Efficient Absorption of SO2 by Deep Eutectic Solvents Formed by

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Efficient absorption of SO2 by deep eutectic solvents formed by biobased aprotic organic compound succinonitrile and [Emim][Cl] Dezhong Yang, Shaoze Zhang, and De-en Jiang ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.9b00851 • Publication Date (Web): 25 Apr 2019 Downloaded from http://pubs.acs.org on April 26, 2019

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ACS Sustainable Chemistry & Engineering

Efficient absorption of SO2 by deep eutectic solvents formed by biobased aprotic organic compound succinonitrile and [Emim][Cl] Dezhong Yang, *† Shaoze Zhang, ‡De-en Jiang*§ †School

of Science, China University of Geosciences, No. 29 Xueyuan Road, Beijing 100083,

China ‡

School of Chemistry & Molecular Engineering, East China University of Science and

Technology, 130 Meilong Road, Shanghai 200237, China §Department

of Chemistry, University of California, 501 Big Spring Road, Riverside,

California 92521, United States Corresponding authors: Dezhong Yang. E-mail: [email protected]; De-en Jiang. E-mail: [email protected]

Keywords: deep eutectic solvents, sulfur dioxide, capture, biobased chemical, hydrogen bonding, ionic liquids .

ACS Paragon Plus Environment

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Abstract: We report that deep eutectic solvents can be formed by biobased aprotic organic compound succinonitrile (SN) functionalized as the hydrogen bond donors with solid ionic liquid 1-ethyl-3-methylimidazolium

chloride

([Emim][Cl])

or

1-ethyl-3-methylimidazolium

hexafluorophosphate ([Emim][PF6]). The results suggested the formation of intermolecular hydrogen bond between the anions of imidazolium salts and the C-H hydrogen of SN. Moreover, the DESs [Emim][Cl]-SN (1:1) exhibited an attractive SO2 absorption capacity (0.120 g SO2/g solvent) at low SO2 partial pressure (2000 ppm), which was more than two times the amount captured by [Emim][Cl]-ethylene glycol(EG) (1:1) (0.047 g SO2/g solvent) at the same condition, although the concentration of [Emim][Cl] in [Emim][Cl]-SN (1:1) (64.7 wt%) was lower than that in [Emim][Cl]-EG (1:1) (70.3 wt%). The high SO2 absorption capacity of [Emim][Cl]-SN (1:1) was mainly because of the strong charge-transfer interaction between S of SO2 and Cl-, which was investigated by using FTIR spectra and theoretical calculations.

INTRODUCTION Sulfur dioxide (SO2), the main air contaminate , is mainly generated from the fossil fuels combustion in industry, posing a serious hazard to human and environment. Among the methods applied to control SO2 emission, the most used technology in industry is the lime-limestone flue gas desulfurization (FGD) process.1 However, the lime-limestone process is irreversible and suffers other inherent shortcomings, including the generation of huge amount of solid byproduct, high cost and wastewater, which will generate second pollution to the environment if not properly treated.2,3 Thus, developing efficient absorbents for reversible SO2 capture is highly needed in regard of practical application. In the past decades, ionic liquids (ILs) have been widely used to capture and separate acid gases because of their unique properties, such as


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extremely low vapor pressures, wide liquidus range, high thermal stability, and relatively high capacity for acid gases.4-7 Up to now, a number of ILs have been studied to capture SO28-12. Among them, the amine-functionalized13-15 and azolide16-17,49 ILs exhibited a high SO2 absorption capacity owing to the strong interaction between S of SO2 and ions in ILs. Deep eutectic solvents (DESs) ,a new class of solvents, have received broad attention over the past decades, which were found by Abbott et al.18-19 DESs generally comprise two or more components which are able to connect with each other through intermolecular interactions, and the melting points of DESs are far lower than that of each parent component.20 Most DESs are formed by phosphonium salts or quaternary ammonium salts with suitable hydrogen bond donors (HBAs) capable of forming intermolecular hydrogen bonds with salts’ anion, resulting a significant decrease of the melting points.21 DESs share many physiochemical properties with ILs, including wide liquidus range, nonflammability, and tunable structures. However, DESs exhibit several advantageous properties compared to ILs, including low cost of production, simple synthesis procedures, no by-product generation and high purity.22-24 Therefore, with all these benefits, DESs have been regarded as attractive alternatives to ILs in many applications, such as catalysis, organic reactions, electrochemistry, nanotechnology, and biodiesel purification.25-28 Moreover, DESs have also been applied to capture acid gases, 29such as CO2,3032NO33

and SO2.34-35,50-52 Betaine-ethylene glycol (EG)36 and azole-based

37-39

DESs exhibited a

high SO2 absorption capacity. In our previous work, we found that DESs formed by [Emim][Cl] with EG40 or TEG41 can also efficiently absorb SO2. Recently, we found that the aprotic organic compound of succinonitrile (SN) can be used as a HBAs to form DESs with quaternary ammonium salts.

