Grain-Boundary-Free Super-Proton Conduction of a Solution-Processed Prussian-Blue Nanoparticle Film

A porous crystal family has been explored as alternatives of Nafion films exhibiting super-proton conductivities of ≥10^-2  S cm^-1 . Here, the proton-conduction natures of a solution-processed film of nanoparticles (NPs) have been studied and compared to those of a Nafion film. A mono-particle film of Prussian-blue NPs is spontaneously formed on a self-assembled monolayer substrate by a one-step solution process. A low-temperature heating process of the densely packed, pinhole-free mono-particle NP film enables a maximum 10⁵ -fold enhancement of proton conductivity, reaching ca. 10^-1  S cm^-1 . The apparent highest conductivity, compared to previously reported data of the porous crystal family, remains constant against humidity changes by an improved water-retention ability of the film. In our proposed mechanism, the high-performing solution-processed NP film suggests that heating leads to the self-restoration of hydrogen-bonding networks throughout their innumerable grain boundaries.