Significantly Enhanced Carbon Dioxide Capture by Anion

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Significantly Enhanced Carbon Dioxide Capture by AnionFunctionalized Liquid Pillar[5]arene through Multiple-Site Interaction Wenjun Lin, Zhiguo Cai, Xiaoyu Lv, Qiaoxin Xiao, Kaihong Chen, Haoran Li, and Congmin Wang Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/acs.iecr.9b02872 • Publication Date (Web): 13 Aug 2019 Downloaded from pubs.acs.org on August 13, 2019

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Significantly Enhanced Carbon Dioxide Capture by Anion-Functionalized Liquid Pillar[5]arene through Multiple-Site Interaction** Wenjun Lin,a Zhiguo Cai,a Xiaoyu lv,a Qiaoxin Xiao,a Kaihong Chen,a Haoran Lia and Congmin Wang*a, b a. Department of Chemistry, ZJU-NHU United R&D Center, Zhejiang University, Hangzhou 310027 (P. R. China). b. Key Laboratory of Biomass Chemical Engineering of Ministry of Education, Zhejiang University, Hangzhou 310027, China. Ionic liquids; Pillar[5]arenes; Carbon dioxide capture; Enhancement. Supporting Information

ABSTRACT: A strategy to prepare liquid anion-functionalized pillar[5]arene by incorporating a large asymmetrical cation on the rims was proposed. This kind of pillar[5]arene-based ionic liquid showed high thermal stability, good CO2 absorption capacity and excellent reversibility. In contrast with neutral pillar[5]arene and noncyclic monomeric analogue, pillar[5]arene-based ionic liquid exhibited significantly enhanced CO2 absorption capacity. Through a combination of absorption experiments, spectroscopic investigations and quantum chemical calculations, the results indicated that the increased capacity originated from multiple-site interactions between CO2 and the carboxylic anion, which was enhanced by the cavity of pillar[5]arene. This work provided an efficient methodology for preparing liquid macrocyclic host as well as improving gas absorption.

INTRODUCTION Carbon dioxide (CO2) in flue gases from the burning of fossil fuel is a significant source of greenhouse gases, which threatens the environment and human health.1-3 As a consequence, novel strategies and materials that can efficiently, reversibly, and economically capture CO2 are highly desired. Recently, a great deal of materials such as carbon based materials,4-8 zeolites,9-13 metal-organic frameworks (MOFs),14-22 covalent organic frameworks (COFs)23-27 and ionic liquids (ILs),28-35 have been widely applied for carbon capture. However, macrocyclic hosts such as crown ether,36 cyclodextrin,37-39 calixarene,40-41 and cucurbituril42-44 are not efficient candidates for CO2 capture because macrocyclic hosts possess insufficient BET surface for CO2 to adhere and the interaction between macrocyclic hosts and CO2 is low.45-55 These hindered the utilization of macrocyclic hosts for CO2 capture. How could we overcome these drawbacks to develop macrocyclic hosts with excellent CO2 capture performance? Recently, a series of functionalized ILs with tunable basic anions were reported for efficient CO2 capture.32-34,5657 This strategy applied in ILs provides us new insights and solutions to realize effective CO2 absorption. Pillararene58-62 is a novel macrocyclic host, which is easy to be synthesized with satisfactory yield in mild condition. It possesses plenty of reactive sites (≥10) at its rims. In contrast with other macrocyclic hosts, reactive sites of pillararene could be

