is analyzed in Figure 11c showing that the main interaction is developed between the Hl and
Ol1 sites, with weaker contributions through the hydrogen bonding through the Ol3 position
and almost negligible interactions through the Ol2 site. Therefore, the [LEV] hydroxyl group
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acts as a strong hydrogen bond donor, both with [CH]+ and other [LEV] molecules and the
intermolecular hydrogen bonding are developed mainly through Ol1, and in minor extension,

Ol3 acceptor sites.
A most detailed picture of the molecular arrangement in CHCL_LEV_1_2 can be obtained
from spatial distribution functions, SDF, reported in Figure 12. The [CH]+-[CH]+ interaction
is well defined in Figure 12a showing the high density cap above the oxygen atom in the
hydroxyl group (accepting H-bonds) and below the hydrogen atom in hydroxyl group (donor
for H-bonds), together with a big cap surrounding the remaining [CH]+ molecular regions
showing the prevailing role of the hydroxyl group for the development of intermolecular
hydrogen bonds. Cl- anions develop a high-density region in the vicinity of the Hc group,
Figure 12b, in agreement with the strong peak in Figure 11a. The arrangement of LEV Hl
atoms around [CH]+, Figure 12c, follows a similar pattern to that of Hc, Figure 12a, showing
that [LEV] and [CH]+ molecules occupy the same regions around a central [CH]+ ion.
Regarding the structuring around [LEV], the high density cap above the Ol1 atom of Hc
atoms, Figure 12d, show that [CH]+ cations tend to concentrate above the Ol1 in LEV –
COOH group, with weaker interactions through the remaining [LEV] H-bond acceptor sites.
The [Cl]- - [LEV] interactions is mainly developed through the hydroxyl head group in
[LEV], Figure 12d, but being placed at larger distances than in the case of Cl- around [CH]+.
Finally, LEV – LEV interactions lead to high-density regions above the Ol1 group, Figure
12e.
The structural features inferred from Figure 11 and Figure 12 show the development of H-
bonding between all the involved molecules through the [CH]+ hydroxyl site and LEV –
COOH group, and thus, the number of H-bonds is reported in Figure 13. A large number of
H-bonds is developed with the [Cl]- anion both through the Hc ([CH]+) and Hl (LEV) sites,
being larger for [LEV]-[Cl]-. The number of [CH]+ - [CH]+ H-bonds (Hc – Oc) is lower than
that for [CH]+ - [LEV] (Hc-Ol1, Hc-Ol2 and Hc-Ol3), which are larger for Hc-Ol1 site as
expected from results in Error! Reference source not found.b, in agreement with results in Figure
12a and Figure 12d. [LEV]-[LEV] H-bonds are developed mainly through the Ol1 site with
minor interactions through the Ol3 site and discarding the H-bonding through Ol2 site. These
results should be analyzed considering that two LEV molecules interact with a central [Cl]-
anion, and thus, this lead to larger LEV-LEV and [CH]+ - LEV H-bonding.
The development of strong H-bonding between all the involved molecules in
CHCL_LEV_1_2 requires an additional analysis about the lifetimes of these intermolecular
interactions. This analysis was carried out through the calculation of residence time, tres, of
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relevant sites around others for characterizing H-bonding. Residence time was calculated
from the exponential decay of conditional probability for a site to stay within a sphere of

defined radius around another molecular site, as explained in previous work.103 Sun et al.102
reported lifetimes of hydrogen bonds in reline DES, showing lifetimes lower than 13 ps for all
the reported H-bonds in the eutectic composition, with values of 12.574 ps for the [CH]+ - Cl-
H-bond, 2.397 ps for the urea (HBD) – [Cl]- H-bond, and 2.952 ps for the urea – urea
interaction. These values are lower than those reported for CHCL_LEV_1_2 in Figure 14a,
but it may be justified that the distance criteria used to define residence times in Figure 14a
(6.0 Å) is roughly the double to that used Sun et al.102 to define their H-bonds lifetimes
(roughly 3 Å). The criteria used in Figure 14 consider the existence of a second solvation shell
around each hydrogen bond donor site, and thus, although H-bonds are destroyed for
distances larger than 3.0 Å, those atoms staying in the 3 to 6 Å rise from the reorganization of
the local H-bonding structure and they may develop a new H-bond in a fast way, and thus
using 6.0 Å may give a realistic picture of the H-bonding around a certain site. The residence
times reported in Figure 14a are very similar for all the considered interactions being in the 35
to 55 ps range. Moreover, the analysis of the temperature evolution of residence times follow
a similar non-Arrhenius pattern for all the studied interactions, and thus, confirming a strong
correlation between the dynamics of all the studied H-bonds.
Results in Figure 15 show the changes in intermolecular interaction energy upon CO2
absorption for CO2 pressures up to 10 bar. The structure of CHCL_LEV_1_2 does not change
upon CO2 absorption from the energetic viewpoint, ion-ion, ion-LEV and LEV-LEV Einter
suffer very minor changes with increasing CO2 mole fraction, Error! Reference source not
found.a; e.g. for [CH]+ - [Cl]-, Einter decreases just a 2.5 % in absolute value. Therefore the
liquid structure of CHCL_LEV_1_2 is able to accommodate CO2 molecules without
remarkable changes in its mechanism of intermolecular interaction. Regarding to the strength
of interactions between CO2 and molecules present in CHCL_LEV_1_2, results in Figure 15b
show that the strength of interactions follow the ordering [LEV] > [CH]+> [Cl]-, and thus,
pointing to a preferential absorption of CO2 molecules through LEV molecules. The structural
features of CO2 absorption are summarized in Figure 16 for radial distribution functions. The
arrangement of CO2 molecules around [CH]+, Figure 16a, show that CO2 molecules are
placed both around the cation hydroxyl group and also around the methyl groups, following a
similar patterns for the first solvation sphere although for the hydroxyl group two additional
maxima in g(r) points to a slightly stronger interaction through that site. This is confirmed by
spatial distribution functions in Figure 17a, which although show high density caps around the
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[CH]+ hydroxyl group also shows a very symmetrical distribution of CO2 molecules around
the methyl group, which would justify the sharp and narrow peak around the [CH]+ nitrogen

