Journal of Environmental Chemical Engineering 9 (2021) 106248

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Journal of Environmental Chemical Engineering

journal homepage: www.elsevier.com/locate/jece

Bicyclic amidine-based deep eutectic solvents for efficient CO2 capture by

multiple sites interaction
Hui Fu a, *, Haina Sang a, Li Su a, Xinming Zhou b, Zhihua Peng a, Yulu Zhou a, Jinhe Liu a
a
College of Science, China University of Petroleum (East China), Qingdao 266580, China
b
School of Materials Science and Engineering, China University of Petroleum (East China), Qingdao 266580, China

A R T I C L E I N F O A B S T R A C T

Editor: Dr. Z. Wen Deep eutectic solvents (DESs) are considered as promising substitutes absorbents for CO2 capture recently. In this
work, several novel DESs based on multiple sites interaction were composed of superbase ILs as hydrogen bond
Keywords: acceptor (HBA) and ethylene glycol (EG) as hydrogen bond donor (HBD). 1,5-diazabicyclo[4.3.0]-non-5-ene N-
Deep eutectic solvents methylthiourea/EG ([DBNH][MTU]:EG) with single-site interaction exhibited absorption uptake up to 0.143 g
CO2 capture
CO2/g absorbent, and [DBNH]2[1,3-dimethylthiourea]/EG ([DBNH]2[DTU]:EG) with double-site showed high
Superbase
absorption of 0.172 g CO2/g absorbent at 313 K and ambient pressure, respectively, which were much higher
Multiple interaction
than that of [DBNH][MTU] (0.075 g CO2/g IL) and [DBNH]2[DTU] (0.104 g CO2/g IL). The superior CO2 ab­
sorption performance can be ascribed to synergistic interaction between DES and CO2 to form carbamate and
carbonate. It is interesting that EG plays an important role during the absorption process. The absorption
mechanism was proposed based on NMR spectra analysis and quantum chemical calculations. The results
revealed that EG can be activated by DBNH+ and thus has the ability to capture CO2, which realized the co­
ordinated absorption by imino and hydroxyl groups. This study provides a novel scheme to design and optimize
superbase DESs for high-efficient CO2 capture.

1. Introduction as promising solvents for CO2 capture and separation owing to their
outstanding properties such as good thermal stability, negligible vapor
With the rapid development of industry, carbon dioxide (CO2) pro­ pressure and adjustable properties [7,8]. Bates et al. [9] reported the
duced by excessive combustion of fossil fuels has caused many serious first case of amino-functionalized IL for CO2 chemical absorption, and
environmental problems, such as global warming and climate change the absorption capacity was up to 0.5 mol CO2/mol IL (0.08 g CO2/g IL)
disasters [1–3]. On the other hand, CO2 is a nontoxic, cheap and at 298 K and 100 kPa. Since the outstanding work in CO2 capture, plenty
abundant natural resource, which can be converted to plenty of chem­ of functionalized ILs have been applied for CO2 absorption, such as
icals [4]. Therefore, the capture and recovery of CO2 is of great signif­ azolide-based ILs [10–12] and amino acid-based ILs [13–15]. However,
icance for the effective utilization of carbon resources. Generally, the complicated synthetic process and high viscosity further limit the
amine-based solvents (including monoethanolamine, diethanolamine, application of functionalized ILs in industry.
N, N-dimethylethanolamine) are the most commonly used CO2 capture In contrast, DESs, a new generation of solvents analogous to ILs, has
technique in industry field [5,6]. However, this approach also leads to been developed, which provided a potential alternative in CO2 absorp­
equipment corrosion, high volatility and intensive energy consumption tion [16,17]. In general, the raw materials used to prepare DESs exhibit
problems. Hence, many researchers focus on developing novel CO2 ab­ satisfactory properties, for instance cheap, recyclability, non-toxicity
sorbents with excellent absorption performance and low energy and biocompatibility [18]. DESs are regarded as promising alterna­
consumption. tives to traditional ILs because they can be synthesized easily with high
After decades of developments, ionic liquids (ILs) have been emerged purity and low-price raw materials at a large scale. The CO2 absorption

