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Electronic Supplementary Material (ESI) for Journal of Materials Chemistry A.This journal is © The Royal Society of Chemistry 2018

Supplementary Information

Ionic Liquid-Decorated COF and Its Covalently Composite Aerogel for

Selective CO2 Adsorption and Catalytic Conversion

Luo-Gang Ding,a Bing-Jian Yao,*a Fei Li,a Shao-Chuan Shi,a Ning Huang,b Hua-Bing Yin,c Qun Guan,a Yu-Bin

Dong*a

a College of Chemistry, Chemical Engineering and Materials Science, Collaborative Innovation Center of Functionalized

Probes for Chemical Imaging in Universities of Shandong, Key Laboratory of Molecular and Nano Probes, Ministry of

Education, Shandong Normal University, Jinan 250014, P. R. China. E-mail: yubindong@sdnu.edu.cn (Y.B. Dong),

yaobingjian1986@163.com (B.J. Yao)b Department of Chemistry, Faculty of Science, National University of Singapore, 3 Science Drive 3, Singapore 117543,

Singaporec Institute of Computational Materials Science, School of Physics and Electronics, Henan University, Kaifeng, 475004, P. R.

China

Electronic Supplementary Material (ESI) for Journal of Materials Chemistry A.This journal is © The Royal Society of Chemistry 2019

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Fig. S1 IR spectrum of intermediate A, (KBr, cm−1): 3100 (w), 2950 (s), 2844 (m), 1712 (s), 1602 (s), 1552 (m), 1461 (m), 1108 (m), 762 (m).

Fig. S2 1H NMR spectrum (in CDCl3) of intermediate A, δ (ppm): 2.65 (3H, s, −CH3), 3.94-3.96 (6H, d, −OCH3), 7.90−7.98 (3H, m, −Ar).

216.0955

231.0587

234.9637 247.1734249.0694 251.1315 254.1102

+MS, 0.1-0.1min #(5-6)

0

2

4

6

5x10Intens.

215 220 225 230 235 240 245 250 255 m/z

Fig. S3 The MS spectrum of intermediate A, calcd for C11H12O4Na+, m/z 231.07, found, m/z 231.06.

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Fig. S4 IR spectrum of intermediate B, (KBr, cm−1): 3100 (w), 2956 (m), 2838 (m), 1720 (s), 1602 (m), 1552 (m), 1461 (m), 1116 (m), 763 (m), 627 (m).

Fig. S5 1H NMR spectrum (in CDCl3) of intermediate B, δ (ppm): 3.95-3.97 (6H, s, −OCH3), 4.96 (2H, s, −ArCH2Br), 8.02−8.13 (3H, m, −Ar).

301.1418

302.3060 304.2608

308.9745

309.9773

310.9726

311.9753

+MS, 0.1-0.1min #(3-4)

0.0

0.2

0.4

0.6

0.8

1.0

1.26x10

Intens.

300 302 304 306 308 310 312 314 m/z

Fig. S6 The MS spectrum of intermediate B, calcd for C11H11O4BrNa+, m/z 308.98; found, m/z 308.9.

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Synthesis of intermediate C: A mixture of intermediate B (0.57 g, 2 mmol), 1-allylimidazole (0.26 g, 2.4 mmol) in acetonitrile (45 mL) was stirred at 80°C for 5 h. After removal of the solvent in vacuum, the residue was purified by column chromatography on silica gel using dichloromethane-methanol (20:1, v/v) as the eluent to generate C as faint yellow solids (0.54 g, 85 %).

Fig. S7 IR spectrum of intermediate C, (KBr, cm−1): 3142 (w), 3074 (s), 2954 (s), 2848 (m), 1718 (s), 1563 (s), 1419 (m), 1306 (s), 1259 (s), 1183 (m),1117 (m), 1073 (m), 931 (w), 773 (s), 749 (s), 631(m).

Fig. S8 1H-NMR spectrum (in DMSO-d6) of intermediate C, δ (ppm): 3.88 (6H, s, -OCH3), 4.87 (2H, q, -NCH2CH-), 5.19-5.37 (2H, d, -CHCH2), 5.78 (2H, s, -ArCH2N-), 6.01-6.05 (1H, m, -CH2CHCH2),7.77 (2H, d, -NCHCHN-), 7.98 (1H, s, -Ar), 8.13 (2H, s, -Ar), 9.18 (1H, s, -NCHN-).

