(Invited) Understanding Carrier-Selective Catalyst/Semiconductor Contacts in Water-Splitting Photoelectrodes and Photocatalyst Particles

Heterogeneous electrochemical processes, including photoelectrochemical water splitting to evolve hydrogen and oxygen using electrocatalyst-coated semiconductors, are driven by the accumulation of charge carriers and thus the interfacial electrochemical potential gradients that promote charge transfer. Conventional electrochemical techniques measure/control potentials at the conductive substrate or semiconductor ohmic contact, but are unable to isolate processes and electrochemical potentials at the surface during operation. I will discuss how the nanoelectrode tip of an atomic-force-microscope cantilever can effectively sense the surface electrochemical potential of electrocatalysts coating semiconductor photoelectrodes during operation. This data can be combined with ex-situ electrical measurements, spectroscopy, and materials characterization approaches to provide a comprehensive physical picture of how excited electrons and holes can be effectively separated and catalyst/semiconductor contacts. This new understanding is particularly important for the design of photocatalyst particles where direct electrical measurements of catalyst/semiconductor interface properties is not possible. In these systems we are applying spectroscopic techniques, for example ambient pressure x-ray photoelectron spectroscopy and Stark-effect spectroscopy to understand electric and electrochemical potential distribution and how nanoscale, adaptive, heterogeneous contacts can be controlled to design higher performance photochemical systems.