Abbreviations: DES, Deep eutectic solvent; HBA, Hydrogen bond acceptor; HBD, Hydrogen bond donor; EG, Ethylene glycol; DBN, 1,5-diazabicyclo [4.3.0]-non-5-
ene; MTU, N-Methylthiourea; DTU, 1,3-Dimethylthiourea; IL, Ionic liquid; TETACl, Triethylenetetramine hydrochloride; BmimCl, 1-butyl-3-methylimidazolium
chloride; Im, Imidazole; EU, 2-Imidazolidinone; DBU, 1,8-Diazabicyclo [5.4.0] undec-7-ene; Dhyd, Dimethylhydantoin; DMSO, Dimethyl sulfoxide.
* Corresponding author.
E-mail address: [email protected] (H. Fu).

https://doi.org/10.1016/j.jece.2021.106248
Received 3 April 2021; Received in revised form 27 July 2021; Accepted 18 August 2021
Available online 20 August 2021
2213-3437/© 2021 Elsevier Ltd. All rights reserved.
H. Fu et al. Journal of Environmental Chemical Engineering 9 (2021) 106248

capacity in different DESs formed by lactic acid, glycerol, or urea with

choline chloride has been studied [19]. However, these traditional DESs
can absorb CO2 by physical interaction, which limits their industrial
application as absorbents to efficiently absorb CO2. Lately, Gu et al. [20]
investigated Henry’s law constant and the equilibrium constant in
physical absorption and chemical absorption. The results show that both
physical absorption and chemical absorption exist during the process of
CO2 capture, and chemical absorption plays a major role. At present,
many studies have indicated that DESs can also capture CO2 by chemical
absorption [21]. Zhang et al. [22] found that DESs made up of triethy­
lenetetramine hydrochloride ([TETA][Cl]) and EG can efficiently absorb
CO2 at ambient pressure, but the desorption temperature is slightly
higher. Sze et al. [23] reported that the addition of 1,5-diazabicyclo
[4.3.0]-non-5-ene (DBN) can increase the number of active sites and
further improve absorption uptake. Zhang et al. [24] investigated CO2
solubility in imidazole derived DESs, and found all parts of DBN-
BmimCl-Im have synergistic interaction. Superbase plays an important
role in absorption process, and the CO2 absorption uptake up to 1.00 mol
CO2/mol absorbent (0.12 g CO2/g absorbent). Subsequently, they [25]
synthesized a series of multiple-site superbase/acylamido-based DESs,
which [DBN][EU] presented decent absorption performance due to the
strong multiple-site interaction between the N atom of EU and CO2.
Lately, the dianionic-functionalized DESs based on [(DBUH)2][Dhyd] as Scheme 1. Chemical structures of prepared absorbents in this work.
HBA, and EG as HBD were investigated by Li et al. [26]. The CO2 ab­
sorption capacity of [(DBUH)2][Dhyd]-EG with the mass ratio of 5:5 was
up to 0.11 g CO2/g DES at 293 K and 0.1 MPa. Hence, it is essential to 99.99%) and nitrogen (N2, 99.99%) were provided from Qingdao Tia­
develop novel absorbents with excellent CO2 capture and recyclability nyuan Gas Manufacturing Co., Ltd., China.
performance at relatively mild conditions.
In order to have a deeper understanding of CO2 absorption by DESs, 2.2. Preparation and characterization of the ILs/DESs
it is necessary to analyze and understand the interactions between
molecules at the molecular level. Density functional theory (DFT) Two target superbase ILs, [DBNH][MTU] and [DBNH]2[DTU] were
simulation is an appropriate tool for obtaining structure-property re­ prepared by the one-step method according to the reported literature [8,
lationships, which can be used to investigate the features of DES and the 31]. Taking [DBNH][MTU] as a typical example, a certain amount of
interaction between CO2 and DES. Importantly, DFT calculation can be MTU was added into round-bottom flask, then equimolar DBN was
combined with spectra to further elucidate the absorption mechanism. slowly added and stirred at 323 K for 4 h until turning into a homoge­
