Solvent molecules form surface redox mediators in situ and cocatalyze O2reduction on Pd

Jason S. Adams, Ashwin Chemburkar, Pranjali Priyadarshini, Tomas Ricciardulli, Yubing Lu, Vineet Maliekkal, Abinaya Sampath, Stuart Winikoff, Ayman M. Karim, Matthew Neurock, David W. Flaherty

Research output: Contribution to journalArticlepeer-review

Abstract

Solvent molecules influence the reactions of molecular hydrogen and oxygen on palladium nanoparticles. Organic solvents activate to form reactive surface intermediates that mediate oxygen reduction through pathways distinct from reactions in pure water. Kinetic measurements and ab initio quantum chemical calculations indicate that methanol and water cocatalyze oxygen reduction by facilitating proton-electron transfer reactions. Methanol generates hydroxymethyl intermediates on palladium surfaces that efficiently transfer protons and electrons to oxygen to form hydrogen peroxide and formaldehyde. Formaldehyde subsequently oxidizes hydrogen to regenerate hydroxymethyl. Water, on the other hand, heterolytically oxidizes hydrogen to produce hydronium ions and electrons that reduce oxygen. These findings suggest that reactions of solvent molecules at solid-liquid interfaces can generate redox mediators in situ and provide opportunities to substantially increase rates and selectivities for catalytic reactions.

Original languageEnglish (US)
Pages (from-to)626-632
Number of pages7
JournalScience
Volume371
Issue number6529
DOIs
StatePublished - Feb 5 2021

Bibliographical note

Publisher Copyright:
© 2021 American Association for the Advancement of Science. All rights reserved.

Copyright:
Copyright 2021 Elsevier B.V., All rights reserved.

PubMed: MeSH publication types

  • Journal Article
  • Research Support, Non-U.S. Gov't

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