Supporting Information. Tuning the Morphology and Activity of Electrospun. Enhance Chemical Warfare Agent Removal

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1 Supporting Information Tuning the Morphology and Activity of Electrospun Polystyrene/UiO-66-NH 2 Metal-Organic Framework Composites to Enhance Chemical Warfare Agent Removal Gregory W. Peterson,*,, Annie X. Lu,,# and Thomas H. Epps, III,± Edgewood Chemical Biological Center, 5183 Blackhawk Rd., APG, MD Department of Materials Science and Engineering, University of Delaware, Newark, DE Defense Threat Reduction Agency, 8725 John J. Kingman Road, Stop 621, Fort Belvoir, VA ± Department of Chemical and Biomolecular Engineering, University of Delaware, Newark, DE *Corresponding author: Gregory W. Peterson, gregory.w.peterson.civ@mail.mil; Phone: (41) S-1

2 Figure S1. Scanning electron microscopy (SEM) images of polystyrene (PS) electrospun from different solvent mixtures containing various ratios of dimethyl formamide (DMF) to tetrahydrofuran (THF). Scale bar is 3 µm in all images. S-2

3 wt% 1 wt% 25 wt% 5 wt% 1% PS 2% PS Figure S2. SEM images of composites electrospun from DMF solutions. The rows correspond to the weight percent of PS in the solution, and the columns correspond the weight percent of MOF in the solution (relative to the polymer). Scale bar = 8 µm in all images. The dashed red circle shows yarn-like fiber bundles. S-3

4 wt% 1 wt% 25 wt% 5 wt% 1% PS 2% PS Figure S3. SEM images of composites electrospun from DMF solutions. The rows correspond to the weight percent of PS in the solution, and the columns correspond the weight percent of MOF in the solution (relative to the polymer). Scale bar = 8 µm in all images. The dashed red circle shows a pea-pod-like MOF/fiber composite structure. S-4

5 Figure S4. SEM image of 1% PS, 25 wt% UiO-66-NH 2 spun from DMF (1PS-25U-DMF). The percentage of PS is expressed in w/v in comparison to the solvent. The weight percentage of MOF is calculated relative to the mass of PS in solution. Figure S5. Photographs of different MOF/fiber composites. (a) 25 wt% UiO-66-NH 2 in 2% PS spun from DMF/THF. (b) 5 wt% UiO-66-NH 2 in 2% PS spun from DMF. Scale bar is 1.25 cm and applies to both images. S-5

6 Figure S6. Sample electrospun from 2% PS with 5 wt% UiO-66-NH 2 using a 5/5 DMF/THF solvent (2PS-5U-DMF/THF). S-6

7 Mass Remaining (%) Mass Remaining (%) Mass Remaining (%) Mass Remaining (%) a b PS-U-DMF 1PS-1U-DMF 1PS-25U-DMF 1PS-5U-DMF UiO-66-NH Temperature ( C) c PS-U-DMF 2PS-1U-DMF 2PS-25U-DMF 2PS-5U-DMF Temperature ( C) d PS-U-DMF/THF 1PS-1U-DMF/THF 1PS-25U-DMF/THF 1PS-5U-DMF/THF Temperature ( C) PS-U-DMF/THF 2PS-1U-DMF/THF 2PS-25U-DMF/THF 2PS-5U-DMF/THF UiO-66-NH Temperature ( C) Figure S7. Thermogravimetric analysis data for composite fibers. (a) 1% PS spun from DMF, (b) 2% PS spun from DMF, (c) 1% PS spun from DMF/THF, and (d) 2% PS spun from DMF/THF. The DMF/THF ratio is 5/5 in panels c and d. Percentages are in w/v relative to the solvent. S-7

