Decreasing the Viscosity in CO 2 Capture by Amino-functionalized Ionic Liquids through the Formation of Intramolecular Hydrogen Bond

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1 Electronic Supplementary Information Decreasing the Viscosity in CO 2 Capture by Amino-functionalized Ionic Liquids through the Formation of Intramolecular Hydrogen Bond Xiao Y. Luo, Xi Fan, Gui L. Shi, Hao R. Li, *,, and Cong M. Wang Department of Chemistry, ZJU-NHU United R&D Center, Zhejiang University, Hangzhou , China Key Laboratory of Biomass Chemical Engineering of Ministry of Education, Zhejiang University, Hangzhou , P. R. China Xiao Y. Luo: chemistrylxy@163.com X. Fan: gaoyi325@qq.com Gui L. Shi: @zju.edu.cn Hao R. Li: lihr@zju.edu.cn Cong M. Wang : chewcm@zju.edu.cn

2 NMR and IR data of ILs and ILs-CO 2 complexes [P ][4NH 2 -PhCOO] (d 6 -DMSO) 1 H NMR (ppm) 0.87 (m, 12H, CH 3 ), (48H, CH 2 ), 2.19 (m, 8H, PCH 2 ), 4.95 (s, 2H, NH 2 ), 6.36 (d, 2H, Ph), 7.50 (d, 2H, Ph); 13 C NMR (ppm) 14.37, 14.44, 17.62, 17.72, 18.09, 18.18, 20.97, 21.04, 21.08, 22.33, 22.61, 28.61, 29.16, 29.23, 29.48, 29.53, 29.55, 29.56, 29.58, 30.19, 30.35, 30.44, 30.55, 30.92, 31.33, and (P ), (Ph, o position of COO), (Ph, o position of NH 2 ), (OOC-C), (H 2 N-C), (C=O); [P ][4NH 2 -PhCOO]-CO 2 (d 6 -DMSO) 1 H NMR (ppm) 0.88 (m, 12H, CH 3 ), (48H, CH 2 ), 2.19 (m, 8H, PCH 2 ), 5.16 (s, NH), 6.41 (d, 2H, Ph), 7.55 (d, 2H, Ph); 13 C NMR (ppm) 14.36, 14.44, 17.63, 17.73, 18.10, 18.20, 20.99, 21.05, 21.10, 22.35, 22.62, 28.63, 29.18, 29.25, 29.50, 29.55, 29.58, 29.60, 30.20, 30.35, 30.41, 30.56, 30.94, 31.35, and (P ), and (o position of COO), and (o position of NH 2 ), (HN-C), (NH-COOH) (C=O); [P ][Me-Gly] (d 6 -DMSO) 1 H NMR (ppm) 0.87 (m, 12H, CH 3 ), (48H, CH 2 ), 2.18 (s, 3H, CH 3 ), 2.24(m, 8H, PCH 2 ), 2.60 (s, 2H, CH 2 );

3 13 C NMR (ppm) 14.19, 14.25, 17.70, 17.78, 18.07, 18.16, 21.00, 21.04, 21.08, 22.26, 22.52, 28.60, 29.14, 29.16, 29.43, 29.46, 29.50, 29.52, 30.18, 30.30, 30.42, 30.54, 30.88, 31.29, 31.45, and (P ), (CH 3 ), (CH 2 ), (COO); [P ][Me-Gly]-CO 2 (d 6 -DMSO) 1 H NMR (ppm) 0.86 (m, 12H, CH 3 ), (48H, CH 2 ), 2.24(m, 8H, PCH 2 ), 2.68 (s, 3H, CH 3 ), 3.42 (s, 2H, CH 2 ), 8.34 (s, 1H, COOH); 13 C NMR (ppm) 14.11, 14.16, 17.74, 17.83, 18.12, 18.20, 21.09, 21.12, 22.28, 22.55, 28.66, 29.14, 29.50, 29.52, 29.56, 30.18, 30.30, 30.44, 30.56, 30.91, 31.33, 31.50, and (P ), (CH 3 ), (CH 2 ), and (COOH), (COO); [P ][Ac-Gly] (d 6 -DMSO) 1 H NMR (ppm) 0.87 (m, 12H, CH 3 ), (m, 48H, CH 2 ), 1.78 (s, 3H, CH 3 ), 2.19 (m, 8H, PCH 2 ), 3.18 (d, 2H, CH 2 ), 3.44 (s, 1H, NH); 13 C NMR (ppm) 14.32, 14.40, 17.61, 17.71, 18.08, 18.18, 20.96, 21.02, 21.06, 22.31, 22.60, 23.21, 28.61, 29.16, 29.23, 29.47, 29.52, 29.55, 29.58, 30.19, 30.34, 30.40, 30.55, 30.91, and (P ), (CH 3 ), (COO), (C=O); [P ][Ac-Gly]-CO 2 (d 6 -DMSO) 1 H NMR (ppm) 0.87 (m, 12H, CH 3 ), (m, 48H, CH 2 ), 1.78 (s, 3H, CH 3 ), 2.23 (m, 8H, PCH 2 ), 3.23 (s, 2H, CH 2 ); 13 C NMR (d6-dmso) 14.26, 14.33, 17.65, 17.74, 18.12, 18.21, 21.07, 21.11, 22.33, 22.61, 23.12, 28.66, 29.21, 29.26, 29.51, 29.55, 29.59, 29.61, 30.22, 30.37, 30.45, 30.60, 30.94, 31.37, 31.83, 44.80, , ;

