Supporting Information

Transcription

1 Supporting Information Controllable Adsorption of CO2 on Smart Adsorbents: An Interplay between Amines and Photoresponsive Molecules Lei Cheng, Yao Jiang, Shi-Chao Qi, Wei Liu, Shu-Feng Shan, Peng Tan, Xiao-Qin Liu, and Lin-Bing Sun* State Key Laboratory of Materials-Oriented Chemical Engineering, Jiangsu National Synergetic Innovation Center for Advanced Materials (SICAM), College of Chemical Engineering, Nanjing Tech University, Nanjing , China. These authors contributed equally. * S-1

2 Table S1 Comparison of the adsorption performance for different amino-functionalized adsorbents Adsorbent SBET (m 2 g 1 ) a T (K) b SCO2/CH4 Ref. A2P2@MS This work P S1 MIL-101/PPD S2 TRI-PE-MCM S3 MIL-101Cr-(p)NH S4 NH2-MIL-53/FDH S5 PPF S6 SAPO-34-ED S7 NUT S8 a The BET surface area measured by N2 sorption isotherm at 77 K, b The selectivity measured temperature. S-2

3 Figure S1. The structural formulas of A and P. S-3

4 Figure S2. 1 H NMR spectrum of the photoresponsive molecule (P) precursor. S-4

5 Intensity (a.u.) MS A 1 P A 2 P A 3 P A 2 P A 2 P (degrees) Figure S3. Wide-angle XRD patterns of the samples before and after loading different amounts of A and P. S-5

6 Figure S4. (A) N2 adsorption-desorption isotherms and (B) pore size distributions of after irradiation with VIS and UV light. S-6

7 Figure S5. (A) N2 adsorption-desorption isotherms and (B) pore size distributions of pristine MS and MS functionalized with different amounts of A. Curves in (B) are plotted offset for clarity. S-7

8 Figure S6. (A) N2 adsorption-desorption isotherms and (B) pore size distributions of pristine MS and MS functionalized with different amounts of P. Curves in (B) are plotted offset for clarity. S-8

9 Figure S7. SEM images of the samples (A) MS and (B) S-9

10 C Intensity (a.u.) N O Si Cu Energy (kev) Figure S8. EDX spectrum of the sample A2P2@MS. The element Cu was originated from the Cu grid used in the measurement. S-10

11 Figure S9. TG curves of pristine MS and MS functionalized with different amounts of (A) A and (B) P. S-11

12 Absorbance Initial UV (1 min) UV (2 min) UV (3 min) Wavelength (nm) Figure S10. UV-vis absorption spectra of the photoresponsive molecule (P) precursor upon UV light irradiation for different time. S-12

13 Absorbance Initial UV (2 min) VIS (2 min) Wavelength (nm) Figure S11. UV-vis absorption spectra of the photoresponsive molecule (P) precursor after UV light irradiation for 2 min, and then VIS light irradiation for 2 min. S-13

14 Absorbance Inital UV (3 min) UV (5 min) Wavelength (nm) Figure S12. UV-vis spectra of after UV light irradiation for different time. S-14

15 Absorbance initial UV (5 min) VIS (5 min) Wavelength (nm) Figure S13. UV-vis spectra of after UV light irradiation for 5 min, and then VIS light irradiation for 5 min. S-15

16 Intensity (a.u.) trans cis (degrees) Figure S14. Low-angle XRD patterns of A2P2@MS during trans/cis isomerization. S-16

17 Transmittance (a.u.) cis trans Initial UV VIS Wavenumber (cm -1 ) Figure S15. IR spectra of the A2P2@MS in the initial state (black), after UV light irradiation (red), and after VIS light irradiation (blue). S-17

18 A P Weight (%) Temperature ( o C) Figure S16. TG curves of of the samples of A2@MS and P2@MS. Inset Table is the elemental anslysis of the samples of A2@MS and P2@MS. TG analysis shows that 3.3 wt% of A was introduced in A2@MS and 12.7 wt% of P was introduced in P2@MS, respectively, which is consistent with the amounts caclcuated from elemental analysis. (Elemental analysis: A2@MS: C, 4.13%; H, 1.74%; N, 0.72%; P2@MS: C, 10.06%; H, 1.88%; N, 2.64). S-18

