Phase Separated Nanofibrous Anion Exchange Membranes with Polycationic

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1 Electronic Supplementary Material (ESI) for Journal of Materials Chemistry A. This journal is The Royal Society of Chemistry 2017 Phase Separated anofibrous Anion Exchange Membranes with Polycationic Side Chains Ebrahim Abouzari-lotf, a,b, * Hossien Ghassemi, c Mohamed M. asef, a,d Arshad Ahmad, a,b Masoumeh Zakeri, a Teo M. Ting, e Ali Abbasi, b Shahram Mehdipour-Ataei f a Advanced Materials Research Group, Center of Hydrogen Energy, Institute of Future Energy, Universiti Teknologi Malaysia, 5100, Kuala Lumpur, Malaysia. b Department of Chemical Engineering, Universiti Teknologi Malaysia, Johor Bahru, Malaysia. c Department of Macromolecular Science & Engineering, Case Western Reserve University, Cleveland, H, USA. d Chemical Engineering Department, Universiti Teknologi Petronas, Seri Iskandar, Perak, Malaysia. e Radiation Processing Technology Division, Malaysian uclear Agency, Kajang, Malaysia. f Iran Polymer and Petrochemical Institute, P.. Box 1965/115, Tehran, Iran. *Corresponding Author. ebrahim@utm.my. Phone/Fax: +60 (0)

2 Figure S1. FESEM images of the electrospun nylon-66 sheets with two different magnifications. The average fiber diameter is 90 nm. Figure S2. FESEM images of the electrospun syn-pp sheets with two different magnifications. The average fiber diameter is 335 nm. 2

3 Figure S3. FESEM images of the functionalized nylon-66 sheet. a) b) Figure S. Photographs of (a) functionalized nanofiber (right) and final membrane (left) and (b) SEM image of final crosslinked dense membrane 3

4 Table S1. Elemental and BET analysis of substrates Sample Formula Elemental analysis (%) BET analysis C H Specific surface area Average pore Pore volume diameter (m 2 /g) (nm) (cm 3 /g) ylon6,6 (C 12 H ) n Cal nanofiber Fou Syn-PP nanofiber (C 3 H 6 ) n Cal Fou VBC-g-y (C 12 H ) 0.53n (C 9 H 9 Cl) 0.7n Cal Fou VBC-g-PP (C 3 H 6 ) 0.86n (C 9 H 9 Cl) 0.1n Cal Fou VBC-g-y - Fou (5.6% crosslinking) VBC-g-PP (6.5% crosslinking) - Fou Equation S1 mm. VBC c = mm. VBC n.c (2 mm. crosslinker) (S1) where n.c refers to non-crosslinked and c. refers to crosslinked fibers, mm is mmol and mmol of introduced crosslinker calculated by gravimetric method according to the following equation: mm. crosslinker = ( W cross W s W s ) (S2) where, W cross and W s are the weights of the crosslinked and noncrosslinked grafted nanofibers, respectively. The value of is a difference in molar mass of crosslinker and leaving groups of chlorine.

5 Figure S5. Arrhenius plot of hydroxide ion conductivity of syn-pp (blue) and y (red) based AEM membrane ( ) and cross-linked membranes with various cross-linking degrees of 3% (- ), 5% ( ), 10% ( ) and 15% (*) as function of temperature. Table S2. Arrhenius activation energy (E a ) of hydroxide ion transport in the membranes. Membranes AEM.PP.I AEM.PP.II AEM.PP.III AEM.PP.IV AEM.PP.V AEM.Y.II AEM.Y.III AEM.Y.IV AEM.Y.V Ea (kj.mol 1 )

6 0 60 H H 2 C H H x y z CH 3 CH2 9 H2 C R H 2 H H R: -CH 3 or -( ) 15 -CH 3 x y z poly(2,6-dimethyl-1,-phenylene oxide)s (PP) H Crosslinked co-pp CH 3 H CH2 R 9 n S m S x m n 60 H 100-x x H H semi-interpenetrating network (SIP AEMs) from two parts quaternized poly(2,6-dimethyl phenylene oxide) (QAPP) Scheme S1. Chemical structure of some published AEMs which used for comparison in Figure 9a. Semiinterpenetrating network (SIP AEMs), 1 quaternized poly(2,6-dimethyl phenylene oxide) (QAPP), 2 functionalization of poly(2,6-dimethyl-1,-phenylene oxide)s (PP), PP based membrane with one, two and triqa- group per chain, 3 and (o) crosslinked co-pp. 1. Pan, J.; Zhu, L.; Han, J.; Hickner, M. A., Mechanically Tough and Chemically Stable Anion Exchange Membranes from Rigid-Flexible Semi-Interpenetrating etworks. Chemistry of Materials 2015, 27 (19), Zhu, L.; Pan, J.; Christensen, C. M.; Lin, B.; Hickner, M. A., Functionalization of Poly(2,6- dimethyl-1,-phenylene oxide)s with Hindered Fluorene Side Chains for Anion Exchange Membranes. Macromolecules 2016, 9 (9), Zhu, L.; Pan, J.; Wang, Y.; Han, J.; Zhuang, L.; Hickner, M. A., Multication Side Chain Anion Exchange Membranes. Macromolecules 2016, 9 (3), Zhang, M.; Liu, J.; Wang, Y.; An, L.; Guiver, M. D.; Li,., Highly stable anion exchange membranes based on quaternized polypropylene. Journal of Materials Chemistry A 2015, 3 (23),