4 [P ][Ac-PhO] (d 6 -DMSO) 1 H NMR (ppm) 0.88 (m, 12H, CH 3 ), (48H, CH 2 ), 1.98 (s, 3H, CH 3 ), 2.15 (m, 8H, PCH 2 ), 3.45 (q, 2H, NH), 5.77 (t, 1H, Ph, p-position of NH), 6.04(d, 1H, Ph, o-position of NH), 6.44(t, 1H, Ph, p-position of O), 7.78 (d, 1H, Ph, o-position of O),; 13 C NMR (ppm) 14.25, 14.33, 17.66, 17.75, 18.04, 18.12, 20.98, 21.03, 21.07, 22.29, 22.40, 22.57, 24.83, 28.61, 29.16, 29.21, 29.45, 29.50, 29.53, 29.56, 30.17, 30.29, 30.40, 30.52, 30.90, 31.32, and (P ), (CH 3 ), , , , , , and (Ph), (C=O); [P ][Ac-PhO]-CO 2 (d 6 -DMSO) 1 H NMR (ppm) 0.87 (m, 12H, CH 3 ), (48H, CH 2 ), 2.06 (s, 3H, CH 3 ), 2.19 (m, 8H, PCH 2 ), 6.48 (t, 1H, Ph, p-position of NH), 6.74(t, 1H, Ph, p-position of O), 6.80(d, 1H, Ph, o-position of NH), 7.91 (d, 1H, Ph, o-position of O), 9.64 (COOH); 13 C NMR (ppm) 14.03, 14.09, 17.55, 17.63, 17.93, 18.01, 20.91, 20.94, 21.36, 21.55, 22.15, 22.26, 22.44, 24.11, 28.52, 29.06, 29.09, 29.35, 29.3, 29.43, 29.45, 30.03, 30.15, 30.28, 30.40, 30.76, 31.20, 31.36, and (P ), , , , , , and (Ph), (PhO-COO), (NCOOH), (C=O);

5 Figure S1. The optimized structures of the anion of amino-functionalized ILs with O after CO 2 absorption. Figure S2. The IR spectroscopy of [P ][2NH 2 -NC] before and after CO 2 capture. Figure S3. The IR spectroscopy of [P ][4NH 2 -BA] before and after CO 2 capture.

6 Figure S4. The IR spectroscopy of [P ][6NH 2 -NC] before and after CO 2 capture. Figure S5. The IR spectroscopy of [P ][Ac-Gly] before and after CO 2 capture. Figure S6. The IR spectroscopy of [P ][Me-Gly] before and after CO 2 capture.

Figure S7. The IR spectroscopy of [P 66614 ][Ac-PhO] before and after CO 2 capture. Figure S8. 13 C NMR spectroscopy [P 66614 ][Ac-PhO] before and after CO 2 capture. Figure S9.

7 Figure S7. The IR spectroscopy of [P ][Ac-PhO] before and after CO 2 capture. Figure S8. 13 C NMR spectroscopy [P ][Ac-PhO] before and after CO 2 capture. Figure S9. The stack plot of FTIR spectra of CO 2 saturated [P ][Me-Gly] dissolved in triethylene glycol dimethyl ether in the weight ratio of 1:0 (black line), 1:1 (red line), 1:2 (blue line), and 1:3 (green line).

8 Table S1. The effect of water content on the viscosity in amino-functionalized ILs [a]. H 2 O content IL IL IL-CO 2 complex Viscosity of IL (cp) Viscosity of IL with 2wt% H 2 O (ppm) (%) [P ][4NH 2 -PhCOO] % [P ][4NH 2 -PyCOO] % [P ][2NH 2 -PyCOO] % [P ][Me-Gly] % [P ][Ac-Gly] % [P ][Ac-PhO] % [a] The viscosity was measured at 30 o C by Brookfield DV-II+ pro viscometer.

