High-Performance All-Solid-State Proton Rectifier Using a Heterogeneous Membrane Composed of Coordination Polymer and Layered Double Hydroxide

Rational control of unidirectional proton transport is highly challenging, primarily owing to the difficulty in introducing an asymmetric factor into proton-conducting media. In this study, free-standing membranes of a proton-conducting two-dimensional porous coordination polymer, Cu2(CuTCPP) (H2TCPP: 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin) and a hydroxide ion-conducting layered double hydroxide, Mg–Al–LDH(NO3), were combined to generate a pH gradient in the conducting media. The current–voltage measurements revealed that the heterogeneous membrane exhibits a significant unidirectional proton transport with a proton rectification ratio exceeding 200 under 90% relative humidity in the initial voltage scan. This value is the highest among the reported all-solid-state proton rectifiers. The high designability of both components with well-defined structures, which is in contrast to the organic polymers used so far, provides a new avenue for developing and understanding the proton-rectifying behavior in the solid state.