Spin-Dependent Oxygen Reduction Electrocatalysis Is Suppressed by Electron-Withdrawing Substitution in Perfluorinated Iron Phthalocyanine
Abstract
The oxygen reduction reaction (ORR) plays a key role in energy conversion systems. Perfluorinated iron phthalocyanine (16(F)FePc), a member of the MN4 molecular catalyst family, has been reported to exhibit enhanced ORR activity compared to unsubstituted iron phthalocyanine (FePc). This is attributed to fluorine-induced electron-withdrawing effects that decrease the electron-density of the FeN4 active site. On the other hand, because O2 is paramagnetic, the electron spin is a relevant factor in ORR electrocatalysis through chirality-induced spin selectivity (CISS). In this work, the interplay between inductive electron-withdrawing effects and CISS-driven electrocatalysis was studied in self-assembled electrode systems based on FePc and 16(F)FePc. The molecular catalysts were immobilized on polycrystalline gold (Au_Poly) and Au(111) substrates using l- and d-methionine as chiral linkers, which act as spin filters. Single-molecule conductance of l- and d-methionine was further evaluated by spin-polarized scanning tunneling microscope break-junction (SP-STM-BJ) measurements to assess chirality-dependent electron transport. ORR activity was examined using a rotating ring−disk electrode configuration to determine the total number of electrons transferred and H2O2 yield. The ORR behavior of FePc and 16(F)FePc assembled on methionine reveals the interplay between CISS and inductive electron-withdrawing effects. FePc shows chirality-dependent electroactivity, favoring the four-electron pathway. In contrast, 16(F)FePc exhibits negligible chirality dependence for ORR, indicating that the strong electron-withdrawing effect of fluorine substituents on the Fe center dominates the reduction process. These results demonstrate that inductive substituent effects can override spin-dependent electrocatalysis, providing insight into the design of molecular catalysts in which CISS contributions are modulated or suppressed.
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References 83 · Cited by 1
- Authors
- Acuña-Saavedra, L., Vilches-Labbé, N., Yupanqui-Mondino, N., Méndez-Torres, A. M., Díaz-Pérez, M. E., Scarpetta-Pizo, L., Ponce-Vergara, J., Zagal, J. H., Aspée, A., Darwish, N., Oñate, R., & Ponce, I.
- Affiliations
- Universidad de Santiago de Chile (CL)
- Universidad de Santiago de Chile , , Av. Libertador Bernardo O'Higgins 336, Estación Central , ,
- Universidad Central de Chile , , Av. Santa Isabel 1186 , ,
- Curtin University (AU)
- Corresponding author
- Acuña-Saavedra, Luis
- Oñate, Rubén
- Ponce, Ingrid
- Venue
- ACS Catalysis
- Publisher
- American Chemical Society (ACS)
- Published
- 2026-06-30
- Volume
- 16
- Issue
- 14
- Pages
- 13473-13487
- ISSN
- 2155-5435 (ISSN-L)
- OpenAlex
- W7166697051
- Cited by
- 1
- References
- 83
- Citations by year
- 2026: 1
- FWCI
- 0.87
- Type
- journal article
- Language
- en
- Open access
- closed
- Licence
- Locations
- ACS Catalysis (publishedVersion)
- Funders
- Fondo Nacional de Desarrollo Científico y Tecnológico (11251644, 1221798, 1251260)
- Agencia Nacional de Investigación y Desarrollo (2023-21232198, 2024-21241434, 2025-21252726)
- Vicerrectoría de Investigación, Desarrollo e Innovación, Universidad de Santiago de Chile (022141AL_Postdoc)
- Topics
- Physical Sciences › Energy › Renewable Energy, Sustainability and the Environment › Electrocatalysts for Energy Conversion
- Physical Sciences › Chemistry › Inorganic Chemistry › Metal-Catalyzed Oxygenation Mechanisms
- Physical Sciences › Engineering › Biomedical Engineering › Surface Chemistry and Catalysis
- Keywords
- oxygen reduction reaction, chirality-induced spin selectivity, electron-withdrawing substituents, fluorine substitution, molecular conductance, four-electron pathway, hydrogen peroxide selectivity, molecular catalysts, Fe-N4 active sites, self-assembled monolayers, gold electrode
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