Stability of multifunctional Pd-Rh electrocatalysts supported on Co3O4(111) in alkaline environment: impact of the electronic metal-support interaction

Simanenko A, Škvára J, Samal PK, Franz E, Hübsch R, Skála T, Tsud N, Mehl S, Schauermann D, Johánek V, Mysliveček J, Brummel O, Lykhach Y, Libuda J (2025)

Publication Type: Journal article

Publication year: 2025

Journal

DOI: 10.1039/d5nr00413f

Abstract

The stabilities of monometallic Rh and Pd nanoparticles and bimetallic Pd-Rh core-shell nanoparticles supported on Co3O4(111) thin films grown on Ir(100) were investigated with respect to the oxidation state and dissolution in alkaline electrolyte under the conditions relevant for electrochemical ethanol oxidation. Towards this aim, the well-defined model systems were characterized by means of synchrotron radiation photoelectron spectroscopy coupled with an ex situ emersion electrochemical cell (EC-SRPES) and scanning tunneling microscopy (STM). We found that the electronic metal-support interaction (EMSI) has a strong influence on the oxidation state of Rh, resulting in a strong oxidation and anchoring of the oxidized Rh³⁺ species on the surface of Co3O4(111). Consequently, the EMSI prevents the dissolution of Rh into the electrolyte regardless of the potential range. In contrast, it has no effect on the oxidation state and dissolution of Pd in the potential range of 0.3-1.1 VRHE. However, extending the potential range to 0.3-1.5 VRHE results in a stronger dissolution of Pd due to the reversible oxidation/reduction of Pd, which is enhanced in the presence of the EMSI. Most importantly, the magnitude of the EMSI and, thus, the extent of noble metal oxidation, can be effectively controlled by the nature of the metal/Co3O4(111) interface in the bimetallic Pd-Rh core-shell nanoparticles.

Authors with CRIS profile

Involved external institutions

Univerzita Karlova v Praze / Charles University in Prague Czech Republic (CZ) Elettra Sincrotrone Trieste S.C.p.A. Italy (IT)

How to cite

APA:

Simanenko, A., Škvára, J., Samal, P.K., Franz, E., Hübsch, R., Skála, T.,... Libuda, J. (2025). Stability of multifunctional Pd-Rh electrocatalysts supported on Co3O4(111) in alkaline environment: impact of the electronic metal-support interaction. Nanoscale. https://doi.org/10.1039/d5nr00413f

MLA:

Simanenko, Alexander, et al. "Stability of multifunctional Pd-Rh electrocatalysts supported on Co3O4(111) in alkaline environment: impact of the electronic metal-support interaction." Nanoscale (2025).

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