Supporting Information Nitrogen-Rich Porous Polymers for Carbon Dioxide and Iodine Sequestration for Environmental Remediation Yomna H. Abdelmoaty, Tsemre-Dingel Tessema, Fatema Akthar Choudhury, Oussama M. El- Kadri *, and Hani M. El-Kaderi * Department of Mechanical and Nuclear Engineering, Virginia Commonwealth University, 401 West Main Street, Richmond, Virginia 23284-2006, United States Department of Nuclear and Radiation Engineering, Alexandria University, Alexandria 21544, Egypt Department of Chemistry, Virginia Commonwealth University, 1001 W. Main St., Richmond, Virginia 23284-2006, United States Department of Biology, Chemistry, and Environmental Sciences, American University of Sharjah, PO Box 26666, Sharjah, United Arab Emirates Correspondence: helkaderi@vcu.edu, +1(804) 828-7505 Table of Contents oelkadri@aus.edu, +971 6 515-2787 Figure S1: Iodine uptake experiment setup Figures S2 - S4: Characterization (XRD study and TGA) Figures S5- S8: Iodine release (UV/vis graphs) Figures S9- S11: Iodine capture in liquid
Figure S1. Iodine uptake experiment setup. NRPP-1 NRPP-2 10 20 30 40 50 60 70 80 Angle (2θ) Figure S2. XRD patterns of NRPPs. S-1
Figure S3. Photographs showing the color change of NRPP-1 after loading with iodine vapor. 100 80 Weight Percent 60 40 loss of I 2 20 Iodine loaded NRPP-1 lodine loaded NRPP-2 0 NRPP-1 NRPP-2 0 200 400 600 800 1000 Temperature ( C) Figure S4. TGA data for inactivated NRPPs and iodine-loaded NRPPs. S-2
Table S1: Surface area, CO 2 uptake and heat of adsorption of selected POPs. 1 POPs S BET (m 2 g -1 ) CO 2 Uptake (mmol g -1 ) Q st (kj mol -1 ) S-3
ALP-1 1235 5.36 29.2 Adsorbent ALP-2 1065 Temperature ( C) Adsorbent 4.8 Capacity (mg I 2 /g) 27.9 P-PCz Cg-5P 1647 ~25 5.57 87 30.9 [Zn(C6H8O8)] 2H2O TSP-2 913 19 4.1 166 30.2 Cg-5C SNU-CL-sca 830 ~25 4.83 239 31.2 [Cd(L)2(ClO4)2] H2O CPOP-1 2220 ~25 4.82 ~460 27 CMPN-1 [10] HAT-CTF-450 756 70 4.4 970 Zn3(DL-lac)2(pybz)2 HAT-CTF-600 899 ~25 5.1 ~1000 HAT-CTF-450/600 1090 6.3 27 Azo-CMP1 1146 3.72 30 PCTF-4 1404 4.66 30 TBILP-2 1080 5.18 29 BILP-3 1306 5.11 28.6 BILP-6 1261 4.8 28.4 APOP-3 1402 4.54 27.5 NOP-50B 1581 3.93 43.7 TAPOP-1 930 3.5 27.8 PECONF-3 851 3.49 26 Table S2: Iodine sorption properties of porous materials. 2 S-4
CMPN-2 70 1100 ZIF-8 75 1200 JUC-Z2 25 1440 HKUST-1 75 ~1500 PAF-21 75 ~1520 Activated carbon 75 30 Cg-5P ~25 87 [Zn(C6H8O8)] 2H2O 19 166 Cg-5C ~25 239 [Cd(L)2(ClO4)2] H2O ~25 ~460 CMPN-1 70 970 Cu-BTC 75 1750 1750 75 1800 CMPN-3 70 2080 CMP-E1 75 2150 Azo-Trip 77 2380 PAF-25 75 2600 PAF-23 75 2710 PAF-24 75 2760 Table S3. Elemental Analysis for NRPPs S-5
Sample Name (N) % (C) % (H) % NRPP-1 27.564 41.062 4.682 NRPP-2 23.256 31.633 3.380 Figure S5. Progress of the iodine release from the NRPP-1 polymers immersed in ethanol. Figure S6. Progress of the iodine release from the NRPP-2 polymers immersed in ethanol. S-6
Absorption 2.5 2.0 1.5 1.0 NRPP-1 10 min 20 min 30 min 24 hr 0.5 0.0 250 300 350 400 450 500 wavelength(nm) Figure S7. The UV/vis spectra of NRPP-1 for the iodine release process. S-7
3.0 2.5 2.0 NRPP-2 10 min 20 min 30 min 24 hr Absorption 1.5 1.0 0.5 0.0 250 300 350 400 450 500 wavelength(nm) Figure S8. The UV/vis spectra of NRPP-2 for the iodine release process. S-8
Figure S9. (a) Different concentrations for iodine in cyclohexane before soaking NRPPs polymers. Photographs showing the visual color changes of the iodine-cyclohexane solution at equilibrium after soaking for 72 hours (b) NRPP-1 and (c) NRPP-2. S-9
Absorbance 0.03 mg/ml 0.05 mg/ml 0.1 mg/ml 0.2 mg/ml 0.3 mg/ml 400 450 500 550 600 650 700 wavelength (nm) Figure S10. UV/Vis for different concentrations of iodine in cyclohexane. S-10