For example, Gregorio et al. [27] used DFT simulation for the first time neous liquid. After the reaction was completed, the obtained IL was
to study CO2 capture by DES at the molecular level. And then Jiang et al. dried under vacuum at 343 K for 24 h to remove the possible traces of
[25] explored the interaction mechanism between DES and CO2 using water. The DESs were synthesized by mixing ILs and EG in different
quantum chemical calculations, and explained high absorption capacity molar ratios and stirred at 323 K for 4 h under nitrogen atmosphere to
from theoretical perspective. Lately, Ahmad et al. [17] used DFT obtain homogeneous liquids. Subsequently, the prepared DESs were
calculation and MD simulations to clarify that the interaction between dried at 343 K under vacuum condition for 24 h to remove contained
CO2 and [MEAHCl][MDEA] is via the -NH2 group in MEAH+ and the water.
-OH group in MDEA. Thus, theoretical simulation as a method to explain The structures of superbase ILs/DESs prepared in this work are
the capture mechanism of DES is essential. presented in Scheme 1. It is obvious that MTU can combine only one
Based on the above analysis, we synthesized novel DESs composed of molecule of DBN in [DBNH][MTU] and [DBNH][MTU]:EG system, so it
superbase-based ILs as HBA and ethylene glycol (EG) as HBD. Previous is called single-site system. However, two molecules of DBN were
research [28–30] emphasized that active sites of anions can play an combined with DTU, which can be regarded as double-site system. And
important role in enhancing the CO2 absorption performance, N-Meth­ most importantly, the number of active sites have a significant impact on
ylthiourea (MTU) and 1,3-Dimethylthiourea (DTU) were selected to absorption performance. Generally speaking, the increase of active sites
synthesize [DBNH][MTU]:EG and [DBNH]2[DTU]:EG. The multiple is conductive to enhance the CO2 absorption capacity.
1
sites effect is considered through the structure of anions. The CO2 ab­ H NMR and 13C NMR spectra were recorded using 400 MHz NMR
sorption capacity of prepared DESs including the influences of temper­ spectrometer (Bruker Ascend TM) in DMSO solution using tetrame­
ature, molar ratio, water content as well as recyclability were thylsilane (TMS) as the standard, which can determine the structures of
systematically evaluated. Moreover, the corresponding CO2 absorption ILs/DESs. The NMR data of the studied ILs/DESs are shown in the
mechanism was proposed through a combination of NMR spectra anal­ Supporting Information. Viscosity measurements were carried out on
ysis and quantum chemical calculations. rheometer viscometer model (MCR302) equipped with a water based
thermostat ( ± 0.1 ℃) using concentric cylinder measuring system
2. Experimental materials and methods (CC27). The accuracy of rheometer viscometer model is 0.01. About
19 mL of IL/DES was loaded in the CC27 measuring system during the
2.1. Chemical process of viscosity measurements. And temperature dependence was
investigated from 293 K to 333 K.
1,5-diazabicyclo [4.3.0] non-5-ene (DBN, 99%), N-Methylthiourea
(MTU, 97%), Ethylene glycol (EG, 99%) used in this experiment were 2.3. CO2 absorption and desorption experiments
purchased from Sun Chemical Technology (Shanghai) Co., Ltd., China.
1,3-Dimethylthiourea (DTU, 97%) was obtained from Sinopharm The experimental procedures for CO2 absorption and desorption
Chemical Reagent (Shanghai) Co., Ltd., China. Carbon dioxide (CO2, have been described in detail in our previous work [8]. In a typical

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H. Fu et al. Journal of Environmental Chemical Engineering 9 (2021) 106248

theory (NBO) charge analysis was performed [36].

