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

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. 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.

Authors:
 [1];  [2];  [3];  [4];  [5];  [5];  [4];  [6];  [1]
+ Show Author Affiliations
  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)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1214336
Grant/Contract Number:  
AC02-06CH11357; FG02-03ER15476; FG02-05ER15688; CBET-1033334; DMR-1437355
Resource Type:
Accepted Manuscript
Journal Name:
Chemical Science
Additional Journal Information:
Journal Name: Chemical Science; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY

Citation Formats

Briggs, Beverly D., Bedford, Nicholas M., Seifert, Soenke, Koerner, Hilmar, Ramezani-Dakhel, Hadi, Heinz, Hendrik, Naik, Rajesh R., Frenkel, Anatoly I., and Knecht, Marc R. Atomic-scale identification of Pd leaching in nanoparticle catalyzed C–C coupling: Effects of particle surface disorder. United States: N. p., 2015. Web. doi:10.1039/C5SC01424G.
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Briggs, Beverly D., Bedford, Nicholas M., Seifert, Soenke, Koerner, Hilmar, Ramezani-Dakhel, Hadi, Heinz, Hendrik, Naik, Rajesh R., Frenkel, Anatoly I., & Knecht, Marc R. Atomic-scale identification of Pd leaching in nanoparticle catalyzed C–C coupling: Effects of particle surface disorder. United States. https://doi.org/10.1039/C5SC01424G
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Briggs, Beverly D., Bedford, Nicholas M., Seifert, Soenke, Koerner, Hilmar, Ramezani-Dakhel, Hadi, Heinz, Hendrik, Naik, Rajesh R., Frenkel, Anatoly I., and Knecht, Marc R. Thu . "Atomic-scale identification of Pd leaching in nanoparticle catalyzed C–C coupling: Effects of particle surface disorder". United States. https://doi.org/10.1039/C5SC01424G. https://www.osti.gov/servlets/purl/1214336.
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@article{osti_1214336,
title = {Atomic-scale identification of Pd leaching in nanoparticle catalyzed C–C coupling: Effects of particle surface disorder},
author = {Briggs, Beverly D. and Bedford, Nicholas M. and Seifert, Soenke and Koerner, Hilmar and Ramezani-Dakhel, Hadi and Heinz, Hendrik and Naik, Rajesh R. and Frenkel, Anatoly I. and Knecht, Marc R.},
abstractNote = {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.},
doi = {10.1039/C5SC01424G},
journal = {Chemical Science},
number = ,
volume = ,
place = {United States},
year = {Thu Jul 23 00:00:00 EDT 2015},
month = {Thu Jul 23 00:00:00 EDT 2015}
}
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https://doi.org/10.1039/C5SC01424G
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