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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 Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (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
Journal Name:
Nature Materials
Additional Journal Information:
Journal Volume: 15; Journal Issue: 8; Journal ID: ISSN 1476-1122
Publisher:
Nature Publishing Group
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. Mon . "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},
issn = {1476-1122},
number = 8,
volume = 15,
place = {United States},
year = {2016},
month = {7}
}

Works referenced in this record:

Photoinduced Conversion of Silver Nanospheres to Nanoprisms
journal, November 2001


Plasmon-Mediated Syntheses of Metallic Nanostructures
journal, November 2013

  • Langille, Mark R.; Personick, Michelle L.; Mirkin, Chad A.
  • Angewandte Chemie International Edition, Vol. 52, Issue 52
  • DOI: 10.1002/anie.201301875

Plasmon-Driven Synthesis of Triangular Core–Shell Nanoprisms from Gold Seeds
journal, November 2007

  • Xue, Can; Millstone, Jill E.; Li, Shuyou
  • Angewandte Chemie International Edition, Vol. 46, Issue 44
  • DOI: 10.1002/anie.200703185

Silver Nanodisk Growth by Surface Plasmon Enhanced Photoreduction of Adsorbed [Ag + ]
journal, November 2003

  • Maillard, Mathieu; Huang, Pinray; Brus, Louis
  • Nano Letters, Vol. 3, Issue 11
  • DOI: 10.1021/nl034666d

Mechanistic Study of Photomediated Triangular Silver Nanoprism Growth
journal, July 2008

  • Xue, Can; Métraux, Gabriella S.; Millstone, Jill E.
  • Journal of the American Chemical Society, Vol. 130, Issue 26
  • DOI: 10.1021/ja8005258

Photovoltage Mechanism for Room Light Conversion of Citrate Stabilized Silver Nanocrystal Seeds to Large Nanoprisms
journal, July 2008

  • Wu, Xiaomu; Redmond, Peter L.; Liu, Haitao
  • Journal of the American Chemical Society, Vol. 130, Issue 29
  • DOI: 10.1021/ja8018669

Stepwise Evolution of Spherical Seeds into 20-Fold Twinned Icosahedra
journal, August 2012


Photochemistry on Metal Nanoparticles
journal, October 2006

  • Watanabe, Kazuo; Menzel, Dietrich; Nilius, Niklas
  • Chemical Reviews, Vol. 106, Issue 10
  • DOI: 10.1021/cr050167g

QM/MM Study of Photoinduced Reduction of a Tetrahedral Ag 20 + Cluster by a Ag Atom
journal, December 2012

  • Chen, Hanning; Ratner, Mark A.; Schatz, George C.
  • The Journal of Physical Chemistry C, Vol. 118, Issue 4
  • DOI: 10.1021/jp310149y

Photovoltage and Photocatalyzed Growth in Citrate-Stabilized Colloidal Silver Nanocrystals
journal, June 2007

  • Redmond, Peter L.; Wu, Xiaomu; Brus, Louis
  • The Journal of Physical Chemistry C, Vol. 111, Issue 25
  • DOI: 10.1021/jp0710436

Controlling anisotropic nanoparticle growth through plasmon excitation
journal, October 2003

  • Jin, Rongchao; Charles Cao, Y.; Hao, Encai
  • Nature, Vol. 425, Issue 6957
  • DOI: 10.1038/nature02020

Light-Driven Transformation Processes of Anisotropic Silver Nanoparticles
journal, June 2013

  • Lee, George P.; Shi, Yichao; Lavoie, Ellen
  • ACS Nano, Vol. 7, Issue 7
  • DOI: 10.1021/nn4013059

Unravelling Kinetic and Thermodynamic Effects on the Growth of Gold Nanoplates by Liquid Transmission Electron Microscopy
journal, March 2015


Chemical stability and degradation mechanisms of triangular Ag, Ag@Au, and Au nanoprisms
journal, January 2014

  • Lee, Kee Eun; Hesketh, Amelia V.; Kelly, Timothy L.
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 24
  • DOI: 10.1039/C4CP00954A

