Interfacial Properties of a PEM Water Electrolysis Pt Electrode Probed by Operando Tender Ambient Pressure X-Ray Photoelectron Spectroscopy

Abstract

The probe of the chemical, structural, and electronic properties at the electrode-electrolyte interfaces under operational conditions is critical for the mechanistic study and optimization of all the electrochemical systems and has therefore been at the center of numerous studies [1]. Soft X-ray Ambient pressure X-ray photoelectron spectroscopy (APXPS) has been known as a promising in-situ/operando technique, but its applications in the probe of a realistic solid/liquid interface under ambient conditions has been limited by the short inelastic mean free path (IMFP) of photoelectrons in the liquid medium. Here, inspired by prior work [2,3] and taking advantage of the synchrotron tender X-ray source (Beamline 9.3.1) at the Advanced Light Source of the Lawrence Berkeley National Laboratory [4], the IMFP can be significantly increased. A larger IMFP enables interfacial characterization under higher background pressures and through liquid overlayer greater than 30 nm in thickness. We have designed and built a graphene sealed operando electrolysis electrochemical cell that is compatible with an existing tender X-ray APXPS setup for the investigation of electrode-electrolyte interfaces under operational conditions. The present setup will be utilized to probe various systems involving solid/liquid interfaces, including but not limited to the interactions of ions, the solvation of salts, and electrocatalysis.In this work, the utilization of tender X-rays (2000 – 6000 eV) facilitates investigations of the electrode-electrolyte interface with a liquid-layer thickness of tens of nanometers, which can be preserved within the sandwiched region between the topmost graphene and the Pt nanoparticle loaded proton exchange membrane (PEM). In addition, the environmental water vapor pressure within the analysis chamber was kept at the water vapor pressure at 298 K (~15 Torr). The setup allows the study of a water splitting electrolyzer under real working conditions, where the electrocatalytic performance and the operando photoemission spectroscopy can be simultaneous investigated. As a proof-of-concept, Pt nanoparticle-catalyzed oxygen evolution reaction (OER) was investigated under operando conditions. The electrochemistry and detailed analysis of the photoemission spectra demonstrating the evolution of the chemical, structural, and electronic properties at the H2O/Pt interface under the influence of external electrical field will be presented.