Geometry-Driven Design of High-Performance ORR Electrocatalysts

The grand challenge in oxygen electrocatalysis lies in overcoming scaling relations, which constrain catalyst performance. The theoretical activity volcano positions the ideal catalyst at its apex, but the intrinsic OH–OOH scaling relation enforces a linear path on the volcano surface, fundamentally limiting catalytic activity. Current state-of-the-art modeling confirms the persistence of this scaling relation, hindering the experimental realization of innovative oxygen reduction reaction (ORR) catalysts and stalling progress in sustainable energy technologies. [1,2] To address this bottleneck, we propose the development of well-defined catalysts with tunable geometry, enabling precise manipulation of structural features to break scaling constraints.[3,4] By systematically adjusting key geometric parameters, these catalysts provide a means to fine-tune the adsorption energies of ORR intermediates and circumvent the limitations imposed by linear scaling relations. Our approach involves synthesizing catalysts with diverse, highly controlled architectures and validating their performance through integrated theoretical and computational modeling. By exploiting the geometry effect, we aim to redefine the state-of-the-art frontier for ORR catalysts. This strategy enables the optimization of reaction mechanisms and adsorption energies, unlocking pathways to switch, push, or bypass scaling relations. References [1] R. Cepitis, A. Kosimov, V. Ivaništšev, N. Kongi, Bifunctional Electrocatalysts – Design Strategies from Theoretical and Computational Studies, in: Multi-Functional Electrocatalysts: Fundamentals and Applications, Royal Society of Chemistry, 2024. https://books.rsc.org/books/edited-volume/2219/chapter/8118324/Bifunctional-Electrocatalysts-Design-Strategies (accessed December 13, 2024). [2] V. Ivaništšev, R. Cepitis, J. Rossmeisl, N. Kongi, Scaling Relations in Oxygen Reduction Reaction Electrocatalysis, (2024). https://doi.org/10.26434/chemrxiv-2024-csxt9. [3] R. Cepitis, N. Kongi, J. Rossmeisl, V. Ivaništšev, Surface Curvature Effect on Dual-Atom Site Oxygen Electrocatalysis, ACS Energy Lett. 8 (2023) 1330–1335. https://doi.org/10.1021/acsenergylett.3c00068. [4] R. Cepitis, V.B. Ivanistsev, J. Rossmeisl, N. Kongi, Bypassing the scaling relations in oxygen electrocatalysis with geometry-adaptive catalysts, Catal. Sci. Technol. 14 (2024) 2105–2113. https://doi.org/10.1039/D4CY00036F.