Supporting Information

Transcription

1 Supporting Information Cotton Fabric Functionalized with a β-cyclodextrin Polymer Captures Organic Pollutants from Contaminated Air and Water Diego M. Alzate-Sánchez, 1,3 Brian J. Smith, 2 Alaaeddin Alsbaiee, 2 Juan P. Hinestroza, 3 * and William R. Dichtel 1,2 * 1 Department of Chemistry, Northwestern University, Evanston, IL, 60208, USA wdichtel@northwestern.edu 2 Department of Chemistry and Chemical Biology, Cornell University Baker Laboratory, Ithaca, NY, 14853, USA 3 Department of Fiber Science & Apparel Design, Cornell University, Ithaca, NY, 14853, USA jh433@cornell.edu I. Additional Characterization Table of Contents A. SEM Images S 2 B. XPS spectra S 3 C. Infrared spectra S 3 D. TGA analysis S-4 E. Tensile testing S-4 II. Additional calculations A. Thermodynamic studies S 5 III. UV-Vis spectra A. BPA experiments S 7 B. Styrene experiments S 9 C. Model compound experiments S 11 IV. References S 11

2 I. Additional Characterization A. SEM Images Figure S1. SEM images of (a) and (b) Untreated cotton S-2

3 B. XPS survey Figure S2. XPS survey of the fabrics. C. Additional Infrared spectra Figure S3. Infrared spectra of the monomers (TFP, β-cd; yellow and green, respectively), isolated polymer (CD-TFP, grey), and cotton samples (untreated, red and functionalized, blue). S-3

4 D. Additional TGA analysis Figure S4. TGA analysis in air atmosphere of the fabrics. Fabric N2 Air 370.3± ±4.1 Untreated cotton 373.7± ±4.6 Table S1. Decomposition temperatures of and Untreated cotton fabrics in nitrogen and air atmosphere. E. Tensile testing Fabric Failure strain (mm/mm) Peak Strength (MPa) Modulus (MPa) ± ± ± 4.3 Untreated cotton ± ± ± 19.9 Reacted cotton ± ± ± 51.3 Table S2. Tensile testing of Untreated cotton and a cotton fabric subjected to the same reaction conditions but without TFP (Reacted cotton). S-4

5 II. Additional calculations Thermodynamic studies: The Langmuir and Freundlich models were selected to study the thermodynamic adsorption of BPA in the fabrics. [S1] The Langmuir model, which treats the material as having a homogeneous adsorption surface, is given in linear form as 1 1 = q e q max,e k c C e q max,e Where q e (mg BPA/g fabric) is the amount of BPA adsorbed per gram of fabric at equilibrium. q max,e (mg BPA/g fabric) is the maximum adsorption capacity of adsorbent at equilibrium, k c (mol -1 ) is the equilibrium constant and C e (mm) is the concentration at equilibrium Figure S5. Langmuir isotherm graphs for (a) CD-TFP@cotton, and (b) untreated cotton. S-5.

6 The Freundlich model, which is used for heterogeneous adsorption surfaces without a saturation of adsorption sites, is expressed in the following linear form: Where q e (mg BPA/g fabric) is the amount of BPA adsorbed per gram of fabric at equilibrium. C e (mm) is the concentration at equilibrium. n F is the Freundlich constant associated to the degree of system heterogeneity. K F ((mg g -1 )(L mmol -1 ) nf ) is a unit capacity coefficient. Figure S6. Freundlich isotherm graphs for (a) CD-TFP@cotton, and (b) untreated cotton. S-6

7 Model Fabric qmax,e (mg g -1 ) kc (mol -1 ) KF ((mg g -1 )(L mmol -1 ) nf ) nf R 2 Langmuir CD TFP@cotton Untreated cotton Freundlich CD TFP@cotton Untreated cotton Table S3. Thermodynamic calculations result of the CD-TFP@cotton and the untreated cotton. III. UV-Vis spectra A. BPA experiments Figure S7. UV-Vis spectra of BPA remained in the solution after the removal of the pollutant by the fabrics as a function of time of (a) CD-TFP@cotton and (b) untreated cotton. The trace labeled Stock corresponds to the initial concentration of the solution. S-7

8 Figure S8. UV-Vis spectra of BPA that remained in the solution after the removal of the pollutant by the fabrics as a function of initial BPA concentration: (a) 0.1 mm; (b) mm; (c) 0.25 mm; (d) 0.5 mm; (e) 1 mm. The trace labeled Stock corresponds to the initial concentration of the solution. S-8

9 B. Styrene experiments Figure S9. UV-Vis spectra of styrene extracted from the fabric samples in the highconcentration vapor phase experiments. The times listed for each spectrum indicate the contact time of the fabric with styrene vapor, with increased contact times generally resulting in increased signal intensity in this experiment. (a) (b) untreated cotton; (c) commercial fabric #1; (d) commercial fabric #2; (e) commercial fabric #3. S-9

10 Figure S10. UV-Vis spectra of styrene extracted from the fabric samples in the lowconcentration vapor phase experiments. The times listed indicate the contact time of the fabric with styrene vapor, such that increased styrene uptake is observed for the CD- (a) over 10 minutes of contact time. In contrast, unmodified cotton (b) shows little to no specific styrene uptake under similar conditions. The trace labeled maximum corresponds to the response expected that would correspond to 100% adsorption of styrene under the experimental conditions. S-10

11 C. Model compound experiments Figure S11. UV-Vis spectra of (a) aniline; (b) benzaldehyde; and (c) styrene, extracted at 10 min contact time from each fabric sample in the gas model compound experiments. The fabric sequesters larger amounts of each compound than untreated cotton and the commercial odor-controlling fabrics. IV. References [S1] F. Zhao, E. Repo, Y. Meng, X. Wang, D. Yin, M. Sillanpää, J. Colloid Interface Sci., 2016, 465, 215. S-11