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315.1335

317.1424

1. +MS, 0.0-0.1min #1-5, -Peak Bkgrnd

0.00

0.25

0.50

0.75

1.00

1.254x10

Intens.

290 300 310 320 330 340 350 m/z

Fig. S9 The MS spectrum of intermediate C, Calcd for C17H19N2O4 M+, m/z 315.13; found, m/z 315.12.

Fig. S10 IR spectrum of IL-ADH, (KBr, cm−1): 3432 (w), 3311 (w), 3258 (m), 3146 (m), 1661 (s), 1640 (s), 1528 (m), 1491 (m), 1333 (s), 1150 (s), 959 (m), 874 (m), 846 (m), 744 (m), 642 (m).

Fig. S11 1H-NMR spectrum (in DMSO-d6) of IL-ADH, δ (ppm): 4.59 (4H, s, -NHNH2), 4.87 (2H, q, -NCH2CH-), 5.19-5.37 (2H, d, -CHCH2), 5.56 (2H, s, -ArCH2N-), 6.01-6.05 (1H, m, -CH2CHCH2),7.77 (2H, d, -NCHCHN-), 7.75 (1H, s, -Ar), 7.82-7.90 (2H, d, -Ar), 9.23 (1H, s, -NCHN-), 9.88-9.94 (2H, d, -NHNH2).

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315.1489

711.2293

+MS, 0.1-0.1min #(3-4)

0.0

0.5

1.0

1.5

6x10Intens.

100 200 300 400 500 600 700 800 900 1000 m/z

Fig. S12 The MS spectrum of IL-ADH, Calcd for C15H19N6O2 M+, m/z 315.16; found, m/z 315.15.

Fig. S13 13C-NMR spectrum (in DMSO-d6) of IL-ADH, δ (ppm): 166.95 (-NHCOAr-), 165.08 (-NHCOAr-), 137.25 (-COAr-), 137.06 (-COAr-), 135.65 (-NCHN-), 133.32 (-ArCH2-), 132.19 (-CH2CHCH2), 129.72 (-Ar), 128.67 (-Ar), 127.8 (-Ar), 123.37 (-NCHCH-), 123.07 (-CHCHN-), 120.7 (-CHCH2), 51.39 (-ArCH2N-), 50.36 (-NCH2CH-)

Fig. S14 IR spectra of IL-ADH, Tp, and COF-IL. The characteristic N−H stretching (3432 cm−1) in IL-ADH and the carbonyl stretching band (1639 cm−1) in Tp disappeared after the reaction. Meanwhile, the strong peaks at 1604 and 1286 cm-1 due to the C=C and C-N stretching, respectively, appeared in the aerogel, indicated the successful condensation reaction.

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Fig. S15 Solid-state 13C-MAS NMR spectrum of COF-IL, δ(ppm): 167.4, 163.3, 147.1, 141.2, 138.1, 134.9, 132.3, 129.7-127.6, 124.34, 123.0, 120.6, 100.4, 53.5, 51.9.

Table S1 Fractional atomic coordinates for the unit cell of COF-IL.a COF-IL AA stacking mode, Space group: P3a = 32.96 Å, b = 32.96 Å, c = 3.62 Åα = 90.0°, β = 90.0°, γ = 120.0°

Atom x y zC1 0.01298 0.55184 0.49924C2 0.96115 0.51298 0.49873C3 0.94818 0.46115 0.50006C4 0.10366 0.57771 0.50012O5 0.11645 0.62856 0.49929N6 0.8583 0.43507 0.49947N7 0.19156 0.60212 0.50011C8 0.22952 0.5892 0.49989C9 0.28143 0.62787 0.49975

C10 0.29475 0.67982 0.49989O11 0.25697 0.69299 0.49988H12 0.93238 0.52258 0.49737H13 0.21976 0.55078 0.49983C14 0.98702 0.44816 0.50076C15 0.03885 0.48702 0.50127C16 0.05182 0.53885 0.49994C17 0.89634 0.42229 0.49988O18 0.88355 0.37144 0.50071N19 0.1417 0.56493 0.50053N20 0.80844 0.39788 0.49989