42SN,

a plastic crystal at room

temperature , can be viewed as biobased material because it can be synthesized from amino acid


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glutamic acid which is present plentifully in many plants. 53 The dielectric constant ,55 (25 oC),of SN is higher than that of many other conventional liquid solvents, 43 . SN also posses many other unique features, such as very low vapor pressure, great thermal stability, excellent electrochemical stability, low flammability, high boiling point of 267 °C, and high solubility for lithium salts.54-56 Therefore, SN has been added as useful additive into commercial electrolyte to enhance the lithium-ion batteries’ performance

57-62or

used as solvent/plasticizer in polymer

electrolyte.63-65 In addition, the applications of SN based solid-state electrolyte have been widely investigated in dye-sensitized solar cells 66-69and supercapacitors.70 Herein, we report the new application of SN-based material for SO2 capture. We found that DESs can also be obtained by mixing SN with the solid IL [Emim][Cl] or [Emim][PF6], and the [Emim][Cl]-SN DESs can efficiently absorb SO2, especially at low SO2 partial pressure. Surprisingly, although the concentration of [Emim][Cl] in [Emim][Cl]-SN(1:1) (64.7 wt%) is lower than that in [Emim][Cl]-EG(1:1)(70.3 wt%), [Emim][Cl]-SN (1:1) showed a much higher absorption capacity (0.120 g SO2/g solvent) than [Emim][Cl]-EG(1:1)(0.047 g SO2/ g solvent) at 2000 ppm. RESULTS AND DISCUSSIONS The DSC thermograms of the [Emim][Cl]-SN system and SN are presented in Figure S1. The solid-state transition (Tpc) of SN was observed at -38°C.43 The melting points for [Emim][Cl] and SN can be observed at 87°C and 58 °C, respectively. However, as shown in Figure S1, no melting point can be found for [Emim][Cl]-SN(1:1) and [Emim][Cl]-SN(1:2), and the Tpc of SN also disappeared in these two systems. With increasing concentration of SN, the Tpc of SN reappeared in [Emim][Cl]-SN(1:4) and [Emim][Cl]-SN(1:8) mixtures, suggesting the existence


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of “inactive” SN. We also studied the phase behaviors of the DESs formed by [Emim][PF6] and SN. The DSC traces of [Emim][PF6]-SN systems are shown in Figure S2. The melting point of [Emim][PF6] is 63°C . As shown in Figure S2, there is also no melting point can be found in [Emim][PF6]-[SN](1:1) and [Emim][PF6]-SN (1:2) DESs. FTIR and NMR results have been utilized to investigate the interactions between [Emim][PF6] and SN. Figure S3 shows the FTIR spectra of [Emim][PF6] and [Emim][PF6]-SN DESs. The C4,5-H and C2-H stretching peaks of cation [Emim]+ in pure [Emim][PF6] can be found at 3180 and 3132 cm-1,respectively.

44As

seen in Figure S3, the stretching peaks of the

imidazolium ring C-H bonds shifted to lower wavenumbers as the SN concentration was increased in [Emim][PF6]-SN DESs. The C4,5-H stretching peaks moved from 3180 cm-1 for [Emim][PF6] to 3163 cm-1 for [Emim][PF6]-SN(1:8), and the C2-H peaks moved from 3132 cm-1 for [Emim][PF6] to 3121 cm-1 for [Emim][PF6]-SN(1:8). The C4,5-H bond showed a bigger downward shift(17 cm-1) than C2-H( 11 cm-1). When the concentration of [Emim][PF6] was increased in the system, the stretching vibration bands of the methylene group (-CH2-) of SN exhibited an upward shift from 2988 cm-1 for SN to 2997 cm-1 for [Emim][PF6]-SN(1:1). It is reported that the C-H stretching bands on imidazolium ring would exhibit a downward shift when the coordination strength of anions was enhanced. 45The weaker interaction anions would lead to the blue shift of the C-H stretching peaks. Accordingly, the downfield shifts of the imidazolium ring C-H stretching peaks and the upfield movement of the methylene stretching peaks of SN indicated that the hydrogen bond acceptor strength of cyano group (-CN) was stronger than that of anion [PF6]-.