3. Results and discussion

3.1. Viscosities of the prepared ILs/DESs

Viscosity plays an important role for practical application of CO2

absorbents, which impacts mass transfer significantly, and lower vis­
cosity is conductive to CO2 capture. Therefore, viscosity of ILs/DESs
were measured in the temperature range of 293–333 K and the rela­
tionship between viscosity and temperature is presented in Fig. 1. The
viscosities of ILs/DESs decreased non-linearly as the temperature rises.
Based on the experimental results, the viscosity of the single-site system
followed the order of [DBNH][MTU] > [DBNH][MTU]:EG (1:1) >
[DBNH][MTU]:EG (1:2) > [DBNH][MTU]:EG (1:4) and they are sensi­
tive to temperature. It is shown that the viscosity decreases significantly
with temperature rises, and decreases as the proportion of EG increases.
The results indicated that EG plays an important role in reducing vis­
Fig. 1. Viscosity of the different absorbents at various temperature. cosity. For double-site system, [DBNH]2[DTU] has a lower viscosity. The
viscosity of absorbent is slightly increase with the addition of EG due to
absorption process, DESs (about 5 g) was added in an absorption vial strong hydrogen bonding. It can be found that EG doesn’t play a role in
which was partly immersed in a thermostatic water bath with the reducing viscosity for double-site system. Combining with the structure
desired temperature. After that, CO2 gas was bubbled through solvents of DES, the hydrogen bond network of [DBNH]2[DTU]:EG (1:2) is denser
at a flow rate of 60 mL/min at different temperatures. The weight of CO2 than that of [DBNH]2[DTU]:EG (1:1), which makes the viscosity of
absorbed was measured at regular intervals by an electronic balance [DBNH]2[DTU]:EG (1:2) slightly greater than that of [DBNH]2[DTU]:EG
with an accuracy of ± 0.0001 g until the amount unchanged. To ensure (1:1). In general, the viscosity of the double-site system does not change
the accuracy of the samples weight measurements, the absorption obviously with the temperature, and the viscosity is generally below
container was dried before weighted. The influence of temperature on 100mPa⋅s.
CO2 absorption in DES was investigated from 303 K to 333 K at ambient In addition, the activation energy of viscous flow is also studied
pressure. In order to explore the effect of water on CO2 absorption ca­ based on the extended Arrhenius equation. The absorption capacity of
pacity, the prepared DESs were diluted with water respectively, and the absorbent is expected to be predicted based on physical property. The
DES aqueous solution with different water content was obtained, and results show that activation of [DBNH][MTU]:EG (1:1) is lower than
then the CO2 absorption experiment was carried out at 313 K. For that of [DBNH][MTU] (Table S1), indicating that the former has better
desorption of CO2 in DES, pure N2 was bubbled through CO2-absorbed CO2 absorption performance. But the trend in activation energy is
DESs at 353 K with a flow rate of 140 mL/min to achieve the regener­ different in double-site system. This phenomenon implies that viscosity
ation of absorbents. Similar to the absorption capacity, the amount of is not the only factor affecting absorption capacity.
CO2 desorption in the DESs depended on the measurement of the weight
of the desorption tube. For cycling the DES, the desorbed DES was
3.2. Absorption performance of CO2 by ILs/DESs
reused for the absorption-desorption process.

To explore the influence of active sites of ILs/DESs on CO2 absorption

2.4. Computational methods performance, CO2 absorption curves of ILs/DESs were measured and
presented in Fig. 2. In addition, the influence of molar ratio between
All calculations herein were carried out with Gaussian 09 software superbase ILs and EG on the CO2 absorption performance was also
package [32], and the density functional theory is considered as a studied. It can be observed clearly that CO2 absorption capacities in ILs
powerful tool to help illustrate the reaction mechanism [33–35]. At the were less than corresponding DESs and the double-site systems have
B3LYP/6–311++G (d,p) level of theory, all geometries of reactants and better performance than the single-site systems, which further reveals
products were optimized, and then the natural valence bond orbital that the increase of active sites can effectively enhance the absorption

Fig. 2. CO2 absorption in different absorbents at 313 K and ambient pressure. (a) [DBNH][MTU]:EG (b) [DBNH]2[DTU]:EG.

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H. Fu et al. Journal of Environmental Chemical Engineering 9 (2021) 106248

Fig. 3. CO2 absorption in different absorbents at 1 bar and different temperature. (a). [DBNH][MTU]:EG (1:1) (b). [DBNH]2[DTU]:EG (1:2).

