Mechanoassisted Synthesis of Sulfonated Covalent Organic. Frameworks with High Intrinsic Proton Conductivity

Transcription

1 Supporting Information Mechanoassisted Synthesis of Sulfonated Covalent Organic Frameworks with High Intrinsic Proton Conductivity Yongwu Peng, [a], Guodong Xu, [b], Zhigang Hu, [a] Youdong Cheng, [a] Chenglong Chi, [a] Daqiang Yuan, [c] Hansong Cheng,* [b] and Dan Zhao* [a] These authors contributed equally to this work. [a] Dr. Y. Peng, Z. Hu, Y. Cheng, C. Chi, Prof. D. Zhao* Department of Chemical & Biomolecular Engineering National University of Singapore 4 Engineering Drive 4, Singapore chezhao@nus.edu.sg [b] Dr. G. Xu, Prof. H. Cheng* Sustainable Energy Laboratory, Faculty of Materials Science and Chemistry, China University of Geosciences Wuhan, 388 Lumo RD, Wuhan, China chghs2@gmail.com [c] Prof. D. Yuan State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences Fuzhou, China S-1

2 Experimental Details Structure Determination The structure determination of NUS-9 and NUS-10 started with manual change of the ligand in the reported COF TpPa-1 using the Materials Studio Visualizer. The AA and AB stacking possibilities were considered for reasons reported in the literature. 1 The geometry optimizations based on molecular mechanics simulations were performed with the Forcite module of Materials Studio. 2 The bonded and the short range (van der Waals) non-bonded interactions between atoms were modelled using the Universal Force Field (UFF), as implemented in Forcite. 3 The long range (electrostatic) non-bonded interactions, which arise due to the presence of partial atomic charges, were modelled using a Coulombic term. A Lennard-Jones cutoff distance of 18.5 Å was used for all geometry optimization simulations. The Ewald sum method was used to compute the electrostatic interactions. Gas and Water Vapor Sorption Measurements Gas and water vapor sorption isotherms were measured up to 1 bar using a Micromeritics ASAP 2020 surface area and pore size analyzer. Before the measurements, the sample (~80 mg) was degassed under reduced pressure (< 10-2 Pa) at 150 C for 10 h. UHP grade gases were used for gas sorption measurements. Oil-free vacuum pumps and oil-free pressure regulators were used to prevent contamination of the samples during the degassing process and isotherm measurement. The temperatures of 77 and 273 K were maintained with a liquid nitrogen bath and an ice water bath, respectively. Pore size distribution data were calculated from the N 2 adsorption isotherms at 77 K based on nonlocal density functional theory (NLDFT) model in the Micromeritics ASAP 2020 software. S-2

3 Figure S1. FTIR spectra of NUS-9(G) and NUS-10(G) along with the starting material TFP. S-3

4 Figure S2. 13 C CP/MAS solid-state NMR spectra of (a) NUS-9(G) and (b) NUS-10(G). Asterisks (*) indicate peaks arising from spinning side band. S-4

5 Figure S3. FTIR and 13 C-NMR spectra of (a, b) NUS-9 and (c, d) NUS-10 before and after recrystallization, respectively. Asterisks (*) indicate peaks arising from spinning side band. S-5

6 Figure S4. PXRD, FTIR and 13 C-NMR spectra of (a, b, c) NUS-9(R) and (d, e, f) NUS-10(R) under various treating conditions, respectively. Asterisks (*) indicate peaks arising from spinning side band. S-6

7 Figure S5. FE-SEM images of (a, b) NUS-9(G) and (c, d) NUS-10(G). S-7

8 Figure S6. TGA curves of NUS-9(G) and NUS-10(G). S-8

9 Figure S7. TEM images of (a) NUS-9(R) and (b) NUS-10(R). S-9

10 Figure S8. Nyquist plot of (a) NUS-9(R) and (b) NUS-10(R) at 298 K and 97% RH in three runs. S-10

11 Figure S9. Proton conductivity of TpPa-1 measured at 298 K and 97% RH. S-11

12 Figure S10. Water uptake of NUS-9(R) and NUS-10(R) pellets at 298 K and different relative humidity. S-12

13 Figure S11. Optical images of (a) NUS-10(R) pellet and (b, c) MMMs. S-13

14 Figure S12. SEM images of COF-containing MMMs: (a, b) (c, d) (e, f) Pure PVDF membrane. S-14

15 Figure S13. PXRD patterns of COFs, PVDF, and COF-containing MMMs. S-15

16 Figure S14. PXRD patterns of PVDF and COF-containing MMMs before and after proton conductivity tests. S-16

17 Figure S15. Home-made humidity chamber (left) and equivalent circuit model representation for the proton conduction measurement (right). S-17

18 Table S1. Crystallographic information of modeled NUS-10. Note: the crystallographic information of modeled NUS-9 has been reported in our previous study. 4 Sample NUS-10 Empirical formula C 12 H 8 N 2 O 8 S 2 F w Stacking method Eclipsed Crystal system Hexagonal Space group P6/m a [Å] b [Å] c [Å] α [deg] 90 β [deg] 90 γ [deg] 120 S-18

19 Table S2. Selected atom sites of modeled NUS-10. Atom site label Atom site fract x Atom site fract y Atom site fract z O1 O4 N5 C6 C7 C8 C9 C10 C11 H12 H13 H14 H15 O16 N17 C18 C19 C20 C21 C22 C23 S24 H25 H26 H27 O(1) H(2) S-19

20 Table S3. Comparison of proton conductivity of NUS-9, NUS-10, and their composite membranes with Nafion and other reported MOFs and COFs ranked in descending order. Material Type σ (S cm -1 ) Condition E a (ev) Reference Nafion Polymeric membrane ~ K, 98% RH 0.22 UiO-66-(SO 3 H) 2 MOF K, 90% RH 0.32 TfOH@MIL-101 MOF K, 15% RH Fe-CAT-5 MOF K, 98% RH 0.24 {[(Me 2 NH 2 ) 3 (SO 4 )] 2 [Zn 2 (ox) 3 ]} MOF K, 98% RH NUS-10 COF K, 98% RH - This work H 2 (dobdc)(h 2 O) 2 (ph = 1.8) MOF K, 95% RH 0.14 PCMOF21/2 MOF K, 90% RH H 2 (dobdc)(h 2 O) 2 (ph = 2.4) NUS-10@PVDF-50* MOF K, 95% RH 0.12 COF MMM K 0.21 This work UiO-66-(SO 3 H) 2 MOF K, 90% RH 0.32 NUS-9 COF K, 98% RH - This work 10 6 (NH 4 ) 2 (H 2 adp)[zn 2 (ox) 3 ] 3H 2 O MOF K, 98% RH 0.63 Ca-PiPhtA-NH 3 MOF K, 98% RH NUS-10@PVDF-50* COF K 0.21 This work MMM NUS-9@PVDF-50* COF MMM K 0.20 This work PCMOF-5 MOF K, 98% RH Cu TCPP nanosheet MOF K, 98% RH 0.28 Cd-5TIA MOF K, 98% RH 0.16 In-IA-2D-1 MOF K, 98% RH NUS-9@PVDF-50* COF K 0.20 This work MMM PA@Tp-Azo COF K,98%RH im@tpb-dmtp-cof COF K, anhydrous 0.38 phytic@tppa-(so 3 H-Py) COF K, anhydrous Asterisks (*) indicate sample being tested in pure water. S-20

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