Triangular Gold Nanoplate Growth by Oriented Attachment of Au Seeds Generated by Strong Field Laser Reduction
journal, April 2015


Galvanic Replacement-Free Deposition of Au on Ag for Core–Shell Nanocubes with Enhanced Chemical Stability and SERS Activity
journal, May 2014

  • Yang, Yin; Liu, Jingyue; Fu, Zheng-Wen
  • Journal of the American Chemical Society, Vol. 136, Issue 23
  • DOI: 10.1021/ja502472x

SIMS imaging of the nanoworld: applications in science and technology
journal, January 2012

  • Senoner, Mathias; Unger, Wolfgang E. S.
  • Journal of Analytical Atomic Spectrometry, Vol. 27, Issue 7
  • DOI: 10.1039/c2ja30015j

Observation of a Quadrupole Plasmon Mode for a Colloidal Solution of Gold Nanoprisms
journal, April 2005

  • Millstone, Jill E.; Park, Sungho; Shuford, Kevin L.
  • Journal of the American Chemical Society, Vol. 127, Issue 15
  • DOI: 10.1021/ja043245a

Shape-Controlled Synthesis of Metal Nanocrystals: Simple Chemistry Meets Complex Physics?
journal, December 2008

  • Xia, Younan; Xiong, Yujie; Lim, Byungkwon
  • Angewandte Chemie International Edition, Vol. 48, Issue 1, p. 60-103
  • DOI: 10.1002/anie.200802248

Halide Anions as Shape-Directing Agents for Obtaining High-Quality Anisotropic Gold Nanostructures
journal, August 2012

  • DuChene, Joseph S.; Niu, Wenxin; Abendroth, John M.
  • Chemistry of Materials, Vol. 25, Issue 8
  • DOI: 10.1021/cm3020397

Anisotropic Noble Metal Nanocrystal Growth: The Role of Halides
journal, September 2013

  • Lohse, Samuel E.; Burrows, Nathan D.; Scarabelli, Leonardo
  • Chemistry of Materials, Vol. 26, Issue 1
  • DOI: 10.1021/cm402384j

Optical Studies of Dynamics in Noble Metal Nanostructures
journal, June 2011


Gold nanoparticle ensembles as heaters and actuators: melting and collective plasmon resonances
journal, July 2006

  • Govorov, Alexander O.; Zhang, Wei; Skeini, Timur
  • Nanoscale Research Letters, Vol. 1, Issue 1
  • DOI: 10.1007/s11671-006-9015-7

Visible-light-enhanced catalytic oxidation reactions on plasmonic silver nanostructures
journal, May 2011

  • Christopher, Phillip; Xin, Hongliang; Linic, Suljo
  • Nature Chemistry, Vol. 3, Issue 6
  • DOI: 10.1038/nchem.1032

Plasmon-Induced Hot Carriers in Metallic Nanoparticles
journal, July 2014

  • Manjavacas, Alejandro; Liu, Jun G.; Kulkarni, Vikram
  • ACS Nano, Vol. 8, Issue 8
  • DOI: 10.1021/nn502445f

Nucleation and Growth of Gold Nanoparticles Studied via in situ Small Angle X-ray Scattering at Millisecond Time Resolution
journal, January 2010

  • Polte, Jörg; Erler, Robert; Thünemann, Andreas F.
  • ACS Nano, Vol. 4, Issue 2
  • DOI: 10.1021/nn901499c

Plasmon Induced Photovoltage and Charge Separation in Citrate-Stabilized Gold Nanoparticles
journal, July 2010

  • Wu, Xiaomu; Thrall, Elizabeth S.; Liu, Haitao
  • The Journal of Physical Chemistry C, Vol. 114, Issue 30
  • DOI: 10.1021/jp102720r

Successive Deposition of Silver on Silver Nanoplates: Lateral versus Vertical Growth
journal, October 2010

  • Zeng, Jie; Xia, Xiaohu; Rycenga, Matthew
  • Angewandte Chemie International Edition, Vol. 50, Issue 1
  • DOI: 10.1002/anie.201005549