atom in g(r) reported in Figure 17a. The CO2 molecules are also strongly structured around
[Cl]-, Figure 17b, the sharp peak in g(r) follows a similar pattern to the interaction between
CO2 molecules and Hc site in [CH]+, and thus, as the absorption of CO2 molecules does not
disrupt anion-cation interactions, CO2 may interact efficiently with both ions at the same time.
The CO2-[LEV] interaction is characterized by the strong features in g(r) around the Hl and
Ol3 sites, with weaker interactions through the Ol3 site, which lead to a CO2 distribution
around the terminal [LEV] methyl group. Therefore, CO2 molecules are placed around the
LEV hydroxyl group and also around the terminal groups of [LEV] molecule, Figure 17b,
with minor concentration around the Ol1 group.
Upon increasing CO2 absorbed amounts, these molecules tend to clusterize, for 1 bar CO2
pressure, the number of absorbed molecules is very low, and thus, CO2 clusters were not
observed, Figure 18, but with increasing CO2 mole fraction (increasing pressure) a well
defined peak at 4.3 Å in g(r) is obtained followed by a second and wider peak. The position of
these peaks does not change with increasing pressure, only their intensity increases with
increasing CO2 absorbed amount. The corresponding running integrals for these g(r) shows
that the first solvation sphere, integrating up to the first minimum, around a central CO2
molecule contains at least two additional CO2 molecules, whereas another two additional CO2
molecules may be found in the second solvation sphere, for the highest studied pressures.
The dynamic of CO2 absorbed molecules may be analyzed considering the residence times of
CO2 around both ions and [LEV] molecules, Figure 19. Results show that the mobility of CO2
molecules is almost twice around [Cl]- and [LEV] than around [CH]+, and in all the cases
these mobility increases with increasing CO2 pressure, with the exception of the change from
1 to 4 bar. This result is surprising considering the strength of the interactions between CO2
molecules and CHCL_LEV_1_2 molecules reported in Figure 15b, which led to larger Einter
for CO2 – LEV than for the other interaction pairs, but it may be explained considering steric
factors around the [CH]+ which hinder the molecular mobility of CO2 molecules interacting
with this ion in comparison with the CO2 absorption sites around LEV.
A remarkable feature that should be analyzed to understand the mechanism of absorption of
CO2 molecules in CHCL_LEV_1_2 is the interfacial behavior of CHCL_LEV_1_2 – CO2
systems. The CO2 capturing from flue gases requires that CO2 molecules are adsorbed in the
sorbent – gas interface and then they diffuse from the interfacial region toward the bulk DES.
Therefore, to analyze this fact a simulation on the properties of CO2-DES interface was
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carried out using molecular dynamics in this work. Pure CO2 gas was put in contact with
CHCL_LEV_1_2 and the behavior was followed as a function of time. For comparison

purposes the CHCL_LEV_1_2 – vacuum interface was also simulated. Density profiles in
Figure 20a,b,c allow to characterize the molecular arrangements of ions and LEV molecules
in the interfacial region with vacuum. The density profiles for ions and LEV center-of-mass in
Figure 20a show that [LEV] molecules occupy outer regions close to the vacuum layer with
ions being placed in inner regions, therefore, the CHCL_LEV_1_2 – vacuum interface is
composed mainly of [LEV] molecules, Figure 21a. Figure 20b shows that [CH]+ cations tend
to orientate parallel to the interface, whereas results in Figure 20c show how [LEV] molecules
are placed perpendicular to the vacuum interface with –COOH group pointing toward the
bulk fluid and terminal methyl group exposed to the vacuum layer. These molecular
arrangements do not change significantly when CHCL_LEV_1_2 is put in contact with a CO2
gas layer, very subtle structural changes occur to accommodate adsorbed CO2 molecules in
the interface, Figure 20d,e,f, but ions and LEV arrangement is similar to the vacuum
interface, Figure 21b.
The main structural feature of CHCL_LEV_1_2 – CO2 interface is the formation of a strongly
adsorbed layer of gas molecules, Figure 21b, which is formed in the first stages of simulations
(0 to 1 ns), then upon the formation of this initial layer its size increases upon increasing
simulation time, Figure 22. The main characteristic of this adsorbed layer is that CO2
molecules are adsorbed very quickly but once they are in this layer above CHCL_LEV_1_2,
in contact mainly with [LEV] molecules, their mobility is very reduced, and thus, the time
that CO2 molecules remains in this layer on top of CHCL_LEV_1_2 is long, Figure 22. In the
first 6 ns of simulation, all the CO2 molecules were placed in the adsorbed layer whereas no
CO2 molecules were able to diffuse toward the bulk CHCL_LEV_1_2. The layer of CO2
adsorbed molecules develop strong interactions with [LEV] molecules and weaker ones with
[CH]+, especially when the adsorbed layer is wide enough (simulation times > 4 ns, Figure
23), which is in agreement with the interface structure inferred from Figure 20a. This
persistence of the CO2 molecules in the initially adsorbed layer at the CHCL_LEV_1_2 - gas
interface before moving toward the bulk liquid phase should be considered for any industrial
application of this DES as a carbon capture agent, the kinetics of the CO2 absorption process
(largely controlled by the high affinity of CO2 molecules for the [LEV]-rich interfacial
region) has to be analyzed together with thermodynamics factors controlling capturing
process.
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3.8 Short-Range Properties through DFT

