Nanoscale Structure Dynamics within Electrocatalytic Materials

Cameron L. Bentley, Minkyung Kang, Patrick R. Unwin

Research output: Contribution to journalArticleResearchpeer-review

66 Citations (Scopus)

Abstract

Electrochemical interfaces used for sensing, (electro)catalysis, and energy storage are usually nanostructured to expose particular surface sites, but probing the intrinsic activity of these sites is often beyond current experimental capability. Herein, it is demonstrated how a simple meniscus imaging probe of just 30 nm in size can be deployed for direct electrochemical and topographical imaging of electrocatalytic materials at the nanoscale. Spatially resolved topographical and electrochemical data are collected synchronously to create topographical images in which step-height features as small as 2 nm are easily resolved and potential-resolved electrochemical activity movies composed of hundreds of images are obtained in a matter of minutes. The technique has been benchmarked by investigating the hydrogen evolution reaction on molybdenum disulfide, where it is shown that the basal plane possesses uniform activity, while surface defects (i.e., few to multilayer step edges) give rise to a morphology-dependent (i.e., height-dependent) enhancement in catalytic activity. The technique was then used to investigate the electro-oxidation of hydrazine at the surface of electrodeposited Au nanoparticles (AuNPs) supported on glassy carbon, where subnanoentity (i.e., sub-AuNP) reactivity mapping has been demonstrated. We show, for the first time, that electrochemical reaction rates vary significantly across an individual AuNP surface and that these single entities cannot be considered as uniformly active. The work herein provides a road map for future studies in electrochemical science, in which the activity of nanostructured materials can be viewed as quantitative movies, readily obtained, to reveal active sites directly and unambiguously.

Original languageEnglish
Pages (from-to)16813-16821
Number of pages9
JournalJournal of the American Chemical Society
Volume139
Issue number46
DOIs
Publication statusPublished - 22 Nov 2017
Externally publishedYes

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