skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Polyvinylpyrrolidone-induced anisotropic growth of gold nanoprisms in plasmon-driven synthesis

Abstract

After more than a decade, it is still unknown whether the plasmon-mediated growth of silver nanostructures can be extended to the synthesis of other noble metals, as the molecular mechanisms governing the growth process remain elusive. Herein, we demonstrate the plasmon-driven synthesis of gold nanoprisms and elucidate the details of the photochemical growth mechanism at the single-nanoparticle level. Our investigation reveals that the surfactant polyvinylpyrrolidone preferentially adsorbs along the nanoprism perimeter and serves as a photochemical relay to direct the anisotropic growth of gold nanoprisms. This discovery confers a unique function to polyvinylpyrrolidone that is fundamentally diferent from its widely accepted role as a crystal-face-blocking ligand. Additionally, we find that nanocrystal twinning exerts a profound influence on the kinetics of this photochemical process by controlling the transport of plasmon-generated hot electrons to polyvinylpyrrolidone. These insights establish a molecular-level description of the underlying mechanisms regulating the plasmon-driven synthesis of gold nanoprisms.

Authors:
; ; ; ; ; ; ; ; ; ; ; ; ORCiD logo; ORCiD logo; ;
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
1290403
Report Number(s):
PNNL-SA-107281
Journal ID: ISSN 1476-1122; 40065; KP1704020
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Nature Materials; Journal Volume: 15; Journal Issue: 8
Country of Publication:
United States
Language:
English
Subject:
Plasmon; gold; nanoprisms; photocatalysis; silver; nanocrystal; photochemistry; Environmental Molecular Sciences Laboratory

Citation Formats

Zhai, Yueming, DuChene, Joseph S., Wang, Yi-Chung, Qiu, Jingjing, Johnston-Peck, Aaron C., You, Bo, Guo, Wenxiao, DiCiaccio, Benedetto, Qian, Kun, Zhao, Evan W., Ooi, Frances, Hu, Dehong, Su, Dong, Stach, Eric A., Zhu, Zihua, and Wei, Wei David. Polyvinylpyrrolidone-induced anisotropic growth of gold nanoprisms in plasmon-driven synthesis. United States: N. p., 2016. Web. doi:10.1038/nmat4683.
Zhai, Yueming, DuChene, Joseph S., Wang, Yi-Chung, Qiu, Jingjing, Johnston-Peck, Aaron C., You, Bo, Guo, Wenxiao, DiCiaccio, Benedetto, Qian, Kun, Zhao, Evan W., Ooi, Frances, Hu, Dehong, Su, Dong, Stach, Eric A., Zhu, Zihua, & Wei, Wei David. Polyvinylpyrrolidone-induced anisotropic growth of gold nanoprisms in plasmon-driven synthesis. United States. doi:10.1038/nmat4683.
Zhai, Yueming, DuChene, Joseph S., Wang, Yi-Chung, Qiu, Jingjing, Johnston-Peck, Aaron C., You, Bo, Guo, Wenxiao, DiCiaccio, Benedetto, Qian, Kun, Zhao, Evan W., Ooi, Frances, Hu, Dehong, Su, Dong, Stach, Eric A., Zhu, Zihua, and Wei, Wei David. 2016. "Polyvinylpyrrolidone-induced anisotropic growth of gold nanoprisms in plasmon-driven synthesis". United States. doi:10.1038/nmat4683.
@article{osti_1290403,
title = {Polyvinylpyrrolidone-induced anisotropic growth of gold nanoprisms in plasmon-driven synthesis},
author = {Zhai, Yueming and DuChene, Joseph S. and Wang, Yi-Chung and Qiu, Jingjing and Johnston-Peck, Aaron C. and You, Bo and Guo, Wenxiao and DiCiaccio, Benedetto and Qian, Kun and Zhao, Evan W. and Ooi, Frances and Hu, Dehong and Su, Dong and Stach, Eric A. and Zhu, Zihua and Wei, Wei David},
abstractNote = {After more than a decade, it is still unknown whether the plasmon-mediated growth of silver nanostructures can be extended to the synthesis of other noble metals, as the molecular mechanisms governing the growth process remain elusive. Herein, we demonstrate the plasmon-driven synthesis of gold nanoprisms and elucidate the details of the photochemical growth mechanism at the single-nanoparticle level. Our investigation reveals that the surfactant polyvinylpyrrolidone preferentially adsorbs along the nanoprism perimeter and serves as a photochemical relay to direct the anisotropic growth of gold nanoprisms. This discovery confers a unique function to polyvinylpyrrolidone that is fundamentally diferent from its widely accepted role as a crystal-face-blocking ligand. Additionally, we find that nanocrystal twinning exerts a profound influence on the kinetics of this photochemical process by controlling the transport of plasmon-generated hot electrons to polyvinylpyrrolidone. These insights establish a molecular-level description of the underlying mechanisms regulating the plasmon-driven synthesis of gold nanoprisms.},
doi = {10.1038/nmat4683},
journal = {Nature Materials},
number = 8,
volume = 15,
place = {United States},
year = 2016,
month = 7
}
  • After more than a decade, it is still unknown whether the plasmon-mediated growth of silver nanostructures can be extended to the synthesis of other noble metals, as the molecular mechanisms governing the growth process remain elusive. In this paper, we demonstrate the plasmon-driven synthesis of gold nanoprisms and elucidate the details of the photochemical growth mechanism at the single-nanoparticle level. Our investigation reveals that the surfactant polyvinylpyrrolidone preferentially adsorbs along the nanoprism perimeter and serves as a photochemical relay to direct the anisotropic growth of gold nanoprisms. This discovery confers a unique function to polyvinylpyrrolidone that is fundamentally different frommore » its widely accepted role as a crystal-face-blocking ligand. Additionally, we find that nanocrystal twinning exerts a profound influence on the kinetics of this photochemical process by controlling the transport of plasmon-generated hot electrons to polyvinylpyrrolidone. Finally, these insights establish a molecular-level description of the underlying mechanisms regulating the plasmon-driven synthesis of gold nanoprisms.« less
  • The synthesis of silica-encapsulated gold nanoprisms (AuNP@SiO{sub 2}) is reported. These nanostructures are remarkably stable and resist etching and rounding of their sharp vertices (a process which begins on unprotected Au nanoprisms in a matter of hours) in many chemical environments (water, ethanol, dimethyl sulfoxide, and tetrahydrofuran). The silica growth process has been studied and occurs according to the shape of the particle, where the edges of the prisms are coated less than the large triangular facets. The AuNP@SiO{sub 2} particles have dielectric sensitivities that are as large as 737 nm/RIU. Discrete dipole approximation calculations have been used to investigatemore » the effects of this variable thickness on dielectric sensitivity and show that for the anisotropic coatings it is significantly higher than for a uniform coating due to the location of electromagnetic hot spots near the tips and edges of the particles. These calculations also show that dipole resonances exhibit greater sensitivity than multipole resonances, due to the shorter range of the multipolar electromagnetic fields.« less