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. 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 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. Finally, these insights establish a molecular-level description of the underlying mechanisms regulating the plasmon-driven synthesis of gold nanoprisms.

Authors:

Zhai, Yueming ^[1]; DuChene, Joseph S. ^[1]; Wang, Yi-Chung ^[2]; Qiu, Jingjing ^[1]; Johnston-Peck, Aaron C. ^[3]; You, Bo ^[1]; Guo, Wenxiao ^[1]; DiCiaccio, Benedetto ^[1]; Qian, Kun ^[1]; Zhao, Evan W. ^[1]; Ooi, Frances ^[1]; Hu, Dehong ^[4]; Su, Dong  ^[3];

• Search DOE PAGES for author "Su, Dong"
• Search DOE PAGES for ORCID "0000-0002-1921-6683"

Stach, Eric A.  ^[3];

• Search DOE PAGES for author "Stach, Eric A."
• Search DOE PAGES for ORCID "0000-0002-3366-2153"

Zhu, Zihua ^[4]; Wei, Wei David ^[1]

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+ Show Author Affiliations

1. Univ. of Florida, Gainesville, FL (United States). Dept. of Chemistry. Center for Nanostructured Electronic Materials
2. Univ. of Florida, Gainesville, FL (United States). Dept. of Chemistry. Center for Nanostructured Electronic Materials; Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab.
3. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials
4. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab.

Publication Date:

Mon Jul 04 00:00:00 EDT 2016

Research Org.:

Brookhaven National Laboratory (BNL), Upton, NY (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Univ. of Florida, Gainesville, FL (United States)

Sponsoring Org.:

USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Biological and Environmental Research (BER); US Air Force Office of Scientific Research (AFOSR); National Science Foundation (NSF)

OSTI Identifier:

1341679

Report Number(s):

BNL-113407-2017-JA
Journal ID: ISSN 1476-1122; R&D Project: 16060; 16060; KC0403020; TRN: US1701804

Grant/Contract Number:  

SC0012704; AC06-76RLO1930; FA9550-14-1-0304; CHE-1308644; CHE-1038015

Resource Type:

Accepted Manuscript

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:

77 NANOSCIENCE AND NANOTECHNOLOGY; Center for Functional Nanomaterials; nanoparticles