Colloidal Gold and Silver Triangular Nanoprisms
journal, March 2009

  • Millstone, Jill E.; Hurst, Sarah J.; Métraux, Gabriella S.
  • Small, Vol. 5, Issue 6
  • DOI: 10.1002/smll.200801480

Shape Control of Colloidal Metal Nanocrystals
journal, March 2008


Shape-Controlled Synthesis of Colloidal Metal Nanocrystals: Thermodynamic versus Kinetic Products
journal, June 2015

  • Xia, Younan; Xia, Xiaohu; Peng, Hsin-Chieh
  • Journal of the American Chemical Society, Vol. 137, Issue 25
  • DOI: 10.1021/jacs.5b04641

Bifunctional Ag@Pd-Ag Nanocubes for Highly Sensitive Monitoring of Catalytic Reactions by Surface-Enhanced Raman Spectroscopy
journal, May 2015

  • Li, Jumei; Liu, Jingyue; Yang, Yin
  • Journal of the American Chemical Society, Vol. 137, Issue 22
  • DOI: 10.1021/jacs.5b03528

Defective twin boundaries in nanotwinned metals
journal, May 2013

  • Wang, Y. Morris; Sansoz, Frederic; LaGrange, Thomas
  • Nature Materials, Vol. 12, Issue 8
  • DOI: 10.1038/nmat3646

Polymerization on Stepped Surfaces: Alignment of Polymers and Identification of Catalytic Sites
journal, April 2012

  • Saywell, Alex; Schwarz, Jutta; Hecht, Stefan
  • Angewandte Chemie International Edition, Vol. 51, Issue 21
  • DOI: 10.1002/anie.201200543

A photovoltaic device structure based on internal electron emission
journal, February 2003


“Hot Electron” Photo-Charging and Electrochemical Discharge Kinetics of Silver Nanocrystals
journal, October 2007

  • Redmond, Peter L.; Brus, Louis E.
  • The Journal of Physical Chemistry C, Vol. 111, Issue 40
  • DOI: 10.1021/jp0741859

Ultrahigh Strength and High Electrical Conductivity in Copper
journal, April 2004


Monodisperse Gold Nanotriangles: Size Control, Large-Scale Self-Assembly, and Performance in Surface-Enhanced Raman Scattering
journal, May 2014

  • Scarabelli, Leonardo; Coronado-Puchau, Marc; Giner-Casares, Juan J.
  • ACS Nano, Vol. 8, Issue 6
  • DOI: 10.1021/nn500727w

High-Yield Seedless Synthesis of Triangular Gold Nanoplates through Oxidative Etching
journal, November 2014

  • Chen, Lei; Ji, Fei; Xu, Yong
  • Nano Letters, Vol. 14, Issue 12
  • DOI: 10.1021/nl504126u

Iodide Ions Control Seed-Mediated Growth of Anisotropic Gold Nanoparticles
journal, August 2008

  • Millstone, Jill E.; Wei, Wei; Jones, Matthew R.
  • Nano Letters, Vol. 8, Issue 8, p. 2526-2529
  • DOI: 10.1021/nl8016253

    Works referencing / citing this record:

    One-Stage Synthesis of Gold Hydrosol with Nanoparticles of Desired Shape
    journal, March 2018


    Self-supported porous 2D AuCu triangular nanoprisms as model electrocatalysts for ethylene glycol and glycerol oxidation
    journal, January 2017

    • Xu, Hui; Yan, Bo; Wang, Jin
    • Journal of Materials Chemistry A, Vol. 5, Issue 30
    • DOI: 10.1039/c7ta04598k

    One-Stage Synthesis of Gold Hydrosol with Nanoparticles of Desired Shape
    journal, March 2018


    Facile fabrication of PdRuPt nanowire networks with tunable compositions as efficient methanol electrooxidation catalysts
    journal, March 2018


    Multifunctional Photonic Nanomaterials for Diagnostic, Therapeutic, and Theranostic Applications
    journal, January 2018


    Efficiency and Bond Selectivity in Plasmon-Induced Photochemistry
    journal, June 2017


