Mechanics under pressure of gold nanoparticle supracrystals: the role of the soft matrix

Ibrahim, Helen; Balédent, V.; Impéror‐Clerc, Marianne; Pansu, B.

doi:10.1039/d2ra03484k

Cited by 3 publications

(6 citation statements)

References 26 publications

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“…First a low pressure series, below 10 GPa, aimed at comparing mechanical behavior such as bulk modlulus of different structure of supercrystals: FCC, BCC and C14. This complete our study previously published 22 on FCC structure in a pressure range where no structural transition is expected. The second series of experiments went up to 45 GPa, to extend our study to eventual structural transition or coalescence as reported in other NPs.…”

Section: Resultssupporting

confidence: 84%

“…The same reasoning can be made with C14 structure, resulting in the hierarchy of bulk modulii: B 0 matrix (BCC) > B 0 matrix (FCC) > B 0 matrix (C14). The fit using the Rault's model gives for the supercrystal: B 0 SC (BCC) = 8.5 ± 1 GPa, B 0 SC (FCC) = 5.3 ± 1 (as reported in our previous experiment 22 ), B 0 SC (C14) = 3 ± 1 GPa. and for the matrix: B 0 matrix (BCC) = 7 ± 1 GPa, B 0 matrix (FCC) = 4 ± 1 Gpa, B 0 matrix (C14) = 1.5 ± 1 GPa.…”

Section: Resultssupporting

confidence: 69%

“…This argument is coherent with the previous observation of a larger bulk modulus of the matrix compared to free ligands, measured on FCC-3-C12 sample and pure dodecane samples. 22 This effect was attributed to a less optimized chain packing under pressure compared to the free chains, as the chains are constrained by both grafting and confinement within the soft matrix. This model is based on perfectly spherical cores and this is not the case.…”

Section: Resultsmentioning

confidence: 99%

“…31,32 Thus the matrix volume, defined as the volume occupied by both the void and grafted ligands per NP ( V M = V ligands + V void ) can be extracted using the relation: V M = V − V c . This is the method used in a previous paper 22 on FCC supercrystal (FCC-5-C12 from Table 1). The volume per particle V as well as the matrix volume per particle V M extracted for each pressure were fitted the equation of state using the eqn (1) with three parameters V *, V 0 , P *, from ref.…”

Section: Methodsmentioning

confidence: 99%

“…In a previous paper, 22 we reported the mechanical behavior of a FCC supercrystal under hydrostatic pressure. Up to 12 GPa, the SC showed a remarkable high structural stability.…”

Section: Introductionmentioning

confidence: 99%

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High-pressure behavior of hydrophobically coated gold nanoparticle supercrystals: role of the structure

et al. 2023

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Section: Resultssupporting

confidence: 84%

Section: Resultssupporting

confidence: 69%

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

“…In a previous paper, 22 we reported the mechanical behavior of a FCC supercrystal under hydrostatic pressure. Up to 12 GPa, the SC showed a remarkable high structural stability.…”

Section: Introductionmentioning

confidence: 99%

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High-pressure behavior of hydrophobically coated gold nanoparticle supercrystals: role of the structure

et al. 2023

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Elucidating Supercrystal Mechanics and Nanoparticle Size and Shape Effects under High Pressure

Hotton,

García‐Lojo,

Modin

et al. 2024

Small Structures

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Supercrystals, extended lattices of closely packed nanoparticles (NPs), present exciting possibilities for various applications. Under high pressures, typically in the gigapascal (GPa) range, supercrystals undergo significant structural changes, including adjustable interparticle distances, phase transformations, and the formation of new nanostructures through coalescence. While prior research has focused on ligand engineering's impact on supercrystal mechanical response, the influence of NP shape remains unexplored, especially for NPs larger than 10 nm coated with hydrosoluble ligands. This study examines the effects of NP shape on the mechanical properties of supercrystals using high‐pressure small‐angle X‐ray scattering and focused ion beam–scanning electron microscopy tomography. Notably, supercrystals exhibit higher hardness levels compared to previously reported values for gold supercrystals, attributed to the use of larger NPs. Spherical and tetrahedral NPs rearrange before collapsing under pressure, whereas rods and octahedra coalesce without prior structural rearrangement, likely due to their higher packing fraction. Additionally, anisotropic deformation of NP lattices and sintering does not always correlate with deviatoric stresses. These findings refine the understanding of complex processes governing supercrystal structure under high pressure, opening new avenues for NP engineering and advancing plasmonic applications under extreme conditions.

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Pressure and Composition Effects on a Common Nanoparticle Ligand–Solvent Pair

Salas Sanabria,

Hanson

2024

J. Phys. Chem. B

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The effect of pressure on the properties of nanoparticles is a growing area of investigation. These measurements are typically performed in a colloidal suspension; however, pressure-induced changes in the interactions between the nanoparticle surface and the solvent are often neglected. Here, we report vibrational spectroscopy of a common nanoparticle ligand, 1-dodecanethiol, and a common solvent, toluene, under pressure. We find that the pressure-induced phase change of the 1dodecanethiol is altered by the presence of toluene and that change depends on the concentration of the free ligand in the solution. At near-equal concentrations, phase segregation is observed and the dodecanethiol crystallizes independently from the toluene. On the other hand, at unequal concentrations, concerted phase transitions are observed in the dodecanethiol and toluene, and a disordered conformation of dodecanethiol is maintained under much higher pressures. These results shed light on the pressure-induced changes in intermolecular interactions between nanoparticle ligands and solvents, which must be considered in the design of high-pressure investigations of colloidal nanoparticles.

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Mechanics under pressure of gold nanoparticle supracrystals: the role of the soft matrix

Abstract: The bulk modulus of 3D FCC supracrystals of spherical gold nanoparticles is determined using high pressure-SAXS measurements. The organic ligand shell is found to be less compressible than pure dodecane with the same chain length.

Cited by 3 publications

References 26 publications

High-pressure behavior of hydrophobically coated gold nanoparticle supercrystals: role of the structure

High-pressure behavior of hydrophobically coated gold nanoparticle supercrystals: role of the structure

Elucidating Supercrystal Mechanics and Nanoparticle Size and Shape Effects under High Pressure

Pressure and Composition Effects on a Common Nanoparticle Ligand–Solvent Pair

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