The fabrication of proton exchange membranes (PEMs) with excellent conductivity and low methanol permeability is critical but challenging for the further development of high-performance direct methanol fuel cells (DMFCs). In this work, two ionic hydrogen-bonded organic frameworks (iHOF-14 and iHOF-15) are obtained from 1,3,5-tris(4-phosphonophenyl)benzene and guanidine hydrochloride under the control of dimethylamine cations. Due to the abundant hydrogen bonding network, iHOF-14 and iHOF-15 exhibit good proton conductivity of over 10–2 S cm−1. In addition, we dope the iHOFs into Nafion matrix to get the PEMs with richer proton transport pathways and good methanol barrier properties. At 100 °C and 98 % RH, the conductivity of 9 %-iHOF-14/Nafion and 9 %-iHOF-15/Nafion reaches up to 1.53 × 10–1 and 1.78 × 10–1 S cm−1, respectively. The 72 h permeation experiment results show that the methanol permeability of the composite membranes is 73.7 % lower than that of the recast Nafion. The maximum power densities of hybrid membranes for DMFCs reach about 80 mW cm−2, which is 1.5 times higher compared to the recast Nafion. This work not only enriches the high proton conductivity of arylphosphonate iHOFs, but also expands iHOFs/Nafion PEMs materials for DMFCs.
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