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

Journal Article · · Chemical Science
DOI:https://doi.org/10.1039/C5SC01424G· OSTI ID:1214336
 [1];  [2];  [3];  [4];  [5];  [5];  [4];  [6];  [1]
  1. Univ. of Miami, Coral Gables, FL (United States)
  2. Air Force Research Lab. (AFRL), Wright-Patterson AFB, OH (United States); Univ. of Miami, Coral Gables, FL (United States); National Inst. of Standards and Technology (NIST), Boulder, CO (United States)
  3. Argonne National Lab. (ANL), Argonne, IL (United States)
  4. Air Force Research Lab. (AFRL), Wright-Patterson AFB, OH (United States)
  5. Univ. of Akron, Akron, OH (United States)
  6. Yeshiva Univ., New York, NY (United States)
+ Show Author Affiliations

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. Thus, 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.

Research Organization:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-06CH11357; FG02-03ER15476; FG02-05ER15688; CBET-1033334; DMR-1437355
OSTI ID:
1214336
Journal Information:
Chemical Science, Journal Name: Chemical Science; ISSN 2041-6520
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 37 works
Citation information provided by
Web of Science

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Cited By (4)

Polyacrylonitrile Interactions with Carbon Nanotubes in Solution: Conformations and Binding as a Function of Solvent, Temperature, and Concentration journal September 2019
Metal Ionic Liquids Produce Metal‐Dispersed Carbon‐Nitrogen Networks for Efficient CO 2 Electroreduction journal June 2019
Solvent effects in palladium catalysed cross-coupling reactions journal January 2019
Reaction mechanisms at the homogeneous–heterogeneous frontier: insights from first-principles studies on ligand-decorated metal nanoparticles journal January 2019

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