Continuous Ion Separations Using Non-Faradaic Capacitive AC Ratcheting

Tuesday, 11 October 2022: 10:50
Room 314 (The Hilton Atlanta)
R. Kautz, E. J. Heffernan (University of California Irvine), A. Herman (Tel Aviv University), J. Ager (Lawrence Berkeley National Laboratory), G. Segev (Tel Aviv University), and S. Ardo (University of California Irvine)
Traditional electrochemical separations processes require Faradaic reactions for sustained currents. We discovered that this limitation can be overcome by oscillating the applied potential across an ion-permeable material that has an asymmetric electric potential profile. We demonstrated this phenomenon for the first time using a flashing ratchet consisting of a nanoporous anodized aluminum oxide membrane infiltrated with salt water and containing metallic contacts on either side. When a symmetric +/-300 mV square-wave potential was applied to the metallic contacts at a frequency of ~100 Hz, an open-circuit potential as large as ~50 mV was observed between Ag/AgCl electrodes immersed in the chloride-containing electrolyte and positioned across the membrane. While this open-circuit potential was determined to be a consequence of net ionic polarization, additional electrochemical data were also consistent with transport of neutral salt across the membrane via a proposed ambipolar transport mechanism. In comparison, application of a DC potential bias resulted in non-Faradaic charging, and a near-zero long-time open-circuit potential. Moreover, high ionic strengths and large pore sizes diminished ratcheting behavior, consistent will more complete screening of surface charges in the nanopores. Collectively, this work represents a new paradigm for direct ion pumping and salt separations that requires no Faradaic reactions or additional transport pathway for ions or electrons.