Supporting Information. Table of content

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1 Supporting Information Nitrogen-Rich Triptycene-Based Porous Polymer for Gas Storage and Iodine Enrichment Hui Ma, Jing-Jing Chen, Liangxiao Tan, Jian-Hua Bu,*, Yanhong Zhu,*, Bien Tan, Chun Zhang*, Key Laboratory of Molecular Biophysics of the Ministry of Education, College of Life Science and Technology, National Engineering Research Center for Nanomedicine, Huazhong University of Science and Technology, Wuhan, Hubei, , China School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan, Hubei, , China Xi an Modern Chemistry Research Institute, Xi an, , China Table of content 1. Experimental Section... S2 2. NMR spectrum of monomer 1... S5 3. SEM image and SEM-EDS spectra of NTP.... S6 4. FT-IR spectra of NTP and monomer 1... S7 5. Powder X-ray diffraction pattern of NTP.... S7 6. TGA plot of NTP.... S8 7. BET surface area plot for NTP calculated from the isotherm.... S8 8. Isosteric enthalpies of adsorption for CO 2 of NTP.... S9 9. Initial gas uptake slopes of NTP at 273 K.... S9 10. Iodine enrichment test of NTP... S10 S1

2 1. Experimental Section Materials and methods Materials 2, 3, 6, 7, 14, 15-Hexaammoniumtriptycene hexachloride was synthesized through the literature, 1 granular activated charcoal was procured from Tianjin Kermel Chemical Co., Ltd., China and the other chemicals are obtained from commercial sources without further purification. Analysis 1 H and 13 C nuclear magnetic resonance (NMR) spectra were recorded on Bruker model AV400 NMR spectrometers, where chemical shifts were determined with TMS. Fourier transform infrared (FT-IR) spectra were recorded on a Bruker model VERTEX 70 infrared spectrometer. X-ray diffraction data were recorded on a PANalytical B.V. model X'Pert PRO diffractometer by depositing powder on glass substrate, from 2θ = 5 up to 90 with 0.02 increment. Thermogravimetric Analysis (TGA) measurements were performed on a PerkinElmer model Pyris1 TGA under N 2, by heating to 800 C at a rate of 10 C min 1. The 13 C cross-polarization magic-angle spinning (CP/MAS) NMR spectra were recorded with a contact time of 2 ms (ramp 100) and pulse delay of 3 s. Field-emission scanning electron microscopy (FE-SEM) measurements were performed on a FEI model Sirion 200 field-emission scanning electron microscope. Transmission electron microscopy (TEM) studies were conducted on a FEI model Tecnai G220 electron microscope. Gas Sorption Analysis Surface areas and pore size distributions were measured by nitrogen adsorption and desorption at 77 K using a Micromeritics ASAP 2020 volumetric adsorption analyzer. Sample was degassed at 200 C for 8 h under vacuum before analysis. H 2 isotherms were measured at 77 K up to 1.0 bar using a Micromeritics ASAP 2020 volumetric adsorption analyzer with the same degassing procedure. CO 2 isotherms were S2