Previously, CHCL_LEV_1_2 structural features and CO2 capture mechanism have been

analyzed in the context of MD simulations. In this section, the main features regarding to
CHCL_LEV_1_2 and CHCL_LEV_1_2···CO2 systems are assessed trough DFT simulations.
The bulk effects that are studied though DFT simulations allow detailed insights of the
studied systems at molecular level as that is useful forecasting macroscopic behavior. Figures
24, 25 and 26 plot optimized structures for [CH][Cl], CHCL_LEV_1_2 and

CHCL_LEV_1_2···CO2 systems, respectively. Table 2 gathers distances for those
intermolecular interactions found in the context of AIM theory, along the electronic density
value (ρ) for the corresponding BCP. Prior to analyze CHCL_LEV_1_2 and
CHCL_LEV_1_2···CO2 systems, this paragraph shows the main features for the [CH][Cl]
ionic compound (Figure 24). As expected, the main interaction between both ions is due to a
coulombic attraction between both ions, which agrees with the high binding energy for the
ionic pair interaction, |∆EIP| = 511.81kJ×mol-1. For the ionic pair, the intermolecular charge
transfer (CTIP) is equal to 0.161e-. In addition, chloride atom stabilizes four intermolecular
hydrogen bonds with the cation (d1-d4), wherein the strongest one is carried out through the
OH (cation) group.
In accordance with MD simulations, the optimized structure for CHCL_LEV_1_2 (Figure 15)
is mainly characterized by intermolecular hydrogen bonds between the chloride atom and
both levulinic acid molecules. Both levulinic acid molecules (through H atom of COOH
group) yield an H-bond with the chloride atom (d5 and d6 for LEV1 and LEV2, respectively).
In addition, both molecules also establish several H-bonds with choline cation. All these
bonds (d7, d8 and d9, d10 for LEV1 and LEV2, respectively) are carried out through COOH
group (levulinic acid) and methylic hydrogen atoms (choline), except d7, which is formed
between COOH group and -CH2 group adjacent to OH motif. As can be seen in Table 2, Cl- -
LEV interactions yields the largest electronic density values, i.e., the key interactions in the
DES structure are those carried out between the levulinic molecules and the chloride atoms.
The interaction energy between ionic pair and [LEV] molecules was |∆EDES| = 141.93 kJ×mol-
1
(Figure 25), showing energetically favored DES. Figure 25 also collect computed charges
over cation, anion and levulinic acid motifs. The largest change on the charges is noted for
chloride atom, which decreases its charge 0.155e- (regarding [CH][Cl] ionic pair. For
CHCL_LEV_1_2 some negative charge is transferred from the anion up to levulinic acid
molecules, 0.066e- and 0.074e- for LEV1 and LEV2, respectively. In addition, there are also
some hydrogen bonds between both ions, very similar to those ones reported in Figure 24. In
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this sense, chloride atom yields three hydrogen bonds (d1-d3) with the cation, which are
weakened compared with the ionic compound. Thus, d1 suffers an elongation of 0.157 Ǻ,

while its electronic density value diminishes 0.0108 a.u. From CHCL_LEV_1_2 optimized
structure, binding energy for the ionic pair has been also calculated through a single point
calculation, which is also used for estimating the interaction strength. For CHCL_LEV_1_2,
|∆EIP| = 503.87kJ×mol-1, i.e., DES formation brings out a weaning on the ionic pair
interaction of around 7.93 kJ×mol-1.

