Efficient Thiazole-Based Polyimines as - ars.els-cdn.com · Web viewSupplementary. Efficient Thiazole-Based Polyimines as. Selective and Reversible Chemical Absorbents for CO 2. Capture

Supplementary

Efficient Thiazole-Based Polyimines as Selective and Reversible Chemical Absorbents for CO2 Capture and Separation: Synthesis,

Characterization and Application

Elaheh Akbarzadeh,*a Abbas Shockravi*a and Vahid Vatanpoura

Faculty of Chemistry, Kharazmi University, Mofatteh Avenue 49, 15719-14911 Tehran, Iran

E-mails: [email protected]; [email protected]; [email protected]

Spectroscopic data of compounds DA-1-3:

5,5'-thiobis(4-(3-nitrophenyl)thiazole-2-amine) (DA-1): yellow powder, mp: 220-221 °C; IR (KBr): 3421, 3305, 3126, 1631, 1531, 1468, 1350, 1328, 1257, 1163, 708, and 682 cm-1; 1H NMR (300 MHz, DMSO-d6): 8.51-8.53 (m, 1H), 8.12−8.18 (m, 2H), 7.59 (dd, J=8, 8 Hz, 1H) and 7.52 (s, NH2, 2H) ppm; 13C NMR (75 MHz, DMSO-d6): 111.2, 122.1, 122.4, 129.8, 135.1, 136.4, 148.1, 152.4, 168.6 ppm.

5,5'-thiobis(4-(4-Bromophenyl)thiazole-2-amine) (DA-2): yellow powder, mp: 190−191 °C; IR (KBr): 3462, 3278, 3263, 3078, 1627, 1608, 1525, 1510, 1459, 1322, 829, and 715 cm-1. 1H NMR (300 MHz, DMSO-d6): 7.63 (d, J=8.4 Hz, 2H), 7.49 (d, J=8.4 Hz, 2H) and 7.38 (s, NH2, 2H) ppm. 13C NMR (75 MHz, DMSO-d6): 109.9, 121.2, 130.4, 130.8, 133.1, 151.4, 168.6 ppm.

5,5′-thiobis(2-amino-4-(2-naphthyl)thiazole) (DA-3): yellow powder, mp: 211−213 °C; IR (KBr): 3455, 3360, 3266, 3092, 1621, 1600, 1527, 1493, 1451, 1322, 1293, 1199, 821, and 748 cm-1. 1H NMR (300 MHz, DMSO-d6): 8.28 (s, 1H), 7.42−7.95 (m, 6H), and 7.38 (s, NH2, 2H) ppm. 13C NMR (75 MHz, DMSO-d6): 110.2, 126.2, 126.4, 126.9, 127.1, 127.4, 127.7, 128.2, 131.5, 132.4, 132.5, 152.2, 168.5 ppm.

Figure S1. 1H NMR of DA-1 in DMSO-d6 at 25 °C

1

Figure S2. 13C NMR (bottom) and DEPT-135 (top) spectra of the DA-1 in DMSO-d6 at 25 °C

Figure S3. FT-IR spectrum of DA-1

2

Figure S4. 1H NMR of DA-2 in DMSO-d6 at 25 °C

Figure S5. 13C NMR of DA-2 in DMSO-d6 at 25 °C

3

Figure S6. FT-IR spectrum of DA-2

Figure S7. 1H NMR of DA-3 in DMSO-d6 at 25 °C

4

Figure S8. 13C NMR of DA-3 in DMSO-d6 at 25 °C

igure S9. FT-IR spectrum of DA-3

5

Spectroscopic data of compounds PIMs:

