Metal alloy nanoparticle synthesis via self-assembled monolayer formation and ultrasound
View Patent ↗Methods and assemblies for the construction of liquid-phase alloy nanoparticles are presented. Particle formation is directed by molecular self-assembly and assisted by sonication. In some embodiments, eutectic gallium-indium (EGaIn) nanoparticles are formed. In these embodiments, the bulk liquid alloy is ultrasonically dispersed, fast thiolate self-assembly at the EGaIn interface protects the material against oxidation. The assembly shell has been designed to include intermolecular hydrogen bonds, which induce surface strain, assisting in cleavage of the alloy particles to the nanoscale. X-ray diffraction and TEM analyses reveal that the nanoscale particles are in an amorphous or liquid phase, with no observed faceting.
1. A method of forming liquid-phase metal alloy nanoparticles comprising:
providing a liquid phase metal alloy material having at least two separate alloying components;
placing the liquid phase metal alloy material into solution with an organic self-assembly molecule, the self-assembly molecule having a first end having a functional group covalently reactive with the liquid phase metal alloy and a second end having one or more functional groups capable of exerting a directional intermolecular bonding interaction with adjacent self-assembly molecules, the directional intermolecular bonding interaction being selected from the group consisting of: hydrogen bonding, coordination chemistry and covalent bonding;
dispersing the liquid phase metal alloy material through the solution by application of ultrasonic treatment such that self-assembly molecules adsorb with the liquid phase metal alloy material;
assembling the liquid phase metal alloy material into nanoparticles of liquid phase metal alloy material via self-assembly of the self-assembly molecules such that a monolayer shell of self-assembly molecules is formed about each of the nanoparticles of liquid phase metal alloy material wherein the first end of each of the self-assembly molecules is covalently bound to the outer surface of the nanoparticle and wherein the second end of each of the self-assembly molecules extends outward from the nanoparticle and interacts with the second ends of adjacent self-assembly molecules in the monolayer shell through the directional intermolecular bonding interaction; and
wherein the directional intermolecular bonding interactions between the adjacent self-assembly molecules of the monolayer shell induce surface strain in the underlying alloy nanoparticle such that the nanoparticle is comprised of a plurality of scissionable domains, each scissionable domain being defined by the presence of local order between the self-assembly molecules.
2. The method of claim 1 , further comprising ultrasonically treating the nanoparticles to further reduce the size of the nanoparticles.
3. The method of claim 1 , wherein an outer surface of the liquid phase metal alloy is passivated.
4. The method of claim 3 , wherein the passivation comprises oxidizing the outer surface of the alloy material.
5. The method of claim 1 , wherein the liquid phase metal alloy is an EGaIn material.
6. The method of claim 5 , wherein the EGaIn material is further doped with at least one additional alloying material.
7. The method of claim 6 , wherein the at least one additional alloying material is selected from the group consisting of the noble metals, arsenic, iron, copper, chrome and combinations thereof.
8. The method of claim 6 , wherein the at least one additional alloying material is a photoactive material.
9. The method of claim 1 , wherein the self-assembly molecule exerts the directional intermolecular bonding interaction through one of either coordination chemistry or direct covalent bonding.
10. The method of claim 1 , wherein the self-assembly molecule has a second end comprising one of the following functional groups: carboxylic groups, metal and nonmetal functional groups, and azide and alkyne functional groups.
11. The method of claim 1 , wherein the self-assembly molecule has a thiol at its first end.
12. The method of claim 1 , wherein the self-assembly molecule is 3-mercapto-N-propionamide.
13. The method of claim 1 , further comprising purifying the nanoparticles via centrifugation.
14. The method of claim 1 , wherein the nanoparticles are spheroids.