capacity of CO2. In general, the molar ratio of HBA to HBD has an is not conductive to the absorption of CO2. There should be a balance
important effect on CO2 uptake. Therefore, the influence of different between them. Therefore, the optimum absorption performance of the
molar ratios on absorption capacity was investigated. Considering that double-site system was obtained when the molar ratio of
the structure of the research system is single-site and double-site, the [DBNH]2[DTU]-EG was 1:2. Based on the above analysis, [DBNH]
CO2 experiment was conducted when the molar ratio of HBA to HBD was [MTU]:EG (1:1) and [DBNH]2[DTU]:EG (1:2) can be regarded as
1:1 and 1:2. It was considered that the single-site system with the ratio promising absorbents for highly efficient CO2 uptake.
1:1 and double-site system with the molar ratio 1:2 may be more stable.
In order to further explore the effect of EG on absorption performance,
the molar ratio was expanded to 1:4. The results show that the absorp­ 3.3. Effect of temperature on CO2 absorption
tion performance becomes worse when the molar ratio of is 1:4, so it is
not considered to further increase the ratio of EG. Analyzing the effect of Temperature plays an important role in CO2 capture process, there­
molar ratio, it is found that single-site systems and double-site systems fore the influence of temperature on CO2 absorption capacity of [DBNH]
show different results. In Fig. 2, [DBNH][MTU]:EG (1:1) and [MTU]:EG (1:1) and [DBNH]2[DTU]:EG (1:2) were performed in the
[DBNH]2[DTU]:EG (1:2) show optimal CO2 absorption amount of range from 303 K to 333 K under ambient pressure as shown in Fig. 3.
0.143 g CO2/g absorbent and 0.172 g CO2/g absorbent, respectively. Herein, single-site ([DBNH][MTU]:EG) system was selected for a
Considering the high viscosity of [DBNH][MTU], the mass transfer is detailed discussion. From 303–313 K, the CO2 absorption capacity
hindered during the process of CO2 absorption, which leads to the low increased with the temperature increasing, indicating that temperature
absorption capacity. When EG was added into [DBNH][MTU] as cosol­ has a positive influence on CO2 absorption performance. However, in
vent, the viscosity of the system decreased significantly, and the ab­ the range of 313–333 K, the absorption capacity of CO2 decreases,
sorption performance was improved. But excessive EG is not conductive indicating that high temperature is conducive to desorption and has
to CO2 capture, which implies that EG does not only play the role of great application prospect in recovering absorbent. It can be seen clearly
decreasing the viscosity of DESs. Thus, the molar ratio of 1:1 is optimum. that the optimal absorption temperature is 313 K, which may be due to
However, for [DBNH]2[DTU], it can be seen from the Fig. 1 that the the equilibrium of reaction dynamics and thermodynamics. For one
viscosity of double-site systems is not obviously different with the thing, increasing the temperature is benefit to reducing viscosity and
change of ratio, thus viscosity is not the only factor influencing the ab­ enhancing mass transfer. For another, CO2 absorption process is
sorption capacity. Instead, EG will play a crucial role. As the ratio of EG exothermic reaction, and temperature rise is not beneficial to gas
increases, the hydrogen bond network between EG and IL become dense, capture.
which may further impede the binding of EG and CO2. When the ratio of Similar results were obtained for double-site system. As can be seen
IL/EG is expanded to 1:4, the system has a large steric hindrance, which from Fig. 3b, the optimal absorption temperature is still 313 K for
[DBNH]2[DTU]:EG, but there is a little difference from Fig. 3a, where

Fig. 4. Effect of water content on CO2 absorption of [DBNH][MTU]:EG (1:1) and [DBNH]2[DTU]:EG (1:2) under 313 K and ambient pressure.

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H. Fu et al. Journal of Environmental Chemical Engineering 9 (2021) 106248

Table 1
Comparison of CO2 absorption capacities.
PCO2 T/ CO2 capacity (g CO2/
Absorbents (atm) K g absorbent) Refs

