Nanoscale Catalyst/Semiconductor Contacts in Water-Splitting Photoelectrodes
Shannon Boettcher a b
a Department of Chemistry and Biochemistry, University of Oregon, US, United States
b Oregon Center for Electrochemistry, University of Oregon, Eugene OR, United States
Materials for Sustainable Development Conference (MATSUS)
Proceedings of nanoGe Fall Meeting 2021 (NFM21)
#SolFuel21. Solar Fuel: In-situ and operando characterization of electrified interfaces
Online, Spain, 2021 October 18th - 22nd
Organizers: Bastian Mei, Jan Philipp Hofmann and María Escudero-Escribano
Invited Speaker, Shannon Boettcher, presentation 081
DOI: https://doi.org/10.29363/nanoge.nfm.2021.081
Publication date: 23rd September 2021

Heterogeneous electrochemical processes, including photoelectrochemical water splitting to evolve hydrogen 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 present our recent work demonstrating that the nanoelectrode tip of an atomic-force-microscope cantilever can effectively sense the surface electrochemical potential of electrocatalysts coating semiconductor photoelectrodes during operation. This technique allowed us to unambiguously show that metal (oxy)hydroxide layers act as both hole collectors and oxygen-evolution catalysts on metal-oxide photoanodes such as Fe2O3 and BiVO4. We also discovered the critical role that heterogeneous interfacial barrier heights, and a related nanoscale pinch-off effect, play in building carrier-selective interfaces in semiconductor photoelectrodes for generating fuel from sunlight. Recent results on Si, InP, and oxide based electrocatalyzed semiconductors will be discussed.

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