High-Resolution Mapping of Photocatalytic Activity by Diffusion-Based and Tunneling Modes of Photo-Scanning Electrochemical Microscopy

Semiconductor nanomaterials and nanostructured interfaces have important technological applications, ranging from fuel production to electrosynthesis. Their photocatalytic activity is known to be highly heterogeneous, both in an ensemble of nanomaterials and within a single entity. Photoelectrochemical imaging techniques are potentially useful for high-resolution mapping of photo(electro)catalytic active sites; however, the nanoscale spatial resolution required for such experiments has not yet been attained. In this article, we report photoreactivity imaging of two-dimensional MoS2 photocatalysts by two modes of photoscanning electrochemical microscopy (photo-SECM): diffusion and tunneling-based modes. Diffusion-based (feedback mode) photo-SECM is used to map the electron transfer and hydrogen evolution rates on mixed-phase MoS2 nanosheets and MoS2 chemical vapor deposition (CVD)-grown triangles. An extremely high resolution of photoelectrochemical imaging (about 1-2 nm) by the tunneling mode of the photo-SECM is demonstrated.