this
[DBNH][MTU] 1 313 0.075 work
[DBNH][MTU]:EG (1:1) 1 313 0.143
[DBNH][MTU]:EG (1:2) 1 313 0.115
[DBNH][MTU]:EG (1:4) 1 313 0.100
[DBNH]2[DTU] 1 313 0.104
[DBNH]2[DTU]:EG (1:1) 1 313 0.134
[DBNH]2[DTU]:EG (1:2) 1 313 0.172
[DBNH]2[DTU]:EG (1:4) 1 313 0.147
[P66614][2-Op] 1 293 0.120 [29]
[Emim][Gly] 1.5 313 0.101(2.29b) [38]
[Emim][Ala] 1.5 313 0.080(1.81b) [38]
[P2222][Triz]:EG (1:2) 1 298 0.106 [37]
[N2222][Im]:EG (1:2) 1 298 0.114 [37]
[DBUH][Im]:EG (7:3)a 1 313 0.141 [39]
[(DBUH)2][Dhyd]:EG(5:5)a 1 313 0.100 [26]
[TETA]Cl: EG (1:3) 1 313 0.170 [22]
Fig. 5. Five consecutive absorption (313 K) and desorption (353 K) cycles of
[TETA]Cl: DG (1:3) 1 313 0.159 [22]
[DBNH][MTU]-EG. [ChCl]-EG (1:2) 58 303 0.137 [40]
30 wt% Monoethanolamine 1 313 0.425(0.59c) [41]
the temperature distribution is relatively uneven. When the absorption 30 wt% N-
methyldiethanolamine 1 313 0.273(0.74c) [41]
temperature is 323 K and 333 K, the mass capacity of CO2 is 0.165 g
30 wt% Diethanolamine 1 313 0.255(0.61c) [41]
CO2/g absorbent and 0.162 g CO2/g absorbent, respectively, which
a
implies that absorption dynamics has a more significant influence on the Mass ratio
b
mol/kg
process of CO2 absorption. In addition, although the CO2 absorption c
mol/mol
capacity of [DBNH]2[DTU]:EG decreased from 0.172 g CO2/g absorbent
to 0.141 g CO2/g absorbent, when the temperature dropped from 313 K
to 303 K, it still presented good absorption capacity under low 3.6. Comparison with other DESs and ILs
temperature.
The CO2 absorption uptake of DESs investigated in this work and
other ILs/DESs reported in previous literature are shown in Table 1. It
3.4. Effect of water content on CO2 absorption can be clearly seen compared with most ILs/DESs reported previously,
the CO2 absorption capacity of DESs studied in this work is competitive
Water content is also crucial factor affecting the CO2 absorption than most ILs/DESs. Moreover, the synthesis of functionalized ILs is
performance of DESs. [DBNH][MTU]:EG (1:1) and [DBNH]2[DTU]:EG complex and costly. Therefore, DESs proposed in this work can be used
(1:2) were selected as the representatives of the single-site and double- as promising CO2 absorbents with excellent absorption performance,
site to investigate the impact of water content. The absorption experi­ simple synthesis process and low cost.
ment of CO2 was performed under the condition of water content of
5–30 wt% at 313 K and ambient pressure. As can be seen in Fig. 4, the
3.7. Mechanism for CO2 absorption
CO2 absorption capacity of [DBNH][MTU]:EG (1:1) and
[DBNH]2[DTU]:EG (1:2) decrease obviously with the increase of water
3.7.1. NMR analysis
content from 0 wt% to 30 wt%, which indicates that water can
With the aim to explore the absorption mechanism of DESs, the