    Amorphous Materials for Enhanced Localized Surface Plasmon Resonances
    journal, February 2018


    Visible-Light-Improved Catalytic Performance for Methanol Oxidation Based on Plasmonic PtAu Dendrites
    journal, February 2018


    Experimental Insights into the Growth of Single Truncated Anatase Bipyramids
    journal, December 2018


    Robust Synthesis of Gold Nanotriangles and their Self‐Assembly into Vertical Arrays
    journal, June 2019

    • Szustakiewicz, Piotr; González‐Rubio, Guillermo; Scarabelli, Leonardo
    • ChemistryOpen, Vol. 8, Issue 6
    • DOI: 10.1002/open.201900082

    Photochemical Formation of Tunable Gold Nanostructures Using Versatile Water-Soluble Thiolate Au(I) Precursor
    journal, September 2018

    • Murshid, Nimer; Smith, D. Scott; Kitaev, Vladimir
    • Particle & Particle Systems Characterization, Vol. 35, Issue 11
    • DOI: 10.1002/ppsc.201800285

    Synthesis and Properties of Au Hydride
    journal, April 2019


    Fabrication of Superior Single‐Atom Catalysts toward Diverse Electrochemical Reactions
    journal, February 2019

    • Zhang, Bin‐Wei; Wang, Yun‐Xiao; Chou, Shu‐Lei
    • Small Methods, Vol. 3, Issue 9
    • DOI: 10.1002/smtd.201800497

    Seeds mediated synthesis of giant gold particles on the glass surface
    journal, March 2018


    Plasmonic hot electron transport drives nano-localized chemistry
    journal, March 2017

    • Cortés, Emiliano; Xie, Wei; Cambiasso, Javier
    • Nature Communications, Vol. 8, Issue 1
    • DOI: 10.1038/ncomms14880

    Iced photochemical reduction to synthesize atomically dispersed metals by suppressing nanocrystal growth
    journal, November 2017


    Detection of Permethrin pesticide using silver nano-dendrites SERS on optical fibre fabricated by laser-assisted photochemical method
    journal, August 2019


    Diameter-controlled Cu nanoparticles on saponite and preparation of film by using spontaneous phase separation
    journal, January 2017

    • Miyagawa, Masaya; Shibusawa, Akane; Maeda, Kaho
    • RSC Advances, Vol. 7, Issue 66
    • DOI: 10.1039/c7ra08659h

    Preparation of bimetallic Au/Pt nanotriangles with tunable plasmonic properties and improved photocatalytic activity
    journal, January 2018

    • Ma, Liang; Ding, Si-Jing; Yang, Da-Jie
    • Dalton Transactions, Vol. 47, Issue 47
    • DOI: 10.1039/c8dt03482f

    Interface engineered surface morphology evolution of Au@Pd core–shell nanorods
    journal, January 2018

    • Xu, Yanchao; Cui, Xiaoqiang; Qi, Kun
    • Nanoscale, Vol. 10, Issue 45
    • DOI: 10.1039/c8nr06835f

    High yield synthesis and surface chemistry exchange of small gold hexagonal nanoprisms
    journal, January 2019

    • Requejo, Katherinne I.; Liopo, Anton V.; Zubarev, Eugene R.
    • Chemical Communications, Vol. 55, Issue 76
    • DOI: 10.1039/c9cc04534a

    Photocatalytic synthesis of gold nanoparticles using TiO 2 nanorods: a mechanistic investigation
    journal, January 2019

    • Lu, Qipeng; Zhu, Lijie; Han, Sumei
    • Physical Chemistry Chemical Physics, Vol. 21, Issue 34
    • DOI: 10.1039/c9cp02493j

    Imaging of nonlocal hot-electron energy dissipation via shot noise
    journal, March 2018


    Using plasmonically generated carriers as redox equivalents
    journal, January 2020

    • Yu, Sungju; Mohan, Varun; Jain, Prashant K.
    • MRS Bulletin, Vol. 45, Issue 1
    • DOI: 10.1557/mrs.2019.293