PIM-1: Brown powder; IR (KBr) ν 468, 1116, 1277, 1376, 1432, 1518, 1533, 1708, 2927, 3437 Cm-1; Anal. Calcd for (C26H14N6O4S3)n: C, 55.99%; H, 3.36%; N, 13.99%. Found: C, 55.90%; H, 3.31%; N, 13.85%.PIM-2: Brown powder; IR (KBr) ν 470, 696, 1193, 1293, 1377, 1433, 1537, 1533, 1660, 1675, 1695, 2925, 3437 Cm -1; Anal. Calcd for (C26H14N6O4S3)n: C, 55.99%; H, 3.36%; N, 13.99%. Found: C, 55.82%; H, 3.29%; N, 13.82%.PIM-3: Brown powder; IR (KBr) ν 463, 1046, 1283, 1346, 1375, 1430, 1519, 1624, 1708, 2927, 3435 Cm-1; Anal. Calcd for (C24H12N6O4S4)n: C, 55.99%; H, 3.36%; N, 13.99%. Found: C, 55.82%; H, 3.29%; N, 13.82%.PIM-4: Black powder; IR (KBr) ν 476, 1010, 1064, 1108, 1201, 1374, 1431, 1513, 1708, 2920, 3437 Cm -1; Anal. Calcd for (C26H14Br2N4S3)n: C, 48.92%; H, 2.21%; N, 8.78%. Found: C, 48.87%; H, 2.27%; N, 8.67%.PIM-5: Black powder; IR (KBr) ν 474, 1122, 1296, 1375, 1432, 1531, 1705, 2927, 3434 Cm-1; Anal. Calcd for (C26H14Br2N4S3)n: C, 48.92%; H, 2.21%; N, 8.78%. Found: C, 48.80%; H, 2.15%; N, 8.65%.PIM-6: Black powder; IR (KBr) ν 466, 1009, 1106, 1266, 1373, 1430, 1515, 1533, 1705, 2925, 3433 Cm -1; Anal. Calcd for (C24H12 Br2N4S4)n: C, 44.73%; H, 1.88%; N, 8.69%. Found: C, 44.62%; H, 1.74%; N, 8.60%.PIM-7: Black powder; IR (KBr) ν 478, 752, 1120, 1295, 1376, 1431, 1527, 1707, 2939, 3054, 3432 Cm-1; Anal. Calcd for (C34H20N4S3)n: C, 70.32%; H, 3.47%; N, 9.65%. Found: C, 70.22%; H, 3.41%; N, 9.62%.PIM-8: Black powder; IR (KBr) ν 479, 754, 1119, 1309, 1372, 1432, 15.24, 1699, 2940, 3053, 3435 Cm -1; Anal. Calcd for (C34H20N4S3)n: C, 70.32%; H, 3.47%; N, 9.65%. Found: C, 70.20%; H, 3.48%; N, 9.58%.PIM-9: Black powder; IR (KBr) ν 477, 750, 1116, 1236, 1373, 1429, 1519, 1699, 2929, 3046, 3330 Cm-1; Anal. Calcd for (C32H18N4S4)n: C, 65.50%; H, 3.09%; N, 9.55%. Found: C, 65.42%; H, 3.02%; N, 9.43%.

Table S1. Solubility of PIMs Chlorofor

mAcetoneTHFPyridineDMFDMAcDMSONMPPolymer Code

-±±++++++++++PIM-1

-±±++++++++++PIM-2

---++++++++++PIM-3

-±±++++++++++PIM-4

-±±++++++++++PIM-5

---++++++++++PIM-6

±±+++++++++++PIM-7

±±+++++++++++PIM-8

±±±++++++++++PIM-9a (++) Soluble at rt, (+) soluble after heating, (±) partially soluble, (-) insoluble. b NMP: N-methyl-2-pyrrolidone; DMSO: dimethyl sulfoxide; DMAc: N,N-dimethylacetamide; DMF: N,N-dimethylformamide; THF: tetrahydrofuran.

