DOI: 10.1073/pnas.1115769108. Proton-coupled electron transfer at modified electrodes by multiple pathways

Proton-coupled electron transfer at modified electrodes by multiple pathways

10.1073/pnas.1115769108

Crossref journal-article

Proceedings of the National Academy of Sciences

Proceedings of the National Academy of Sciences (341)

Abstract

In single site water or hydrocarbon oxidation catalysis with polypyridyl Ru complexes such as [Ru II (Mebimpy)(bpy)(H 2 O)] 2+ [where bpy is 2,2′-bipyridine, and Mebimpy is 2,6-bis(1-methylbenzimidazol-2-yl)pyridine] 2 , or its surface-bound analog [Ru II (Mebimpy)(4,4 ′ -bis-methlylenephosphonato-2,2 ′ -bipyridine)(OH 2 )] 2+ 2 - PO 3 H 2 , accessing the reactive states, Ru V = O 3+ /Ru IV = O 2+ , at the electrode interface is typically rate limiting. The higher oxidation states are accessible by proton-coupled electron transfer oxidation of aqua precursors, but access at inert electrodes is kinetically inhibited. The inhibition arises from stepwise mechanisms which impose high energy barriers for 1e - intermediates. Oxidation of the Ru III -OH 2+ or forms of 2 - PO 3 H 2 to Ru IV = O 2+ on planar fluoride-doped SnO 2 electrode and in nanostructured films of Sn(IV)-doped In 2 O 3 and TiO 2 has been investigated with a focus on identifying microscopic phenomena. The results provide direct evidence for important roles for the nature of the electrode, temperature, surface coverage, added buffer base, pH, solvent, and solvent H 2 O/D 2 O isotope effects. In the nonaqueous solvent, propylene carbonate, there is evidence for a role for surface-bound phosphonate groups as proton acceptors.

Bibliography

Chen, Z., Vannucci, A. K., Concepcion, J. J., Jurss, J. W., & Meyer, T. J. (2011). Proton-coupled electron transfer at modified electrodes by multiple pathways. Proceedings of the National Academy of Sciences, 108(52).

Authors 5

Zuofeng Chen (first)
Aaron K. Vannucci (additional)
Javier J. Concepcion (additional)
Jonah W. Jurss (additional)
Thomas J. Meyer (additional)

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Dates

Type	When
Created	13 years, 8 months ago (Dec. 13, 2011, 12:15 a.m.)
Deposited	3 years, 4 months ago (April 14, 2022, 9:06 p.m.)
Indexed	4 months, 1 week ago (April 22, 2025, 7:25 a.m.)
Issued	13 years, 8 months ago (Dec. 12, 2011)
Published	13 years, 8 months ago (Dec. 12, 2011)
Published Online	13 years, 8 months ago (Dec. 12, 2011)
Published Print	13 years, 8 months ago (Dec. 27, 2011)

Funders 0

None

BibTeX

@article{Chen_2011, title={Proton-coupled electron transfer at modified electrodes by multiple pathways}, volume={108}, ISSN={1091-6490}, url={http://dx.doi.org/10.1073/pnas.1115769108}, DOI={10.1073/pnas.1115769108}, number={52}, journal={Proceedings of the National Academy of Sciences}, publisher={Proceedings of the National Academy of Sciences}, author={Chen, Zuofeng and Vannucci, Aaron K. and Concepcion, Javier J. and Jurss, Jonah W. and Meyer, Thomas J.}, year={2011}, month=dec }

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