facilely modified with functional groups partially or totally without interference of each other because of its symmetrical pillar architecture. The presence of functional groups at the reactive sites would affect the physical and chemical properties of pillararene significantly. Accordingly, pillararene was an excellent platform to be functionalized for CO2 capture. Effective capture of CO2 requires strong chemical absorption as well as sufficient gas transfer. Most of pillararenes were solid compounds because of their highly symmetrical architectures. Although there is a cavity in the corn of pillararene, it does not contain enough BET surface to adhere CO2 molecule due to an insufficient cavity length. According to our previous work63 liquid pillararene may overcome the drawback of gas transfer existed in solid state. Yang64 and Ogoshi65 have reported gas physical adsorption by pillar[5]arene through constructing extrinsic cavities or channels to increase gas contact, however, the capture capacity was still low. Pillararene with functional anions toward CO2 in liquid state maybe led to an effective CO2 capture. Herein, a kind of pillar[5]arene based IL [P66614][DCP5] was prepared (Scheme 1) by replacing H with large asymmetrical cation [P66614] on the rims of carboxylic pillar[5]arene, thus liquid pillar[5]arene was achieved. Generally, carboxylic anion just has a weak interaction with CO2 and its CO2 capture capacity is low, only about 0.3 mol CO2 per mol anion.66-72 To be surprised, compared with noncyclic monomeric analogue [P66614][DC], [P66614][DCP5] exhibited significantly enhanced

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CO2 capacity. Though a combination of experimental absorptions, quantum chemical calculations, FT-IR and NMR spectroscopic investigations, the results indicated that the high capacity originated from multiple-site interactions between CO2 and carboxylic anions on pillar[5]arene, and the cavity of pillar[5]arene strengthened the negative charges on O atoms of carboxylic anions, leading to enhanced chemical absorption of CO2.

Scheme 1. Structures of pillar[5]arene-based ionic liquids [P66614] [DCP5] and other related absorbents used for CO2 absorption.

RESULTS AND DISCUSSION Pillar[5]arene-based IL [P66614][DCP5] was synthesized by the acid-base neutralization between carboxylic pillar[5]arene DCP5 and [P66614][OH]. Herein, DCP5 was prepared according to the references,73-74 while [P66614][OH] was synthesized from [P66614][Br] by the anion-exchange method.32 Furthermore, [EMIM][DCP5] was prepared to investigate the effect of the cation. In order to investigate the role of the cavity, noncyclic monomeric IL [P66614][DC] was also prepared. The structures and purities of these pillar[5]arenes were verified by 1H NMR, 13 C NMR, two dimensional NMR including 1H-1H COSY, HMBC, HMQC, and MALDI TOF-MS method, which were shown in Figure S1-S16 of Supporting Information. The water content of absorbents was measured by Mettler Toledo DL 32 karl fischer coulometer. All of the absorbents contained less than 0.5 w% of water. The effect of the cation was investigated, which was listed in Table 1. As seen, [P66614][DCP5] was a liquid in room temperature due to its large asymmetrical structure, while [EMIM][DCP5] was a solid. In addition, the former had a higher thermal stability, whose decomposition temperature was 327.2 °C (Figure S17). CO2 absorption by these absorbents was investigated, which was shown in Table 1. In a typical experiment, CO2 of atmospheric pressure was passed through a drying column to avoid moisture contamination and then bubbled through about 0.8 g sample in a glass container with an inner diameter of 10 mm. The flow rate was about 60 ml·min-1. The glass container was partly immersed in a circulation water bath of desirable temperature. The amount of CO2 absorbed was determined at regular intervals by the electronic balance with an accuracy of ±0.1 mg. Here, CO2 absorption was carried out at 50°C because the viscosity of [P66614][DCP5] was a little high (1885 cP at 293K). It can be seen that CO2 absorption capacity of [P66614][DCP5] was 5.52 mol/mol, an over 16 folds increase compared with neutral analogue DMP5 (0.34 mol/mol), which is also much higher than solid ionic analogues [EMIM][DCP5] (1.08 mol/mol). CO2 capacity by [EMIM][DCP5] increased to 4.08 mol/mol due to its improved gas transfer when it was dissolved in methanol. It

