Alkyl Selenide- and Alkyl Thiolate-Functionalized Gold Nanoparticles: Chain Packing and Bond Nature

Chanel K. Yee, Abraham Ulman, Julia D. Ruiz, Atul Parikh, Henry White, Miriam Rafailovich

Research output: Contribution to journalArticle

94 Citations (Scopus)

Abstract

We have studied the effects of relative mole ratios of the reactant precursors in the one-phase synthesis of alkaneselenoate- and alkanethiolate-functionalized gold nanoparticles. Specifically, we prepared a series of dodecaneselenoate (DDSe)- and dodecanethiolate (DDT)-functionalized gold nanoparticles using four different Se/Au and S/Au mole ratios in reactant mixtures at two different reaction temperatures employing three different solvents. In all cases, the synthesis relied on the reduction of H[AuCl 4], in the presence of dodecanethiol (DDT) and didodecyl diselenide (DD2Se2) using lithium triethylborohydride (superhydride) as the reducing agent. Nanoparticle formation, structure, and bonding characteristics were investigated using a combination of transmission electron microscopy, UV absorption spectroscopy, thermogravimetric analysis, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. Passivation by alkyl selenide was more efficient and was characterized by greater chain density and stronger Au-Se bond strength when high ligand/substrate ratios were employed. Particle size was surprisingly uniform in all cases, independent of mole ratio. By contrast, particle size (2-5 nm) was found to increase with increasing mole ratios when the passivating ligand was alkanethiolate, whose chain grafting density increased with increasing mole ratio, fully coincided with the literature. These results can be reconciled in terms of a simple mechanistic scenario wherein the nanoparticle formation using alkanethiolate ligands proceeds via the formation of a "polymer-like" intermediate between the Au ions and the alkanethiolate ligands prior to reduction whereas such an intermediate is not formed when selenoate is used as the binding ligand.

Original languageEnglish (US)
Pages (from-to)9450-9458
Number of pages9
JournalLangmuir
Volume19
Issue number22
DOIs
StatePublished - Oct 28 2003

Fingerprint

selenides
Gold
Ligands
gold
Nanoparticles
nanoparticles
ligands
Particle size
Reducing Agents
Fourier analysis
Reducing agents
synthesis
high strength
Ultraviolet spectroscopy
Absorption spectroscopy
Lithium
Passivation
passivity
Fourier transform infrared spectroscopy
Thermogravimetric analysis

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Colloid and Surface Chemistry

Cite this

Yee, C. K., Ulman, A., Ruiz, J. D., Parikh, A., White, H., & Rafailovich, M. (2003). Alkyl Selenide- and Alkyl Thiolate-Functionalized Gold Nanoparticles: Chain Packing and Bond Nature. Langmuir, 19(22), 9450-9458. https://doi.org/10.1021/la020628i

Alkyl Selenide- and Alkyl Thiolate-Functionalized Gold Nanoparticles : Chain Packing and Bond Nature. / Yee, Chanel K.; Ulman, Abraham; Ruiz, Julia D.; Parikh, Atul; White, Henry; Rafailovich, Miriam.

In: Langmuir, Vol. 19, No. 22, 28.10.2003, p. 9450-9458.

Research output: Contribution to journalArticle

Yee, CK, Ulman, A, Ruiz, JD, Parikh, A, White, H & Rafailovich, M 2003, 'Alkyl Selenide- and Alkyl Thiolate-Functionalized Gold Nanoparticles: Chain Packing and Bond Nature', Langmuir, vol. 19, no. 22, pp. 9450-9458. https://doi.org/10.1021/la020628i
Yee CK, Ulman A, Ruiz JD, Parikh A, White H, Rafailovich M. Alkyl Selenide- and Alkyl Thiolate-Functionalized Gold Nanoparticles: Chain Packing and Bond Nature. Langmuir. 2003 Oct 28;19(22):9450-9458. https://doi.org/10.1021/la020628i
Yee, Chanel K. ; Ulman, Abraham ; Ruiz, Julia D. ; Parikh, Atul ; White, Henry ; Rafailovich, Miriam. / Alkyl Selenide- and Alkyl Thiolate-Functionalized Gold Nanoparticles : Chain Packing and Bond Nature. In: Langmuir. 2003 ; Vol. 19, No. 22. pp. 9450-9458.
@article{69b49233298a4e0d9137bea85a25a503,
title = "Alkyl Selenide- and Alkyl Thiolate-Functionalized Gold Nanoparticles: Chain Packing and Bond Nature",
abstract = "We have studied the effects of relative mole ratios of the reactant precursors in the one-phase synthesis of alkaneselenoate- and alkanethiolate-functionalized gold nanoparticles. Specifically, we prepared a series of dodecaneselenoate (DDSe)- and dodecanethiolate (DDT)-functionalized gold nanoparticles using four different Se/Au and S/Au mole ratios in reactant mixtures at two different reaction temperatures employing three different solvents. In all cases, the synthesis relied on the reduction of H[AuCl 4], in the presence of dodecanethiol (DDT) and didodecyl diselenide (DD2Se2) using lithium triethylborohydride (superhydride) as the reducing agent. Nanoparticle formation, structure, and bonding characteristics were investigated using a combination of transmission electron microscopy, UV absorption spectroscopy, thermogravimetric analysis, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. Passivation by alkyl selenide was more efficient and was characterized by greater chain density and stronger Au-Se bond strength when high ligand/substrate ratios were employed. Particle size was surprisingly uniform in all cases, independent of mole ratio. By contrast, particle size (2-5 nm) was found to increase with increasing mole ratios when the passivating ligand was alkanethiolate, whose chain grafting density increased with increasing mole ratio, fully coincided with the literature. These results can be reconciled in terms of a simple mechanistic scenario wherein the nanoparticle formation using alkanethiolate ligands proceeds via the formation of a {"}polymer-like{"} intermediate between the Au ions and the alkanethiolate ligands prior to reduction whereas such an intermediate is not formed when selenoate is used as the binding ligand.",
author = "Yee, {Chanel K.} and Abraham Ulman and Ruiz, {Julia D.} and Atul Parikh and Henry White and Miriam Rafailovich",
year = "2003",
month = "10",
day = "28",
doi = "10.1021/la020628i",
language = "English (US)",
volume = "19",
pages = "9450--9458",
journal = "Langmuir",
issn = "0743-7463",
publisher = "American Chemical Society",
number = "22",

