Materials Seminar – Prof. James Mayer (Yale University)

Title: Redox Reactions of Colloidal Nanoparticles: Atom Transfers and Surface Heterogeneity

Abstract: The formation and cleavage of surface–H and surface–O chemical bonds are central to many processes at metal and semiconductor interfaces. This seminar will present recent studies of the stoichiometry, thermochemistry, and reactivity of hydrogen atoms on colloidal cerium oxide, iridium oxide, and gold nanoparticles. Connections will be made to NiO electrodes, high-surface-area cobalt phosphide (CoP), and colloidal TiO₂. These diverse materials show surprising similarities. They all react by proton-coupled electron transfer (PCET) / hydrogen atom transfer (HAT)—related processes because a hydrogen atom is a proton plus an electron. Most of these materials bind substantial amounts of H, with a range of surface–H bond dissociation free energies (broad binding isotherms). The presence of surface H and its range of thermochemistry have substantial effects on surface reactivity. These effects seem to carry over to oxygen atom transfer reactions as well.

Bio: James M. Mayer (Jim) was born and raised New York City. He attended the United Nations International School, Hunter College (CUNY), and Harvard University. He received his PhD in 1982 from Caltech working with Professor John Bercaw. After 2 years as a visiting scientist in the Central Research Department of the DuPont Company, he joined the faculty at the University of Washington, where he taught for 30 years. He moved to Yale University in 2014, where he is now the Charlotte Fitch Roberts Professor of Chemistry. His research is in the fundamental properties of chemical reactivity, both of molecules in solution and of materials. His work centers around proton-coupled electron transfer in coordination chemistry, physical organic chemistry, catalysis and electrocatalysis, nano- and interfacial chemistry, and bioinorganic and organometallic chemistry.

Professor Mayer is a fellow of the American Association for the Advancement of Science, the American Chemical Society, and the American Academy of Arts and Sciences. He served as an associate editor of the journal Inorganic Chemistry and is a recipient of the ACS Award in Inorganic Chemistry. Recent overview articles include:

• “Free Energies of Proton-Coupled Electron Transfer Reagents and Their Applications” Agarwal,* R. G.; Coste, S. C.; Groff, B. D.; Heuer, A. M.; Noh, H.; Parada, G. A.; Wise, C. F.; Nichols, E. M.; Warren, J. J.; Mayer, J. M.* Rev. 2022, 122, 1-49.
  DOI: 10.1021/acs.chemrev.1c00521
• “Bonds over Electrons: Proton Coupled Electron Transfer at Solid-Solution Interfaces” Mayer, J. M., invited Perspective, Am. Chem. Soc. 2023, 145, 7050–7064. DOI: 10.1021/jacs.2c10212
• “A Continuum of Proton-Coupled Electron Transfer Reactivity” Darcy, J. W.^†, Koronkiewicz, B.^†; Parada, G. A.; Mayer, J. M. Acc. Chem. Res. 2018, 51, 2391–2399.
  DOI: 10.1021/acs.accounts.8b00319

Keywords: Interfacial reactions, Proton-coupled electron transfer, Hydrogen atom transfer, Nanoparticles, Thermochemistry, Kinetics

Host: Prof. Marcel Schreier