1.2 experiment linear fit 1.0 Absorbance 0.8 0.6 0.4 0.2 Equation y = a + b*x Adj. R-Square 0.99269 Value Standard Error AC Intercept 0.04613 0.02763 AC Slope 3.80636 0.1632 0.05 0.10 0.15 0.20 0.25 0.30 Concentration(mg/ml) Figure S11. Calibration curve of dissolved iodine in cyclohexane with UV/Vis adsorption values. Table S4. Langmuir and Freundich parameters of NRPPs for Iodine Langmuir Freundlich q m K l R 2 1/n K f R 2 NRPP-1 302.11 0.025 0.9623 0.8875 0.72 0.9982 NRPP-2 505.05 0.00378 0.9954 0.5244 2.6 0.9997 Langmuir model: q m = maximum monolayer coverage capacity (mg/g) K L = Langmuir S-11
isotherm constant (L/mg) for Freundlich model: K f = Freundlich isotherm constant (mg/g) n = adsorption intensity. Adsorption isotherm Adsorption isotherms were collected as follow: different concentrations of iodine-cyclohexane 0.03 mg/ml, 0.05 mg/ml, 0.1 mg/ml, 0.2 mg/ml, 0.3 mg/ml and 0.4 mg/ml were prepared. 5 mg of fresh NRPPs samples were soaked in 5 ml of each concentration for 72 hr to reach equilibrium. The samples were filtered and solvent used for UV vis spectrophotometer. The corresponding concentration of iodine in each solvent were used to fit the isotherm using both Langmuir and Freundlich isotherm models. Langmuir model were linearly fitted by plotting vs according to the following equation: 1 1 = 1 + 1 q q K C q Where: C e = the equilibrium concentration of adsorbate (mg/l), qe = the amount of metal adsorbed per gram of the adsorbent at equilibrium (mg/g). q m = maximum monolayer coverage capacity (mg/g) K L = Langmuir isotherm constant (L/mg). Freundlich isotherm model were linearly fitted by plotting (lnq ) Vs(lnC ), according to Freundlich equation: lnq =lnk + 1 n lnc Where K f = Freundlich isotherm constant (mg/g) n = adsorption intensity; C e = the equilibrium concentration of adsorbate (mg/l) Q e = the amount of metal adsorbed per gram of the adsorbent at equilibrium (mg/g). S-12
The IAST selectivities were calculated by fitting pure component gas isotherms at 298 K with dual site Langmuir (DSL) (for CO 2 ) and single site Langmuir isotherm models (CH 4 and N 2 ). The obtained fitting parameters were then used to calculate the IAST selectivity values. = + =, 1+ +, 1+ Here, q is the amount of gas adsorbed (mmol/g) at pressure p (bar), q sat is the saturation capacity (mmol/g) at sites A and B, b is the Langmuir-Freundlich parameter (bar 1 ) at sites A and B. The fitting parameters are given in Tables S1 and S2. Table S5: Dual-site Langmuir fitting parameters for CO 2 adsorption. q sat, (A) b (A) q sat, (B) b (B) mmol g -1 bar -1 mmol g -1 bar -1 Reduced R 2 Adjusted R 2 NRPP-1 2.26204 2.1843 23.9331 9.95E-02 5.09E-05 0.99997 NRPP-2 1.11308 9.25647 11.46374 0.502 4.36983E-05 0.99998 Table S6: Single-site Langmuir fitting parameters for CH 4 adsorption. q sat, (A) b (A) mmol g -1 bar -1 Reduced R 2 Adjusted R 2 NRPP-1 4.87126 0.29994 4.44E-06 0.99997 NRPP-2 5.2078 0.25956 2.52190E-05 0.9998 Table S7: Single-site Langmuir fitting parameters for N 2 adsorption. q sat, (A) b (A) mmol g -1 bar -1 Reduced R 2 Adjusted R 2 NRPP-1 489732.3582 6.39E-07 1.01E-05 0.99912 NRPP-2 393233.3683 6.02E-07 1.57854E-04 0.97604 S-13
References 1. Huang, N.; Day, G.; Yang, X.; Drake, H.; Zhou, H. C. Engineering porous organic polymers for carbon dioxide capture. Sci. China: Chem., 2017, 60, 1007-1014. 2. Ma, H.; Chen, J. J.; Tan, L.; Bu, J. H.; Zhu, Y.; Tan, B.; Zhang, C. Nitrogen-Rich Triptycene-Based Porous Polymer for Gas Storage and Iodine Enrichment. ACS Macro Lett., 2016, 5, 1039-1043. S-14