Inverse kinetic isotope effects in the oxygen reduction reaction at platinum single crystals
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http://hdl.handle.net/10045/129283
Title: | Inverse kinetic isotope effects in the oxygen reduction reaction at platinum single crystals |
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Authors: | Yang, Yao | Agarwal, Rishi G. | Hutchison, Phillips | Rizo, Rubén | Soudackov, Alexander V. | Lu, Xinyao | Herrero, Enrique | Feliu, Juan M. | Hammes-Schiffer, Sharon | Mayer, James M. | Abruña, Héctor D. |
Research Group/s: | Electroquímica de Superficies |
Center, Department or Service: | Universidad de Alicante. Departamento de Química Física | Universidad de Alicante. Instituto Universitario de Electroquímica |
Keywords: | Oxygen reduction reaction | Platinum single crystals | Kinetic isotope effects |
Issue Date: | 10-Nov-2022 |
Publisher: | Springer Nature |
Citation: | Nature Chemistry. 2023, 15: 271-277. https://doi.org/10.1038/s41557-022-01084-y |
Abstract: | Although the oxygen reduction reaction (ORR) involves multiple proton-coupled electron transfer processes, early studies reported the absence of kinetic isotope effects (KIEs) on polycrystalline platinum, probably due to the use of unpurified D2O. Here we developed a methodology to prepare ultra-pure D2O, which is indispensable for reliably investigating extremely surface-sensitive platinum single crystals. We find that Pt(111) exhibits much higher ORR activity in D2O than in H2O, with potential-dependent inverse KIEs of ~0.5, whereas Pt(100) and Pt(110) exhibit potential-independent inverse KIEs of ~0.8. Such inverse KIEs are closely correlated to the lower *OD coverage and weakened *OD binding strength relative to *OH, which, based on theoretical calculations, are attributed to the differences in their zero-point energies. This study suggests that the competing adsorption between *OH/*OD and *O2 probably plays an important role in the ORR rate-determining steps that involve a chemical step preceding an electrochemical step (CE mechanism). |
Sponsor: | This work was primarily supported by the Center for Alkaline-Based Energy Solutions (CABES), part of the Energy Frontier Research Center (EFRC) program supported by the US Department of Energy, under grant no. DE-SC-0019445. R.G.A. and J.M.M. acknowledge funding from the Molecular Electrochemistry Multi-University Research Initiative (MURI) supported by the US Air Force Office of Scientific Research, under grant nos. FA9550-18-1-0420; the US National Science Foundation award no. CHE-1904813 for support; and a supplement that supported R.G.A’s visit to the Koper laboratory in Leiden. P.H. and R.G. A acknowledge support from National Science Foundation Graduate Research Fellowships. R.R, E.H and J.M.F. acknowledge funding from Ministerio de Ciencia e Innovación (Spain) under grant no. PID2019-105653GB-I00. R.G.A. would also like to thank M. Koper and the members of his laboratory for their hospitality during his short stay in Leiden, and for introducing him to the challenges of preparing high-purity D2O. |
URI: | http://hdl.handle.net/10045/129283 |
ISSN: | 1755-4330 (Print) | 1755-4349 (Online) |
DOI: | 10.1038/s41557-022-01084-y |
Language: | eng |
Type: | info:eu-repo/semantics/article |
Rights: | © 2022 Springer Nature Limited |
Peer Review: | si |
Publisher version: | https://doi.org/10.1038/s41557-022-01084-y |
Appears in Collections: | INV - EQSUP - Artículos de Revistas |
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File | Description | Size | Format | |
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Yang_etal_2023_NatChem_final.pdf | Versión final (acceso restringido) | 2,45 MB | Adobe PDF | Open Request a copy |
Yang_etal_2023_NatChem_preprint.pdf | Preprint (acceso abierto) | 1,1 MB | Adobe PDF | Open Preview |
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