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Title: Solvent-mediated plasmon-tuning in a gold nanoparticle-poly(ionic liquid) composite.

Abstract

The design, synthesis, and characterization of a hierarchically ordered composite whose structure and optical properties can be reversibly switched by adjustment of solvent conditions are described. Solvent-induced swelling and de-swelling is shown to provide control over the internal packing arrangement and hence, optical properties of in situ synthesized metal nanoparticles. Specifically, a gold-nanoparticle-containing ionic-liquid-derived polymer is synthesized in a single step by UV irradiation of a metal-ion-precursor-doped, self-assembled ionic liquid gel, 1-decyl-3-vinylimidazolium chloride. Small-angle X-ray scattering (SAXS) studies indicate that in the de-swollen state, the freestanding polymer adopts a perforated lamellar structure. Optical spectroscopy of the dried composite reveals plasmon resonances positioned in the near-IR. Strong particle-particle interactions arise from matrix-promoted formation of aggregated 1D clusters or chains of gold nanoparticles. Upon swelling in alcohol, the composite undergoes a structural conversion to a disordered structure, which is accompanied by a color change from purple to pale pink and a shift in the surface plasmon resonance to 527 nm, consistent with isolated, non-interacting particles. These results demonstrate the far-field tuning of the plasmonic spectrum of gold nanoparticles by solvent-mediated changes in its encapsulating matrix, offering a straightforward, low-cost strategy for the fabrication of nanophotonic materials.

Authors:
; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
962534
Report Number(s):
ANL/MSD/JA-56548
Journal ID: ISSN 1616-301X; TRN: US0902879
DOE Contract Number:
DE-AC02-06CH11357
Resource Type:
Journal Article
Resource Relation:
Journal Name: Adv. Functional Mater.; Journal Volume: 17; Journal Issue: 8 ; May 2007
Country of Publication:
United States
Language:
ENGLISH
Subject:
72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS; COLOR; DESIGN; FABRICATION; GOLD; IRRADIATION; OPTICAL PROPERTIES; PLASMONS; POLYMERS; RESONANCE; SCATTERING; SOLVENTS; SPECTROSCOPY; SWELLING; SYNTHESIS; TUNING

