Anisotropic Superprotonic Conduction in a Layered Single‐Component Hydrogen‐Bonded Organic Framework with Multiple In‐Plane Open Channels

Abstract Hydrogen‐bonded organic frameworks (HOFs) are promising proton conductive materials because of their inherent and abundant hydrogen‐bonding sites. However, most superprotonic‐conductive HOFs are constructed from multiple components to enable favorable framework architectures and structural integrity. In this contribution, layered HOF‐TPB‐A 3 with a single component is synthesized and exfoliated. The exfoliated nanoplates exhibited anisotropic superprotonic conduction, with in‐plane proton conductivities reaching 1.34 × 10 −2 S cm −1 at 296 K and 98% relative humidity (RH). This outperforms the previously reported single‐component HOFs and is comparable with the state‐of‐the‐art multiple‐component HOFs. The high and anisotropic proton conductive properties can be attributed to the efficient proton transport along multiple open channels parallel to their basal planes. Moreover, an all‐solid‐state (ASS) proton rectifier device is demonstrated by combining HOF‐TPB‐A 3 and a hydroxide ion‐conducting layered double hydroxide (LDH). This work suggests that single‐component HOFs with multiple open channels offer more opportunities as versatile platforms for proton conductors, making them promising candidates for conducting media in protonic devices.