Electrophilic Aromatic Substitution Functionalized Metal ... · Functionalized Metal-Organic Framework via Electrophilic Aromatic Substitution ... Zero-background discs were used
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Supporting Information
Removal of Chlorine Gas by an Amine Functionalized Metal-Organic Framework via
Electrophilic Aromatic Substitution
Jared B. DeCoste,1* Matthew A. Browe2, George W. Wagner2, Joseph A. Rossin3, and Gregory W. Peterson2*
1 Leidos, Inc., PO Box 68, Gunpowder, MD 21010
2Edgewood Chemical Biological Center, 5183 Blackhawk Rd., Aberdeen Proving Ground, MD 21010, United States
3Guild Associates, Inc., 5750 Shier Rings Rd., Dublin, OH 43016, United States
Figure S1. Chlorine microbreakthrough plots of various materials vs. normalized time. Plots on right are zoomed out to capture the higher performing materials.
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Figure S2. PXRD patterns from 2θ = 3 to 90° of UiO-66-NH2 pre and post-exposed to Cl2.
Figure S3. PXRD patterns from 2θ = 3 to 90° of UiO-66 pre and post-exposed to Cl2.
Figure S7. FTIR spectra from 1800 to 400 cm-1 of UiO-66 pre and post-exposed to Cl2.
40060080010001200140016001800Wavenumber (cm-1)
ZrOCl2UiO-66-NH2 Cl2UiO-66-NH2
Figure S8. FTIR spectra from 1800 to 400 cm-1 of UiO-66-NH2 pre and post-exposed to Cl2. ZrOCl2 spectra is given as a reference.
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Figure S9. 1H NMR spectra of UiO-66-NH2 pre and post exposed to Cl2 digested in a 10% H2SO4/DMSO solution.
6.877.27.47.67.88δ (ppm)
Figure S10. 1H NMR spectra of 2-amino terephthalic acid (2-ATA) exposed to Cl2 in acetonitrile, 2-ATA is represented at δ ≈ 7.82 (d), 7.35 (d), and 7.10 (dd) ppm, while 2-amino-3-chloroterephthalic acid is represented at δ ≈ 7.82 (d), and 6.87 (d) ppm and 2-amino-5-chloroterephthalic acid δ ≈ 7.78 (s), and 7.12 (s) ppm.
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Table S2. GC-MS results for 2-ATA exposed to Cl2 in acetonitrile. 1H NMR showed two separate isomers, but they could not be separated by GC and appear as one product in the MS. The parent peak was not observed, due to the ease of fragmentation of the aryl carboxylate bond.
m/z Relative to parent Species215.0 M C6H2(Cl)(NH2)(COOH)2171.1 M-44 C6H3(Cl)(NH2)(COOH)+
154.0 M-61 C6H2(Cl)(COOH)+
137.1 M-78 C6H4(NH2)(COOH)+
126.1 M-89 C6H3(Cl)(NH2)+
120.1 M-95 C6H3(COOH)+
0 10 20 30 40 50 602θ
MIL-53-NH2 (Al) post-Cl2MIL-53-NH2 (Al)
Figure S11. PXRD patterns from 2θ = 3 to 90° of MIL-53-NH2 (Al) pre and post-exposed to Cl2.
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40060080010001200140016001800Wavenumber (cm-1)
MIL-53-NH2 (Al) post Cl2MIL-53-NH2 (Al)
Figure S12. FTIR spectra from 1800 to 400 cm-1 of MIL-53-NH2 (Al) pre and post-exposed to Cl2.
6.97.17.37.57.77.98.1δ (ppm)
MIL-53-NH2 (Al) Cl2MIL-53-NH2 (Al)
Figure S13. 1H NMR spectra of MIL-53-NH2 (Al) pre and post exposed to Cl2 digested in an HF/DMSO solution.
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(3) Glover, T. G.; Peterson, G. W.; Schindler, B. J.; Britt, D.; Yaghi, O. Chem. Eng. Sci. 2011, 66, 163.
(4) Decoste, J. B.; Peterson, G. W. Journal of Visualized Experiments 2013, e51175.