Simultaneous Topography and Reaction Flux Mapping at and around Electrocatalytic Nanoparticles

Minkyung Kang, David Perry, Cameron L. Bentley, Geoff West, Ashley Page, Patrick R. Unwin

Research output: Contribution to journalArticleResearchpeer-review

42 Citations (Scopus)

Abstract

The characterization of electrocatalytic reactions at individual nanoparticles (NPs) is presently of considerable interest but very challenging. Herein, we demonstrate how simple-to-fabricate nanopipette probes with diameters of approximately 30 nm can be deployed in a scanning ion conductance microscopy (SICM) platform to simultaneously visualize electrochemical reactivity and topography with high spatial resolution at electrochemical interfaces. By employing a self-referencing hopping mode protocol, whereby the probe is brought from bulk solution to the near-surface at each pixel, and with potential-time control applied at the substrate, current measurements at the nanopipette can be made with high precision and resolution (30 nm resolution, 2600 pixels μm-2, <0.3 s pixel-1) to reveal a wealth of information on the substrate physicochemical properties. This methodology has been applied to image the electrocatalytic oxidation of borohydride at ensembles of AuNPs on a carbon fiber support in alkaline media, whereby the depletion of hydroxide ions and release of water during the reaction results in a detectable change in the ionic composition around the NPs. Through the use of finite element method simulations, these observations are validated and analyzed to reveal important information on heterogeneities in ion flux between the top of a NP and the gap at the NP-support contact, diffusional overlap and competition for reactant between neighboring NPs, and differences in NP activity. These studies highlight key issues that influence the behavior of NP assemblies at the single NP level and provide a platform for the use of SICM as an important tool for electrocatalysis studies.

Original languageEnglish
Pages (from-to)9525-9535
Number of pages11
JournalACS Nano
Volume11
Issue number9
DOIs
Publication statusPublished - 26 Sep 2017
Externally publishedYes

Keywords

  • electrocatalysis
  • electrochemical imaging
  • finite element method modeling
  • nanoparticles
  • scanning ion conductance microscopy

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