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Title: Revisiting the Polyol Synthesis of Silver Nanostructures: Role of Chloride in Nanocube Formation

Abstract

Chloride (Cl ) is normally used together with polyvinylpyrrolidone (PVP) in the polyol synthesis of Ag nanocubes. In the literature, shape control is attributed predominantly to the preferential binding of PVP to Ag(100) facets compared to Ag(111) facets, whereas the role of Cl has not been well studied. Several hypotheses have been proposed regarding the role of Cl ; however, there is still no consensus regarding the exact influence of Cl in the shape-controlled synthesis of Ag nanocubes. To examine the influence of Cl , we undertook a joint theoretical–experimental study. Experimentally, we examined the influence of Cl concentration on the shape of Ag nanoparticles (NPs) at constant H + concentration. In the presence of H +, in situ formed HNO3 etches the initially formed Ag seeds and slows down the overall reduction of Ag +, which promotes the formation of monodisperse Ag NPs. Ex situ experiments probed the evolution of Cl during the growth of Ag nanocubes, which involves the initial formation of AgCl nanocubes, and their subsequent dissolution to release Cl , which adsorbs onto the surfaces of single crystal seeds to impact shape evolution through apparent thermodynamic control. The formation of cubes ismore » independent of the source of AgCl, indicating temporal control of the Cl chemical potential in solution leads to high-yield synthesis of Ag nanocubes. Increasing the concentration of Cl alone leads to a progression in shape from truncated octahedra, to cuboctahedra, truncated cubes, and ultimately cubes, directly demonstrating the importance of Cl in Ag NP shape control. Here, we used ab initio thermodynamics calculations based on density functional theory to probe the role of Cl in directing shape control. With increasing Cl chemical potential (surface coverage), calculated surface energies γ of Ag facets transition from γ 111 < γ 100 to γ 100 < γ 111 and predict Wulff shapes terminated with an increasing (100) contribution, consistent with experimental observations. The combination of theory and experiment is beneficial for advancing the understanding of nanocrystal formation.« less

Authors:
 [1];  [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Pennsylvania State Univ., University Park, PA (United States)
Publication Date:
Research Org.:
Pennsylvania State Univ., University Park, PA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1594115
Grant/Contract Number:  
FG02-07ER46414
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ACS Nano
Additional Journal Information:
Journal Volume: 13; Journal Issue: 2; Journal ID: ISSN 1936-0851
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY; Silver nanocubes; Chloride; Polyol Synthesis; Shape control; ab initio thermodynamics

Citation Formats

Chen, Zhifeng, Balankura, Tonnam, Fichthorn, Kristen A., and Rioux, Robert M. Revisiting the Polyol Synthesis of Silver Nanostructures: Role of Chloride in Nanocube Formation. United States: N. p., 2019. Web. doi:10.1021/acsnano.8b08019.
Chen, Zhifeng, Balankura, Tonnam, Fichthorn, Kristen A., & Rioux, Robert M. Revisiting the Polyol Synthesis of Silver Nanostructures: Role of Chloride in Nanocube Formation. United States. doi:10.1021/acsnano.8b08019.
Chen, Zhifeng, Balankura, Tonnam, Fichthorn, Kristen A., and Rioux, Robert M. Wed . "Revisiting the Polyol Synthesis of Silver Nanostructures: Role of Chloride in Nanocube Formation". United States. doi:10.1021/acsnano.8b08019. https://www.osti.gov/servlets/purl/1594115.
@article{osti_1594115,
title = {Revisiting the Polyol Synthesis of Silver Nanostructures: Role of Chloride in Nanocube Formation},
author = {Chen, Zhifeng and Balankura, Tonnam and Fichthorn, Kristen A. and Rioux, Robert M.},
abstractNote = {Chloride (Cl–) is normally used together with polyvinylpyrrolidone (PVP) in the polyol synthesis of Ag nanocubes. In the literature, shape control is attributed predominantly to the preferential binding of PVP to Ag(100) facets compared to Ag(111) facets, whereas the role of Cl– has not been well studied. Several hypotheses have been proposed regarding the role of Cl–; however, there is still no consensus regarding the exact influence of Cl– in the shape-controlled synthesis of Ag nanocubes. To examine the influence of Cl–, we undertook a joint theoretical–experimental study. Experimentally, we examined the influence of Cl– concentration on the shape of Ag nanoparticles (NPs) at constant H+ concentration. In the presence of H+, in situ formed HNO3 etches the initially formed Ag seeds and slows down the overall reduction of Ag+, which promotes the formation of monodisperse Ag NPs. Ex situ experiments probed the evolution of Cl– during the growth of Ag nanocubes, which involves the initial formation of AgCl nanocubes, and their subsequent dissolution to release Cl–, which adsorbs onto the surfaces of single crystal seeds to impact shape evolution through apparent thermodynamic control. The formation of cubes is independent of the source of AgCl, indicating temporal control of the Cl– chemical potential in solution leads to high-yield synthesis of Ag nanocubes. Increasing the concentration of Cl– alone leads to a progression in shape from truncated octahedra, to cuboctahedra, truncated cubes, and ultimately cubes, directly demonstrating the importance of Cl– in Ag NP shape control. Here, we used ab initio thermodynamics calculations based on density functional theory to probe the role of Cl– in directing shape control. With increasing Cl chemical potential (surface coverage), calculated surface energies γ of Ag facets transition from γ111 < γ100 to γ100 < γ111 and predict Wulff shapes terminated with an increasing (100) contribution, consistent with experimental observations. The combination of theory and experiment is beneficial for advancing the understanding of nanocrystal formation.},
doi = {10.1021/acsnano.8b08019},
journal = {ACS Nano},
issn = {1936-0851},
number = 2,
volume = 13,
place = {United States},
year = {2019},
month = {1}
}

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Works referencing / citing this record:

Synthesis and Applications of Silver Nanowires for Transparent Conductive Films
journal, May 2019


Synthesis and Applications of Silver Nanowires for Transparent Conductive Films
journal, May 2019