46

Furthermore, the stretching peaks of anion [PF6]- moved

from 818 ([Emim][PF6]) to 838 ([Emim][PF6]-SN(1:8)) cm-1, demonstrating an upward shift of 20 cm-1, and the stretch bands of –CN group shifted slightly from 2254 (SN) to 2255


5


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([Emim][PF6]-SN(1:1)) cm-1, indicating that both anion [PF6]- and –CN group participated to form intermolecular hydrogen bonds. Therefore, it can be found that two kinds of intermolecular hydrogen bonds were formed in [Emim][PF6]-SN system: one between the anion [PF6]- and the methylene hydrogen of SN; the other one between the nitrogen of the –CN group and the hydrogen on imidazolium ring.

Figure 1. The FTIR spectra of [Emim][Cl]-SN system. The FTIR spectra of [Emim][Cl], SN and [Emim][Cl]-SN system are shown in Figure 1. The [Emim][Cl] spectra was recorded when [Emim][Cl] was liquid. The stretching peaks of C4H and C2-H on imidazolium ring shifted to higher wavenumbers from 3138 ([Emim][Cl]) to 3144 ([Emim][Cl]-SN(1:1)) cm-1and from 3038([Emim][Cl]) to 3044 ([Emim][Cl]-SN(1:1)) cm-1 (Figure 1a), respectively. Conversely, the C-H stretching peaks of SN moved to lower wavenumbers from 2988 (SN) to 2973 ([Emim][Cl]-SN(1:1)) cm-1.These results suggested the hydrogen bonds were formed between anion Cl- and the C-H hydrogen of SN and indicated that the hydrogen bond acceptor strength of Cl- was stronger than that of –CN group.47 The stretch peaks of –CN group exhibited downward shift from 2254 (SN) to 2249 ([Emim][Cl]-SN(1:1)) cm-1 (Figure 1b). The –CN wavenumber was 2249 cm-1 in [Emim][Cl]-SN (1:1),

which was


6

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lower than that in [Emim][PF6]-SN(1:1)(2255 cm-1), suggesting the stronger interaction between –CN and Cl- than that between [PF6]- and –CN. Moreover, NMR spectra were also applied to further study the interactions between imidazolium salts and SN (Figure S4). The chemical shifts of the methylene hydrogen of SN moved from 2.59 ([Emim][PF6]-SN(1:1) ) to 3.09 ppm ([Emim][Cl]-SN(1:1))(Figure S4a), and the 13C signals of methylene carbon of SN changed from 14.1 ppm in [Emim][PF6]-SN(1:1) to 15.3 ppm in [Emim][Cl]-SN(1:1)( Figure S4b). The signal of the –CN carbon shifted from 118. 8 ([Emim][PF6]-SN (1:1)) to 119.6 ppm ([Emim][Cl]-SN (1:1)).The NMR results also suggested the strong interaction between SN and Cl-.

Figure 2. The interactions between organic salts and SN . (a), [Emim][Cl]-SN(1:1); (b),[Emim][PF6]-SN (1:1). Cl, green; C, grey; H, white; N, blue; P, brown; F, cyan Theoretical calculations were also performed to investigate the interactions between SN and imidazolium salts, As shown in Figure 2, Cl- formed hydrogen bonds with -CH2- group of SN ,and the anion Cl- also interacts with the carbon of –CN group. Figure 2b shows the intermolecular hydrogen bonds formed by [Emim][PF6] with SN and the interaction between the [PF6]- and the carbon of –CN. Moreover, the interaction energy between [Emim][Cl] and SN was -48.4 kJ/mol, which is lower than that between [Emim][PF6] and SN (-41.7 kJ/mol), indicating


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the stronger interaction between SN and [Emim][Cl]. The calculation data are in accordance with experimental results.

Figure 3. The SO2 absorption by [Emim][Cl]-SN DESs at 20 °C and 1.0 atm. The results of SO2 absorption by [Emim][Cl]-SN DESs at 20 °C and 1.0 atm are shown in Figure 3. As shown in Figure 3, the SO2 absorption capacity of [Emim][Cl]-SN(1:1) could reach 1.13 g SO2 / g solvent, which is higher than that of [Emim][Cl]-EG(1:1) (1.03 g SO2/ g solvent) and comparable with that of [Emim][Cl]-EG(2:1) (1.15 g SO2/g solvent) at the same condition. 40 With decreasing concentration of [Emim][Cl] in the solvent, the absorption capacity of the DES was decreased to 0.96 g SO2 / g solvent for [Emim][Cl]-SN(1:2) and 0.79 g SO2/ g solvent for [Emim][Cl]-SN(1:4). Moreover, SN only captured 0.50 g SO2 /g solvent at 20 °C and 1.0 atm, which was much lower than the capacity of [Emim][Cl]-SN (1:1), suggesting the important role of [Emim][Cl] for the high SO2 capacity of the DESs. Interestingly, the solid SN turned into liquid after interacting with SO2. The high SO2 absorption capacity of [Emim][Cl]-SN (1:1) is probably because of the strong charge-transfer interaction between Cl- and SO2, 48which will be discussed in the following section..