Figure 26 draws optimized structure for CHCL_LEV_1_2···CO2. Three different
arrangements (a, b, and c) were found for the interaction between the DES and the CO2
molecule. As noted from MD simulations, the structure of CHCL_LEV_1_2 does not change
upon CO2 absorption. In this sense, the same intermolecular H-bonds reported for the DES
structure (d1-d10) were also found in presence of CO2 molecule. As can be seen in Table 2,
intermolecular distances and their electronic density values slightly change in presence of
CO2 molecule. ∆EIP y ∆EDES were also computed for CHCL_LEV_1_2···CO2 optimized
structures. For these arrangements, |∆EIP| ~ 503.30 kJ×mol-1 and |∆EDES| ~139.80 kJ×mol-1,
very similar than those values computed for CHCL_LEV_1_2. There are some similarities
between arrangements a and c. From a structural viewpoint, for arrangement a/c, CO2
molecule is mainly linked to Cl atom (d11/d14) and COOH group of LEV1/LEV2 (d12/d15),
being the latter this one with the largest electronic density values for the associated BCP. In
addition, d11/d12 features are similar to d14/d15. Nevertheless, |∆EDES-CO2a| (17.46 kJ×mol-1) is
larger than |∆EDES-CO2b| (14.77 kJ×mol-1). This energy difference could be related with
difference charge distributions. For arrangement a, LEV1 is more negative than LEV1 in
CHCL_LEV_1_2, which allows a slightly large charge transfer up to the CO2 molecule
(whose charge is 0.027e-). However, negative charge over LEV2 in arrangement c does not
vary, being the charge transfer up to CO2 molecule of around 0.014 e-. As far as Cl charge are
concerned, the largest charges are noted for arrangement c. Regarding to arrangement b, CO2
molecules are mainly interacting with COOH group of LEV2, through d13 which is stronger
(based on lower /larger intermolecular distances /electronic density values) than those
interactions found in arrangements a and c. Although the charge over LEV2 is still very
small, LEV2 decreases its charge 0.037 e-, while charges over LEV1, choline and chloride
remain unaffected. This interactions provides the largest binding energies for CO2 capture,
|∆EDES-CO2c| = 24.90 kJ×mol-1. According with DFT results, CHCL_LEV_1_2 displays three
different positions for CO2 adsorption, whose high values would point out energetically
favored process.
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4. Conclusions
This extensive study combines both experimental and theoretical investigation of the DES

system made by mixing CHCl and LEV with 1:2 mixing ratio. Experimental studies are
focused on obtaining detailed physical characteristics of the studied system; and CO2
solubility at high pressures was the most important part of the experimental study. A
promising 2.316 mmol of CO2 per gram of DES sample at 293 K has been obtained at 50
bars. Moreover, a detailed corrosivity study that deals with CO2 saturated DES system
showed a great corrosion resistance with a corrosion rate of 0.027 mm/year, whereas the same
experiments showed 0.54 mm/year corrosion rate for CO2 saturated MEA system.
Molecular dynamics and DFT results allowed analyzing the structural properties of
CHCL_LEV_1_2 both in pure state and after CO2 absorption. CHCL_LEV_1_2 liquid phase
is characterized by the development of intermolecular hydrogen bonding between [LEV
molecules and both Cl- and [CH]+ ions, with [LEV] molecules mainly accepting H-bonds
through the Ol1 atom in -COOH group and as a H-bond donor through the hydrogen atom of
the hydroxyl group. Likewise, [CH]+ are also self associated through H-bonding, and thus, the
characteristics of the functional groups available in the molecules composing
CHCL_LEV_1_2 allow the development of a very efficient network of H-bonds, which is the
main reason of the properties of this fluid. This structuring does not change upon CO2
absorption for pressures lower than 10 bars, with the CO2 molecules developing stronger
interactions with [LEV] molecules than with the ions. The CO2 capturing process by
CHCL_LEV_1_2 is also characterized by the strong affinity of CO2 molecules for the
interfacial DES - gas region, which is very rich in [LEV] molecules, and thus, leading to large
lifetimes of adsorbed molecules in the interfacial region with slow migration toward the bulk
fluid region.
The combined experimental and computational results reported in this work allow a detailed
characterization of CHCL_LEV_1_2 DES both from the macroscopic and nanoscopic
viewpoints and its relationship with their possible use as carbon capture agent.
Acknowledgements
This work was made possible by NPRP grant # 6-330-2-140 from the Qatar National
Research Fund (a member of Qatar Foundation), Ministerio de Economía y Competitividad
(Spain, project CTQ2013-40476-R) and Junta de Castilla y León (Spain, project BU324U14).
Gregorio García acknowledges the funding by Junta de Castilla y León, cofunded by
24
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European Social Fund, for a postdoctoral contract. We also acknowledge The Foundation of
Supercomputing Center of Castile and León(FCSCL, Spain),Computing and Advanced