remarkably influence on DESs. When the water content was 30 wt%, the
interaction between the DESs and CO2 were investigated using 13C NMR
absorption capacity was reduced by half compared with pure [DBNH]
spectroscopy. NMR spectra of [DBNH][MTU], [DBNH]2[DTU], [DBNH]
[MTU]:EG (1:1) and [DBNH]2[DTU]:EG (1:2). This may be due to the
[MTU]:EG as well as [DBNH]2[DTU]:EG systems before and after CO2
formation of hydrogen bond complex between water and absorbent,
absorption were compared and shown in Fig. 6 and Fig. S3. As for
which reduces the effective action sites, thus makes the CO2 absorption
[DBNH][MTU], it was observed that there was one new peak at
capacity decrease greatly. In order to ensure the excellent CO2 absorp­
159.7 ppm formed after CO2 capture due to the formation of carbamate
tion capacity of [DBNH][MTU]:EG and [DBNH]2[DTU]:EG, DESs should
according to the structure of MTU. In [DBNH][MTU]:EG system after
be vacuum dried before the absorption experiment to ensure a very low
CO2 absorption, the peak at 159.2 ppm appeared which is analogous to
water content.
the system of [DBNH][MTU]. While, compared with the 13C NMR
spectrum of fresh [DBNH][MTU]:EG, three additional signals at
3.5. Regeneration of DESs 61.5 ppm, 66.1 ppm, as well as 157.4 ppm could be seen after CO2
capture. The new peaks at 61.5 ppm and 66.1 ppm were the singles of
The recycling performance of absorbent is also a crucial index for methylene groups of carbonates [37]. Moreover, the new carbon signal
industry application because it has a great impact on the operating cost. appeared at 157.4 ppm was attributed to the carbonyl carbon of car­
To further evaluate the regeneration of DBN-based DESs, CO2-saturated bonate. The hydroxyl hydrogen of EG is activated under the impact of
DES systems were recycled and reused for CO2 capture. As shown in DBNH+, which makes EG have the ability to absorb CO2. Based on the
Fig. 5 and Fig. S2, the CO2 absorption-desorption cycles of [DBNH] above analysis, it can be concluded that [DBNH][MTU]:EG generates
[MTU]:EG (1:1) and [DBNH]2[DTU]:EG (1:2) were investigated. It can carbamate and carbonate after absorbing CO2.
be seen that the absorption capacity is slightly decreased after five As can be seen from Fig. S3, the double-site system has similar
absorption-desorption cycles. The results displayed [DBNH][MTU]:EG phenomenon. The new peak at 159.5 ppm can be found due to the
(1:1) and [DBNH]2[DTU]:EG (1:2) as novel CO2 absorbents can be formation of RNCOO-, which is similar to the system of [DBNH][MTU].
reused for CO2 absorption due to excellent absorption capacity and As for [DBNH]2[DTU]:EG, the additional new signals at 157.3 ppm,
favorable regeneration. 61.7 ppm and 66.1 ppm were attributed to generation of RCO3-. In

