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Title: How Ag Nanospheres Are Transformed into AgAu Nanocages

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.7b06724· OSTI ID:1393316
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  1. Department of Materials Science and Engineering, ‡Department of Biomedical Engineering, §Department of Chemistry, ∥Department of Physics and Astronomy, and ⊥International Institute for Nanotechnology, Northwestern University, Evanston, Illinois 60208, United States
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Bimetallic hollow, porous noble metal nanoparticles are of broad interest for biomedical, optical and catalytic applications. The most straightforward method for preparing such structures involves the reaction between HAuCl4 and well-formed Ag particles, typically spheres, cubes, or triangular prisms, yet the mechanism underlying their formation is poorly understood at the atomic scale. By combining in situ nanoscopic and atomic-scale characterization techniques (XAFS, SAXS, XRF, and electron microscopy) to follow the process, we elucidate a plausible reaction pathway for the conversion of citrate-capped Ag nanospheres to AgAu nanocages; importantly, the hollowing event cannot be explained by the nanoscale Kirkendall effect, nor by Galvanic exchange alone, two processes that have been previously proposed. We propose a modification of the bulk Galvanic exchange process that takes into account considerations that can only occur with nanoscale particles. This nanoscale Galvanic exchange process explains the novel morphological and chemical changes associated with the typically observed hollowing process.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Northwestern Univ., Evanston, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
FG02-08ER46539
OSTI ID:
1393316
Alternate ID(s):
OSTI ID: 1408113; OSTI ID: 1508252
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Vol. 139 Journal Issue: 35; ISSN 0002-7863
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 63 works
Citation information provided by
Web of Science

Cited By (12)

Chirality on Hierarchical Self-Assembly of Au@AuAg Yolk-Shell Nanorods into Core-Satellite Superstructures for Biosensing in Human Cells journal June 2018
Self‐Templating Approaches to Hollow Nanostructures journal July 2018
Controllably Hollow AgAu Nanoparticles via Nonaqueous, Reduction Agent-Assisted Galvanic Replacement journal January 2018
Integration of Sequential Reactions in a Continuous Flow Droplet Reactor: A Route to Architecturally Defined Bimetallic Nanostructures journal August 2019
Dynamically Switchable Multicolor Electrochromic Films journal January 2019
In Situ Techniques for Probing Kinetics and Mechanism of Hollowing Nanostructures through Direct Chemical Transformations journal August 2018
Atomic spectrometry update: review of advances in the analysis of metals, chemicals and materials journal January 2018
Artificial intelligence in nanomedicine journal January 2019
Au–Ag and Pt–Ag bimetallic nanoparticles@halloysite nanotubes: morphological modulation, improvement of thermal stability and catalytic performance journal January 2018
Ag–Au bimetallic nanocomposites stabilized with organic–inorganic hybrid microgels: synthesis and their regulated optical and catalytic properties journal January 2018
Conversion of bimetallic PtNi 3 nanopolyhedra to ternary PtNiSn nanoframes by galvanic replacement reaction journal January 2019
Decoration of plasmonic Mg nanoparticles by partial galvanic replacement journal December 2019

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