▎ 摘　　要

Thin porous layers of palladium deposited onto gold or Pd bulk metal treated by cathodic reduction in the presence of CsI under super-dry conditions were tested to establish their reactivity towards electrolytes. Specifically, an iono-metallic layer [Pd-4(-),TMA(+) {TMABF(4)}]was found to be generated in tetra-alkylammonium salts, especially TMA(+), BF4-. This material is then taken as a starting substrate for in situ exchange between BF4- and many electrogenerated organic acceptor anions. Importantly, the list includes doped graphene and electro-active conducting organic polymers in their basic form. Thus, for example, an intriguing Pd-graphene layer can be created as a relatively thick interface, and may be either doped or un-doped, depending On the applied potential. The method was also shown to work with many organic acceptors (coronene, anthraquinone, etc.) immobilized in their reduced state. The proposed method suggests a new strategy for building stable composite materials of considerable interest for use as electrodes and/or in 3D redox applications. (C) 2016 Elsevier B.V. All rights reserved.