6

Figure S10. FT-IR spectrum of PIM-1 before CO2 uptake

Figure S11. FT-IR spectrum of PIM-1 after CO2 uptake

7

Figure S12. FT-IR spectrum of PIM-2 before CO2 uptake

Figure S13. FT-IR spectrum of PIM-2 after CO2 uptake

8

Figure S14. FT-IR spectrum of PIM-3 before CO2 uptake

Figure S15. FT-IR spectrum of PIM-3 after CO2 uptake

9

Figure S16. FT-IR spectrum of PIM-4 before CO2 uptake

Figure S17. FT-IR spectrum of PIM-4 after CO2 uptake

10

Figure S18. FT-IR spectrum of PIM-5 before CO2 uptake

Figure S19. FT-IR spectrum of PIM-5 after CO2 uptake

11

Figure S20. FT-IR spectrum of PIM-6 before CO2 uptake

Figure S21. FT-IR spectrum of PIM-6 after CO2 uptake

12

Figure S22. FT-IR spectrum of PIM-7 before CO2 uptake

Figure S23. FT-IR spectrum of PIM-7 after CO2 uptake

13

Figure S24. FT-IR spectrum of PIM-8 before CO2 uptake

Figure S25. FT-IR spectrum of PIM-8 after CO2 uptake

14

Figure S26. FT-IR spectrum of PIM-9 before CO2 uptake

Figure S27. FT-IR spectrum of PIM-9 after CO2 uptake

15

Table S2. Comparison of various materials with respect to their CO2 uptake and selectivity at 1 bar and 298 K (273 K).

Material CO2 Uptake(mmol g-1

sorbent)CO2 Uptake(mg g-1

sorbent)Selectivity

CO2/N2

SelectivityCO2/CH4

Reference

PIM-1 3.42 150.48 70.2 12.5 This work

PIM-2 1.91 84.04 58.2 8 This work

PIM-3 2.84 124.96 64 11.2 This work

PIM-4 3.72 163.68 77.3 13.7 This work

PIM-5 1.96 86.24 60.4 8.5 This work

PIM-6 3.21 141.24 68.2 12 This work

PIM-7 2.76 121.44 63.3 10.6 This work

PIM-8 1.77 77.88 55 6.2 This work

PIM-9 1.86 81.84 57 7 This work

CBZ 1.37 (2.1) - 76 (100) 5.8 (13.2) [1]a

DBF 2.20 (2.6) - 63 (80) 6.2 (11.6) [1]a

IN 1.10 (1.7) - 66 (65) 4.3 (15) [1]a

BT 1.39 (2.42) - 49 (51) 4.0 (12.6) [1]a

BF 1.37 (2.42) - 41 (43) 2.9 (14.9) [1]a

TBILP-1 - 78 63 9 [2]a

TBILP-2 - 146 40 7 [2]a

BILP-1 - 131 (188) 36 (70) 7 (10) [3]a

BILP-2 - 104 (149) 71 (113) 12 (17) [4]a

BILP-3 - 145 (225) 31 (59) 5 (8) [5]a

BILP-4 - 158 (235) 32 (79) 7 (10) [4]a

TH-COF-1 2.2 97 - - [6]

COF-LZU1 0.95 42 - - [6]

[HO]100%-H2P-COF - 35 (63) - - [7]

[HO2C]100%-H2P-COF - 76 (174) - - [7]a Selectivity (mol mol−1) was calculated from initial slope calculations.

References:[1] Saleh, M.; Lee, H. M.; Kemp, K. CH.; Kim, K. S. Appl. Mater. Interfaces 2014, 6, 7325-7333.[2] Sekizkardes, A. K.; Altarawneh, S.; Kahveci, Z.; Islamoglu, T.; El-Kaderi, H. M. Macromolecules, 2014, 47 (23), 8328–

8334.[3] Rabbani, M. G.; El-Kaderi, H. M. Chem. Mater. 2011, 23, 1650-1653.[4] Rabbani, M. G.; El-Kaderi, H. M. Chem. Mater. 2012, 24, 1511-1517.[5] Rabbani, M. G.; Reich, T. E.; Kassab, R. M.; Jackson, K. T.; ElKaderi, H. M. Chem. Commun. 2012, 48, 1141-1143.[6] Wang, L.; Dong, B.; Ge, R.; Jiang, F.; Xiong, J.; Gao, Y. Xu, J. Microporous Mesoporous Mater. 2016, 224, 95-99.[7] Huang, N.; Chen, X.; Krishna, R.; Jiang, D. Angew. Chem. Int. Ed. 2015, 54, 2986–2990.

16