3 measured at 273 and 298 K up to 1.0 bar using a Micromeritics ASAP 2020 volumetric adsorption analyzer with the same degassing procedure. Synthesis of monomer 1 2, 3, 6, 7, 14, 15-Hexaammoniumtriptycene hexachloride (115 mg, 0.2 mmol, 1.0 equiv), 4, 4'-dibromobenzil (221 mg, 0.6 mmol, 3.0 equiv) and potassium acetate (157 mg, 1.6 mmol, 8.0 equiv) was dissolved in CHCl 3 (37.5 ml), EtOH (25 ml) and glacial acetic acid (2.5 ml) in a two-necked flask. The mixture was refluxed under argon overnight. After cooling to room temperature, the solvents were removed by rotary evaporation. The residue then purified by column chromatography over silica gel (CH 2 Cl 2 /ethyl acetate 10:1) to give the product as a yellow solid (210 mg, 80%). 1 H NMR (600 MHz, CDCl 3, δ): 8.27 (s, 6H), 7.49 (d, J = 8.4 Hz, 12H), 7.37 (d, J = 8.4 Hz, 12H), 6.13 (s, 2H). 13 C NMR (150 MHz, CDCl 3, δ): 53.1, 123.8, 124.0, 131.4, 131.7, 137.5, 140.4, 144.0, Synthesis of NTP Monomer 1 (585 mg, 0.44 mmol, 1.0 equiv), 1, 5-cyclooctadiene (cod, 430 µl, 3.50 mmol, 8.0 equiv), bis (1, 5-cyclooctadiene) nickel (0) ([Ni(cod)2], 960 mg, 3.49 mmol, 8.0 equiv), and 2, 2 -bipyridyl (547 mg, 3.50 mmol, 8.0 equiv ) was dissolved in dehydrated DMF (40 ml), and the mixture was reflux at 85 C under argon for 96 h. After cooling to room temperature, concentrated hydrochloric acid was added to the mixture. After filtration, the residue was washed with EtOH, acetone, CHCl 3, THF and H 2 O, then purified by Soxhlet extraction in methanol for 2 days. Dried in vacuum at 60 C afforded the product (yellow powder, 363 mg). Yield = 95.8%. Uptake of iodine vapor S3

4 NTP powder (100.0 mg) was loaded in a glass vial which is weighted before, then put the vial and excess solid iodine together in a closed system at 75 C and ambient pressure. After certain time intervals, the vial was took out and weighted, and then loaded back into vapor of iodine to continue iodine absorption. After 48 hours, no further change in the iodine loading amount was observed. Iodine uptake was measured by the gravimetric method. (180 %) Using the same experimental procedure, we studied the iodine capacity for activated carbon. Uptake of I - 3 in aqueous solution Adsorption of I - 3 was accomplished by immersing 4.0 mg NTP in 4.0 ml KI/I 2 aqueous solution (0.2 mmol L -1 ) and magnetically stirring. The suspension was separated by centrifugation (10000 rpm, 10 min) at different time points, the solution was then detected by UV-vis spectrum. Moreover, NTP (4.0 mg) powder was soaked in 4.0 ml KI/I 2 aqueous solution of different concentration (0.4, 0.6, 0.8, 1.0, 1.4, 1.8 mmol L -1 ). The mixture was stirred overnight. After separation by centrifugation (10000 rpm, 10 min), the solution was detected by UV-vis spectrum. The data were fitted to the Langmuir isotherm model ( C / Q = 1/ ( K Q ) + C / Q ) and the Freundlich isotherm model e e L m e m ( ln Q = ln K + 1/ nln C ). where Q e (mg g 1 ) is the equilibrium adsorption capacity, e F e C e (mg L 1 ) is the equilibrium I 3 - concentration, Q m (mg g 1 ) is maximum adsorption capacity, K L is the Langmuir constant, K F and n are the Freundlich constant related to the sorption capacity and sorption intensity, respectively. S4

5 Scheme S1. Synthesis of monomer 1. Reagents and conditions: 4, 4'-Dibromobenzil, potassium acetate, glacial acetic acid, CHCl 3, EtOH, reflux, overnight. 2. NMR spectrum of monomer 1 Figure S1. 1 H NMR spectrum of monomer 1(600 MHz, CDCl 3, 298K). S5

6 Figure S2. 13 C NMR of monomer 1(150 MHz, CDCl 3, 298K). 3. SEM image and SEM-EDS spectra of NTP. Figure S3. SEM image and SEM-EDS spectra of NTP. S6

7 4. FT-IR spectra of NTP and monomer 1 Figure S4. FT-IR spectra of NTP (red line) and monomer 1(black line). 5. Powder X-ray diffraction pattern of NTP. Figure S5. Powder X-ray diffraction pattern of NTP. S7

8 6. TGA plot of NTP. Figure S6. TGA plot of NTP. 7. BET surface area plot for NTP calculated from the isotherm. Figure S7. BET surface area plot for NTP calculated from the isotherm. S8

