Supporting Information

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1 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 , 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 , 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) Table of Contents oelkadri@aus.edu, 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

2 Figure S1. Iodine uptake experiment setup. NRPP-1 NRPP Angle (2θ) Figure S2. XRD patterns of NRPPs. S-1

3 Figure S3. Photographs showing the color change of NRPP-1 after loading with iodine vapor Weight Percent loss of I 2 20 Iodine loaded NRPP-1 lodine loaded NRPP-2 0 NRPP-1 NRPP Temperature ( C) Figure S4. TGA data for inactivated NRPPs and iodine-loaded NRPPs. S-2

4 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

5 ALP Adsorbent ALP Temperature ( C) Adsorbent 4.8 Capacity (mg I 2 /g) 27.9 P-PCz Cg-5P 1647 ~ [Zn(C6H8O8)] 2H2O TSP Cg-5C SNU-CL-sca 830 ~ [Cd(L)2(ClO4)2] H2O CPOP ~ ~ CMPN-1 [10] HAT-CTF Zn3(DL-lac)2(pybz)2 HAT-CTF ~ ~1000 HAT-CTF-450/ Azo-CMP PCTF TBILP BILP BILP APOP NOP-50B TAPOP PECONF Table S2: Iodine sorption properties of porous materials. 2 S-4

6 CMPN ZIF JUC-Z HKUST-1 75 ~1500 PAF ~1520 Activated carbon Cg-5P ~25 87 [Zn(C6H8O8)] 2H2O Cg-5C ~ [Cd(L)2(ClO4)2] H2O ~25 ~460 CMPN Cu-BTC CMPN CMP-E Azo-Trip PAF PAF PAF Table S3. Elemental Analysis for NRPPs S-5

7 Sample Name (N) % (C) % (H) % NRPP NRPP 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

8 Absorption NRPP-1 10 min 20 min 30 min 24 hr wavelength(nm) Figure S7. The UV/vis spectra of NRPP-1 for the iodine release process. S-7

9 NRPP-2 10 min 20 min 30 min 24 hr Absorption wavelength(nm) Figure S8. The UV/vis spectra of NRPP-2 for the iodine release process. S-8

10 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

11 Absorbance 0.03 mg/ml 0.05 mg/ml 0.1 mg/ml 0.2 mg/ml 0.3 mg/ml wavelength (nm) Figure S10. UV/Vis for different concentrations of iodine in cyclohexane. S-10

12 1.2 experiment linear fit 1.0 Absorbance Equation y = a + b*x Adj. R-Square Value Standard Error AC Intercept AC Slope 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 NRPP Langmuir model: q m = maximum monolayer coverage capacity (mg/g) K L = Langmuir S-11

13 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 = 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

14 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 E E NRPP E 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 E NRPP E 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 E E NRPP E E S-13

15 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, 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, S-14

MOF-76: From Luminescent Probe to Highly Efficient U VI Sorption Material

MOF-76: From Luminescent Probe to Highly Efficient U VI Sorption Material Weiting Yang, a Zhi-Qiang Bai, b Wei-Qun Shi*, b Li-Yong Yuan, b Tao Tian, a Zhi-Fang Chai*, c Hao Wang, a and Zhong-Ming Sun*