Construction of effective transmission channels by anchoring metal‐organic framework on side‐chain sulfonated poly(arylene ether ketone sulfone) for fuel cells

Abstract

A series of novel organic-inorganic hybrid membranes assembled by side-chain type sulfonated poly(arylene ether ketone sulfone) with amino groups (Am-SPAEKS-DBS) and ZIF-67 were prepared. Am-SPAEKS-DBS containing double bonds was synthesized by condensation polymerization, and the AMPS was grafted onto the main chain by post sulfonation. ZIF-67 was prepared by an ordinary solvent method. The structures of ZIF-67, Am-SPAEKS-DBS, and hybrid membranes were analyzed by proton nuclear magnetic resonance ( 1 H NMR), scanning electron microscopy (SEM), powder X-ray diffraction (PXRD) and Fourier transform infrared (FT-IR). All hybrid membranes had good dimensional stability and excellent oxidation stability. In addition, the swelling ratios of all hybrid membranes were low (<17.46%) at even 100 C, and the oxidative stability was higher than 92%. The proton conductivities of this series of membranes were much higher (0.0540.069 S cm À1 at 30 C, 0.088-0.116 S cm À1 at 80 C) than pure membrane (0.038 S cm À1 at 30 C, 0.076 S cm À1 at 80 C).The experimental results exhibited that the comprehensive properties of hybrid membranes are good, and hybrid membranes had substantially possible as proton exchange membranes. Highlights• Metal-organic frameworks were anchored on side-chain type organic polymer backbone.• The hybrid PEMs showed good dimensional stability and excellent oxidation stability.• The imidazole as a ligand in ZIF-67 contributes a part of the dissociated protons. K E Y W O R D Sorganic-inorganic hybrid membranes, proton conductivities, side-chains, sulfonated poly(arylene ether ketone sulfone), ZIF-67 Mengchi Ju and Qingyuan Shi contributed equally to this work.

TiO2 nanoparticle enhanced high temperature proton conductivity in hyperbranched sulfonated polyarylene aliphatic ketones for proton exchange membrane fuel cell applications

“…18 For instance, Liu et al studied a sulfonated N-heterocyclic containing poly(aryl ether ketone)s with suspended phenyl moities for PEMFCs, which showed a swelling rate of 5.6%, and proton conductivity of 9.8-103 mS cm À1 at 75 C. 19 Ju et al constructed an effective proton transport channel by introducing metal-organic framework on the linked of sulfonated poly(arylene ether ketone sulfone). The MOFpolymer membrane showed a proton conductivities of 0.054-0.069 S cm À1 at 30 C, 0.088-0.116 S cm À1 at 80 C. 20 Traizole pendant sulfonated poly(arylene ether ketone sulfone) was reported to have a proton conductivity of 0.166 S cm À1 at 120 C, which was more significant than that of Nafion 117. 21 Itoh et al synthesized a phosphoric acid doped hyperbranched polymer for PEMFC and obtained a proton conductivity of 1.2 Â 10 À5 and 2.6 Â 10 À6 S cm À1 due to the hyperbranched structure providing better water permeability.…”

“…Ju et al constructed an effective proton transport channel by introducing metal–organic framework on the linked of sulfonated poly(arylene ether ketone sulfone). The MOF‐polymer membrane showed a proton conductivities of 0.054–0.069 S cm −1 at 30°C, 0.088–0.116 S cm −1 at 80°C 20 . Traizole pendant sulfonated poly(arylene ether ketone sulfone) was reported to have a proton conductivity of 0.166 S cm −1 at 120°C, which was more significant than that of Nafion 117 21 .…”

Comb‐shaped block poly(arylene ether sulfone ketone)s for anion exchange membranes

“…Numerous polymers have been explored as the AEMs' backbones, including poly(arylene ether ketone) (PEK), 9,10 poly(arylene ether sulfone) (PES), 11,12 poly(phenylene oxide) (PPO), 13,14 polybenzimidazole (PBI), 15,16 poly(crown ether) (PCE) 17,18 and several heteroatom-free polymers like poly(arylene alkylene), [19][20][21] polyfluorenes 22 and polyalkenes. 23 In addition, various functional cationic groups, such as quaternary ammonium, 10,20-22 imidazolium, 9,11 guanidinium, 24 phosphonium, 25 pyrrolidinium, 26 piperidinium 27,28 and some metal-based cations, 29 have been studied and utilized for AEMs. In particular, recent research demonstrated the cationic groups carrying alkyl chains or bulky groups showed better alkaline stability, which could be attributed to the steric hindrance effect.…”

Enhancing proton conductivity of proton exchange membranes via anchoring imidazole‐loaded MIL‐101‐NH 2 onto sulfonated poly (arylene ether ketone sulfone) by chemical bonding

“…The commercial PEMs of Nafion membranes produced by DuPont exhibit good stability and high proton conductivity 8,9 . However, the disadvantages, such as excessively expensive price, high fuel permeability, strong dependence on water, and rapid performance degradation at elevated temperatures, limit the large‐scale use of Nafion membranes 10,11 . Sulfonated aromatic polymers with excellent mechanical properties and chemical stability are considered to be possible to replace Nafion membranes 12,13 .…”

“…dependence on water, and rapid performance degradation at elevated temperatures, limit the large-scale use of Nafion membranes. 10,11 Sulfonated aromatic polymers with excellent mechanical properties and chemical stability are considered to be possible to replace Nafion membranes. 12,13 Wang et al prepared sulfonated poly(ether ether ketone) (SPEEK) membranes with different sulfonation degrees, and the proton conductivities of SPEEK membranes with degrees of sulfonation (DS) of 39% and 47% were close to that of Nafion115 membranes.…”