Observing Transient Bipolar Electrochemical Coupling on Single Nanoparticles Translocating through a Nanopore

We report the observation of transient bipolar electrochemical coupling on freely moving 40 nm silver nanoparticles. The use of an asymmetric nanoelectrochemical environment at the nanopore orifice, for example, an acid inside the pipette and halide ions in the bulk, enabled us to observe unusually large current blockages of single Ag nanoparticles. We attribute these current blockages to the formation of H2 nanobubbles on the surface of Ag nanoparticles due to the coupled faradaic reactions, in which the reduction of protons and water is coupled to the oxidation of Ag and water under potentials higher than 1 V. The appearance of large current blockages was strongly dependent on the applied voltage and the choice of anions in the bulk solution. The correlation between large current blockages with the oxidation of Ag nanoparticles and their nanopore translocation was further supported by simultaneous fluorescence and electric recordings. This study demonstrates that transient bipolar electrochemistry can take place on small metal nanoparticles below 50 nm when they pass through nanopores where the electric field is highly localized. The use of a nanopore and the resistive-pulse sensing method to study transient bipolar electrochemistry of nanoparticles may be extended to future studies in ultrafast electrochemistry, nanocatalyst screening, and gas nucleation on nanoparticles