Chemistry Mediated Mechanical Behavior of Inorganic Nanostructures

Date
2021-08-31
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Abstract

Unique and fascinating chemistry transpires at surfaces that cannot take place in bulk materials due to the presence of dangling bonds as well as strained or otherwise unusual coordination environments. As the size of an object becomes smaller, the fraction of surface atoms to bulk atoms increases. Ultimately, for nanometer-sized particles, surface effects become so large that the behavior of the system can change completely, leading to many of the unique properties associated with nanoscale materials. At this length scale, forces that would ordinarily have little to no influence on atoms in the bulk can have an enormous impact on surface atoms and thus dictate the behavior of the system. Since all inorganic nanoparticles are capped with organic ligands that provide them stability in solution, the chemistry at the surface atom-ligand interface can be leveraged to drive new chemical processes or physical phenomena that would be impossible at any other length scale. Colloidal silver nanoplates can be readily synthesized that are several nanometers thin, maximizing the fraction of surface atoms and making them an ideal candidate for studying the effects of surface chemistry on nanoparticle properties. Their high aspect ratio renders them unusually flexible such that when draped over much small spherical nanoparticles, the plates deform, a process that can be observed via distinctive bend contours in electron microscopy images. Topographically, this locally deformed region presents as an axially symmetric bump on the surface of the nanoplate, as confirmed by atomic force microscopy measurements. To understand the structural nature of this deformation, an analytical model based on Kirchhoff-Love plate theory was developed. This reveals that the local deformation of the nanoplate around the spherical particle is driven by the Van der Waals (VdW) interaction between the nanoplate and the experimental substrate. The ability for the VdW interaction to deform the nanoplate is shown to be heavily dependent on the thickness of the nanoplate; and it is estimated that structures thicker than ~10 nm would not be deformable. For the experimentally observed deformation to be possible, the analytical model must include plastic deformation, the occurrence of which was further confirmed by finite element simulations (COMSOL) as well as electron microscopy studies. The size of the described bend contour is related to the extent of the topographical deformation in the nanoplate. This was confirmed by varying the size of the sphere over which the nanoplate was deformed, displaying that the size of the bend contour was directly related to the size of the spherical nanoparticle. With this in mind, we hypothesized that the bend contours could be used to study the potential influence of surface chemistry on mechanical properties. As synthesized, the nanoplates are capped with a weakly bound citrate ligand which can be replaced with a library of other commonly used molecules: pyrrolidone (PVP), a phosphine, a thiol, and an N-heterocyclic carbene. It was found that the spatial extent of the bend contour changed proportionally to the binding strength of the surface ligand, suggesting that the mechanical strength of the nanoplate is also proportionally related to binding strength. We postulate that this mechano-chemical coupling arises from the atomic reorganization of surface atoms upon interactions with increasingly strongly binding ligands, changing the surface stress and the yield strength. In the case of more strongly binding ligands, the atomic reorganization of the surface layers of atoms is so severe that the nanoplate becomes stronger and the extent of the spatial deformation is larger than for weaker bound ligands. This work investigates a fundamentally new size-dependent interaction driven by the surface chemistry of inorganic nanoparticles. We envision using these results as a basis for being able to create a new class of nanoscale materials capable of physical bending and structurally reconfiguring themselves via chemical cues to adapt to the needs of a given application.

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Degree
Doctor of Philosophy
Type
Thesis
Keywords
nanoplate, nanostructure, post-synthetic modification, nanomechanics, mechanics, deformation, curvilinear, mechanochemistry, surface chemistry, functionalization, transmission electron microscopy
Citation

Rehn, Sarah M. "Chemistry Mediated Mechanical Behavior of Inorganic Nanostructures." (2021) Diss., Rice University. https://hdl.handle.net/1911/111346.

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