8 N 2 Uptake (cm 3 /g) N 2 Uptake (cm 3 /g) N 2 Uptake (cm 3 /g) N 2 Uptake (cm 3 /g) 25 2 a 25 2 b 15 1PS-U-DMF 1PS-1U-DMF 1PS-25U-DMF 1PS-5U-DMF 15 2PS-U-DMF 2PS-1U-DMF 2PS-25U-DMF 2PS-5U-DMF UiO-66-NH₂ P/P c 25 2 P/P d 15 1PS-U-DMF/THF 1PS-1U-DMF/THF 1PS-25U-DMF/THF 1PS-5U-DMF/THF 15 2PS-U-DMF/THF 2PS-1U-DMF/THF 2PS-25U-DMF/THF 2PS-5U-DMF/THF UiO-66-NH P/P Figure S8. Nitrogen isotherms for composite fibers. (a) 1% PS spun from DMF, (b) 2% PS spun from DMF, (c) 1% PS spun from DMF/THF, and (d) 2% PS spun from DMF/THF. The DMF/THF ratio is 5/5 in panels c and d. Percentages are in w/v relative to the solvent P/P S-8

9 1..8 a 1..8 b C/C PS-U-DMF.4 1PS-1U-DMF 1PS-25U-DMF 1PS-5U-DMF.2. 1, 2, 3, 4, Weighted Time (min/g) c C/C PS-U-DMF 2PS-1U-DMF 2PS-25U-DMF 2PS-5U-DMF UiO-66-NH2 UiO-66-NH 2 1, 2, 3, 4, Weighted Time (min/g) d C/C PS-U-DMF/THF 1PS-1U-DMF/THF 1PS-25U-DMF/THF 1PS-5U-DMF/THF 1, 2, 3, 4, Weighted Time (min/g) C/C PS-U-DMF/THF 2PS-1U-DMF/THF 2PS-25U-DMF/THF 2PS-5U-DMF/THF 1, 2, 3, 4, Weighted Time (min/g) Figure S9. Chlorine microbreakthrough for composite fibers. (a) 1% PS spun from DMF, (b) 2% PS spun from DMF, (c) 1% PS spun from DMF/THF, and (d) 2% PS spun from DMF/THF. The DMF/THF ratio is 5/5 in panels c and d. Percentages are in w/v relative to the solvent. Weighted time is defined as time divided by mass of sorbent used in the test. C/C is a normalized concentration, with C defined as the feed concentration to the composite, and C defined as the concentration exiting the composite at time t. S-9

10 a b c d 6 min 5 min 5 min 6 min 13 min 129min 129min 16 min 358 min 334 min 333 min 333 min Figure S1. 31 P solid state nuclear magnetic resonance (SS NMR) spectra for soman degradation as a function of time. Initial doublet peaks (~28, 35 ppm) are representative of soman. As soman degrades, a single peak at ~3 ppm grows in, suggesting the hydrolysis of soman to pinacolyl methylphosphonic acid. 1 Panels correspond to (a) 1PS-25U-DMF, (b) 2PS-25U-DMF, (c) 1PS-25U-DMF/THF, and (d) 2PS-25U-DMF/THF. The DMF/THF ratio is 5/5 in panels c and d. S-1

11 ln(area) PS-25U-DMF 2PS-25U-DMF y = -.71x y = -.48x PS-25U-DMF/THF 2PS-25U-DMF/THF UiO-66-NH₂ y = -.45x y = -.73x y = -.21x Time (min) Figure S11. Natural log of soman peak area as a function of time for four samples tested using 31 P SS NMR. The data from Figure S1 were integrated to determine the area under the peaks. The slopes of the curves in this figure were used to calculate half-life of soman exposed to the various electrospun composites. S-11

12 Figure S12. SEM images of 25 wt% UiO-66-NH 2 PS fibers. (a) 1PS-25U-DMF, (b) 2PS-25U-DMF, (c) 1PS-25U-DMF/THF, and (d) 2PS-25U-DMF/THF. The DMF/THF ratio is 5/5 in panels c and d. References (1) Wagner, G. W.; Chen, Q.; Wu, Y. Reactions of VX, GD, and HD with Nanotubular Titania. J. Phys. Chem. C 28, 112 (31), S-12