19 Adsorbed amount (mg g -1 ) VIS UV Pressure (mm Hg) Figure S17. Adsorption isotherms of CO2 on the sample MS at 0 C after irradiation with VIS and UV light. S-19

20 Adsorbed amount (cm 3 g -1 ) VIS UV Pressure (mm Hg) Figure S18. Adsorption isotherms of CO2 on the sample A2@MS at 0 C after irradiation with VIS and UV light. S-20

21 Adsorbed amount (mg g -1 ) VIS UV Pressure (mm Hg) Figure S19. Adsorption isotherms of CO2 on the sample P2@MS at 0 C after irradiation with VIS and UV light. S-21

22 Adsorbed amount (cm 3 g -1 ) VIS UV Pressure (mm Hg) Figure S20. Adsorption isotherms of CO2 on the sample A2P2@MS at 25 C after irradiation with VIS and UV light. S-22

23 Adsorbed amount (mg g -1 ) VIS UV Pressure (mm Hg) Figure S21. Adsorption isotherms of CO2 on the sample A1P2@MS at 0 C after irradiation with VIS and UV light. S-23

24 Adsorbed amount (mg g -1 ) VIS UV Pressure (mm Hg) Figure S22. Adsorption isotherms of CO2 on the sample A3P2@MS at 0 C after irradiation with VIS and UV light. S-24

25 Adsorbed amount (mg g -1 ) VIS UV Pressure (mm Hg) Figure S23. Adsorption isotherms of CO2 on the sample A2P1@MS at 0 C after irradiation with VIS and UV light. S-25

26 Adsorbed amount (mg g -1 ) VIS UV Pressure (mm Hg) Figure S24. Adsorption isotherms of CO2 on the sample A2P3@MS at 0 C after irradiation with VIS and UV light. S-26

27 References S1 Shi, Y.-Q.; Zhu, J.; Liu, X.-Q.; Geng, J.-C.; Sun, L.-B. Molecular Template- Directed Synthesis of Microporous Polymer Networks for Highly Selective CO2 Capture. ACS Appl. Mater. Interfaces 2014, 6, S2 Babaei, M.; Salehi, S.; Anbia, M.; Kazemipour, M. Improving CO2 Adsorption Capacity and CO2/CH4 Selectivity with Amine Functionalization of MIL-100 and MIL-101. J. Chem. Eng. Data 2018, DOI: /acs.jced.8b S3 Belmabkhout, Y.; Serna-Guerrero, R.; Sayari, A. Adsorption of CO2-Containing Gas Mixtures over Amine-Bearing Pore-Expanded MCM-41 Silica: Application for CO2 Separation. Adsorption 2011, 17, S4 Khutia, A.; Janiak, C. Programming MIL-101Cr for Selective and Enhanced CO2 Adsorption at Low Pressure by Postsynthetic Amine Functionalization. Dalton Trans. 2014, 43, S5 Tien-Binh, N.; Vinh-Thang, H.; Chen, X. Y.; Rodrigue, D.; Kaliaguine, S. Polymer Functionalization to Enhance Interface Quality of Mixed Matrix Membranes for High CO2/CH4 Gas Separation. J. Mater. Chem. A 2015, 3, S6 Zhu, Y.; Long, H.; Zhang, W. Imine-Linked Porous Polymer Frameworks with High Small Gas (H2, CO2, CH4, C2H2) Uptake and CO2/N2 Selectivity. Chem. Mater. 2013, 25, S7 Venna, S. R.; Carreon, M. A. Amino-Functionalized SAPO-34 Membranes for CO2/CH4 and CO2/N2 Separation. Langmuir 2011, 27, S8 Mane, S.; Gao, Z.-Y.; Li, Y.-X.; Xue, D.-M.; Liu, X.-Q.; Sun, L.-B. Fabrication of Microporous Polymers for Selective CO2 Capture: The Significant Role of Crosslinking and Crosslinker Length. J. Mater. Chem. A 2017, 5, S-27