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was revealed that both functional anion on pillar[5]arene and benign mass transfer were very important for improving CO2 capture. [P66614][DCP5] possesses a cavity in its core, so the role of this cavity on CO2 absorption was also investigated by comparing with its noncyclic monomeric analogue [P66614][DC] (Table 1 and Figure 1). Clearly, [P66614][DCP5] has a higher CO2 capture capacity than [P66614][DC] for per carboxylic anion at any conditions. For instance, [P66614][DCP5] absorbed 0.55 mol CO2 per anion at 50°C and 1bar, while [P66614][DC] could only absorbed 0.29 mol CO2 per anion. Herein, it seemed that the presence of the cavity promoted the interactions between the carboxylic anion and CO2 molecule. The effect of temperature on CO2 absorption by [P66614][DCP5] was also investigated (Table S1). It was seen that CO2 absorption capacity decreased from 0.55 to 0.25 mol·mol-1. Therefore, [P66614][DCP5] could be regenerated conveniently by heating after CO2 absorption. 20 cycles of CO2 absorption and desorption by [P66614][DCP5] was investigated, which was shown in Figure 2. It can be seen that CO2 absorption capacity was well maintained during 20 cycles. In addition, the 1H and 13C NMR spectra of [P66614][DCP5] were also well-maintained after 20 cycles in comparison with fresh [P66614][DCP5] (Figure S19-S20). These results indicated that CO2 absorption and desorption processes by [P66614][DCP5] was highly reversible. Clearly, this kind of pillar[5]arene-based IL [P66614][DCP5] exhibited significantly enhanced CO2 capacity and excellent reversibility, which is superior to conventional macrocyclic hosts and other traditional ILs with carboxylic anion (Table S2). Why this pillar[5]arene-based IL showed so different CO2 absorption performance? We believe that there must lie in the enhanced interaction between the carboxylic anion of pillar[5]arene and CO2, where the cavity played an important role. Table 1. CO2 absorption by pillar[5]arene-based ionic liquids [P66614][DCP5] and other related absorbents. T[b] / °C

Capacity[c] / mol·mol-1

Capacity[d] / mol·mol-1

DMP5

248.8

0.34

0.03

DCP5

297.3

0.48

0.05

Absorbent

T[a] / °C

[EMIM][DCP5]

273.4

96.2

1.08

0.11

[EMIM][DCP5][e]

273.4

96.2

4.08

0.41

[P66614][DCP5]

327.2

-50.0

5.52

0.55

[P66614][DC]

333.1

-55.7

0.58

0.29

[a] Decomposition temperature. [b] Melting point or Glass transition temperature. [c] CO2 absorption was carried out at 50°C, 1 bar. [d] Absorption capacity of per carboxylic anion. [e] Absorption was carried out in methanol. To investigate the interactions between the carboxylic anion and CO2, quantum chemical calculations were performed using the Gaussian 09 program at the B3LYP/6-31+G (d, p) level to optimize structure and to calculate the frequency as well as natural bond orbital (NBO) charges,75 which were shown in Figure


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3 and Figure S21-S28. It was seen that there lay in ten-site interaction between [DCP5] anion and CO2, where each site of [DCP5] could interact with CO2, which was not affected by each other, leading to high CO2 capacity.

Figure 1. Partial pressure absorption comparison between [P66614][DC] black square and [P66614][DCP5] red circle of single anion at 50°C.

Figure 2. CO2 absorption by [P66614][DCP5] for 20 cycles. CO2 absorption was carried out at 50°C for 60 min, and desorption was performed at 80°C under N2 for 30 min.

