Correlating the Local Electrocatalytic Activity of Amorphous Molybdenum Sulfide Thin Films with Microscopic Composition, Structure, and Porosity

Cameron L. Bentley, Roland Agoston, Binglin Tao, Marc Walker, Xiangdong Xu, Anthony P. O'Mullane, Patrick R. Unwin

Research output: Contribution to journalArticleResearchpeer-review

Abstract

Thin-film electrodes, produced by coating a conductive support with a thin layer (nanometer to micrometer) of active material, retain the unique properties of nanomaterials (e.g., activity, surface area, conductivity, etc.) while being economically scalable, making them highly desirable as electrocatalysts. Despite the ever-increasing methods of thin-film deposition (e.g., wet chemical synthesis, electrodeposition, chemical vapor deposition, etc.), there is insufficient understanding on the nanoscale electrochemical activity of these materials in relation to structure/composition, particularly for those that lack long-range order (i.e., amorphous thin-film materials). In this work, scanning electrochemical cell microscopy (SECCM) is deployed in tandem with complementary, colocated compositional/structural analysis to understand the microscopic factors governing the electrochemical activity of amorphous molybdenum sulfide (a-MoSx) thin films, a promising class of hydrogen evolution reaction (HER) catalyst. The a-MoSx thin films, produced under ambient conditions by electrodeposition, possess spatially heterogeneous electrocatalytic activity on the tens-of-micrometer scale, which is not attributable to microscopic variations in elemental composition or chemical structure (i.e., Mo and/or S bonding environments), shown through colocated, local energy-dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) analysis. A new SECCM protocol is implemented to directly correlate electrochemical activity to the electrochemical surface area (ECSA) in a single measurement, revealing that the spatially heterogeneous HER response of a-MoSx is predominantly attributable to variations in the nanoscale porosity of the thin film, with surface roughness ruled out as a major contributing factor by complementary atomic force microscopy (AFM). As microscopic composition, structure, and porosity (ECSA) are all critical factors dictating the functional properties of nanostructured materials in electrocatalysis and beyond (e.g., battery materials, electrochemical sensors, etc.), this work further cements SECCM as a premier tool for structure-function studies in (electro)materials science.

Original languageEnglish
Pages (from-to)44307-44316
Number of pages10
JournalACS Applied Materials & Interfaces
Volume12
Issue number39
DOIs
Publication statusPublished - 30 Sep 2020
Externally publishedYes

Keywords

  • electrochemistry
  • HER
  • hydrogen evolution reaction
  • MoS
  • scanning electrochemical cell microscopy
  • SECCM

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