}

TY - JOUR

T1 - Alkyl Selenide- and Alkyl Thiolate-Functionalized Gold Nanoparticles

T2 - Chain Packing and Bond Nature

AU - Yee, Chanel K.

AU - Ulman, Abraham

AU - Ruiz, Julia D.

AU - Parikh, Atul

AU - White, Henry

AU - Rafailovich, Miriam

PY - 2003/10/28

Y1 - 2003/10/28

N2 - We have studied the effects of relative mole ratios of the reactant precursors in the one-phase synthesis of alkaneselenoate- and alkanethiolate-functionalized gold nanoparticles. Specifically, we prepared a series of dodecaneselenoate (DDSe)- and dodecanethiolate (DDT)-functionalized gold nanoparticles using four different Se/Au and S/Au mole ratios in reactant mixtures at two different reaction temperatures employing three different solvents. In all cases, the synthesis relied on the reduction of H[AuCl 4], in the presence of dodecanethiol (DDT) and didodecyl diselenide (DD2Se2) using lithium triethylborohydride (superhydride) as the reducing agent. Nanoparticle formation, structure, and bonding characteristics were investigated using a combination of transmission electron microscopy, UV absorption spectroscopy, thermogravimetric analysis, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. Passivation by alkyl selenide was more efficient and was characterized by greater chain density and stronger Au-Se bond strength when high ligand/substrate ratios were employed. Particle size was surprisingly uniform in all cases, independent of mole ratio. By contrast, particle size (2-5 nm) was found to increase with increasing mole ratios when the passivating ligand was alkanethiolate, whose chain grafting density increased with increasing mole ratio, fully coincided with the literature. These results can be reconciled in terms of a simple mechanistic scenario wherein the nanoparticle formation using alkanethiolate ligands proceeds via the formation of a "polymer-like" intermediate between the Au ions and the alkanethiolate ligands prior to reduction whereas such an intermediate is not formed when selenoate is used as the binding ligand.

AB - We have studied the effects of relative mole ratios of the reactant precursors in the one-phase synthesis of alkaneselenoate- and alkanethiolate-functionalized gold nanoparticles. Specifically, we prepared a series of dodecaneselenoate (DDSe)- and dodecanethiolate (DDT)-functionalized gold nanoparticles using four different Se/Au and S/Au mole ratios in reactant mixtures at two different reaction temperatures employing three different solvents. In all cases, the synthesis relied on the reduction of H[AuCl 4], in the presence of dodecanethiol (DDT) and didodecyl diselenide (DD2Se2) using lithium triethylborohydride (superhydride) as the reducing agent. Nanoparticle formation, structure, and bonding characteristics were investigated using a combination of transmission electron microscopy, UV absorption spectroscopy, thermogravimetric analysis, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. Passivation by alkyl selenide was more efficient and was characterized by greater chain density and stronger Au-Se bond strength when high ligand/substrate ratios were employed. Particle size was surprisingly uniform in all cases, independent of mole ratio. By contrast, particle size (2-5 nm) was found to increase with increasing mole ratios when the passivating ligand was alkanethiolate, whose chain grafting density increased with increasing mole ratio, fully coincided with the literature. These results can be reconciled in terms of a simple mechanistic scenario wherein the nanoparticle formation using alkanethiolate ligands proceeds via the formation of a "polymer-like" intermediate between the Au ions and the alkanethiolate ligands prior to reduction whereas such an intermediate is not formed when selenoate is used as the binding ligand.

UR - http://www.scopus.com/inward/record.url?scp=0242491817&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0242491817&partnerID=8YFLogxK

U2 - 10.1021/la020628i

DO - 10.1021/la020628i

M3 - Article

AN - SCOPUS:0242491817

VL - 19

SP - 9450

EP - 9458

JO - Langmuir

JF - Langmuir

SN - 0743-7463

IS - 22

ER -