Citation Formats

Batra, D., Seifert, S., Varela, L., and Firestone, M. A. Solvent-mediated plasmon-tuning in a gold nanoparticle-poly(ionic liquid) composite.. United States: N. p., 2007. Web. doi:10.1002/adfm.200600797.
Batra, D., Seifert, S., Varela, L., & Firestone, M. A. Solvent-mediated plasmon-tuning in a gold nanoparticle-poly(ionic liquid) composite.. United States. doi:10.1002/adfm.200600797.
Batra, D., Seifert, S., Varela, L., and Firestone, M. A. Tue . "Solvent-mediated plasmon-tuning in a gold nanoparticle-poly(ionic liquid) composite.". United States. doi:10.1002/adfm.200600797.
@article{osti_962534,
title = {Solvent-mediated plasmon-tuning in a gold nanoparticle-poly(ionic liquid) composite.},
author = {Batra, D. and Seifert, S. and Varela, L. and Firestone, M. A.},
abstractNote = {The design, synthesis, and characterization of a hierarchically ordered composite whose structure and optical properties can be reversibly switched by adjustment of solvent conditions are described. Solvent-induced swelling and de-swelling is shown to provide control over the internal packing arrangement and hence, optical properties of in situ synthesized metal nanoparticles. Specifically, a gold-nanoparticle-containing ionic-liquid-derived polymer is synthesized in a single step by UV irradiation of a metal-ion-precursor-doped, self-assembled ionic liquid gel, 1-decyl-3-vinylimidazolium chloride. Small-angle X-ray scattering (SAXS) studies indicate that in the de-swollen state, the freestanding polymer adopts a perforated lamellar structure. Optical spectroscopy of the dried composite reveals plasmon resonances positioned in the near-IR. Strong particle-particle interactions arise from matrix-promoted formation of aggregated 1D clusters or chains of gold nanoparticles. Upon swelling in alcohol, the composite undergoes a structural conversion to a disordered structure, which is accompanied by a color change from purple to pale pink and a shift in the surface plasmon resonance to 527 nm, consistent with isolated, non-interacting particles. These results demonstrate the far-field tuning of the plasmonic spectrum of gold nanoparticles by solvent-mediated changes in its encapsulating matrix, offering a straightforward, low-cost strategy for the fabrication of nanophotonic materials.},
doi = {10.1002/adfm.200600797},
journal = {Adv. Functional Mater.},
number = 8 ; May 2007,
volume = 17,
place = {United States},
year = {Tue May 01 00:00:00 EDT 2007},
month = {Tue May 01 00:00:00 EDT 2007}
}
  • Glucose oxidase (GOx) adsorbed on an ionic liquid-derived polymer containing internally organized columns of Au nanoparticles exhibits direct electron transfer and bioelectrocatalytic properties towards the oxidation of glucose. The cationic poly(ionic liquid) provides an ideal substrate for the electrostatic immobilization of GOx. The encapsulated Au nanoparticles serve to both promote the direct electron transfer with the recessed enzyme redox centers and impart electronic conduction to the composite, allowing it to function as an electrode for electrochemical detection.
  • Six vinyl-based, imidazolium room-temperature ionic liquid (RTIL) monomers were synthesized and photopolymerized to form dense poly(RTIL) membranes. The effect of polymer backbone (i.e., poly(ethylene), poly(styrene), and poly(acrylate)) and functional cationic substituent (e.g., alkyl, fluoroalkyl, oligo(ethylene glycol), and disiloxane) on ideal CO2/N-2 and CO2/CH4 membrane separation performance was investigated. The vinyl-based poly(RTIL)s were found to be generally less CO2-selective compared to analogous styrene- and acrylate-based poly(RTIL)s. The CO2 permeability of n-hexyl-(69 barrers) and disiloxane- (130 barrers) substituted vinyl-based poly(RTIL)s were found to be exceptionally larger than that of previously studied styrene and acrylate poly(RTIL)s. The CO2 selectivity of oligo(ethylene glycol)-functionalized vinylmore » poly(RTIL)s was enhanced, and the CO2 permeability was reduced when compared to the n-hexyl-substituted vinyl-based poly(RTIL). Nominal improvement in CO2/CH4 selectivity was observed upon fluorination of the n-hexyl vinyl-based poly(RTIL), with no observed change in CO2 permeability. However, rather dramatic improvements in both CO2 permeability and selectivity were observed upon blending 20 mol % RTIL (emim Tf2N) into the n-hexyl- and disiloxane-functionalized vinyl poly(RTIL)s to form solid liquid composite films.« less
  • The transport properties of self-supporting Au nanoparticle-ionic liquid-derived polymer composites were characterized. Topographic AFM images confirm the perforated lamellar composite architecture determined by small-angle X-ray scattering (SAXS) and further show that the in situ synthesized Au nanoparticles are localized within the hydrophilic (water) domains of the structure. At low Au nanoparticle content, the images reveal incomplete packing of spherical particles (i.e., voids) within these columns. The confinement and organization of the Au nanoparticles within the hydrophilic columns give rise to a large manifold of optical resonances in the near-IR region. The bulk composite conductivity, R{sub b}, was determined by acmore » electrochemical impedance spectroscopy (EIS) for samples prepared with increasing Au{sup 3+} content over a frequency range of 10 Hz to 1 MHz. A 100-fold increase was observed in the bulk conductivity at room temperature for composites prepared with the highest amount of Au{sup 3+} (1.58 {+-} 0.065 {micro}mol) versus the no Au composite, with the former reaching a value of 1.3 x 10{sup -4} S cm{sup -1} at 25 C. The temperature dependence of the conductivity recorded over this range was well-modeled by the Arrhenius equation. EIS studies on samples containing the highest Au nanoparticle content over a broader range of frequencies (2 x 10{sup -2} Hz to 5 x 10{sup 5} Hz) identified a low frequency component ascribed to electronic conduction. Electronic conduction due to aggregated Au nanoparticles was further confirmed by dc conductivity measurements. This work identifies a nanostructured composite that exhibits both ionic transport through the polymeric ionic liquid and electronic conduction from the organized encapsulated columns of Au nanoparticles.« less
  • No abstract prepared.