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Title: Tailoring Morphology of Cu–Ag Nanocrescents and Core–Shell Nanocrystals Guided by a Thermodynamic Model

Abstract

The ability to predict and control the formation of bimetallic heterogeneous nanocrystals is desirable for many applications in plasmonics and catalysis. In this work, we observe the synthesis and characterization of stable, monodisperse, and solution-processed Cu-Ag bimetallic nanoparticles with specific but unusual elemental arrangements that are consistent with a recently developed thermodynamic model. Using air-free scanning transmission electron microscopy with energy-dispersive X-ray spectroscopy, the distribution of Cu and Ag positions was unambiguously identified within individual nanocrystals (NCs), leading to the discovery of a Cu-Ag nanocrescent shape. A simple yet versatile thermodynamic model was applied to illustrate how the interplay between surface and interface energies determines the particle morphology. It is found that there exists a range of surface-to-interface energy ratios under which crescent-shaped nanocrystals are the thermodynamically favored products, with the morphology tunable by adjusting the Ag content. Moreover, we show the conversion of Cu-Ag nanocrescents into Ag@Cu 2O upon mild oxidation, whereas fully core-shell Cu@Ag NCs are robust against oxidation up to 100 °C. The plasmonic and interband absorptions of Cu-Ag NCs depend on the composition and the degree of Cu oxidation, which may find application in light-driven catalysis.

Authors:
ORCiD logo [1];  [2];  [2];  [3];  [1]; ORCiD logo [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
  2. Univ. of California, Berkeley, CA (United States)
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
OSTI Identifier:
1532329
Grant/Contract Number:  
AC02-05CH11231; SC0004993
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 140; Journal Issue: 27; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Osowiecki, Wojciech T., Ye, Xingchen, Satish, Pratima, Bustillo, Karen C., Clark, Ezra L., and Alivisatos, A. Paul. Tailoring Morphology of Cu–Ag Nanocrescents and Core–Shell Nanocrystals Guided by a Thermodynamic Model. United States: N. p., 2018. Web. doi:10.1021/jacs.8b04558.
Osowiecki, Wojciech T., Ye, Xingchen, Satish, Pratima, Bustillo, Karen C., Clark, Ezra L., & Alivisatos, A. Paul. Tailoring Morphology of Cu–Ag Nanocrescents and Core–Shell Nanocrystals Guided by a Thermodynamic Model. United States. doi:10.1021/jacs.8b04558.
Osowiecki, Wojciech T., Ye, Xingchen, Satish, Pratima, Bustillo, Karen C., Clark, Ezra L., and Alivisatos, A. Paul. Sun . "Tailoring Morphology of Cu–Ag Nanocrescents and Core–Shell Nanocrystals Guided by a Thermodynamic Model". United States. doi:10.1021/jacs.8b04558. https://www.osti.gov/servlets/purl/1532329.
@article{osti_1532329,
title = {Tailoring Morphology of Cu–Ag Nanocrescents and Core–Shell Nanocrystals Guided by a Thermodynamic Model},
author = {Osowiecki, Wojciech T. and Ye, Xingchen and Satish, Pratima and Bustillo, Karen C. and Clark, Ezra L. and Alivisatos, A. Paul},
abstractNote = {The ability to predict and control the formation of bimetallic heterogeneous nanocrystals is desirable for many applications in plasmonics and catalysis. In this work, we observe the synthesis and characterization of stable, monodisperse, and solution-processed Cu-Ag bimetallic nanoparticles with specific but unusual elemental arrangements that are consistent with a recently developed thermodynamic model. Using air-free scanning transmission electron microscopy with energy-dispersive X-ray spectroscopy, the distribution of Cu and Ag positions was unambiguously identified within individual nanocrystals (NCs), leading to the discovery of a Cu-Ag nanocrescent shape. A simple yet versatile thermodynamic model was applied to illustrate how the interplay between surface and interface energies determines the particle morphology. It is found that there exists a range of surface-to-interface energy ratios under which crescent-shaped nanocrystals are the thermodynamically favored products, with the morphology tunable by adjusting the Ag content. Moreover, we show the conversion of Cu-Ag nanocrescents into Ag@Cu2O upon mild oxidation, whereas fully core-shell Cu@Ag NCs are robust against oxidation up to 100 °C. The plasmonic and interband absorptions of Cu-Ag NCs depend on the composition and the degree of Cu oxidation, which may find application in light-driven catalysis.},
doi = {10.1021/jacs.8b04558},
journal = {Journal of the American Chemical Society},
issn = {0002-7863},
number = 27,
volume = 140,
place = {United States},
year = {2018},
month = {6}
}

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