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The reversibility of the solvent is also a crucial factor for the practical application of SO2 capture, and we investigated the reusability of the [Emim][Cl]-SN DESs. Figure S5 presents the five consecutive absorption-desorption process of [Emim][Cl]-SN (1:1). Most SO2 (~98%) captured by [Emim][Cl]-SN(1:1) could be desorbed at 80 ℃ within ~80 min by N2 sweeping. [Emim][Cl]-SN (1:2) can release all the absorbed SO2 at 80 ℃ within ~70 min (Figure S6). Furthermore, [Emim][Cl]-SN (1:4) can release all the absorbed SO2 at 70 ℃(Figure S7).Clearly, no significant loss of the absorption capacity can be observed during five absorption/desorption cycles, suggesting the good reversibility of the [Emim][Cl]-SN DESs. The different desorption behaviors of the DESs are mainly owing to the fact that the interaction strength between SO2 and Cl- is tuned upon the addition of SN. As the concentration of SN is increased, more SN would interact with the Cl-, which decreases the interaction strength between SO2 and Cl-, benefitting the release of SO2. Furthermore, we investigated the thermal stability of the DESs [Emim][Cl]SN(1:1) by N2 sweeping, the results are presented in Figure S8. [Emim][Cl]-SN(1:1) was sweeped with N2 at 80 °C for 10 hours, and no obvious weight loss of the sample can be found, proving the high stability of [Emim][Cl]-SN(1:1)(Figure S8). The effect of temperature on SO2 absorption is presented in Figure S9. The SO2 absorption capacity of [Emim][Cl]-SN(1:1) decreased as temperature increased. The absorption capacity of [Emim][Cl]-SN(1:1) decreased from 1.13 g SO2/g solvent at 20°C to 0.661 g SO2/g solvent at 50 °C . [Emim][Cl]-SN(1:1) could capture 0.773 g SO2/g solvent at 40°C and 1.0 atm, which is much higher than the absorption capacity of L-car:EG(1:3) (0.365 g SO2/ g solvent) at the same condition.36


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As we know, the concentration of SO2 in flue gases is extremely low (~0.20 Vol%), so [Emim][Cl]-SN DESs’ SO2 absorption capacity at 2000 ppm of SO2 and 20 ℃ was also determined. [Emim][Cl]-SN (1:1), [Emim][Cl]-SN (1:2) and [Emim][Cl]-SN (1:4) can capture 0.120, 0.085 and 0.051 g SO2/g solvent, respectively. [Emim][Cl]-EG (1:1) can only absorb 0.047 g SO2/g solvent at 20℃ and 2000 ppm of SO2. Above results suggested that the absorption capacity of [Emim][Cl]-SN(1:1) was more than two times that of [Emim][Cl]-EG(1:1) at 2000 ppm, although the concentration of [Emim][Cl] in [Emim][Cl]-[SN](1:1) (64.7 wt%) was lower than that in [Emim][Cl]-EG(1:1)(70.3% wt%), indicating the important role of the HBDs for SO2 absorption. The higher capacity of [Emim][Cl]-[SN](1:1) is mainly because that the hydrogen bond donor strength of -CH2- of SN is weaker than that of –OH of EG. Therefore, when EG is replaced by SN in DESs, the strength of hydrogen bonding between HBDs and Cl- will be reduced, which is beneficial to enhancing the interaction strength between SO2 and Cl-, improving the uptake of SO2 by [Emim][Cl]-[SN]. The ability of DESs [Emim][Cl]-SN(1:1) to capture CO2 was also determined, and [Emim][Cl]-SN(1:1) only absorbed 0.010 g CO2/g solvent at 20 °C and 1.0 atm, which was much lower than its’ absorption capacity of SO2 (1.13 g SO2/g solvent). To investigate the interactions between SO2 and [Emim][Cl]-SN (1:1) DESs, the FTIR spectra of [Emim][Cl]-SN (1:1) with and without SO2 were studied. As seen in Figure 4, two new peaks at 1287 and 1126 cm-1 can be found after SO2 absorption, which are the asymmetrical (Vas) and symmetrical (Vs) stretching bands of SO2, respectively. These peaks centered at 1337 and 1148 cm-1 for SO2 captured by SN. The above results showed the stretching bands of SO2 shifted to lower frequencies when the [Emim][Cl] was added into the absorbent, suggesting the strong interaction between S atom of SO2 and Cl-. Furthermore, the Vas and Vs peaks were found


