Journal
JOURNAL OF PHYSICAL CHEMISTRY C
Volume 113, Issue 37, Pages 16387-16393Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jp905141h
Keywords
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Funding
- U.S. Department of Energy
- Basic Energy Sciences [DE-FG02-05ER46235, DE-FG36-06G01G016029]
- National Science Foundation [NSF 0313661]
- W.M. Keck Foundation
- Department of Defense
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Triphenylphosphine (PPh3)-capped 1.8 nm diameter gold nanoparticles (AuNPs) are characterized by a combination of H-1, H-2, and P-31 solution- and solid-state NMR. The P-31{H-1} NMR resonance associated with the surface-bound PPh3 is clearly identified and is present as a broad peak centered at 56 ppm. P-31 abd H-1 hole burning NMR experiments show that the line broadening associated with the surface-bound PPh3 is primarily due to a variety of different chemical shift environments at the surface of the nanoparticles. The surface bound PPh3 can be displaced with either d(15)-PPh3 or Au(d(15)-PPh3)Cl in CD2Cl2 solution. In both cases, exchange results in loss of Au(PPh3)Cl from the nanoparticle surface, with no evidence for loss of the PPh3 ligand alone, Solution-state NMR was used to determine the room temperature rate constants for these exchange processes, with values of 0.17 and 0.20 min(-1), respectively. Thus, essentially the same rate is observed for displacement of Au(PPh3)Cl from the surface with either d(15)-PPh3 or Au(d(15)-PPh3)Cl. The observed P-31 chemical shift of surface-bound PPh3 is consistent with mixed valence Au(0) and Au(I) at the nanoparticle surfaces, suggesting the presence of surface-bound Au complexes.
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