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13
Fig. 6. C NMR spectra of [DBNH][MTU] and [DBNH][MTU]:EG before and after CO2 absorption.

Fig. 7. Optimized structures of (a) [DBNH][MTU]-CO2 and (b) [DBNH][MTU]:EG-CO2. Carbon: grey; hydrogen: white; oxygen: red; nitrogen: blue; sulfur: yellow.
(For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

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H. Fu et al. Journal of Environmental Chemical Engineering 9 (2021) 106248

Scheme 2. Proposed CO2 absorption mechanism of [DBNH][MTU](a) and [DBNH][MTU]:EG(b).

addition, review the absorption performance of double-site system. It which further explains the absorption capacity of the absorbents.
can explain why the difference of absorption capacity produced by Based on the 13C NMR spectra, experimental results and quantum
changing the molar ratio of [DBNH]2[DTU]:EG. For [DBNH]2[DTU]:EG chemistry calculation, the possible absorption mechanism was proposed
(1:1), one mole DBNH+ reacts with one mole EG to form bicarbonate, as presented in Scheme 2. We considered that both IL and EG can
when the molar ratio becomes 1:2, two mole bicarbonate can be ob­ simultaneously interact with CO2 to produce carbamate and carbonate,
tained. When the ratio continues to expand to 1:4, the absorption which differs from the mechanism reported in previous literature [37].
amount decreases, indicating that the excess EG cannot play the role of For [DBNH][MTU]:EG system, the hydroxyl hydrogen of EG can be
absorption, so the absorption performance becomes worse. activated by DBNH+, which makes it have the ability to capture CO2,
and further realizes the synergistic absorption by imino and hydroxyl
3.7.2. Quantum chemistry calculations groups. Moreover, MTU has a certain fixed effect on EG-CO2. In addi­
Based on the 13C NMR analysis, it can be found that both [DBNH] tion, the absorption performance of [DBNH][MTU]:EG is closely related
[MTU]:EG and [DBNH]2[DTU]:EG generate carbamate and carbonate to the molar ratio of DBNH+ to EG. To conclude, carbamate and car­
after CO2 absorption. In order to further demonstrate the absorption bonate were formed during CO2 absorption process in [DBNH][MTU]:
mechanism proposed above, DFT calculations were carried out. Herein, EG by the synergistic interaction of CO2 with IL and EG.
the single-site system [DBNH][MTU]:EG is discussed in detail as an
example. Firstly, the geometry configuration and energy optimization 4. Conclusion
were calculated. The optimized structures of [DBNH][MTU]-CO2 and
[DBNH][MTU]:EG-CO2 are exhibited in Fig. 7. It can be found that In the present work, the design, synthesis, and absorption perfor­
hydrogen bonds are formed between the N29-H30 and O34 atom of CO2 in mance of CO2 based on superbase DESs with single-site and double-site
[DBNH][MTU]-CO2 (1.495 Å) and [DBNH][MTU]:EG-CO2 (1.582 Å), is discussed, being focused on the effect of active sites on the absorption
which proves that there are strong interactions between DBN and MTU. capacity of DESs. The CO2 absorption capacity under different condi­
Compared with [DBNH][MTU]-CO2, multiple hydrogen bonds (C44- tions (temperature, HBA/HBD mole ratio, active sites), recyclability
O45⋅⋅⋅H16, C44-O45⋅⋅⋅H14 and C23-H24⋅⋅⋅O43) are formed in [DBNH] performance, as well as the absorption mechanism, were systematically
[MTU]:EG during CO2 capture process, while the hydrogen bond of N29- investigated. It can be found that EG not only improves the absorption
H30⋅⋅⋅O34 is weakened. Meanwhile, the distance between the N2 atom of capacity, but also decreases the viscosity of CO2-saturated system,
MTU and H42 atom of EG is 2.039 Å, which indicates that MTU has a thereby [DBNH][MTU]:EG and [DBNH]2[DTU]:EG exhibit better ab­
certain fixed effect on EG-CO2. Furthermore, the bond length of N31-C32 sorption properties than pure ionic liquids. Through the spectral analysis
in [DBNH][MTU]-CO2 and [DBNH][MTU]:EG-CO2 are 1.444 Å and and theoretical calculation, it is believed that the synergistic effect of IL
1.458 Å, respectively. This phenomenon explains the formation of and EG promotes the absorption process of CO2, that is, the synergistic
chemical bond and further confirms the existence of chemical absorption of imino and hydroxyl groups in DESs is realized. IL and EG
absorption. can combine with CO2 to form carbamate and carbonate. Moreover,
From the NBO charge analysis in Table S2, it can be observed that the [DBNH][MTU]:EG with single-site and [DBNH]2[DTU]:EG with double-
charge changes of N31 in [DBNH][MTU] is 0.078 during the process of site show good absorption uptake with 0.143 g CO2/ g absorbent and
CO2 absorption, while [DBNH][MTU]:EG decreases more obviously and 0.172 g CO2/g absorbent at 313 K and ambient pressure, respectively.
reaches 0.116. This phenomenon explains why [DBNH][MTU]:EG has The results indicate that multiple sites interaction can result in excellent
better absorption capacity than [DBNH][MTU]. absorption performance, and it can be observed from the corresponding
In addition, the structures were optimized at the B3LYP/6–311++G ILs. In conclusion, these novel absorbents with single-site and double-
(d, p) level and carried out the binding energy calculation. As shown in site can provide a new strategy to design more highly efficient DESs
Table S3, ΔE is the binding energy. [DBNH][MTU]:EG (1:1)-CO2 in for CO2 capture in industrial application.
single-site system has the biggest binding energy, which indicates that
[DBNH][MTU]:EG (1:1) has more efficient absorption capacity. For CRediT authorship contribution statement
double-site system, [DBNH]2[DTU]:EG (1:2)-CO2 has bigger binding
energy compared with [DBNH]2[DTU]:EG (1:1)-CO2 and Hui Fu: Conceptualization, Formal analysis, Writing – review &
[DBNH]2[DTU]:EG (1:4)-CO2, which implies that [DBNH]2[DTU]:EG editing, Supervision. Haina Sang: Investigation, Formal analysis,
(1:2) should have better absorption capacity. Therefore, the theoretical Writing – original draft. Li Su: Validation. Formal analysis. Xinming
calculation results are in good agreement with the experimental results, Zhou: Resources. Zhihua Peng: Resources. Yulu Zhou: Resources.

7
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