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.
The dinuclear title compound, [Cd2(C7H5O3)4(C12H8N2)2], is located on a crystallographic rotation twofold axis. The two CdII ions are connected by two tridentate bridging 2-hydroxybenzoate anions. Each CdII ion is seven-coordinated by five O atoms from three 2-hydroxybenzoate ligands and two N atoms from 1,10-phenanthroline. The 2-hydroxybenzoate molecules adopt two kinds of coordination mode, bidentate chelating and tridentate bridging–chelating. Intramolecular hydrogen bonds between hydroxy and carboxylate groups from 2-hydroxybenzoate groups and π–π stacking interactions between parallel 1,10-phenanthroline ligands [centroid–centroid distances = 3.707 (3) and 3.842 (3) Å] are observed. Furthermore, adjacent benzene rings from 2-hydroxybenzoate ligands are involved in π–π interactions with interplanar distances of 3.642 (3) Å, thereby forming a chain along the a axis direction.
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