Technologies Foundation of Extremadura (CénitS, LUSITANIA Supercomputer, Spain), and
Consortium of Scientific and Academic Services of Cataluña (CSUC, Spain) for providing
supercomputing facilities. The statements made herein are solely the responsibility of the
authors.
Associated content
Electronic Supplementary Information (ESI)
Table S1 (forcefield parameterization), Table S3 (physicochemical properties), Table S4
(NMR data) and Figure S1 (in-situ FTIR apparatus setup), Figure S2 (sorption apparatus
setup) and Figure S3 (in-situ FTIR data).
25
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Table 1. Energy differences between liquid and gas phases for CHCl_LEV_1_2 calculated from molecular
dynamics simulations. ∆Hvap stands for vaporization enthalpy, ∆Epot,BONDED for bonded potential energy (bond,

angle and dihedral contributions) difference, ∆Epot,NON-BONDED for the non-bonded potential energy (Lennard-
Jones and coulombic contributions) difference, ∆Epot,TOT for the total potential energy difference and ∆Epot,INTER
for the intermolecular interactions potential energy difference. All values at 298 K
∆Hvap / kJ×mol-1 ∆Epot,TOT / kJ×mol-1 ∆Epot,BONDED / kJ×mol-1 ∆Epot,NON-BONDED / kJ×mol-1 ∆Epot,INTER / kJ×mol-1
52.05 49.57 -4.76 54.34 40.74
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Table 2. Intermolecular distances along their corresponding electronic density (ρ) values for the main
intermolecular interactions for [CH][Cl], CHCL_LEV_1_2 and CHCL_LEV_1_2···CO2 systems estimated at

DFT/B3LYP-D2/6-31+G** theoretical level. See Figures 17, 18 and 19. Estimated binding energies are also
collected.
Length/ ρ / a.u. Length/ ρ / a.u. ∆E / kJ×mol-1
Ǻ Ǻ
[CH][Cl] d1 2.084 0.0341 d3 2.418 0.0184 |∆EIP|=511.81
d2 2.383 0.0197 d4 2.809 0.0104
CHCL_LEV_1_2 d1 2.241 0.0233 d7 2.317 0.0132 |∆EDES|=141.93

d2 2.626 0.0120 d8 2.528 0.0099 |∆EIP|=503.83
d3 2.637 0.0116 d9 2.366 0.0113
d5 2.069 0.0331 d10 2.375 0.0117
d6 2.088 0.0315
CHCL_LEV_1_2···CO2 a) d1 2.247 0.0230 d8 2.526 0.0100 |∆EDES-CO2a|=17.46
d2 2.646 0.0115 d9 2.381 0.0112 |∆EDES a|=140.18
d3 2.661 0.0110 d10 2.377 0.0114 |∆EIP a|=503.03
d5 2.076 0.0329 d11 3.468 0.0050
d6 2.098 0.0307 d12 2.960 0.0082
d7 2.351 0.0122
CHCL_LEV_1_2···CO2 b) d1 2.241 0.0232 d7 2.325 0.0130 |∆EDES-CO2b|=5.93
d2 2.666 0.0112 d8 2.511 0.0101 |∆EDES b|=140.12
d3 2.632 0.0117 d9 2.471 0.0094 |∆EIP b|=503.39
d5 2.073 0.0329 d10 2.383 0.0113
d6 2.066 0.0332 d13 2.733 0.0128
CHCL_LEV_1_2···CO2 c) d1 2.246 0.0230 d8 2.503 0.0102 |∆EDES-CO2c|=3.52
d2 2.628 0.0120 d9 2.363 0.0115 |∆EDES c|=139.10
d3 2.630 0.0118 d10 2.360 0.0120 |∆EIP c|=503.51
d5 2.080 0.0322 d14 3.446 0.0051
d6 2.092 0.0317 d15 2.949 0.0078
d7 2.311 0.0133
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Figure Captions.

Figure 1. Molecular structure of [CH][Cl] salt and levulinic acid.
Figure 2. Experimental set-up for electrochemical corrosion tests
Figure 3. Experimental (a) density, ρ, refraction index, nD, and (b) viscosity, η, data for CHCL_LEV_1_2 DES
system. In panel b, a comparison of η data with those reported by Florindo et al.60 is reported considering the
water content (wt %) of used samples. Error bars are not reported because they are smaller than point size.
Figure 4. FTIR characterization results for [CH][Cl], [LEV] and CHCL_LEV_1_2 DES system.
Figure 5. Thermal gravimetric analysis of CHCL_LEV_1_2 DES system.
Figure 6. Corrosion resistance performance experiments for CO2 saturated CHCL_LEV_1_2 DES system and
its comparison with CO2saturated MEA system.
Figure 7. High pressure CO2 solubility in CHCL_LEV_1_2 DES system at various isotherms up to 30 bars.
Points show experimental data and lines are plotted for guiding purposes.
Figure 8. Isobaric CO2 solubility in CHCL_LEV_1_2 DES kinetics: (a)1 bar and (b) 30 bars. Points show
experimental data and lines are plotted for guiding purposes.
Figure 9. Deviation between density data for CHCL_LEV_1_2 calculated from molecular dynamics
simulations, ρMD, and experimental density, ρEXP, for experimental data obtained in this work and for data by
Florindo et al. ρMD at 1 bar and ρEXP at atmospheric pressure.
Figure 10. Intermolecular interaction energies, Einter, in CHCL_LEV_1_2 calculated from molecular dynamics
simulations at different temperatures and 1 bar. C stands for [CH]+, A for Cl-, LEV for levulinic acid, and
TOTAL for the sum of all intermolecular interaction contributions. Lines show linear fits.
Figure 11. Site – sire radial distribution functions, g(r), in CHCL_LEV_1_2 calculated from molecular
dynamics simulations at 298 K and 1 bar.
Figure 12. Spatial distribution functions of relevant atoms around [CH] cation (panels a,b and c) and around
LEV (panels d, e and f) in CHCL_LEV_1_2 calculated from molecular dynamics simulations at 298 K and 1
bar. All values show isodensity plots corresponding to 4-times bulk density. Atom names as in Figure 14.
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Figure 13. Number of hydrogen bonds, NH, between the different donor-acceptor interaction sites for
CHCL_LEV_1_2 calculated from molecular dynamics simulations. Values calculated for a simulation box

