Real-Time <i>In Situ</i> Observations Reveal a Double Role for Ascorbic Acid in the Anisotropic Growth of Silver on Gold

Aliyah, Kinanti; Lyu, Jieli; Goldmann, Claire; Bizien, Thomas; Hamon, Cyrille; Alloyeau, Damien; Constantin, Doru

doi:10.1021/acs.jpclett.0c00121

Cited by 27 publications

(41 citation statements)

References 46 publications

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“…redox chemistry and reaction kinetics, to directly observe the impacts on nanoparticle formation mechanisms. [34][35][36][37][38][39][40] However, there remains the challenge of demonstrating the chemistry involved in LP-TEM electron beam synthesis is representative of bench scale wet chemistry. 41 Ideally, the electron beam should only reduce metal precursors and not drive undesirable side reactions like oxidation of organic capping ligands or nanoparticles.…”

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confidence: 99%

Visualizing Ligand-Mediated Bimetallic Nanocrystal Formation Pathways with In Situ Liquid Phase Transmission Electron Microscopy Synthesis

Wang

Leff

et al. 2020

Preprint

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Colloidal synthesis of alloyed multimetallic nanocrystals with precise composition control remains a challenge and a critical missing link in theory-driven rational design of functional nanomaterials. Liquid phase transmission electron microscopy (LP-TEM) enables directly visualizing nanocrystal formation mechanisms that can inform discovery of design rules for colloidal multimetallic nanocrystal synthesis, but it remains unclear whether the salient chemistry of the flask synthesis is preserved in the extreme electron beam radiation environment during LPTEM. Here we demonstrate controlled in situ LP-TEM synthesis of alloyed AuCu nanoparticles while maintaining the molecular structure of electron beam sensitive metal thiolate precursor complexes. Ex situ flask synthesis experiments showed that nearly equimolar AuCu alloys formed from heteronuclear metal thiolate complexes, while gold-rich alloys formed in their absence. Systematic dose rate-controlled in situ LP-TEM synthesis experiments established a range of electron beam synthesis conditions that formed alloyed AuCu nanoparticles with similar alloy composition, random alloy structure, and particle size distribution shape as those from ex situ flask synthesis, indicating metal thiolate complexes were preserved under these conditions. Reaction kinetic simulations of radical-ligand reactions revealed that polymer capping ligands acted as effective hydroxyl radical scavengers during LP-TEM synthesis and prevented metal thiolate oxidation at low dose rates. In situ synthesis experiments and ex situ atomic scale imaging revealed that a key role of metal thiolate complexes was to prevent copper atom oxidation and facilitate formation of prenucleation cluster intermediates. This work demonstrates that complex ion precursor chemistry can be maintained during LP-TEM imaging, enabling probing nanocrystal formation mechanisms with LP-TEM under reaction conditions representative of ex situ flask synthesis.

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Visualizing Ligand-Mediated Bimetallic Nanocrystal Formation Pathways with In Situ Liquid Phase Transmission Electron Microscopy Synthesis

Wang

Leff

et al. 2020

Preprint

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“…Furthermore, changing the reaction conditions can provide insight into the role of various additives, as we have shown recently for the dual action of ascorbic acid in the growth of silver onto gold bipyramids. 7 Single-crystal gold nanorods (AuNRs) exhibit a transverse octogonal cross section enclosed by {520} facets and terminated by a combination of {110} and {111} facets at the tips. 17,18 After silver coating, the resulting BPs adopt a cuboidal shape enclosed by six {100} facets.…”

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confidence: 99%

Growth Kinetics of Core–Shell Au/Ag Nanoparticles

Hamon

Constantin

2020

J. Phys. Chem. C

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We study by synchrotron-based time-resolved small angle X-ray scattering the growth of silver shells on gold nanorods in the presence of hexadecyltrimethylammonium chloride (CTAC) as a function of the silver/gold molar ratio K. For all but the highest K values, the silver precursor is completely converted to the solid phase. The growth rate of the width decreases exponentially, and its starting value is linear in K, with a slope of 10.3 ± 0.2 nm/s/M. A simple growth model including these features accounts for the magnitude of the evolution time. Assuming that permeation across the CTAC bilayer is the rate-limiting step we obtain a permeability of 1 µm/s.

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“…Recently, complex particle growth and dissolution studies investigating gold-silver heterostructures obtained high interest in research [2,8]. In order to support the proposed interpretation of experimental results, we elaborate an adaption of Schneider's radiolysis script to describe the reaction chemistry of aerated AgNO3 solutions in presence of bromide ions, which originate from stabilizing agents like cetrimonium bromide (CTAB).…”

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confidence: 93%

Modelling the Radiolysis of Silver Nitrate Solutions in presence of Bromide Ions in Liquid-Phase Transmission Electron Microscopy

et al. 2021

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Real-Time In Situ Observations Reveal a Double Role for Ascorbic Acid in the Anisotropic Growth of Silver on Gold

Cited by 27 publications

References 46 publications

Visualizing Ligand-Mediated Bimetallic Nanocrystal Formation Pathways with In Situ Liquid Phase Transmission Electron Microscopy Synthesis

Visualizing Ligand-Mediated Bimetallic Nanocrystal Formation Pathways with In Situ Liquid Phase Transmission Electron Microscopy Synthesis

Growth Kinetics of Core–Shell Au/Ag Nanoparticles

Modelling the Radiolysis of Silver Nitrate Solutions in presence of Bromide Ions in Liquid-Phase Transmission Electron Microscopy

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