Patterning of BiVO4 Surfaces and Monitoring of Localized Catalytic Activity Using Scanning Photoelectrochemical Microscopy.

There is a lot of interest in understanding localized catalytic activities at the micro and nanoscale and designing robust catalysts for photoelectrochemical oxidation of water to address the pressing energy and environmental challenges. Here, we demonstrate that scanning photoelectrochemical microscopy (SPECM) can be effectively employed as a novel technique (i) to modify a photocatalyst surface with an electrocatalyst layer in a matrix fashion and (ii) to monitor its localized activity toward the photoelectrochemical (PEC) water oxidation reaction. The three-dimensional SPECM image clearly shows that the loading of the FeOOH electrocatalyst on the BiVO4 semiconductor surface strongly affects its local PEC reaction activity. The optimal photoelectrodeposition time of FeOOH on the BiVO4 photocatalyst was found to be ∼20 min when FeOOH was employed as the electrocatalyst. The electrocatalyst optimization process was conducted on a single photoanode electrode surface, making the optimization process efficient and reliable. The morphology of the formed photocatalyst/electrocatalyst hybrid, inclusive of its localized activity toward the water oxidation reaction, was simultaneously probed. A photoanode surface comprising CuWO4/BiVO4/FeOOH was further prepared in this study and investigated. It was found that the localized photoactivity truly reflects the activity of the local area, differs from region to region, and is contingent on the morphology of the surface. Moreover, the Pt UME is determined as an efficient probe to analyze the photoactivity of the PEC water splitting reaction. This work highlights the novel SPECM technique for enhancement and examination of the catalytic activity of the nanostructured materials.