containing 250 [CH][Cl] ion pairs and 250 LEV molecules. Reported values show averages in the 298 K to 348
K temperature range with error bars showing standard deviations for that temperature range. All values
calculated considering 3.0 Å and 50.0º as donor-acceptor distance and angle cut-offs, respectively.
Figure 14. Residence time, tres, of selected atoms around other atoms in DES_LEV_1_2. tres was calculated from
the exponential decay of conditional probability P with R = 6.0 Å.
Figure 15. Intermolecular interaction energies, Einter, in CHCL_LEV_1_2 + CO2 systems calculated from
molecular dynamics simulations at different CO2 pressures and 298 K. C stands for [CH]+, A for Cl-, LEV for
levulinic acid. Lines are plotted for guiding purposes.
Figure 16. Site – sire radial distribution functions, g(r), in CHCL_LEV_1_2 + CO2 systems calculated from
molecular dynamics simulations at 10 bar CO2 pressure and 298 K. Atom names as in Figure 14; CD stands for
carbon atoms in CO2, Hm stands for all the hydrogen atoms in methyl groups bonded to Nc atom in [CH]+; Ht
stands for all the hydrogen atoms in methyl group of LEV.
Figure 17. Spatial distribution functions of CO2 carbon atoms around (a) [CH]+ and (b) LEV, in
CHCL_LEV_1_2 + CO2 systems calculated from molecular dynamics simulations at 10 bar CO2 pressure and
298 K. All values show isodensity plots corresponding to 4-times bulk density.
Figure 18. CD – CD site – site radial distribution functions, g(r), in CHCL_LEV_1_2 + CO2 systems calculated
from molecular dynamics simulations as a function of CO2 pressure and 298 K. CD stands for carbon atoms in
CO2.
Figure 19. Residence time, tres, of CO2 carbon atoms around the center of mass of [CH]+, [Cl]-,and LEV
molecules in CHCL_LEV_1_2 + CO2 systems calculated from molecular dynamics simulations as a function of
CO2 pressure, p, and 298 K. CD stands for carbon atoms in CO2. tres was calculated from the exponential decay
of conditional probability P with R = 6.0 Å.
Figure 20. Density profiles for (a,d) center of mass of [CH]+, Cl- and LEV, and for relevant atoms in (b,e) [CH]+
and (c,f) LEV, molecules in CHCL_LEV_1_2 + (a,b,c) vacuum and (d,e,f) CO2 interfaces systems calculated
from molecular dynamics simulations at 298 K. z stands for the coordinate perpendicular to the corresponding
interfaces, and zGDS for the coordinate of the Gibbs dividing surface. Profiles obtained as averages in the 4 to 5.5
ns timeframe.
Figure 21. Snapshot of the CHCL_LEV_1_2 – (a) vacuum or (b) CO2 interfaces calculated from molecular
dynamics simulations at 298 K. Color code: (blue) [CH]+, (green) Cl-, (red) LEV, and (yellow) CO2. Snaphots
obtained after 5.5 ns simulations.
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Figure 22. Density profiles for CO2 molecules in CHCL_LEV_1_2 + CO2 interfacesystem calculated from
molecular dynamics simulations at 298 K. z stands for the coordinate perpendicular to the corresponding

interfaces, and zGDS for the coordinate of the Gibbs dividing surface. Profiles obtained as averages in the reported
timeframes.
Figure 23. Intermolecular interaction energy, Eint, between CO2 and molecules forming CHCL_LEV_1_2
CHCL_LEV_1_2 + CO2 interfacesystem as a function of simulation time, calculated from molecular dynamics
simulations at 298 K.
Figure 24. Optimized structures for [CH][Cl] at B3LYP-D2/6-31+G** level, along the main structural
parameters related with intermolecular interactions. Computed charges over choline (qCH+) and chloride (qCl-)
motifs, as well as the binding energy (∆EIP) for ionic pair interaction are also shown.
Figure 25. Optimized structures for CHCL_LEV_1_2 at B3LYP-D2/6-31+G** level, along the main structural
parameters related with intermolecular interactions. Computed charges over choline (qCH+), chloride (qCl-) and
levulinic (qLev) motifs, as well as the binding energy (∆EDES) for corresponding for DES formation are also
shown.
Figure 26. Optimized structures for CHCL_LEV_1_2···CO2 system (three different arrangements were found)
at B3LYP-D2/6-31+G** level, along the main structural parameters related with intermolecular interactions.
Computed charges over choline (qCH+), chloride (qCl-), levulinic (qLev) and CO2 (qCO2) motifs, as well as the
binding energy (∆EDES-CO2) corresponding for CO2 catch by selected DES are also shown. For clarity,
intermolecular bonds labels corresponding to DES have been omitted, since we followed the same nomenclature
used in Figure 25.
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CH3 O

