Self-assembly methods for forming hedgehog-shaped particles
Self-assembly methods are provided for making hedgehog-shaped microparticles or nanoparticles. The method may comprise combining a metal-containing (e.g., Fe, Au) precursor, a chalcogen-containing precursor (e.g., Se, S), and a self-assembly additive (e.g., dodecanethiol (DT), oleylamine (OLA), hexadecyltrimethylammonium bromide (CTAB)). At least one hedgehog-shaped nanoscale, mesoscale, or microscale particle is formed that defines a core region formed of a first material and a plurality of needles connected to and substantially orthogonal to a surface of the core region. The needles comprise a second material. At least one of the first or the second material comprises iron or gold and optionally selenium or sulfur, for example, iron diselenide (FeSe2). Hedgehog-shaped microparticles or nanoparticles formed from such self-assembly methods are also provided. The semiconductor nature of FeSe2 hedgehog-shaped particles enables their utilization in biomimetic catalysis, drug delivery, optics, and energy storage, by way of non-limiting example.
1. A self-assembly method for making a hedgehog-shaped particle, the method comprising:
combining a metal-containing precursor, a chalcogen-containing precursor, and a self-assembly additive; and
forming at least one hedgehog-shaped particle via self-assembly by first forming a plurality of platelet-like nanoparticles that assemble together into a nanosheet, wherein the nanosheet rolls into a hollow structure that defines a needle to form one of a plurality of needles connected to and substantially orthogonal to a surface of a core region formed of a first material, wherein the plurality of needles comprises a second material, wherein at least one of the first material or the second material comprises a metal and a chalcogen.
2. The self-assembly method of claim 1 , wherein the nanosheet comprises a single crystal morphology.
3. The self-assembly method of claim 1 , wherein the combining further comprises forming a first liquid by combining the metal-containing precursor with a first portion of the self-assembly additive and heating the first liquid; and
forming a second liquid comprising the chalcogen-containing precursor and a second portion of the self-assembly additive; and
injecting the second liquid into the first liquid to form the at least one hedgehog-shaped nanoscale, mesoscale, or microscale particle.
4. The self-assembly method of claim 3 , wherein the first liquid is heated to greater than or equal to about 175° C.
5. The self-assembly method of claim 1 , wherein the metal-containing precursor is an iron-containing precursor or a gold-containing precursor.
6. The self-assembly method of claim 5 , wherein the iron-containing precursor comprises iron chloride (FeCl 3 ) and the chalcogen-containing precursor comprises selenium (Se).
7. The self-assembly method of claim 5 , wherein the gold-containing precursor comprises gold hydrochloride (HAuCl 4 ) and the chalcogen-containing precursor comprises sulfur (S).
8. The self-assembly method of claim 1 , wherein at least one of the first material or the second material comprises iron diselenide (FeSe 2 ).
9. The self-assembly method of claim 1 , wherein at least one of the first material or the second material comprises a gold thiolate.
10. The self-assembly method of claim 1 , wherein the self-assembly additive is selected from the group consisting of: dodecanethiol (DT), oleylamine (OLA), hexadecyltrimethylammonium bromide (CTAB), and combinations thereof.
11. The self-assembly method of claim 1 , wherein the combining further comprises a metal dopant.
12. The self-assembly method of claim 1 , wherein the metal is selected from the group consisting of: iron (Fe), gold (Au), nickel (Ni), molybdenum (Mo), niobium (Nb), technetium (Tc), tungsten (W), tantalum (Ta), chromium (Cr), manganese (Mn), copper (Cu), vanadium (V), titanium (Ti), zirconium (Zr), hafnium (Hf), ruthenium (Ru), osmium (Os), zinc (Zn), rhenium (Re), and combinations thereof and combinations thereof; and
the chalcogen is selected from the group consisting of selenium, sulfur, and combinations thereof.
13. The self-assembly method of claim 1 , wherein the at least one hedgehog-shaped particle comprises a plurality of hedgehog-shapes particles having an average particle size diameter of greater than or equal to about 50 nm to less or equal to about 15 μm.
14. The self-assembly method of claim 1 , wherein an average length of each respective needle of the plurality of needles is greater than or equal to about 5 nm to less or equal to about 5 μm, an average diameter of the respective needle of the plurality of needles is greater than or equal to about greater than or equal to about 1 nm to less or equal to about 500 nm, and an average wall thickness of the respective needle of the plurality of needles is greater than or equal to about 0.5 nm and less than or equal to about 100 nm.
15. The self-assembly method of claim 1 , wherein the at least one hedgehog-shaped particle comprises a plurality of hedgehog-shapes particles having an average diameter of the core region of greater than or equal to about 30 nm to less or equal to about 10 μm.
16. A self-assembly method for making a hedgehog-shaped particle, the method comprising:
combining a metal-containing precursor, a chalcogen-containing precursor, and a self-assembly additive selected from the group consisting of: dodecanethiol (DT), oleylamine (OLA), hexadecyltrimethylammonium bromide (CTAB), and combinations thereof, wherein the metal-containing precursor comprises iron chloride (FeCl 3 ) and the chalcogen-containing precursor contains selenium (Se) or the metal-containing precursor comprises gold hydrochloride (HAuCl 4 ) and the chalcogen-containing precursor contains sulfur (S); and
forming at least one hedgehog-shaped particle via self-assembly by first forming a plurality of platelet-like nanoparticles, wherein a portion of the platelet-like nanoparticles defines a core region and further wherein a portion of the platelet-like nanoparticles assembles together into a nanosheet that rolls into a hollow structure and defines a needle to form one of a plurality of needles connected to and substantially orthogonal to a surface of the core region, wherein the core region and the plurality of needles comprises either iron diselenide (FeSe 2 ) or gold thiolate.
17. The self-assembly method of claim 16 , wherein the nanosheet comprises a single crystal morphology.
18. The self-assembly method of claim 16 , wherein the combining further comprises forming a first liquid by combining the metal-containing precursor with a first portion of the self-assembly additive and heating the first liquid; and
forming a second liquid comprising the chalcogen-containing precursor and a second portion of the self-assembly additive; and
injecting the second liquid into the first liquid to form the at least one hedgehog-shaped nanoscale, mesoscale, or microscale particle.
19. The self-assembly method of claim 18 , wherein the first liquid is heated to greater than or equal to about 175° C.
20. The self-assembly method of claim 16 , wherein the iron-containing precursor comprises iron chloride (FeCl 3 ) and the chalcogen-containing precursor comprises selenium (Se).
21. The self-assembly method of claim 16 , wherein the gold-containing precursor comprises gold hydrochloride (HAuCl 4 ), the chalcogen-containing precursor comprises sulfur (S), the self-assembly additive is selected from the group consisting of: dodecanethiol (DT), oleylamine (OLA), and combinations thereof, and the first material and the second material comprises iron diselenide (FeSe 2 ).
22. The self-assembly method of claim 16 , wherein the metal-containing precursor comprises gold hydrochloride (HAuCl 4 ), the chalcogen-containing precursor contains sulfur (S), the self-assembly additive comprises hexadecyltrimethylammonium bromide (CTAB) and the first material and the second material comprises a gold thiolate.
23. The self-assembly method of claim 16 , wherein the combining further comprises a metal dopant.