The idea of spatial confinement has gained widespread interest in myriad applications. Especially, the confined short hydrogen-bond (SHB) network could afford an attractive opportunity to enable proton transfer in a nearly barrierless manner, but its practical implementation has been challenging. Herein, we report a SHB network confined on the surface of ionic covalent organic framework (COF) membranes decorated by densely and uniformly distributed hydrophilic ligands. Combined experimental and theoretical evidences have pointed to the confinement of water molecules allocated to each ligand, achieving the local enrichment of hydronium ions and the concomitant formation of SHBs in water-hydronium domains. These overlapped water-hydronium domains create an interconnected SHB network, which yields an unprecedented ultrahigh proton conductivity of 1389 mS cm−1 at 90 °C, 100% relative humidity.
Side‐chain engineering of covalent organic frameworks as advanced ion conductors is a critical issue to be explored. Herein, ionic covalent organic framework membranes (iCOFMs) with spacer‐engineered ionic channel are de novo designed and prepared. The ionic channels are decorated with side chains comprising spacers having different carbon chain lengths and the –SO3H groups at the end. Attributed to the synergistic contribution from the spacers and the –SO3H groups, the iCOFM with moderate‐length spacer exhibit the highest through‐plane proton conductivity of 889 mS cm‐1 at 90 °C.
Robust and highly conductive proton exchange membranes are urgently required in fuel cells. Inspired by the underwater adhesion in sandcastle worm, herein, ultra-robust and highly conductive polymer carbon dots membranes...
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