OH
+ CH3
H3C N
HO
CH3 Cl−
O
[CH][Cl] levulinic acid

Figure 1.
31
32
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1.15 1.468 400
(a) ρ (b) this work 1.69 wt %
nD Florindo et al. 0.23 wt %
1.14 Florindo et al. 9.88 wt %
1.464 300
1.13
ρ / g×cm-3
η / mPa×s
nD
1.12 1.46 200
1.11
1.456 100
1.1
1.09 1.452 0
280 300 320 340 360 380 280 300 320 340 360 380
T/K T/K
Figure 3.
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3540-3200
2990-2885
Transmission (%)
Levulinic acid 1485-1415

T%
13
80
-1
34
5
4000 3600 3200 2800 2400 2000 1600 1200 800 400
-1
Wave number (cm )
17
20
T%
12
-1
Choline chloride
70
25
1
-1
10
4000 3600 3200 2800 2400 2000 1600 1200 800 400 1720-1695
0
4000 3600 3200 2800 2400 2000 1600 1200 800 400
-1
Waven number (cm )
Figure 4.
34
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weigth loss %
0
0.4
0.8
1.2
300
450
35
Figure 5.
600
T/K
750
900
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10-2
CHCL_LEV_1_2 +CO2
MEA+CO2

10-3
current density / A×cm-2

10-4
10-5
-6
10
10-7
-1.2 -1 -0.8 -0.6 -0.4 -0.2 0
potential / V vs Ag/AgCl
Figure 6.
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absorption / mmol×g
0
0.5
1
1.5
2
2.5
0
323 K
318 K
308 K
298 K
293 K
10
37
Figure 7.
P / bar
20
30
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absorption / mmol×g-1
0
0.02
0.04
0.06
0.08
0
(a)
10
t / min
20
1 bar
30
38
Figure 8.
absorption / mmol×g-1
0
0.5
1
1.5
2
2.5
0
(b)
10
t / min
20
30 bar
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-0.6
ρEXP (this work)
ρEXP (Florindo et al.)

100×(ρEXP − ρMD) / ρEXP
-0.7
-0.8
-0.9
280 300 320 340 360
T/K
Figure 9.
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800 C-C
C-A
C-LEV

400 A-A
A-LEV
LEV-LEV
Einter / kJ×mol-1
TOTAL
0
-400
-800
-1200
280 300 320 340 360
T/K
Figure 10.
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ion – ion ion – LEV LEV – LEV

25 20 8
(a) (b) (c)

20
18
15 6
10 16
g(r)
g(r)
g(r)
14 4
1.5
12
Hc-Ol1
1 Hc-Ol2 Hl-Ol2
8 2 Hl-Ol1
Hc-Ol3
Hc-Oc Hl-Oc Hl-Ol3
0.5 4
Cl-Cl Cl-Hl
Hc-Cl
0 0 0
0 5 10 15 0 5 10 15 0 5 10 15
r/Å r/Å r/Å
Ol3
Oc
Nc Ol1
Hm Hc Ht
Ol2 Hl
Figure 11.
41
Hl (c)
Cl (b)
Hc (a)
42
Figure 12.
Hl (f)
Cl (e)
Hc (d)
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180
160

140
120
100
NH
80
60
40
20
0
HC-OC HC-Cl HC-Ol1 HC-Ol2 HC-Ol3 Hl-OC Hl-Cl Hl-Ol1 Hl-Ol2 Hl-Ol3
Figure 13.
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4
Hc ar Oc Hc ar Ol1 Hl ar Ol1
Hc ar Cl Hc ar Ol2 Hl ar Ol2
Hc ar Ol3 Hl ar Ol3
Hl ar Oc
60
Hl ar Cl
(a)

3.6
50
ln(tres / ps)
tres / ps
40
30
3.2
20
10
(b) (c) (d)
0 2.8
Hc-Oc Hc-Cl Hc-Ol1 Hc-Ol2 Hc-Ol3 Hl-Oc Hl-Cl Hl-Ol1 Hl-Ol2 Hl-Ol3
2.8 2.9 3 3.1 3.2 3.3 3.4 2.8 2.9 3 3.1 3.2 3.3 3.4 2.8 2.9 3 3.1 3.2 3.3 3.4
103×T-1 / K-1 103×T-1 / K-1 103×T-1 / K-1
Figure 14.
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400 C-A
20 C-CO2
(a) C-LEV (b) A-CO2
A-LEV LEV-CO2

LEV-LEV CO2-CO2
0
Einter / kJ×mol-1 0
Einter / kJ×mol-1
-400
-20
-800
-1200 -40
0 2 4 6 8 10 0 2 4 6 8 10
p / bar p / bar
Figure 15.
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2.5
CD - Hc CD - Cl CD - Hl
(a) CD - Nc
(b) (c) CD - Ol1
CD - Hm

CD - Ol3
2 CD - Ht
1.5
g(r)
1
0.5
0
0 5 10 15 0 5 10 15 0 5 10 15
r/Å r/Å r/Å
Figure 16.
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5 16
g (10 bar)
g (7 bar)
g (4 bar)