9 8. Isosteric enthalpies of adsorption for CO 2 of NTP. Figure S8. Isosteric enthalpies of adsorption for CO 2 of NTP. 9. Initial gas uptake slopes of NTP at 273 K. Figure S9. Initial gas uptake slopes of NTP at 273 K. S9

10 10. Iodine enrichment test Figure S10. Photographs showing the color change before and after iodine capture for NTP (a), Gravimetric uptake of iodine vapor by NTP as a function of time at 75 C (b). Figure S11. Photographs showing progress of the iodine release from NTP, when the containing iodine polymer was immersed in ethanol. S10

11 Figure S12. Recycle test of NTP in iodine vapor adsorption. Figure S13. FT-IR spectra of NTP before (a) and after 1-5 recycles (b- f), respectively. S11

12 Figure S14. Photographs showing the color change of iodine enrichment progress when 30 mg of NTP was immersed in a hexane solution of iodine (1 mmol L -1, 3 ml). Table S1. Iodine sorption properties of porous materials. Adsorbent Temperature ( C) Adsorbent Capacity (mg I 2 /g) References Activated carbon Our work Cg-5P ~25 87 [2] [Zn(C6H 8 O 8 )] 2H 2 O [3] Cg-5C ~ [2] [Cd(L) 2 (ClO 4 ) 2 ] H 2 O ~25 ~460 [4] CMPN [10] Zn 3 (DL-lac) 2 (pybz) 2 ~25 ~1000 [5] CMPN [10] ZIF [6] JUC-Z [7] HKUST-1 75 ~1500 [6] PAF ~1520 [9] S12

13 Cu-BTC [8] NTP Our work PAF [7] CMPN [10] CMP-E1 75 ~2150 [9] Azo-Trip [11] PAF ~2600 [9] PAF ~2710 [9] PAF ~2760 [9] References [1]. a) Chong, J. H.; MacLachlan, M. J.; Inorg. Chem. 2006, 45, b) Mastalerz, M.; Sieste, S.; Cenic, M.; Oppel, I. M. J. Org. Chem. 2011, 76, [2]. Riley, B. J.; Chun, J.; Ryan, J. V.; Matyáš, J.; Li, X. S.; Matson, D. W.; Sundaram, S. K.; Strachan, D. M.; Vienna, J. D. RSC Adv. 2011, 1, [3]. Abrahams, B. F.; Moylan, M.; Orchard, S. D.; Robson, R. Angew. Chem. Int. Ed. 2003, 42, [4]. Liu, Q. K.; Ma, J. P.; Dong, Y. B. Chem. Commun. 2011, 47, [5]. Zeng, M. H.; Wang, Q. X.; Tan, Y. X.; Hu, S.; Zhao, H. X.; Long, L. S.; Kurmoo, M. J. Am. Chem. Soc. 2010, 132, [6]. Sava, D. F.; Garino, T. J.; Nenoff, T. M. Ind. Eng. Chem. Res. 2012, 51, [7]. Pei, C. Y.; Ben, T.; Xu, S. X.; Qiu, S. L. J. Mater. Chem. A 2014, 2, [8]. Sava, D. F.; Chapman, K. W.; Rodriguez, M. A.; Greathouse, J. A.; Crozier, P. S.; Zhao, H. Y.; Chupas, P. J.; Nenoff, T. M. Chem. Mater. 2013, 25, [9]. Yan, Z. J.; Yuan, Y.; Tian, Y. Y.; Zhang, D. M.; Zhu, G. S. Angew. Chem. Int. Ed. 2015, 54, [10]. Chen, Y. F.; Sun, H. X.; Yang, R. X.; Wang, T. T.; Pei, C. J.; Xiang, Z. T.; Zhu, Z. Q.; Liang, W. D.; Li, A.; Deng, W. Q. J. Mater. Chem. A 2015, 3, [11]. Dang, Q. Q.; Wang, X. M.; Zhan, Y. F.; Zhang, X. M. Polym. Chem. 2016, 7, S13