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at 1298 and 1135 cm-1 for SO2 captured by [Emim][Cl]-EG (1:1), respectively. Therefore, the Vas and Vs bands for SO2 captured by [Emim][Cl]-SN (1:1) were lower than those for SO2 captured by [Emim][Cl]-EG(1:1), indicating the stronger interaction between SO2 and Cl- in [Emim][Cl]SN (1:1) than that in [Emim][Cl]-EG (1:1).

Figure 4. FTIR spectra of [Emim][Cl]-SN (1:1) with and without SO2.

Figure 5. Optimized structures of [Emim][Cl]-SN (1:1) + SO2 system. C, grey; H, white; N, blue; Cl, green; S, yellow; O, red. Theoretical calculations were also utilized to study the interactions between SO2 and EmimCl-SN(1:1). Figure 5 shows the optimized structure presenting the interactions between SO2 and [Emim][Cl]-SN (1:1). As shown in Figure 5, the anion Cl- mainly interacts with S of


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SO2, and the interaction energy of SO2 with [Emim][Cl]-SN (1:1) is -69.8 kJ/mol, indicating the strong interaction between anion Cl- and SO2. CONCLUSIONS In summary, biobased aprotic compound SN acted as HBDs can form DESs with solid ionic liquids ([Emim][Cl] or [Emim][PF6]). Results showed that the formation of intermolecular hydrogen bonds between C-H hydrogen of SN and anions of imidazolium salts. The DESs formed by [Emim][Cl] and SN could efficiently capture SO2 and can be reused. [Emim][Cl]SN(1:1) exhibited a much higher absorption capacity of 0.120 g SO2/ g solvent at 2000 ppm than [Emim][Cl]-EG(1:1) (0.047 g SO2/g solvent). We believe this work will promote the development of the DESs field for SO2 capture.

ASSOCIATED CONTENT Supporting Information. Experimental section, computational methodology, DSC traces of DESs, FTIR and NMR data for DESs, reversibility and thermal stability of DESs, and effect of temperature on absorption. AUTHOR INFORMATION Corresponding Author D. Yang. E-mail: [email protected]. D. Jiang. E-mail: [email protected].


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Notes The authors declare no competing financial interests. ACKNOWLEDGMENT The authors thank the financial support by the National Natural Science Foundation of China (No.21503196). REFERENCES (1)Tailor, R.; Abboud, M.; Sayari, A., Supported Polytertiary Amines: Highly Efficient and Selective SO2 Adsorbents. Environ. Sci. Technol. 2014, 48, 2025-2034, DOI 10.1021/es404135j. (2)Córdoba, P., Status of Flue Gas Desulphurisation (FGD) systems from coal-fired power plants: Overview of the physic-chemical control processes of wet limestone FGDs. Fuel 2015, 144, 274-286, DOI 10.1016/j.fuel.2014.12.065. (3)Srivastava, R. K.; Jozewicz, W., Flue gas desulfurization: The state of the art. J. Air Waste Manage. Assoc. 2001, 51, 1676-1688, DOI 10.1080/10473289.2001.10464387. (4)Egorova, K. S.; Gordeev, E. G.; Ananikov, V. P., Biological Activity of Ionic Liquids and Their Application in Pharmaceutics and Medicine. Chem. Rev. 2017, 117, 7132-7189, DOI 10.1021/acs.chemrev.6b00562. (5)Dong, K.; Liu, X.; Dong, H.; Zhang, X.; Zhang, S., Multiscale Studies on Ionic Liquids. Chem. Rev. 2017, 117, 6636-6695, DOI 10.1021/acs.chemrev.6b00776. (6)Xie, L.-Y.; Peng, S.; Lu, L.-H.; Hu, J.; Bao, W.-H.; Zeng, F.; Tang, Z.; Xu, X.; He, W.-M., Brønsted Acidic Ionic Liquid-Promoted Amidation of Quinoline N-Oxides with Nitriles. ACS Sustainable Chem. Eng. 2018, 6, 7989-7994, DOI 10.1021/acssuschemeng.8b01358.


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TOC

SYNOPSIS: Deep eutectic solvents consisting of biobased succinonitrile and [Emim][Cl] exhibit a high SO2 absorption capacity at low SO2 partial pressure.


23

Efficient Absorption of SO2 by Deep Eutectic Solvents Formed by

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