[Type text] Supporting Information

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1 Electronic Supplementary Material (ESI) for RSC Advances. This journal is The Royal Society of Chemistry 2017 [Type text] Supporting Information 1

2 Effective Removal of Chemical Warfare Agent Simulants Using Water Stable Metal-Organic Frameworks: Mechanistic Study and Structure-Property Correlation P. Asha, a Mekhola Sinha, a Sukhendu Mandal a* a School of Chemistry, Indian Institute of Science Education and Research-Thiruvananthapuram, Kerala, Thiruvananthapuram , India. sukhendu@iisertvm.ac.in 2

3 (a) (b) (i) (i) (ii) (ii) (iii) ppm ppm Figure S1. 1 H NMR data showing the adsorption of 2-CEES and/or its hydrolysis products in water (a) (i) Before adsorption with NU-1000 (ii) 30 minutes after the process of adsorption, intensity of every peak decreased considerably. (b)(i) Before adsorption with UiO-67 (ii) 30 minutes after the process of adsorption.the new peaks may corresponds to the hydrolysis products of 2-CEES (iii) 1 hour after the adsorption process 3

4 Figure S2. 1 H NMR spectrum of 2-CEES in CHCl 3 solvent. Note that 2-CEES was not hydrolyzed in CHCl 3 solvent 4

5 (a) (b) (i) (i) (ii) (ii) ppm ppm Figure S3. 31 P NMR data of DMMP in water (a) (i) before adsorption with NU-1000; (ii) 30minutes after the process of adsorption; (b) (i) before adsorption with UiO-67; (ii) 30minutes after the process of adsorption 5

6 (a) (b) Intensity(a.u.) NU-1000 synthesized NU-1000 simulated Intensity (a.u.) UiO-67 synthesized UiO-67 simulated (degree) (degree) Figure S4. PXRD plots showing the purity of (a) NU-1000 and (b) UiO-67 6

7 (a) (b) (c) (d) Figure S5. SEM images of (a) & (b) NU-1000 and (c) & (d) UiO-67 showing their uniform particle sizes 7

8 Figure S6. Surface properties measurement of NU

9 (a) (b) Figure S7. TGA plots of (a) NU-1000 and (b) UiO-67 9

10 (a) (b) Figure S8. Pictorial representation showing the cluster node and three dimensional structures of (a) NU-1000 and (b) UiO-67 10

11 NU CEES trial 2 washed UiO-67+2-CEES trial 1 Intensity (a.u.) NU CEES trial 1 washed NU-1000 synthesized Intensity (a.u.) UiO-67 synthesized UiO-67 Simulated NU-1000 simulated degree) 2θ (degree) degree) 2θ (degree) Figure S9. PXRD data of (a) NU-1000 and (b) UiO-67 after adsorption of 2-CEES. 11

12 (a) (b) UiO-67+DMMP trial 1 NU-1000+DMMP trial 1 washed Intensity (a.u.) NU-1000+DMMP trial 2 washed NU-1000 synthesized Intensity (a.u.) UiO-67 synthesized UiO-67 simulated NU-1000 simulated (degree) (degree) Figure S10. Powder XRD data of (a) NU-1000 and (b) UiO-67 on adsorption of DMMP. 12

13 (a) (b) Figure S11. SEM-EDX data of adsorption of 2-CEES and/or its hydrolysis products on NU (a) after adsorption study and (b) after removal 13

14 (a) (b) Figure S12. SEM-EDX data of adsorption of 2-CEES and/or its hydrolysis products on UiO-67 (a) after adsorption study and (b) after removal 14

15 Figure S13. SEM-EDX data of DMMP on NU-1000 (a) after adsorption study and (b) after removal 15

16 (a) (b) Figure S14. SEM-EDX data of adsorption of DMMP on UiO-67 (a) after adsorption study and (b) after removal 16

17 NU CEES NU-1000+DMMP NU-1000 T(%) 2-CEES T(%) NU-1000 DMMP (a) Wavenumber(cm-1) (b) Wavenumber(cm -1 ) UiO-67 T(%) T(%) UiO-67+2-CEES 2-CEES (c) (d) UiO-67 UiO-67+DMMP DMMP Wavenumber(cm -1 ) Wavenumber(cm -1 ) Figure S15. FT-IR spectra of the combinations (a) NU CEES; (b) NU-1000-DMMP; (c) UiO-67-2-CEES and (d) UiO-67-DMMP 17

18 Figure S16. q t vs. t graph for the adsorption of 2-CEES on NU-1000 MOF 18

19 Equation y = a + b*x Weight No Weighting Residual Sum of Squares Pearson's r Adj. R-Square Value Standard Error B Intercept Slope E E-4 Figure S17. Pseudo first order kinetic plot and the corresponding data for the adsorption of 2- CEES on NU-1000 MOF 19

20 Equation y = a + b*x Weight No Weighting Residual Sum of Squares Pearson's r Adj. R-Square Value Standard Error B Intercept Slope Figure S18. Pseudo second order kinetic plot and the corresponding data for the adsorption of 2- CEES on NU-1000 MOF 20

21 Figure S19. Intra-particle diffusion model for the adsorption of 2-CEES on NU-1000 MOF 21

22 Figure S20. q t vs. t graph for the adsorption of DMMP on NU-1000 MOF 22

23 Equation y = a + b*x Weight No Weighting Residual Sum of Squares Pearson's r Adj. R-Square Value Standard Error B Intercept Slope E-4 Figure S21. Pseudo first order kinetic plot and the corresponding data for the adsorption of DMMP on NU-1000 MOF 23

24 Equation y = a + b*x Weight No Weighting Residual Sum of Squares Pearson's r Adj. R-Square B Value Standard Error Intercept Slope Figure S22. Pseudo second order kinetic plot and the corresponding data for the adsorption of DMMP on NU-1000 MOF 24

25 Equation y = a + b*x Weight No Weighting Residual Sum of Squares Pearson's r Adj. R-Square Value Standard Error B Intercept Slope Figure S23. Intra-particle diffusion model and the corresponding data for the adsorption of DMMP on NU-1000 MOF 25

26 Table S1. Decrease in concentration of 2-CEES and/or C and DMMP on adsorption with NU-1000 and UiO-67 and in the control experiments without the MOFs (ICP-AES data) Sl.No Time(s) Conc. of S/Zr (mg/l) 2-CEES Time(s) Conc. of P/Zr (mg/l) DMMP NU-1000 UiO-67 Control NU-1000 UiO-67 Control S Zr S Zr P Zr P Zr Table S2. Reusability of NU-1000 in adsorbing 2-CEES and/or C and DMMP (ICP-AES data) NU-1000 Conc. of S in 2-CEES( mg/l) Conc. of P in DMMP( mg/l) Time(min) Time(min) Trial Trial Trial