studying-effects-temperature-on-nucleation-growth-nanoparticles

Studying the Effects of Temperature on the Nucleation and Growth of Nanoparticles by Liquid-Cell Transmission Electron Microscopy

Temperature control is a recent development that provides an additional degree of freedom to study nanochemistry by liquid cell transmission electron ...

Université de Paris – CNRS

Ostwald ripening has been broadly studied because it plays a determinant role in the evolution of cluster size during both chemical and physical synthesis of nanoparticles. This thermoactivated process causes large particles to grow, drawing material from the smaller particles, which shrink. However, this phenomenon becomes more complex when considering the coarsening of metallic alloy clusters. The present experimental and theoretical investigations show that the relative composition of CoPt nanoparticles can be strongly modified during high temperature annealing and displays a size-dependent behavior. This compositional change originates from the higher evaporation rate of Co atoms from the nanoparticles. More importantly, this effect is expected in all alloy clusters containing species with different mobilities.

Ostwald ripening in nanoalloys: when thermodynamics drives a size-dependent particle composition.

What happens to inorganic nanoparticles (NPs), such as plasmonic gold or silver, superparamagnetic iron oxide, or fluorescent quantum dot NPs after they have been administrated to a living being? This review discusses the integrity, biodistribution, and fate of NPs after in vivo administration. The hybrid nature of the NPs is described, conceptually divided into the inorganic core, the engineered surface coating comprising of the ligand shell and optionally also bio-conjugates, and the corona of adsorbed biological molecules. Empirical evidence shows that all of these three compounds may degrade individually in vivo and can drastically modify the life cycle and biodistribution of the whole heterostructure. Thus, the NPs may be decomposed into different parts, whose biodistribution and fate would need to be analyzed individually. Multiple labeling and quantification strategies for such a purpose will be discussed. All reviewed data indicate that NPs in vivo should no longer be considered as homogeneous entities, but should be seen as inorganic/organic/biological nano-hybrids with complex and intricately linked distribution and degradation pathways.

In vivo degeneration and the fate of inorganic nanoparticles.

Liquid-cell TEM has enabled an interdisciplinary community of scientists to carry out atomic- / nano-scale studies of solid/liquid interfaces. Nevertheless, the restricted resolution of TEM in liquid media and the necessity to reduce the electron dose to avoid harmful radiolytic effects induced by the beam have limited the use of high resolution imaging to study the atomic structure of nanomaterials in liquid. Here we show that STEM nanodiffraction can be exploited in liquid-cell TEM experiments to overcome these two limitations. We evidence that this technique allows quick analysis of the structure of single gold nanoparticles whatever their zone axis orientation, which substantially increases the percentage of analysable nanostructures with respect to HRTEM investigations. Moreover, STEM nanodiffraction can also be used in very low dose conditions. The electron dose irradiating the analyzed nanostructures during data acquisition can be reduced by almost four orders of magnitude compared to conventional HRTEM analysis. Finally, dynamical analyses in reciprocal space are used to provide new insights into the shape-dependent rotation of nanocrystals in the liquid-cell.

Structural analysis of single nanoparticles in liquid by low-dose STEM nanodiffraction.

Rational nanoparticle design is one of the main goals of materials science, but it can only be achieved via a thorough understanding of the growth process and of the respective roles of the molecular species involved. We demonstrate that a combination of complementary techniques can yield novel information with respect to their individual contributions. We monitored the growth of long aspect ratio silver rods from gold pentatwinned seeds by three  techniques (small-angle X-ray scattering, optical extinction spectroscopy and liquid-cell transmission electron microscopy). Exploiting the difference in reaction speed between the bulk synthesis and the nanoparticle formation in the TEM cell, we show that the anisotropic growth is thermodynamically controlled (rather than kinetically) and that ascorbic acid, widely used for its mild reductive properties, plays a shape-directing role, by stabilizing the {100} facets of the silver cubic lattice, in synergy with the halide ions. This approach can easily be applied to a wide variety of synthesis strategies.

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

The selective shortening of gold nanorods (NRs) is a directional etching process that has been intensively studied by UV-Vis spectroscopy because of its direct impact on the optical response of these plasmonic nanostructures. Here, liquid-cell transmission electron microscopy is exploited to visualize this peculiar corrosion process at the nanoscale and study the impacts of reaction kinetics on the etching mechanisms. In situ imaging reveals that anisotropic etching requires a chemical environment with a low etching power to make the tips of NRs the only reaction site for the oxidation process. Then, aberration-corrected TEM and atomistic simulations were combined to demonstrate that the disparity between the reactivity of the body and the ends of NRs does not derive from their crystal structure but results from an inhomogeneous surface functionalization. In a general manner, this work highlights the necessity to consider the organic/inorganic natures of nanostructures to understand their chemical reactivity.

Article	Year
Ostwald ripening in nanoalloys: when thermodynamics drives a size-dependent particle composition. Physical review letters\| PubMed ID: 21231603	2010
In vivo degeneration and the fate of inorganic nanoparticles. Chemical Society reviews\| PubMed ID: 26862602	2016
Structural analysis of single nanoparticles in liquid by low-dose STEM nanodiffraction. Micron (Oxford, England : 1993)\| PubMed ID: 30265881	2019
Real-Time Observations Reveal a Double Role for Ascorbic Acid in the Anisotropic Growth of Silver on Gold. The journal of physical chemistry letters\| PubMed ID: 32200632	2020
Selective shortening of gold nanorods: when surface functionalization dictates the reactivity of nanostructures. Nanoscale\| PubMed ID: 33155612	2020

Damien Alloyeau

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