4 g (1 bar)
N (10 bar)
12
N (7 bar)
3 N (4 bar)
N (1 bar)
g(r)
8
N
2
4
1
0 0
0 5 10 15
r/Å
Figure 18.
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55
around [CH]+
around [Cl]-
around LEV

50
tres / ps
45
40
35
30
25
0 2 4 6 8 10
p / bar
Figure 19.
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0.002
(a) [CH]+ (b) Nc (c) Hl
Cl- C5 Ol2

LEV C6 Ol1
Oc C1
0.0015 Hc C2
C3
C4
ρ / Å-3
Ol3
0.001 C5
0.0005
0
-10 -5 0 5 10 -10 -5 0 5 10 -10 -5 0 5 10
z-zGDS / Å z-zGDS / Å z-zGDS / Å
C5 Ol3
Oc
Nc C6 C5 C3 C1 Ol1
Hm Hc Ht C4 C2
Ol2 Hl
0.002
(d) (e) (f)
0.0015
ρ / Å-3
0.001
0.0005
0
-10 -5 0 5 10 -10 -5 0 5 10 -10 -5 0 5 10
z-zGDS / Å z-zGDS / Å z-zGDS / Å
Figure 20.
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(a)
51
Figure 21.
(b)
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0.04
0-1 ns
1-2 ns
2-3 ns

3-4 ns
0.03
4-5 ns
5-6 ns
ρ / Å-3
0.02
0.01
0
-30 -20 -10 0 10 20
z-zGDS / Å
Figure 22.
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-4
Eint / kJ×mol-1
-8
-12 CO2 - [CH]+

CO2 - Cl-
CO2 - LEV
CO2 - CO2
-16
0 2 4 6
t / ns
Figure 23.
53
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A Detailed Study of Cholinium Chloride and Levulinic Acid Deep Eutectic

Physical Chemistry Chemical Physics Accepted Manuscript

Tariq,a and Santiago Apariciob*

Keywords: Deep eutectic solvents; carbon capture; thermodynamics; molecular simulations.

Physical Chemistry Chemical Physics Accepted Manuscript

Physical Chemistry Chemical Physics Accepted Manuscript

fuels combustion for transportation, power generation and industrial purposes.10,11,12In

Physical Chemistry Chemical Physics Accepted Manuscript

Physical Chemistry Chemical Physics Accepted Manuscript

2.2 Experimental details

The pH and conductivity measurements were performed at 293.15 K by pH/conductivity

Physical Chemistry Chemical Physics Accepted Manuscript

Physical Chemistry Chemical Physics Accepted Manuscript

Physical Chemistry Chemical Physics Accepted Manuscript

experimental adsorption isotherm up to 1 MPa (samples CHCl_LEV_1_2_CO2_I,

Physical Chemistry Chemical Physics Accepted Manuscript

In the case of MD simulation for the analysis of interfacial behavior, a box of

3. Results and discussion

Physical Chemistry Chemical Physics Accepted Manuscript

Physical Chemistry Chemical Physics Accepted Manuscript

3.2 NMR and FTIR

3.3 In-situ FTIR

Physical Chemistry Chemical Physics Accepted Manuscript

3.5 Corrosion Measurements

Physical Chemistry Chemical Physics Accepted Manuscript

3.6 CO2 Solubility

Physical Chemistry Chemical Physics Accepted Manuscript

Wbuoy,sample = Vsample× dgas = buoyancy correction due to sample

Physical Chemistry Chemical Physics Accepted Manuscript

Physical Chemistry Chemical Physics Accepted Manuscript

Physical Chemistry Chemical Physics Accepted Manuscript

Physical Chemistry Chemical Physics Accepted Manuscript

Physical Chemistry Chemical Physics Accepted Manuscript

Physical Chemistry Chemical Physics Accepted Manuscript

Physical Chemistry Chemical Physics Accepted Manuscript

3.8 Short-Range Properties through DFT

Physical Chemistry Chemical Physics Accepted Manuscript

24, 25 and 26 plot optimized structures for [CH][Cl], CHCL_LEV_1_2 and

Physical Chemistry Chemical Physics Accepted Manuscript

interaction of around 7.93 kJ×mol-1.

Physical Chemistry Chemical Physics Accepted Manuscript

Physical Chemistry Chemical Physics Accepted Manuscript

Physical Chemistry Chemical Physics Accepted Manuscript

Physical Chemistry Chemical Physics Accepted Manuscript

CHCL_LEV_1_2 d1 2.241 0.0233 d7 2.317 0.0132 |∆EDES|=141.93

Physical Chemistry Chemical Physics Accepted Manuscript

Figure 2. Experimental set-up for electrochemical corrosion tests

Figure 5. Thermal gravimetric analysis of CHCL_LEV_1_2 DES system.

Physical Chemistry Chemical Physics Accepted Manuscript

the exponential decay of conditional probability P with R = 6.0 Å.

Physical Chemistry Chemical Physics Accepted Manuscript

Physical Chemistry Chemical Physics Accepted Manuscript

[CH][Cl] levulinic acid

Physical Chemistry Chemical Physics Accepted Manuscript

Physical Chemistry Chemical Physics Accepted Manuscript