Mechanically flexible, easy-to-process, and environmentally benign materials capable of current rectification are interesting alternatives to "hard" silicon-based devices. Among these materials are metallic/charged-organic nanoparticles in which electronic currents though metal cores are modulated by the gradients of counterions surrounding the organic ligands. Although layers of oppositely charged particles can respond to both electronic and chemical signals and can function even under significant mechanical deformation, the rectification ratios of these "chemoelectronic" elements have been, so far, low. This work shows that significantly steeper counterion gradients and significantly higher rectification ratios can be achieved with nanoparticles of only one polarity but in contact with a porous electrode serving as a counterion "sink." These composite structures act as rectifiers even at radio frequencies, providing a new means of interfacing counterions' dynamics with high-frequency electronic currents.