Figure 3. Multiple-sites interactions between [DCP5] anion and CO2 molecules: a) [DCP5] and 1 CO2 molecule; (b) [DCP5] and 2 CO2 molecules; (c) [DCP5] and 3 CO2 molecules; (d) [DCP5] and 10 CO2 molecules. The enhanced interaction between [P66614][DCP5] and CO2 was further investigated by FT-IR and NMR spectroscopy (Figure 5). Firstly, C=O asymmetrical stretching vibration of carboxylic anion in [DCP5] appeared at 1602 cm-1, 12 cm-1 lower than in [DC], which meant that [DCP5] had a more negative charge on carboxylic anion than [DC] as shown in Figure 5a and S29.79-81 Furthermore, after the uptake of CO2 by [P66614][DCP5], new peaks produced at 161.25 ppm and 126.31 ppm, which could be assigned to CO2 chemical and physical absorption, respectively (Figure 5b). On the other hand, after CO2 absorption by [EMIM][DCP5], two new peaks were detected by 13C NMR due to the presence of two chemisorption mechanism, where the signal at 161.26 ppm was assigned to CO2-carboxylate complex, and the signal at 158.81 ppm was corresponded to CO2-carbene complex (Figure S30). However, for IL [P66614][DC], only a peak at 127.45 ppm appeared that belonged to CO2 physical absorption (Figure 5c, S31-32).

To further explain the reason on the enhancement caused by the cavity of pillar[5]arene, the natural bond orbital (NBO) charges on the atoms of the carboxylic anion in [DC] and [DCP5] were calculated and compared, respectively (Figure 4). The sum of NBO charges on the two oxygen atoms of [DC] anion was -1.581, while that of each anion in [DCP5] was in a small range -1.636 ~ -1.623. Thus, the interaction between the anion in [DCP5] and CO2 increased because of the lower charges on the oxygen atoms of the latter.76-78 Furthermore, the OCO bond angle and the distance between the O atom in the carboxylic anion and the C atom in CO2 were also investigated (Figure 4). It was seen that the OCO bond angle in [DCP5]CO2 complex was smaller than that in [DC]-CO2 complex, and the distance in [DCP5]-CO2 complex was shorter than that in [DC]-CO2 complex, indicating the stronger interaction of the former. For instance, the bond length between [DC] and CO2 were 1.723 Å, which was shortened to 1.522 Å when [DCP5] existed, and its OCO bond angle varied from 143.65°to 133.41°.



Figure 4. NBO charges distributions of a) [DC] anion and (b) [DCP5] anion. Bond length between anion and CO2 molecule: (c) [DC] anion with CO2; (d) [P66614][DCP5] anion with CO2.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: Supporting Information

AUTHOR INFORMATION Corresponding Author *Fax: +86-571-8827-3181. E-mail: [email protected]. Author Contributions †

These authors contributed equally to this work.

Notes The authors declare no competing financial interest.

ACKNOWLEDGMENT This work was supported by the National Key Basic Research Program of China (2015CB251401), the National Natural Science Foundation of China (No. 201176205, 21322602), the Zhejiang Provincial Natural Science Foundation of China (LZ17060001), and the Fundamental Research Funds of the Central Universities.

Supporting Information Experimental and structure characterization; Figure S1-S32; Table S1-S2; This material is available free of charge via the Internet at http://pubs.acs.org.

Figure 5. a) FT-IR spectra comparison between [P66614][DC] (gray shadow) and [P66614][DCP5] (red line). (b) 13C NMR spectra of [P66614][DCP5] before (black line) and after CO2 absorption (red line). (c) 13C NMR spectra of [P66614][DC] before (black line) and after CO2 absorption (red line).

CONCLUSIONS In conclusion, we reported a kind of novel pillar[5]arenebased IL through introducing a large asymmetrical cation on the rims, which exhibited good CO2 absorption and excellent reversibility. Compared with traditional ILs, this kind of liquid pillar[5]arene showed significantly enhanced CO2 absorption performance. Through a combination of FT-IR, NMR and quantum chemical calculations, the results indicated that the enhanced CO2 uptake originated from multiple-site interactions between the anion and CO2, where these interactions were reinforced by the cavity of the pillar[5]arene. The strategy proposed in this work provided a novel aspect for gas absorption and supramolecular utilization.

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Significantly Enhanced Carbon Dioxide Capture by Anion

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