Abstract

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) (H2 TCPP: 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.

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