9 Table S2. The comparison for CO 2 capture by different amino-functionalized ILs. IL T ( o C) Capacity (mol CO 2 / mol IL) Viscosity increase (fold) Reference [P ][Ac-PhO] This work [apmim][bf 4 ] 22 ~0.5 Dramatic increase Bates, ED 1 [aemmim][tau] Dramatic increase Xue, ZM 2 [P ][Gly] [P ][Ala] [P ][Sar] Goodrich, BF 3 [P ][Ile] [P ][Pro] [N 2224 ][L-Ala] (25 o C) Goodrich, BF 3 Jiang, YY 4 Yu,H 5 [ap 4443 ][AA] 25 ~0.2/1.2(ILs on porous SiO 2 ) Dramatic increase Zhang, YQ Dramatic increase Soutullo, MD 7

10 Table S3. The IR absorption of captured CO 2. IL Product IR absorption of product Reference (cm -1 ) carboxlate 1666 Bates, D.E. 1 [P ][Lys] ~1640 Saravanamurugan, S. 8 DAIL 1637 Zhang, J. Z. 9 [P ][Pro] Carbamic 1689 Gurkan, B. E. 10 [P ][Met] acid 1718 [P ][o-aa] 1735 Luo, X.Y. 11 [P ][p-aa] 1724, 1661 [N ][Lys] ~1700 (dimeric) Saravanamurugan, S. 8 References: 1. Bates, E. D.; Mayton, R. D.; Ntai, I.; Davis, J. H., CO 2 capture by a task-specific ionic liquid. J. Am. Chem. Soc., 2002, 124 (6), Xue, Z. M.; Zhang, Z. F.; Han, J.; Chen, Y.; Mu, T. C., Carbon dioxide capture by a dual amino ionic liquid with amino-functionalized imidazolium cation and taurine anion. Int. J. Greenh. Gas Con., 2011, 5 (4), Goodrich, B. F.; de la Fuente, J. C.; Gurkan, B. E.; Zadigian, D. J.; Price, E. A.; Huang, Y.; Brennecke, J. F., Experimental Measurements of Amine-Functionalized Anion-Tethered Ionic Liquids with Carbon Dioxide. Ind. Eng. Chem. Res., 2011, 50 (1), Jiang, Y. Y.; Wang, G. N.; Zhou, Z.; Wu, Y. T.; Geng, J.; Zhang, Z. B., Tetraalkylammonium amino acids as functionalized ionic liquids of low viscosity. Chem. Commun., 2008, (4), Yu, H.; Wu, Y. T.; Jiang, Y. Y.; Zhou, Z.; Zhang, Z. B., Low viscosity amino acid ionic liquids with asymmetric tetraalkylammonium cations for fast absorption of CO 2. New J. Chem., 2009, 33 (12), Zhang, Y. Q.; Zhang, S. J.; Lu, X. M.; Zhou, Q.; Fan, W.; Zhang, X. P., Dual Amino-Functionalised Phosphonium Ionic Liquids for CO 2 Capture. Chem.-Eur. J., 2009, 15 (12), Soutullo, M. D.; Odom, C. I.; Wicker, B. F.; Henderson, C. N.; Stenson, A. C.; Davis, J. H., Reversible CO 2 capture by unexpected plastic-, resin-, and gel-like ionic soft materials discovered during the combi-click generation of a TSIL library. Chem. Mater., 2007, 19 (15), Saravanamurugan, S.; Kunov-Kruse, A. J.; Fehrmann, R.; Riisager, A., Amine-Functionalized Amino Acid- based Ionic Liquids as Efficient and High- Capacity Absorbents for CO 2. Chemsuschem, 2014, 7 (3), Zhang, J. Z.; Jia, C.; Dong, H. F.; Wang, J. Q.; Zhang, X. P.; Zhang, S. J., A Novel Dual Amino-Functionalized Cation-Tethered Ionic Liquid for CO 2 Capture. Ind. Eng. Chem. Res., 2013, 52 (17), Gurkan, B. E.; de la Fuente, J. C.; Mindrup, E. M.; Ficke, L. E.; Goodrich, B. F.; Price, E. A.; Schneider, W. F.; Brennecke, J. F., Equimolar CO 2 Absorption by Anion-Functionalized Ionic Liquids. J. Am. Chem. Soc., 2010, 132 (7), Luo, X. Y.; Ding, F.; Lin, W. J.; Qi, Y. Q.; Li, H. R.; Wang, C. M., Efficient and Energy-Saving CO 2 Capture through the Entropic Effect Induced by the Intermolecular Hydrogen Bonding in Anion-Functionalized Ionic Liquids. J. Phys. Chem. Lett., 2014, 5 (2),

Electronic Supplementary Information

Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 2014 Electronic Supplementary Information Highly efficient CO 2 capture by carbonyl-containing ionic