Transparent Ultramicroelectrodes for Studying Interfacial Charge-Transfer Kinetics of Photoelectrochemical Water Oxidation at TiO Nanorods with Scanning Electrochemical Microscopy.

Scanning electrochemical microscopy (SECM) has been extensively applied to the electrochemical analysis of the surfaces and interfaces of a photoelectrochemical (PEC) system. A semiconductor photoelectrode with a well-defined geometry and active surface area comparable to SECM's tip is highly desired for accurately quantifying interfacial charge-transfer activities and photoelectrochemically generated redox species, where the broadening effects due to the mass transfer gradient and nonlocal electron transfer at a planar semiconductor surface can be minimized. Here, we present a newly developed platform as a SECM substrate for investigating semiconductor PEC activities, which is based on a transparent ultramicroelectrode (UME) fabricated by using two-step photolithographic patterning and ion milling methods. This transparent UME with a 25 μm recessed disk shape is fully characterized with SECM for quantifying the interfacial charge-transfer rates of IrCl/IrCl by comparing with theoretical results from finite element simulations in COMSOL Multiphysics. When coated with TiO nanorods as a model semiconductor material, the transparent UME can be used to quantify the catalytic PEC water oxidation in a feedback mode of SECM by sampling tip and substrate current signals simultaneously. This transparent UME-SECM study provides insights into the potential-dependent PEC water oxidation reaction mechanism and the quantitative analysis of photocurrent contributions from water oxidation and the SECM tip-generated redox mediator. The transparent UME-SECM method can be potentially expanded to other SECM operation modes such as surface interrogation for understanding the dynamics of the electrode surfaces and interfaces of a PEC system.