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C21 0.77048 0.4108 0.50011C22 0.71857 0.37213 0.50025C23 0.70525 0.32018 0.50011O24 0.74303 0.30701 0.50012H25 0.06762 0.47742 0.50263H26 0.78024 0.44922 0.50017C27 0.40838 0.43815 0.49924N28 0.3843 0.3842 0.49924C29 0.40019 0.35469 0.7217C30 0.36598 0.30267 0.63673N31 0.32895 0.30003 0.36175C32 0.34026 0.35042 0.27678C33 0.28006 0.25808 0.36175C34 0.26811 0.20654 0.36175C35 0.21669 0.16668 0.36175Br36 0.63653 0.93752 0.58487H37 0.39465 0.44869 0.24819H38 0.39343 0.44588 0.7578H39 0.4307 0.36489 0.9208H40 0.37116 0.27436 0.77293H41 0.31713 0.35679 0.07768H42 0.26112 0.26246 0.11345H43 0.26056 0.259 0.62031H44 0.29742 0.1977 0.36175H45 0.20525 0.13505 0.17256H46 0.19008 0.1688 0.55095H47 0.59089 0.56562 0.50076

COF-IL AB stacking mode, Space group: P3a = 32.96 Å, b = 32.96 Å, c = 7.24 Åα = 90.0°, β = 90.0°, γ = 120.0°

Atom x y zC1 0.01298 0.55184 0.26057C2 0.96115 0.51298 0.26037C3 0.94818 0.46115 0.26089C4 0.10366 0.57771 0.26092O5 0.11645 0.62856 0.26059N6 0.8583 0.43507 0.26066N7 0.19156 0.60212 0.26091C8 0.22952 0.5892 0.26083C9 0.28143 0.62787 0.26077

C10 0.29475 0.67982 0.26083O11 0.25697 0.69299 0.26082

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H12 0.93238 0.52258 0.25984H13 0.21976 0.55078 0.2608C14 0.98702 0.44816 0.26117C15 0.03885 0.48702 0.26137C16 0.05182 0.53885 0.26085C17 0.89634 0.42229 0.26082O18 0.88355 0.37144 0.26115N19 0.1417 0.56493 0.26108N20 0.80844 0.39788 0.26083C21 0.77048 0.4108 0.26091C22 0.71857 0.37213 0.26097C23 0.70525 0.32018 0.26091O24 0.74303 0.30701 0.26092H25 0.06762 0.47742 0.2619H26 0.78024 0.44922 0.26094C27 0.40838 0.43815 0.26057N28 0.3843 0.3842 0.26057C29 0.40019 0.35469 0.34762C30 0.36598 0.30267 0.31437N31 0.32895 0.30003 0.20677C32 0.34026 0.35042 0.17352C33 0.28006 0.25808 0.20677C34 0.26811 0.20654 0.20677C35 0.21669 0.16668 0.20677Br36 0.63653 0.93752 0.29408H37 0.39465 0.44869 0.16234H38 0.39343 0.44588 0.36175H39 0.4307 0.36489 0.42553H40 0.37116 0.27436 0.36767H41 0.31713 0.35679 0.09562H42 0.26112 0.26246 0.10961H43 0.26056 0.259 0.30795H44 0.29742 0.1977 0.20677H45 0.20525 0.13505 0.13274H46 0.19008 0.1688 0.28081H47 0.59089 0.56562 0.26117C48 -0.65369 1.21851 0.76057C49 0.29448 1.17965 0.76037C50 0.28151 1.12782 0.76089C51 -0.56301 1.24438 0.76092O52 -0.55022 1.29523 0.76059N53 0.19163 1.10174 0.76066N54 -0.47511 1.26879 0.76091

