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Proton-exchange membrane water electrolyzers, pivotal for sustainable hydrogen production, encounter challenges in the oxygen evolution reaction (OER) marked by high overpotential and limited electrocatalyst stability. This study delves into the computational exploration of two metal substitutions, titanium (Ti) and zirconium (Zr), within ruthenium oxide (RuO 2 ), aiming to enhance catalytic stability. The investigation encompasses nanoscale titanium-substituted and zirconium-substituted rutile RuO 2 , (Ru 1-x M x O 2 ) and evaluating their atomic and electronic structures, OER activity, and dissolution behavior. In the case of Ti substitution, varying concentrations (x = 0–50 at %) were systematically investigated. Our experiments and theoretical analyses elucidate concentration-dependent effects on the electronic structure, showcasing shifts in the d-band and O2p band centers. Titanium substitution induces electron accumulation and depletion regions on the surface, influencing OER activity and stability. Electrochemical testing corroborates the theory, demonstrating that lower Ti concentrations (12.5 and 20 at %) enhance catalyst stability and mitigate ruthenium dissolution. Specifically, Ti substitution influences reaction pathways, with penta-coordinated Ru sites exhibiting the lowest barriers for OER, while hexa-coordinated Ru sites facilitate lower energetic barriers for dissolution. Simultaneously, the study extends to the substitution of Zr within rutile RuO 2 . Computational and experimental analyses reveal anisotropic shifts in the rutile unit cell, dependent on Zr concentration. Zr substitution induces alterations in the electronic structure, impacting the surface density of states and electron density distribution. Experimentally, lower OER activity is observed for Zr-substituted RuO 2 compared to pure RuO2 , consistent with computational averages across all sites. However, specific sites with Zr substitution exhibit higher theoretical OER activity. Dissolution analyses underscore the complexity of interactions, with Zr affecting activation barriers for Ru dissolution, thus influencing OER stability. Notably, the dissolution behavior emerges as a critical aspect of this investigation. In Ti-substituted RuO 2 , experimental accelerated durability testing showcases enhanced stability and reduced Ru dissolution at low and intermediate Ti concentrations. Computational analyses corroborate these findings, indicating site-specific effects on both OER activity and stability. Conversely, Zr-substituted RuO 2 exhibits lower Ru dissolution compared to commercial RuO 2 , emphasizing the role of Zr in impeding Ru dissolution while contributing to surface restructuring. In conclusion, this comprehensive exploration of Ti and Zr substitutions within ruthenium oxide advances our understanding of their effects on atomic and electronic structures, OER activity, and dissolution dynamics. The intricate interplay between specific sites, metal concentrations, and substituents provides valuable insights for designing high-performance, cost-effective OER nanoscale electrocatalysts. The findings underscore the importance of considering both activity and stability in the pursuit of efficient and durable electrocatalysts for sustainable hydrogen production.
Acevedo et al. (Fri,) studied this question.