Tunneling Mode of Scanning Electrochemical Microscopy: Probing Electrochemical Processes at Single Nanoparticles

Electrochemical experiments at individual nanoparticles (NPs) can provide new insights into their structure–activity relationships. By using small nanoelectrodes as tips in a scanning electrochemical microscope (SECM), we recently imaged individual surface‐bound 10–50 nm metal NPs. Herein, we introduce a new mode of SECM operation based on tunneling between the tip and a nanoparticle immobilized on the insulating surface. The obtained current vs. distance curves show the transition from the conventional feedback response to electron tunneling between the tip and the NP at separation distances of less than about 3 nm. In addition to high‐resolution imaging of the NP topography, the tunneling mode enables measurement of the heterogeneous kinetics at a single NP without making an ohmic contact with it. The developed method should be useful for studying the effects of nanoparticle size and geometry on electrocatalytic activity in real‐world applications. Too close for comfort: The transition from conventional SECM feedback response to electron tunneling between the nanotip and metal nanoparticle occurs at a separation distance of circa 2 nm. At such close distances, the particle potential is controlled by the tip, and the heterogeneous kinetics can be measured without attaching it to an electrode.