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C55 -0.43715 1.25587 0.76083C56 -0.38524 1.29454 0.76077C57 -0.37192 1.34649 0.76083O58 -0.4097 1.35966 0.76082H59 0.26571 1.18925 0.75984H60 -0.4469 1.21745 0.7608C61 0.32035 1.11483 0.76117C62 -0.62782 1.15369 0.76137C63 -0.61485 1.20552 0.76085C64 0.22967 1.08896 0.76082O65 0.21688 1.03811 0.76115N66 -0.52497 1.2316 0.76108N67 0.14177 1.06455 0.76083C68 0.10381 1.07747 0.76091C69 0.0519 1.0388 0.76097C70 0.03858 0.98685 0.76091O71 0.07636 0.97368 0.76092H72 -0.59905 1.14408 0.7619H73 0.11357 1.11588 0.76094C74 -0.25829 1.10482 0.76057N75 -0.28237 1.05087 0.76057C76 -0.26647 1.02136 0.84762C77 -0.30068 0.96933 0.81437N78 -0.33772 0.96669 0.70677C79 -0.3264 1.01708 0.67352C80 -0.38661 0.92475 0.70677C81 -0.39856 0.87321 0.70677C82 -0.44997 0.83335 0.70677Br83 -0.03013 1.60418 0.79408H84 -0.27202 1.11536 0.66234H85 -0.27323 1.11255 0.86175H86 -0.23597 1.03155 0.92553H87 -0.2955 0.94102 0.86767H88 -0.34954 1.02346 0.59562H89 -0.40555 0.92912 0.60961H90 -0.4061 0.92566 0.80795H91 -0.36925 0.86437 0.70677H92 -0.46142 0.80172 0.63274H93 -0.47659 0.83547 0.78081H94 -0.07577 1.23229 0.76117

a Compared to AB-type staggered structure, the eclipsed model is more energetic preferential depending on the force-field-based molecular mechanics calculations.

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Isosteric heat adsorption: The isosteric heat of adsorption represents the strength of the interactions between adsorbate molecules and the adsorbent lattice atoms and can be used as a measurement of the energetic heterogeneity of a solid surface. The isosteric heat of adsorption at a given amount can be calculated by the Clausius-Clapeyron equation as

anst TPRTQ )ln(2

Where Qst is the isosteric heat of adsorption (kJ/mol), P is the pressure (kPa), T is the temperature, R is the gas constant, and na is the adsorption amount (mmol/g).

Fig. S16 The Qst value of COF-IL for CH4, N2, and H2.

For selective adsorption evaluation: the gas adsorption experiments of CO2, N2, CH4, H2 were carried out at 273 K in an ice-water bath, and at 298 K in a temperature controlled circular bath, respectively. The ideal adsorption selectivity (Henry adsorption selectivity) toward CO2/N2, CO2/CH4, and CO2/H2 of the sample was based on the linear fitting of the low-pressure Henry region of the gas adsorption isotherms.

Fig. S17 Adsorption selectivity calculated using the initial slope in the low-pressure Henry region of the single-component gas isotherms for COF-IL at 273 K based on Henry’s law. At 273 K, CO2/N2, CO2/CH4 and CO2/H2 is up to 43.38, 15.95, and 235.37 respectively.

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Fig. S18 Adsorption selectivity calculated using the initial slope in the low-pressure Henry region of the single-component gas isotherms for COF-IL at 298 K based on Henry’s law. At 298 K, CO2/N2, CO2/CH4 and CO2/H2 is up to 58.96, 13.85, and 216.98 respectively.

Fig. S19 Compressive curve of the cylindrical aerogel using an AGS-H 5kN instrument from Shimadzu, Japan. The axial direction of the cylindrical aerogel (12 mm in height, 20 mm in diameter) was compressed at 5 mm min−1. A highest strength of 13.8 MPa could be achieved in the range of 0~75 % compressed strain.

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Fig. S20 Solid-state 13C CP-MAS NMR spectra of chitosan-SH, COF-IL, and COF-IL@chitosan aerogel. The new resonance peaks at 36.5 and 23.2 ppm corresponding to the carbon atoms on the C-S-C and C-C moieties.

Fig. S21 IR spectra of chitosan-SH, COF-IL, and COF-IL@chitosan aerogel. The peaks of C=C at 1628 cm-

1 in COF-IL and S-H at 2568 cm-1 in chitosan-SH disappeared after the reaction. Meanwhile, the characteristic peak at 1073 cm-1 associated with C-S-C appeared, indicating the formation of thioether linkage.

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Fig. S22 Solvent-stability of the aerogels with different soak time (0.5 amd 72 h, respectively). (a) Pure chitosan-SH aerogel in water; and COF-IL@chitosan aerogel in water (b), ethanol (c), and acetone (d).

