Direct Vibrational Stark Shift Probe of Quasi-Fermi Level Alignment in Metal Nanoparticle Catalyst-Based Metal-Insulator-Semiconductor Junction Photoelectrodes

Sa Suo; Colton Sheehan; Fengyi Zhao; Langqiu Xiao; Zihao Xu; Jinhui Meng; Thomas E Mallouk; Tianquan Lian

doi:10.1021/jacs.3c02333

Direct Vibrational Stark Shift Probe of Quasi-Fermi Level Alignment in Metal Nanoparticle Catalyst-Based Metal-Insulator-Semiconductor Junction Photoelectrodes

J Am Chem Soc. 2023 Jul 5;145(26):14260-14266. doi: 10.1021/jacs.3c02333. Epub 2023 Jun 22.

Authors

Sa Suo¹, Colton Sheehan², Fengyi Zhao¹, Langqiu Xiao², Zihao Xu¹, Jinhui Meng¹, Thomas E Mallouk², Tianquan Lian¹

Affiliations

¹ Department of Chemistry, Emory University, Atlanta, Georgia 30322, United States.
² Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, United States.

Abstract

Photoelectrodes consisting of metal-insulator-semiconductor (MIS) junctions are a promising candidate architecture for water splitting and for the CO₂ reduction reaction (CO₂RR). The photovoltage is an essential indicator of the driving force that a photoelectrode can provide for surface catalytic reactions. However, for MIS photoelectrodes that contain metal nanoparticles, direct photovoltage measurements at the metal sites under operational conditions remain challenging. Herein, we report a new in situ spectroscopic approach to probe the quasi-Fermi level of metal catalyst sites in heterogeneous MIS photoelectrodes via surface-enhanced Raman spectroscopy. Using a CO₂RR photocathode, nanoporous p-type Si modified with Ag nanoparticles, as a prototype, we demonstrate a selective probe of the photovoltage of ∼0.59 V generated at the Si/SiO_x/Ag junctions. Because it can directly probe the photovoltage of MIS heterogeneous junctions, this vibrational Stark probing approach paves the way for the thermodynamic evaluation of MIS photoelectrodes with varied architectural designs.