title: Cyclic Voltammetry Probe Approach Curves with Alkali Amalgams at Mercury Sphere-Cap Scanning Electrochemical Microscopy Probes.
abstract: We report a method of precisely positioning a Hg-based ultramicroelectrode (UME) for scanning electrochemical microscopy (SECM) investigations of any substrate. Hg-based probes are capable of performing amalgamation reactions with metal cations, which avoid unwanted side reactions and positive feedback mechanisms that can prove problematic for traditional probe positioning methods. However, prolonged collection of ions eventually leads to saturation of the amalgam accompanied by irreversible loss of Hg. In order to obtain negative feedback positioning control without risking damage to the SECM probe, we implement cyclic voltammetry probe approach surfaces (CV-PASs), consisting of CVs performed between incremental motor movements. The amalgamation current, peak stripping current, and integrated stripping charge extracted from a shared CV-PAS give three distinct probe approach curves (CV-PACs), which can be used to determine the tip-substrate gap to within 1% of the probe radius. Using finite element simulations, we establish a new protocol for fitting any CV-PAC and demonstrate its validity with experimental results for sodium and potassium ions in propylene carbonate by obtaining over 3 orders of magnitude greater accuracy and more than 20-fold greater precision than existing methods. Considering the timescales of diffusion and amalgam saturation, we also present limiting conditions for obtaining and fitting CV-PAC data. The ion-specific signals isolated in CV-PACs allow precise and accurate positioning of Hg-based SECM probes over any sample and enable the deployment of CV-PAS SECM as an analytical tool for traditionally challenging conditions.
authors.affiliation: Department of Chemistry, University of Illinois at Urbana-Champaign , 600 South Mathews Avenue, Urbana, Illinois 61801, United States.
authors.forename: Zachary J
authors.identifier: 0000-0001-6856-7634
authors.initials: ZJ
authors.lastname: Barton
authors.affiliation: Department of Chemistry, University of Illinois at Urbana-Champaign , 600 South Mathews Avenue, Urbana, Illinois 61801, United States.
authors.forename: Joaquín
authors.initials: J
authors.lastname: Rodríguez-López