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Commentary Open Access

Molecular Persistence in an Electrochemical Extreme: Ruthenium Stability in PEM Systems

Brodie Tricarico1, Diskin Posner2*

1Institute of Chemistry, Inorganic Chemistry, University of Rostock, Albert-Einstein-Strasse 3A, 18059, Rostock, Germany

2Department of Chemistry, Institute of Inorganic Chemistry, University of Hamburg, Martin-Luther-King Platz 6, 20146, Hamburg, Germany

Diskin Posner, et al./Int.J. Chemical Concepts. 2023,9(2),pp 41-26
Abstract
Polymer electrolyte membrane (PEM) water electrolysis represents one of the most chemically aggressive operational environments encountered in modern electrochemical technology. Strongly acidic media, high anodic potentials, oxidative intermediates, and dynamic interfacial conditions collectively impose constraints that have traditionally excluded molecular catalysts from practical consideration. Instead, catalyst design for PEM systems has overwhelmingly favored heterogeneous metal oxides, particularly iridium- and ruthenium-based solids, under the assumption that molecular coordination compounds lack the robustness required for sustained operation. The observation of remarkable stability in a molecular ruthenium complex under PEM electrolysis conditions therefore challenges long-standing assumptions regarding catalyst durability, decomposition pathways, and the boundary between homogeneous and heterogeneous electrocatalysis. This commentary examines the significance of such molecular persistence not as an isolated anomaly, but as a signal that prevailing design paradigms may be incomplete. By exploring chemical bonding, coordination dynamics, interfacial effects, and electrochemical stress factors, this article argues that molecular stability in PEM environments is not inherently implausible, but historically underexplored. The discussion emphasizes conceptual implications for catalyst design, mechanistic interpretation, and the future integration of molecular systems into electrochemical technologies traditionally reserved for solid-state materials.

Keywords

PEM water electrolysis; Molecular electrocatalysis; Ruthenium complexes; Catalyst stability; Acidic electrochemistry; Coordination chemistry; Oxygen evolution reaction; Electrochemical durability.