2026-10-13T09:27:22Z https://api.figshare.com/v2/oai

oai:figshare.com:article/34024051 2026-09-29T13:36:59Z category_4 category_21 category_873 category_39 category_734 category_135 portal_63 item_type_3 month_year_09_2026

Capture and Characterization of High-Valent Uranium on Carbon Electrodes with a Hybrid Molecular Platform T. Davis Curry (14822919) Julia L. Martin (9034397) Taylor Parsons (12226437) Benjamin R. Heiner (25137262) Emily R. Mikeska (18270139) Marco Caricato (1272165) Miles F. Beaux (25137265) Ronald L. Grimm (1981771) James D. Blakemore (1705078) Biochemistry Biotechnology Chemical Sciences not elsewhere classified Ecology Biological Sciences not elsewhere classified Computational Biology transfer kinetics (< ray photoelectron spectroscopy pyrene groups installed organic chelating group noncovalent interactions enabled molecular coordination complexes laviron analysis shows fast heterogeneous electron extended cathodic polarization computational structural predictions applied actinide chemistry molecular actinide species prototypical uranyl dication bound uranyl species surface molecular species processable organic ligand noncovalent immobilization strategies hybrid molecular strategy 0 </ sup reversibly release uranium desired species strategy relies k </ hybrid ligand >< sup surface control graphite surface defined surface understanding bonding selectively immobilized previously explored monolayer coverages held tightly graphite electrodes enabling electrochemical electronic properties effect originating carbon electrodes assemble quasi Studies of molecular actinide species on conducting surfaces could enable new approaches to understanding bonding, electronic properties, and reactivity, but no strategies have been described to date that afford on-surface control over the composition, structure, redox, or stability of molecular actinide species. Here, a hybrid molecular strategy for uranium capture on surfaces in the form of the prototypical uranyl dication (UO₂²⁺) is described. This strategy relies on a solution-processable organic ligand for uranyl that can be selectively immobilized, enabling electrochemical and spectroscopic studies of well-defined surface-bound uranyl species. Flexible, noncovalent interactions enabled by pyrene groups installed on the periphery of an organic chelating group have been used to assemble quasi-monolayer coverages of the desired species on graphite electrodes. Thermodynamic adsorption isotherm measurements, along with computational structural predictions, demonstrate that uranium is held tightly to the graphite surface in a manner that is enhanced by the presence of uranium in the ligand. In accord with these findings, Laviron analysis shows that the uranium redox on this platform is characterized by fast heterogeneous electron-transfer kinetics (<i>k</i>⁰ = 5 s^–1). X-ray photoelectron spectroscopy (XPS) reveals rather intense U 4f satellite features for the on-surface molecular species, an effect originating in covalency between U and the hybrid ligand but not previously explored for molecular coordination complexes. Extended cathodic polarization can reversibly release uranium from the electrode, showcasing the potential of noncovalent immobilization strategies for studies of fundamental and applied actinide chemistry. 2026-09-29T00:00:00Z Dataset Dataset 10.1021/jacs.6c10561.s002 https://figshare.com/articles/dataset/Capture_and_Characterization_of_High-Valent_Uranium_on_Carbon_Electrodes_with_a_Hybrid_Molecular_Platform/34024051 CC BY-NC 4.0