Atomic-scale identification of Pd leaching in nanoparticle catalyzed C-C coupling: effects of particle surface disorder

Beverly D. Briggs, Nicholas M. Bedford, Soenke Seifert, Hilmar Koerner, Hadi Ramezani-Dakhel, Hendrik Heinz, Rajesh R. Naik, Anatoly I. Frenkel, Marc Knecht

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Abstract

C-C coupling reactions are of great importance in the synthesis of numerous organic compounds, where Pd nanoparticle catalyzed systems represent new materials to efficiently drive these reactions. Despite their pervasive utility, the catalytic mechanism of these particle-based reactions remains highly contested. Herein we present evidence of an atom leaching mechanism for Stille coupling under aqueous conditions using peptide-capped Pd nanoparticles. EXAFS analysis revealed Pd coordination changes in the nanoparticle consistent with Pd atom abstraction, where sizing analysis by SAXS confirmed particle size changes associated with a leaching process. It is likely that recently discovered highly disordered surface Pd atoms are the favored catalytic active sites and are leached during oxidative addition, resulting in smaller particles. Probing the mechanism of nanoparticle-driven C-C coupling reactions through structural analyses provides fundamental information concerning these active sites and their reactivity at the atomic-scale, which can be used to improve catalytic performance to meet important sustainability goals.

Original languageEnglish (US)
Pages (from-to)6413-6419
Number of pages7
JournalChemical Science
Volume6
Issue number11
DOIs
StatePublished - Jul 23 2015

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ASJC Scopus subject areas

  • Chemistry(all)

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Briggs, B. D., Bedford, N. M., Seifert, S., Koerner, H., Ramezani-Dakhel, H., Heinz, H., Naik, R. R., Frenkel, A. I., & Knecht, M. (2015). Atomic-scale identification of Pd leaching in nanoparticle catalyzed C-C coupling: effects of particle surface disorder. Chemical Science, 6(11), 6413-6419. https://doi.org/10.1039/c5sc01424g