Fig. S23 CO2, CH4, N2 and H2 adsorption isotherms for pure chitosan-SH aerogel at 273 and 298 K, respectively.

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Fig. S24 Adsorption selectivity at 273 K calculated using the initial slope in the low-pressure Henry region of the single-component gas isotherms for COF-IL@chitosan aerogel based on Henry’s law. The CO2/N2, CO2/CH4, and CO2/H2 on COF-IL@chitosan aerogel is up to 93.65, 20.02, and 153.96, respectively.

Fig. S25 Adsorption selectivity at 298 K calculated using the initial slope in the low-pressure Henry region of the single-component gas isotherms for COF-IL@chitosan aerogel based on Henry’s law. The CO2/N2, CO2/CH4, and CO2/H2 on COF-IL@chitosan aerogel is up to 98.82, 11.73, and 123.94, respectively.

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Fig. S26 1H-NMR spectrum (in DMSO-d6) of the styrene oxide and its catalytic product over COF-IL. The corresponding cyclic carbonates was isolated in 98 % yield within 48 h.

OO

OHNHNNH

O

HNNH

O

OO

O

HNNHO

HN ONHO

O

OHN NHO

HN NHO

OONH

HN

ONH

HN

O

OO

NHHN

NHOHN

OO

O

NH

HN NHO O

O

O

NH

O

NH

HN

HN

HN

NH

Fig. S27 Left: The idealized structure of TeTp-1 (C7H5N2O2)n, which was synthesized according our previous method.1 Right: 1H-NMR spectrum (in DMSO-d6) of the styrene oxide and its catalytic product over TeTp-1. The corresponding cyclic carbonates was isolated in 4.93 % yield within 48 h. Reaction condition: solvent free, 13.0 mmol of epoxy styrene, CO2 (1 atm), 80 °C, TeTp-1 (58.1 mg, 3.0 % mol according to its building block).

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Fig. 28. The proposed mechanism for CO2 cycloaddition over COF-IL. (i) Activation of the epoxide by COF-IL; (ii) Ring opening of the epoxide by Lewis base Br- to form the anionic intermediate; (iii) Insertion of CO2 into the oxygen anion and the formation of alkylcarbonate anion; (iv) Release of the anion via intramolecular substitution of halide, meanwhile, the imidazolium in COF-IL is regenerated.

Fig. S29 1H-NMR spectra (DMSO-d6) of the epichlorohydrin and its catalytic product over COF-IL. The corresponding cyclic carbonate was isolated in 98 % yield within 48 h.

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Fig. S30 1H-NMR spectra (DMSO-d6) of the epibromohydrin and its catalytic product over COF-IL. The corresponding cyclic carbonate was isolated in 100 % yield within 48 h.

Fig. S31 1H-NMR spectra (DMSO-d6) of the allyl glycidyl ether and its catalytic product over COF-IL. The corresponding cyclic carbonate was isolated in 97 % yield within 48 h.

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Fig. S32 1H-NMR spectra (DMSO-d6) of the 1,2-epoxyoctane and its catalytic product over COF-IL. The corresponding cyclic carbonate was isolated in 89 % yield within 48 h.

Fig. S33 1H-NMR spectra (DMSO-d6) of the glycidyl phenyl ether and its catalytic product over COF-IL. The corresponding cyclic carbonate was isolated in 71 % yield within 48 h.

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Fig. S34 1H-NMR spectra (DMSO-d6) of the 1,2-epoxyoctadecane and its catalytic product over COF-IL. The corresponding cyclic carbonate was isolated in 7 % yield within 48 h.

Fig. S35 Photograph of reaction device based on a cuplike reactor.

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Fig. S36 1H-NMR spectra (DMSO-d6) of the styrene oxide and its catalytic product over COF-IL@chitosan-based cup reactor (the first run). The corresponding cyclic carbonate was isolated in 91 % yield within 72 h.

Fig. S37 1H-NMR spectra (DMSO-d6) of the styrene oxide and its catalytic product over COF-IL@chitosan-based cup reactor (the fifth run). The corresponding cyclic carbonate was isolated in 89 % yield within 72 h.

References1. F. Li, L.-G. Ding, B.-J. Yao, N. Huang, J.-T. Li, Q.-J. Fu, Y.-B. Dong, J. Mater. Chem. A, 2018, 6, 11140–11146.